WO2013046897A1 - Système d'affichage d'image stéréoscopique - Google Patents

Système d'affichage d'image stéréoscopique Download PDF

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WO2013046897A1
WO2013046897A1 PCT/JP2012/069087 JP2012069087W WO2013046897A1 WO 2013046897 A1 WO2013046897 A1 WO 2013046897A1 JP 2012069087 W JP2012069087 W JP 2012069087W WO 2013046897 A1 WO2013046897 A1 WO 2013046897A1
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group
film
acid
carbon atoms
retardation
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PCT/JP2012/069087
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English (en)
Japanese (ja)
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賢治 三島
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コニカミノルタアドバンストレイヤー株式会社
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Priority to JP2013536019A priority Critical patent/JP5915660B2/ja
Publication of WO2013046897A1 publication Critical patent/WO2013046897A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B35/00—Stereoscopic photography
    • G03B35/18—Stereoscopic photography by simultaneous viewing
    • G03B35/26—Stereoscopic photography by simultaneous viewing using polarised or coloured light separating different viewpoint images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
    • G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
    • G02B30/22—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type
    • G02B30/25—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type using polarisation techniques

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  • the present invention relates to a stereoscopic image display system. More specifically, the present invention relates to a stereoscopic image display system with improved hue (color tone) change and crosstalk in an oblique direction, and more particularly, to a stereoscopic image display system provided with an organic electroluminescence element.
  • a stretched film obtained by stretching a resin film is used as an optical material such as a component of a display device by utilizing its optical anisotropy.
  • the stretched film is used as a retardation film for optical compensation such as anti-coloring and viewing angle expansion, or the stretched film and a polarizer are bonded together to be used as a polarizing plate. It has been known.
  • organic electroluminescence display devices hereinafter also referred to as “organic EL display devices”
  • stereoscopic image display devices In recent years, the retardation film has been required for improving the display quality of organic electroluminescence display devices (hereinafter also referred to as “organic EL display devices”) and stereoscopic image display devices.
  • a self-luminous display device in which a light source corresponding to each color is turned on, such as an organic EL display device, it is not necessary to install a color filter that causes a reduction in contrast, so that the contrast can be further increased.
  • a reflector such as an aluminum plate is provided on the back side of the display in order to increase the light extraction efficiency. Therefore, external light incident on the display is reflected by the reflector and the image is displayed. There is a problem of lowering the contrast. For this reason, it is known that the stretched film and a polarizer are bonded to form a circularly polarizing plate and used on the surface side of the display in order to improve contrast of light and darkness by preventing external light reflection (see Patent Document 1).
  • the circularly polarizing plate needs to have the in-plane slow axis of the stretched film bonded at a desired angle with respect to the transmission axis of the polarizer, and has a phase difference value of 1 ⁇ 4 of the wavelength of the viewing light.
  • a retardation film also referred to as a ⁇ / 4 retardation film or a ⁇ / 4 plate in this application
  • An example is the combination.
  • stereoscopic image display devices On the other hand, several methods are known for stereoscopic image display devices. One of them is a stereoscopic image viewing glasses with a liquid crystal shutter function. There is a method of allowing an observer to recognize a (three-dimensional: 3D) image. What is currently viewed as promising in this method is that the right-eye image and the left-eye image, which are parallax images, are alternately displayed in time series on the display that displays the image, and the observer uses glasses for viewing stereoscopic images. A method of wearing an image and viewing an image of a liquid crystal display device (see, for example, Patent Document 5).
  • a stereoscopic image display device when viewing a stereoscopic (three-dimensional: 3D) image of a liquid crystal display device by wearing polarized glasses, the polarization angle of the polarized glasses and the angle of polarization emitted from the liquid crystal display device are determined from appropriate angles. There was a problem that the image was doubled when shifted. In order to prevent this, there is a need for a retardation film having a retardation value (also referred to as “retardation value”) that is 1 ⁇ 4 of the wavelength of the viewing light.
  • retardation value also referred to as “retardation value”
  • an organic EL stereoscopic image display device (hereinafter also referred to as “3D-OLED”) in which an organic EL light emitting element and a stereoscopic image display device are combined has become a new need in the market.
  • the 3D-OLED has a problem that the hue (hue) change when viewed from an oblique direction is more remarkable than that of a normal (two-dimensional) organic EL display device.
  • a polarizing plate protected with a retardation film having both in-plane retardation of ⁇ / 4 is pasted on a display device, and a ⁇ / 4 retardation film is also pasted on shutter glasses. It can be predicted from the prior art that a circularly polarizing plate is used.
  • the present invention has been made in view of the above-described problems and situations, and a solution to that problem is a stereoscopic image display system with improved hue (color) change and crosstalk in an oblique direction, particularly an organic electroluminescence element.
  • a stereoscopic image display system is provided.
  • the present inventor has solved the above-mentioned problem by using a polarizing plate including a retardation film having specific optical characteristics in a stereoscopic image display device.
  • the inventors have found that the problem can be solved, and have reached the present invention.
  • a stereoscopic image display system comprising an image display device having at least a polarizing plate and a light emitting element and glasses having at least a polarizer, wherein the polarizing plate satisfies the following requirements (a) to (c): Stereoscopic image display system characterized by (A) On the both sides of the polarizer drawn out from the long roll, the retardation film having the following optical characteristics is drawn out from the long roll in the same direction as the long direction of the polarizer. It is formed by bonding.
  • the slow axis of the retardation film bonded to both surfaces of the polarizer is in the direction between the two different from the longitudinal direction and the width direction of the polarizer, and is on both surfaces of the polarizer.
  • the slow axes of the retardation film are bonded in directions orthogonal to each other.
  • C The in-plane retardation value Ro of the retardation film and the retardation value Rt in the thickness direction measured at an optical wavelength of 550 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% are respectively represented by the following formulas ( 1) to (4) are satisfied.
  • Rt (T1) represents the retardation value Rt in the thickness direction of the retardation film T1 bonded to the viewing side of the polarizer of the polarizing plate laminated on the light emitting element.
  • Rt (T2) Represents the retardation value Rt in the thickness direction of the retardation film T2 bonded to the light emitting element side of the polarizer of the polarizing plate laminated on the light emitting element.
  • an image display device with improved hue (color) change and crosstalk in an oblique direction, particularly a stereoscopic image display system provided with an organic electroluminescence element.
  • the stereoscopic image display system of the present invention is a stereoscopic image display system including an image display device having at least a polarizing plate and a light-emitting element, and glasses having at least a polarizer. A) to (c) are satisfied.
  • the light emitting element is an organic electroluminescence element from the viewpoint of the effect of the present invention.
  • the retardation film contains a cellulose ester having a total acyl group substitution degree in the range of 2.0 to 2.6 because predetermined optical characteristics can be obtained.
  • ⁇ 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.
  • the stereoscopic image display system of the present invention is a stereoscopic image display system including an image display device having at least a polarizing plate and a light emitting element, and glasses having at least a polarizer, and the polarizing plate has the following requirements ( A) to (c) are satisfied.
  • the retardation film having the following optical characteristics is drawn out from the long roll in the same direction as the long direction of the polarizer. It is formed by bonding.
  • the slow axis of the retardation film bonded to both surfaces of the polarizer is in the direction between the two different from the longitudinal direction and the width direction of the polarizer, and is on both surfaces of the polarizer.
  • the slow axes of the retardation film are bonded in directions orthogonal to each other.
  • C The in-plane retardation value Ro of the retardation film and the retardation value Rt in the thickness direction measured at an optical wavelength of 550 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% are respectively represented by the following formulas ( 1) to (4) are satisfied.
  • Rt (T2) Represents the retardation value Rt in the thickness direction of the retardation film T2 bonded to the light emitting element side of the polarizer of the polarizing plate laminated on the light emitting element.
  • the said light emitting element is an organic electroluminescent element.
  • the retardation film contains a cellulose ester having a total acyl group substitution degree in the range of 2.0 to 2.6 since the predetermined optical characteristics can be obtained.
  • the polarizing plate according to the present invention has the following three roles.
  • the above (a) and (b) are roles as a solution to a known problem.
  • a ⁇ / 4 retardation film is bonded to one surface of the polarizer, and the other surface does not have a retardation value (particularly an in-plane retardation value).
  • a polarizer protective film is bonded. At this time, the polarizer is bonded at an angle between the absorption axis of the polarizer and the slow axis of the ⁇ / 4 retardation film in the range of 25 to 65 °, preferably 45 °.
  • the difference between (a) and (b) is whether the ⁇ / 4 retardation film is arranged on the viewing side or the display panel side with respect to the polarizer.
  • the above-mentioned role can be achieved by arranging a ⁇ / 4 retardation film on the viewing side (T1) in (a) and on the panel side (T2) in (b).
  • a circularly polarizing plate is required for shutter glasses for stereoscopic (3D) video.
  • a ⁇ / 4 retardation film is bonded to both sides of the polarizer.
  • the laminating direction is such that the angle formed by the absorption axis of the polarizer and the slow axis of the ⁇ / 4 retardation film is 45 °, and ⁇ / The slow axes of the four retardation films are orthogonal to each other.
  • the means is (i) and (ii) above.
  • the range of the retardation value Rt in the thickness direction required for the ⁇ / 4 retardation film disposed at T1 and T2 is slightly different as represented by the equations (2) and (3).
  • the range of Rt required for the ⁇ / 4 retardation film of T1 is in the range of 20 to 250 nm, preferably in the range of 50 to 150 nm, and more preferably in the range of 60 to 100 nm.
  • the range of Rt required for the ⁇ / 4 retardation film of T2 is in the range of 0 to 100 nm, preferably in the range of 10 to 80 nm, and more preferably in the range of 20 to 50 nm.
  • a ⁇ / 4 retardation film outside this range is arranged at T2
  • the color variation due to the viewing angle increases.
  • Rt ratio value Rt (T2) / Rt (T1) of ⁇ / 4 retardation film of T1 and T2 is in the range of 0 to 1.7, preferably in the range of 0.1 to 1.2. More preferably, it is in the range of 0.4 to 1.0.
  • the ⁇ / 4 retardation film (also referred to as “ ⁇ / 4 plate”) according to the present invention has a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).
  • the ⁇ / 4 retardation film has an in-plane retardation value Ro of about 1 ⁇ 4 for a predetermined wavelength of light (usually in the visible light region).
  • Ro (550) measured at a wavelength of 550 nm is preferably in the range of 108 to 168 nm, Ro (550) is preferably 120 to 160 nm, and Ro (550) is 130. More preferably, it is ⁇ 150 nm.
  • the ⁇ / 4 retardation film according to the present invention has a phase difference (retardation) of approximately 1 ⁇ 4 of the wavelength in the visible light wavelength range in order to obtain almost perfect circularly polarized light in the visible light wavelength range.
  • a retardation film is preferred.
  • a phase difference (retardation) of approximately 1 ⁇ 4 in the wavelength range of visible light is expressed by the following formula (I) measured at a wavelength of 450 nm.
  • the difference Ro (550) ⁇ Ro (450) between the phase difference value Ro (450) and the phase difference value Ro (550) measured at a wavelength of 550 nm is preferably in the range of 2 to 34 nm. Is more preferable, and a range of 8 to 28 nm is particularly preferable.
  • Formula (I): Ro (n x ⁇ n y ) ⁇ d
  • Rt ⁇ (n x + n y ) / 2 ⁇ n z ⁇ ⁇ d
  • n x, n y, n z is, 23 °C ⁇ 55% RH, say 450 nm
  • Ny reffractive index in the direction perpendicular to the slow axis in the film plane
  • nz reffractive index of the film in the thickness direction
  • d is the thickness (nm) of the film.
  • Retardation values Ro and Rt can be measured using an automatic birefringence meter.
  • Ro and Rt are calculated by birefringence measurement at each wavelength in an environment of 23 ° C. and 55% RH.
  • a circularly polarizing plate is obtained by laminating so that the angle between the slow axis of the ⁇ / 4 retardation film and the transmission axis of the polarizer described later is substantially 45 °.
  • “Substantially 45 °” means a range of 40 to 50 °.
  • the angle between the in-plane slow axis of the ⁇ / 4 retardation film and the transmission axis of the polarizer is preferably in the range of 41 to 49 °, more preferably in the range of 42 to 48 °, 43 A range of ⁇ 47 ° is more preferred, and a range of 44-46 ° is most preferred.
  • the cellulose ester according to the present invention preferably has a total acyl group substitution degree in the range of 2.0 to 2.6, more preferably in the range of 2.2 to 2.5.
  • the total acyl group substitution degree is the average value of the number of esterified (acylated) hydroxy groups (hydroxyl groups) among the three hydroxy groups (hydroxyl groups) of each anhydroglucose constituting the cellulose. Indicates a value in the range of 0-3.
  • the part which is not substituted usually exists as a hydroxy group (hydroxyl group).
  • substitution degree of the acyl group was determined by the method prescribed in ASTM-D817-96 (test method for cellulose acetate and the like).
  • the number average molecular weight (Mn) of the cellulose ester according to the present invention is preferably in the range of 30,000 to 300,000, since the mechanical strength of the resulting film is strong. Further, 50,000 to 200,000 are preferably used.
  • the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester is preferably 1.4 to 3.0.
  • the weight average molecular weight Mw and number average molecular weight Mn of the cellulose ester were measured using gel permeation chromatography (GPC).
  • the measurement conditions are as follows.
  • the cellulose as a raw material of the cellulose ester 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 ester 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,
  • a predetermined organic acid such as acetic acid
  • acid anhydride such as acetic anhydride
  • a catalyst such as sulfuric acid
  • the ⁇ / 4 retardation film according to the present invention may contain calcium and magnesium.
  • the total amount of calcium and magnesium and the amount of acetic acid preferably satisfy the following relational expression (a).
  • the acid catalyst especially sulfuric acid
  • It may be added as a hydroxide or metal salt (inorganic acid salt, organic acid salt).
  • you may add as a metal oxide, a metal hydroxide, and a metal salt (inorganic acid salt, organic acid salt) at the time of optical film forming.
  • acetic anhydride or acetic acid is used as a reaction solvent or an esterifying agent. Unreacted acetic anhydride is hydrolyzed by a reaction stopper (water, alcohol, acetic acid, etc.) to produce acetic acid.
  • a reaction stopper water, alcohol, acetic acid, etc.
  • the amount of acetic acid contained in the ⁇ / 4 retardation film refers to the total amount of residual acetic acid and free acetic acid.
  • the total amount of calcium and magnesium contained in the ⁇ / 4 retardation film is preferably in the range of 5 to 130 ppm, more preferably in the range of 5 to 80 ppm, and still more preferably in the range of 5 to 50 ppm.
  • the calcium and magnesium contained in the ⁇ / 4 retardation film can be quantified by a known method. For example, after the dried cellulose ester is completely burned, the ash is dissolved in hydrochloric acid and pretreated. It can be measured by the atomic absorption method after the measurement. The measured value is obtained in units of ppm as the calcium and magnesium contents in 1 g of the completely dry cellulose ester.
  • the amount of acetic acid contained in the ⁇ / 4 retardation film is preferably in the range of 20 to 500 ppm, more preferably in the range of 25 to 250 ppm, and still more preferably in the range of 30 to 150 ppm.
  • a known method can be used for quantification of acetic acid contained in the ⁇ / 4 retardation film.
  • the following method can be used.
  • the ⁇ / 4 retardation film is dissolved in methylene chloride, and methanol is added to perform reprecipitation.
  • the amount of acetic acid can be obtained by filtering the supernatant and measuring the supernatant with gas chromatography.
  • the melting point of the ⁇ / 4 retardation film according to the present invention is preferably in the range of 200 to 290 ° C.
  • Methods for adjusting the melting point within the above range include controlling the degree of substitution of the cellulose ester or adding a plasticizer.
  • the ⁇ / 4 retardation film according to the present invention can be used in combination with a thermoplastic resin other than the cellulose ester as long as the effects of the present invention are not impaired.
  • thermoplastic resin refers to a resin that becomes soft when heated to the glass transition temperature or melting point and can be molded into the desired shape.
  • thermoplastic resins polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc) Teflon (registered trademark) (polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), and the like can be used.
  • PE polyethylene
  • PVC polyvinyl chloride
  • PS polyvinylidene chloride
  • PS polystyrene
  • PVAc polyvinyl acetate
  • Teflon polytetrafluoroethylene
  • AS resin acrylic resin
  • PMMA acrylic resin
  • PA polyamide
  • nylon polyacetal
  • PC polycarbonate
  • m-PPE modified polyphenylene ether
  • PBT polybutylene terephthalate
  • PET Polyethylene terephthalate
  • GF-PET glass fiber reinforced polyethylene terephthalate
  • COP cyclic polyolefin
  • polyphenylene sulfide PPS
  • polytetrafluoroethylene PTFE
  • polysulfone polyethersulfone
  • amorphous polyarylate liquid crystal polymer
  • polyether Ether ketone thermoplastic polyimide (PI)
  • PAI polyamideimide
  • the residual sulfuric acid content in the cellulose ester according to the present invention is preferably in the range of 0.1 to 40 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 40 ppm, the deposit on the die lip during heat melting increases, such being undesirable. Moreover, since it becomes easy to fracture
  • a smaller amount is preferable, but if it is less than 0.1, it is not preferable because the load of the cellulose ester washing process becomes too large, and it is not preferable because it may easily break. This is not well understood, although an increase in the number of washings may affect the resin. Further, the range of 0.1 to 30 ppm is preferable.
  • the residual sulfuric acid content can be similarly measured by ASTM-D817-96.
  • the total residual acid amount including other (such as acetic acid) residual acid is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less.
  • a poor solvent such as methanol or ethanol, or, as a result, a mixed solvent of a poor solvent and a good solvent can be used if it is a poor solvent. Organic impurities can be removed.
  • cellulose ester In order to improve the heat resistance, mechanical properties, optical properties, etc. of cellulose ester, it can be dissolved in a good solvent of cellulose ester and then reprecipitated in a poor solvent to remove low molecular weight components and other impurities of cellulose ester. it can. Furthermore, another polymer or a low molecular weight compound may be added after the reprecipitation treatment of the cellulose ester.
  • the cellulose ester used in the present invention preferably has few bright spot foreign matters when formed into a film.
  • a bright spot foreign material is an arrangement in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is placed between them, light from the light source is applied from one side, and the cellulose ester film is applied from the other side. This is the point where the light from the light source appears to leak when observed.
  • the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used.
  • the cause of bright spot foreign matter is considered to be one of the causes of unacetylated or low acetylated cellulose contained in cellulose ester.
  • Use of cellulose ester with little bright spot foreign substance and filtration of molten cellulose ester or cellulose ester solution It is also possible to remove the bright spot foreign matter through the filtration step in the same manner once in the solution state in at least one of the process of synthesizing the cellulose ester and the process of obtaining the precipitate. Since the molten resin has a high viscosity, the latter method is more efficient.
  • 0.01 mm or more is preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, further preferably 50 pieces / cm 2 or less, and 30 pieces / cm 2 or less.
  • the number is preferably 10 pieces / cm 2 or less, but most preferably none.
  • the bright spots of 0.005 to 0.01 mm or less are preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, and 50 pieces / cm 2 or less.
  • the number is preferably 30 pieces / cm 2 or less, more preferably 10 pieces / cm 2 or less, and most preferably none.
  • the cellulose ester composition (also referred to as a dope) to which a plasticizer, an ultraviolet absorber, an antioxidant, a stabilizer and the like are added and mixed is filtered rather than filtering the cellulose ester alone.
  • the cellulose ester may be dissolved in a solvent during the synthesis and reduced by filtration. Filtration is preferably performed with the viscosity of the melt containing the cellulose ester being 10,000 P or less, more preferably 5000 P or less, still more preferably 1000 P or less, and even more preferably 500 P or less.
  • the filter medium conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluorine resins such as tetrafluoroethylene resin are preferably used, and ceramics and metals are particularly preferably used.
  • the absolute filtration accuracy is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. These can be used in combination as appropriate.
  • the filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.
  • the ⁇ / 4 retardation film according to the present invention may be obtained by appropriately mixing polymer components other than the cellulose ester resin.
  • the polymer component to be mixed is preferably one having excellent compatibility with the cellulose ester, and the transmittance when formed into a film is preferably 80% or more, more preferably 90% or more, and further preferably 92% or more.
  • Organic solvents that dissolve cellulose esters and are useful for forming cellulose ester solutions or dopes include chlorinated organic solvents and non-chlorinated organic solvents.
  • Methylene chloride methylene chloride
  • non-chlorine organic solvent examples include 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, Examples include 1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane.
  • a dissolution method at room temperature can be used, but an insoluble material can be obtained by using a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. Can be reduced, which is preferable.
  • Methylene chloride can be used for cellulose esters other than cellulose triacetate, but methyl acetate, ethyl acetate, and acetone are preferably used. Particularly preferred is methyl acetate.
  • an organic solvent having good solubility with respect to the cellulose ester is referred to as a good solvent, and has a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main ( Organic) solvent.
  • the dope used in the present invention preferably contains an alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • these are gelling solvents that make dope film (web) gel when the dope is cast on a metal support and the solvent starts to evaporate and the ratio of alcohol increases, making the web strong and easy to peel off from the metal support. When these ratios are small, there is also a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent.
  • the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, and has good drying properties.
  • These organic solvents are called poor solvents because they are not soluble in cellulose esters alone.
  • the concentration of the cellulose ester in the dope is adjusted in the range of 15 to 30% by mass and the dope viscosity in the range of 100 to 500 Pa ⁇ s.
  • Additives added to the dope include plasticizers, ultraviolet absorbers, retardation adjusting agents, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, fine particles, and the like.
  • additives other than fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, or the like that imparts heat and moisture resistance to the polarizing plate used in the liquid crystal image display device. The additive will be described below.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, and R 1 to R 8 are mutually May be the same or different.
  • the total average degree of substitution of the compound represented by the general formula (1) added to the cellulose ester film in the present invention is in the range of 6.1 to 6.9, and the range of the degree of substitution is 4.0 to 6.9. A range of 8.0 is preferable.
  • the substitution degree distribution may be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds having different substitution degrees.
  • Plasticizer A compound known as a plasticizer is added to the ⁇ / 4 retardation film according to the present invention for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor transmission rate, adjusting retardation, etc.
  • phosphoric acid esters and carboxylic acid esters are preferably used.
  • the plasticizer is preferably contained in the ⁇ / 4 retardation film in the range of 1 to 40% by mass, particularly in the range of 1 to 30% by mass.
  • phosphate ester examples include triphenyl phosphate, tricresyl phosphate, phenyl diphenyl phosphate, and the like.
  • carboxylic acid esters examples include phthalic acid esters and citric acid esters; phthalic acid esters such as dimethyl phthalate, diethyl phosphate, dioctyl phthalate and diethyl hexyl phthalate; and citrate esters such as acetyl triethyl citrate and acetyl citrate. Mention may be made of tributyl. Other examples include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and triacetin. Alkylphthalylalkyl glycolates are also preferably used for this purpose.
  • the alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms.
  • 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, propyl phthalyl ethyl glycolate, methyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl Phthalyl ethyl glycolate, propyl phthalyl butyl
  • citrate plasticizers represented by the following compounds (CAE-1) to (CAE-3) described in Japanese Patent No. 3793184 as a plasticizer.
  • Polyhydric alcohol esters are also preferably used.
  • the polyhydric alcohol used in the ⁇ / 4 retardation film according to the present invention is represented by the following general formula (a).
  • R 1 represents an n-valent organic group
  • n represents a positive integer of 2 or more
  • the OH group represents an alcoholic and / or phenolic hydroxy group (hydroxyl group).
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of 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.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • polyhydric alcohols examples include the following, but the present invention is not limited to these.
  • Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms 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.
  • 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 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, tridecylic acid, Saturated fatty acids such as 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, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferred alicyclic monocarboxylic acids 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 biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid.
  • benzoic acid and toluic acid 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 biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid.
  • the aromatic monocarboxylic acid which has, or those derivatives can be mentioned.
  • 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 preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are. JP-A-2006-113239, paragraphs [0058] to [0061]] can be referred to for specific examples of the polyhydric alcohol ester plasticizer used in the present invention.
  • the polyhydric alcohol ester plasticizer used in the present invention is preferably contained in a range of 1 to 30% by mass, preferably 1 to 20% by mass with respect to the cellulose ester.
  • a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable.
  • the polyhydric alcohol ester plasticizer used in the present invention may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.
  • an aromatic terminal ester plasticizer represented by the following general formula (b).
  • benzene monocarboxylic acid component of the aromatic terminal ester plasticizer used in the present invention examples include, for example, benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, There are normal propyl benzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively.
  • alkylene glycol component having 2 to 12 carbon atoms of the aromatic terminal ester plasticizer used in the present invention examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, , 3-butanediol, 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-1,3propanediol (3,3-dimethylolheptane), 3-methyl- 1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl There
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the aromatic terminal ester include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. It can be used as a mixture of two or more.
  • aryl glycol component having 6 to 12 carbon atoms of the aromatic terminal ester examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol, etc., and these glycols are used as one kind or a mixture of two or more kinds. it can.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the aromatic terminal ester examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These are used as one kind or a mixture of two or more kinds.
  • aryl dicarboxylic acid component having 6 to 12 carbon atoms examples include phthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid and the like.
  • the number average molecular weight of the aromatic terminal ester plasticizer is preferably in the range of 300 to 2000, more preferably in the range of 500 to 1500.
  • the acid value is 0.5 mgKOH / g or less, the hydroxy group (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxy group (hydroxyl group) value is 15 mgKOH / g or less. Those are preferred.
  • the acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present at the molecular end) contained in 1 g of the sample.
  • the acid value and hydroxy group (hydroxyl group) value are measured in accordance with JIS K0070 (1992).
  • Example No. 1 (Aromatic terminal ester sample)> A reaction vessel was charged with 820 parts (5 moles) of phthalic acid, 608 parts (8 moles) of 1,2-propylene glycol, 610 parts (5 moles) of benzoic acid, and 0.30 parts of tetraisopropyl titanate as a catalyst. While stirring in an air stream, a reflux condenser was attached to reflux the excess monohydric alcohol, and heating was continued in the range of 130 to 250 ° C. until the acid value became 2 or less, and the generated water was continuously removed. . Next, the distillate is removed under a reduced pressure of 6.65 ⁇ 10 3 Pa to 4 ⁇ 10 2 Pa or less in the range of 200 to 230 ° C., and then filtered to obtain an aromatic terminal ester having the following properties: Got.
  • Viscosity 25 ° C., mPa ⁇ s); 19815 Acid value: 0.4 ⁇ Sample No. 2 (Aromatic terminal ester sample)> A sample was used except that 500 parts (3.5 moles) of adipic acid, 305 parts (2.5 moles) of benzoic acid, 583 parts (5.5 moles) of diethylene glycol, and 0.45 parts of tetraisopropyl titanate as a catalyst were used in the reaction vessel. No. In the same manner as in No. 1, an aromatic terminal ester having the following properties was obtained.
  • Viscosity 25 ° C., mPa ⁇ s); 90 Acid value: 0.05 ⁇ Sample No. 3 (Aromatic terminal ester sample)> Sample No. except that 410 parts (2.5 moles) of phthalic acid, 610 parts (5 moles) of benzoic acid, 737 parts (5.5 moles) of dipropylene glycol and 0.40 parts of tetraisopropyl titanate as the catalyst were used in the reaction vessel. . In the same manner as in No. 1, an aromatic terminal ester plasticizer having the following properties was obtained.
  • Viscosity 25 ° C., mPa ⁇ s
  • 43400 Acid value 0.2 JP-A-2009-192681, paragraphs [0123] to [0124] can be referred to for specific examples of the aromatic terminal ester plasticizer used in the present invention.
  • the content of the aromatic terminal ester plasticizer used in the present invention is preferably in the range of 1 to 20% by mass, particularly preferably in the range of 3 to 11% by mass in the cellulose ester film.
  • the polyester polyol used in the present invention is a polymer having a terminal hydroxyl group that can be obtained by a condensation reaction between a dibasic acid or an ester-forming derivative thereof and glycol.
  • the ester-forming derivative as used herein refers to an esterified dibasic acid, dibasic acid chloride, or dibasic acid anhydride.
  • the polyester polyol is obtained by dehydration condensation reaction of aromatic dibasic acid and glycol, addition of glycol to aromatic anhydride dibasic acid and dehydration condensation reaction, or by alcohol removal of esterified product of aromatic dibasic acid and glycol. It can be obtained by a condensation reaction.
  • an aromatic dicarboxylic acid having 10 to 16 carbon atoms or an ester-forming derivative thereof can be used.
  • a benzene ring structure, a naphthalene ring structure, Dicarboxylic acids having an aromatic ring structure such as anthracene ring structure and ester-forming derivatives thereof can be used.
  • orthophthalic acid having a substituent isophthalic acid having a substituent, terephthalic acid having a substituent, substituted Group-containing phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6 -Anthracene dicarboxylic acid and the like, esterified products thereof, acid chlorides, 1,8-naphth Etc.
  • acid anhydrides of dicarboxylic acids can be mentioned acid anhydrides of dicarboxylic acids, these may have a substituent on the aromatic ring, can be used in combination used or two or more of these alone.
  • 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid and esterified products thereof are preferable.
  • Preferred are 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and esterified products thereof, and particularly preferred are 2,6-naphthalenedicarboxylic acid and esterified products thereof.
  • the average carbon number of the dibasic acid of the polyester polyol means the carbon number of the dibasic acid when the polyester polyol is polymerized using a single dibasic acid.
  • the polyester polyol is polymerized using, it means the sum of the products of the carbon number of each dibasic acid and the molar fraction of the dibasic acid.
  • the average number of carbon atoms of the dibasic acid used as a raw material for the polyester polyol is in the range of 10 to 16. If the average carbon number of the dibasic acid is 10 or more, the retardation is excellent. If the average carbon number is 16 or less, the compatibility with the cellulose ester is remarkably excellent.
  • the dibasic acid preferably has an average carbon number of 10 to 14, more preferably an average carbon number of 10 to 12.
  • the aromatic dibasic acid having 10 to 16 carbon atoms and other dibasic acids can be used in combination.
  • the dibasic acid that can be used in combination is preferably a dicarboxylic acid having 4 to 9 carbon atoms or an ester-forming derivative thereof.
  • a dicarboxylic acid having 4 to 9 carbon atoms or an ester-forming derivative thereof for example, succinic acid, glutaric acid, adipic acid, maleic acid, succinic anhydride, maleic anhydride, orthophthalic acid
  • acids isophthalic acid, terephthalic acid, phthalic anhydride and the like, esterified products, and acid chlorides thereof.
  • glycol examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3 -Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclohexane Diols can be used alone or in combination of two or more, and ethylene glycol, diethylene glycol, 1,2-propylene glycol, 2-methyl-1,3-propanediol are preferable, and ethylene glycol, Diethylene glycol, 1 2-propylene glycol.
  • the polyester polyol of the present invention is well known for 10 to 25 hours in the temperature range of 180 to 250 ° C., for example, in the presence of an esterification catalyst, if necessary, with the dibasic acid or their ester-forming derivatives and glycol. It can manufacture by making it esterify by a conventional method.
  • a solvent such as toluene or xylene may be used, but a method using no solvent or glycol used as a raw material as a solvent is preferable.
  • esterification catalyst for example, tetraisopropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, dibutyltin oxide and the like can be used.
  • the esterification catalyst is preferably used in the range of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of dibasic acids or their ester-forming derivatives.
  • the molar ratio when the dibasic acid or their ester-forming derivative is reacted with the glycol must be a molar ratio in which the terminal group of the polyester becomes a hydroxyl group, and therefore, 1 mol of the dibasic acid or their ester-forming derivative.
  • glycol is 1.1 to 10 mol.
  • glycol is 1.5 to 7 moles per mole of dibasic acid or ester-forming derivative thereof, and more preferably, per mole of dibasic acid or ester-forming derivative thereof.
  • the glycol is 2-5 moles.
  • the carboxy group terminal in the polyester polyol lowers the humidity stability, so that the content is preferably low.
  • the acid value is preferably 5.0 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less.
  • the acid value means the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample.
  • the acid value is measured according to JIS K0070.
  • the polyester polyol preferably has a hydroxy group (hydroxyl group) value (OHV) in the range of 35 to 220 mg / g.
  • the hydroxy group (hydroxyl group) value here means the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to the hydroxy group (hydroxyl group) when OH group contained in 1 g of a sample is acetylated.
  • Acetic anhydride is used to acetylate OH groups in the sample, and unused acetic acid is titrated with a potassium hydroxide solution, and obtained from the difference from the initial titration value of acetic anhydride.
  • the content of hydroxy group (hydroxyl group) in the polyester polyol is preferably 70% or more.
  • the hydroxy group (hydroxyl group) content is preferably 70% or more, more preferably 90% or more, and most preferably 99% or more.
  • a compound having a hydroxy group (hydroxyl group) content of 50% or less is not included in the polyester polyol because one of the end groups is substituted with a group other than the hydroxy group (hydroxyl group).
  • the hydroxy group (hydroxyl group) content can be determined by the following formula (A).
  • Formula (A): Y / X ⁇ 100 hydroxy group content (%)
  • X Hydroxy group value (OHV) of the polyester polyol
  • Y 1 / (number average molecular weight (Mn)) ⁇ 56 ⁇ 2 ⁇ 1000
  • the polyester polyol preferably has a number average molecular weight within the range of 300 to 3,000, and more preferably has a number average molecular weight within the range of 350 to 2,000.
  • the degree of dispersion of the molecular weight of the polyester polyol of the present invention is preferably in the range of 1.0 to 3.0, and more preferably in the range of 1.0 to 2.0. If the degree of dispersion is within the above range, a polyester polyol having excellent compatibility with the cellulose ester can be obtained.
  • the polyester polyol preferably contains 50% or more of components having a molecular weight in the range of 300 to 1800. By setting the number average molecular weight within the above range, the compatibility can be greatly improved.
  • the degree of dispersion and the component content within the above preferred ranges 2 to 5 mol of glycol is used per 1 mol of dibasic acid or ester-forming derivative thereof, and unreacted glycol is used.
  • a method of distilling off under reduced pressure is preferred.
  • the temperature to be distilled off under reduced pressure is preferably in the range of 100 to 200 ° C., more preferably in the range of 120 to 180 ° C., and particularly preferably in the range of 130 to 170 ° C.
  • the degree of reduced pressure during distillation under reduced pressure is preferably in the range of 0.1 to 500 Torr, more preferably in the range of 0.5 to 200 Torr, and most preferably in the range of 1 to 100 Torr.
  • Polyester polyol number average molecular weight (Mn) and dispersity can be measured using gel permeation chromatography (GPC).
  • measurement conditions is as follows, but is not limited to this, and an equivalent measurement method can also be used.
  • Solvent Tetrahydrofuran (THF) Column: TSKgel G2000HXL (Tosoh Co., Ltd. uses two connected) Column temperature: 40 ° C Sample concentration: 0.1% by mass Apparatus: HLC-8220 (manufactured by Tosoh Corporation) Flow rate: 1.0ml / min Calibration curve: A calibration curve by PStQuick F (manufactured by Tosoh Corporation) is used.
  • the polyester polyol is preferably contained in the range of 5 to 30% by mass in the film. More preferably, it is in the range of 5 to 20% by mass.
  • dibasic acids having 10 to 16 carbon atoms are shown below, but the present invention is not limited thereto.
  • ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. A benzotriazole-based compound with little coloring is preferable. Further, ultraviolet absorbers described in JP-A-10-182621, JP-A-8-337574, JP-A-2001-72782, JP-A-6-148430, JP-A-2002-31715, JP-A-2002-169020, 2002-2002. Polymer ultraviolet absorbers described in 47357, 2002-363420, and 2003-113317 are also preferably used.
  • an ultraviolet absorber from the viewpoint of preventing the deterioration of polarizers and liquid crystals, it is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, the absorption of visible light having a wavelength of 400 nm or more is small. Is preferred.
  • UV absorbers useful in the present invention include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis ( 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 ' tert-butyl-5'-methylphenyl) -5-chlorobenzotriazo
  • TINUVIN 109 As commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by BASF Japan) can be preferably used.
  • An example of the polymeric ultraviolet absorber is a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd.
  • benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-) 5-benzoylphenylmethane) and the like, but are not limited thereto.
  • the ultraviolet absorber described above preferably used in the present invention is preferably a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber, which has high transparency and is excellent in the effect of preventing the deterioration of the polarizing plate and the liquid crystal element, and unnecessary coloring.
  • a benzotriazole-based ultraviolet absorber with a lower content is particularly preferably used.
  • the ultraviolet absorber can be added to the dope without limitation as long as it dissolves the ultraviolet absorber in the dope.
  • the ultraviolet absorber is cellulose such as methylene chloride, methyl acetate, dioxolane and the like.
  • Dope by dissolving in a good solvent for the ester, or a mixed solvent of a good solvent and a poor solvent such as a lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) and adding it to the cellulose ester solution as an ultraviolet absorber solution Is preferred.
  • a lower aliphatic alcohol methanol, ethanol, propanol, butanol, etc.
  • the content of the ultraviolet absorber is preferably in the range of 0.01 to 5% by mass, particularly preferably in the range of 0.5 to 3% by mass.
  • antioxidant hindered phenol compounds are preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di-t A phosphorus processing stabilizer such as -butylphenyl phosphite may be used in combination.
  • the amount of these compounds added is preferably in the range of 1 ppm to 1.0% by mass ratio with respect to the cellulose ester, and more preferably in the range of 10 to 1000 ppm.
  • R 2 to R 5 each independently represent a hydrogen atom or a substituent
  • R 6 represents a hydrogen atom or a substituent
  • n 1 or 2.
  • R 1 represents a substituent
  • R 1 represents a divalent linking group.
  • R 2 to R 5 each independently represent a hydrogen atom or a substituent.
  • the substituent represented by R 2 to R 5 is not particularly limited, and examples thereof include alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group).
  • alkyl groups eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group).
  • cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • aryl group eg, phenyl group, naphthyl group, etc.
  • acylamino group eg, acetylamino group, benzoylamino
  • alkylthio group eg, methylthio group, ethylthio group, etc.
  • arylthio group eg, phenylthio group, naphthylthio group, etc.
  • alkenyl group eg, vinyl group, 2-propenyl group, 3-butenyl group, 1- Methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group , Cyclohexenyl group etc.
  • halogen atom eg fluorine atom, chlorine atom, bro
  • Coxycarbonylamino group eg methoxycarbonylamino group, phenoxycarbonylamino group etc.
  • alkoxycarbonyl group eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.
  • aryloxycarbonyl group eg phenoxycarbonyl group etc.
  • R 2 to R 5 are preferably a hydrogen atom or an alkyl group.
  • R 6 represents a hydrogen atom or a substituent, and examples of the substituent represented by R 6 include the same groups as the substituents represented by R 2 to R 5 .
  • R 6 is preferably a hydrogen atom.
  • n 1 or 2.
  • R 1 when n is 1, R 1 represents a substituent, and when n is 2, R 1 represents a divalent linking group.
  • R 1 represents a substituent examples of the substituent include the same groups as the substituents represented by R 2 to R 5 .
  • R 1 represents a divalent linking group examples of the divalent linking group include an alkylene group that may have a substituent, an arylene group that may have a substituent, an oxygen atom, a nitrogen atom, and a sulfur atom. Or a combination of these linking groups.
  • n is preferably 1, and R 1 at that time is preferably a substituted or unsubstituted phenyl group, and more preferably a phenyl group substituted with an alkyl group.
  • the compounds represented by the general formula (L) can be used singly or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention. Is usually in the range of 0.001 to 10.0 parts by mass, preferably in the range of 0.01 to 5.0 parts by mass, and more preferably in the range of 0.1 to 3.0 parts by mass.
  • Retardation adjuster As a compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656A2 can be used.
  • the aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. Particularly preferred is an aromatic heterocycle, and the aromatic heterocycle is generally an unsaturated heterocycle. Of these, a 1,3,5-triazine ring is particularly preferred.
  • the number of aromatic rings contained in the aromatic compound is preferably 2 to 20, more preferably 2 to 12, still more preferably 2 to 8, and most preferably 3 to 6.
  • the bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting via a linking group (for aromatic rings). , Spiro bonds cannot be formed).
  • the bond relationship may be any of (a) to (c).
  • Examples of the condensed ring of (a) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a naphthacene ring, a pyrene ring, Indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine Ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pter
  • the single bond is preferably a bond between carbon atoms of two aromatic rings.
  • Two aromatic rings may be bonded by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.
  • the linking group is also preferably bonded to carbon atoms of two aromatic rings.
  • the linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.
  • the aromatic ring and the linking group may have a substituent.
  • substituents include a halogen atom (F, Cl, Br, I), hydroxy, carboxy, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl group , Aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic Substituted sulfamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.
  • a halogen atom
  • the alkyl group preferably has 1 to 8 carbon atoms.
  • a chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable.
  • the alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group).
  • Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl.
  • the alkenyl group preferably has 2 to 8 carbon atoms.
  • a chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable.
  • the alkenyl group may further have a substituent.
  • alkenyl groups include vinyl, allyl and 1-hexenyl.
  • the alkynyl group preferably has 2 to 8 carbon atoms.
  • a chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable.
  • the alkynyl group may further have a substituent. Examples of the alkynyl group include ethynyl, 1-butynyl and 1-hexynyl.
  • the aliphatic acyl group preferably has 1 to 10 carbon atoms.
  • Examples of the aliphatic acyl group include acetyl, propanoyl and butanoyl.
  • the number of carbon atoms in the aliphatic acyloxy group is preferably 1-10.
  • Examples of the aliphatic acyloxy group include acetoxy.
  • the number of carbon atoms of the alkoxy group is preferably 1-8.
  • the alkoxy group may further have a substituent (eg, an alkoxy group).
  • Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy and methoxyethoxy.
  • the number of carbon atoms in the alkoxycarbonyl group is preferably 2-10.
  • alkoxycarbonyl group examples include methoxycarbonyl and ethoxycarbonyl.
  • the number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10.
  • alkoxycarbonylamino group examples include methoxycarbonylamino and ethoxycarbonylamino.
  • the alkylthio group preferably has 1 to 12 carbon atoms.
  • Examples of the alkylthio group include methylthio, ethylthio and octylthio.
  • the alkylsulfonyl group preferably has 1 to 8 carbon atoms.
  • Examples of the alkylsulfonyl group include methanesulfonyl and ethanesulfonyl.
  • the aliphatic amide group preferably has 1 to 10 carbon atoms. Examples of the aliphatic amide group include acetamide. The number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8.
  • Examples of the aliphatic sulfonamido group include methanesulfonamido, butanesulfonamido and n-octanesulfonamido.
  • the number of carbon atoms of the aliphatic substituted amino group is preferably 1-10.
  • Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino.
  • the aliphatic substituted carbamoyl group preferably has 2 to 10 carbon atoms.
  • Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl.
  • the number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8.
  • Examples of the aliphatic substituted sulfamoyl group include methylsulfamoyl and diethylsulfamoyl.
  • the number of carbon atoms in the aliphatic substituted ureido group is preferably 2 to 10.
  • Examples of the aliphatic substituted ureido group include methylureido.
  • non-aromatic heterocyclic groups include piperidino and morpholino.
  • the molecular weight of the retardation adjusting agent is preferably 300 or more and 800 or less. This can arbitrarily select the polarity of the molecular structure from the viewpoint of suppressing the outflow at the time of use and processing of the polarizing plate.
  • X 1 is a single bond, —NR 4 —, —O— or —S—
  • X 2 is a single bond, —NR 5 —, —O— or —S—
  • X 3 is a single bond, —NR 6 —, —O— or —S—
  • R 1 , R 2 and R 3 are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group
  • R 4 , R 5 and R 6 are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
  • the compound represented by the general formula (R) is particularly preferably a melamine compound.
  • X 1 , X 2 and X 3 are —NR 4 —, —NR 5 — and —NR 6 —, respectively, or X 1 , X 2 and X 3 3 is a single bond, and R 1 , R 2 and R 3 are heterocyclic groups having a free valence on the nitrogen atom.
  • -X 1 -R 1 , -X 2 -R 2 and -X 3 -R 3 are preferably the same substituent.
  • R 1 , R 2 and R 3 are particularly preferably aryl groups.
  • R 4 , R 5 and R 6 are particularly preferably hydrogen atoms.
  • the alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group.
  • a linear alkyl group is preferred to a branched alkyl group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 6 is most preferred.
  • the alkyl group may have a substituent.
  • the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy).
  • the alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group.
  • a linear alkenyl group is preferable to a branched chain alkenyl group.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, and further preferably 2 to 6 is most preferred.
  • the alkenyl group may have a substituent.
  • substituents include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).
  • the aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.
  • the aryl group may have a substituent.
  • substituents include, for example, a halogen atom, hydroxy, cyano, nitro, carboxy, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio Group
  • alkyl part of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group are also synonymous with the alkyl group described above.
  • the alkenyl group has the same meaning as the alkenyl group described above.
  • alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamido group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.
  • aryl group examples include groups such as phenyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.
  • aryloxy group examples include aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.
  • the heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds.
  • the heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.
  • the hetero atom in the heterocyclic ring is preferably an atom such as N, S or O, and particularly preferably an N atom.
  • the aromatic heterocyclic ring is particularly preferably a pyridine ring (the heterocyclic group is, for example, each group such as 2-pyridyl or 4-pyridyl).
  • the heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.
  • the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom.
  • the heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred.
  • the heterocyclic group may have a plurality of nitrogen atoms.
  • hetero atom in the heterocyclic group may have a hetero atom other than the nitrogen atom (for example, O atom, S atom).
  • the heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.
  • heterocyclic group having a free valence on the nitrogen atom are shown below. JP-A-2006-113239, paragraphs [0143] to [0179] can be referred to for specific examples of the compound having a 1,3,5-triazine ring used in the present invention.
  • two or more kinds of compounds having 1,3,5-triazine ring may be used in combination.
  • Two or more kinds of discotic compounds for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton
  • a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton may be used in combination.
  • a benzoic acid phenylester compound it is preferable to use at least 1 type of a benzoic acid phenylester compound as a retardation regulator, and it is preferable to add the benzoic acid phenylester compound shown by the following general formula (H) to a cellulose ester especially.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 and R 10 each independently represents a hydrogen atom or a substituent, and R 1 , R 2 , At least one of R 3 , R 4 and R 5 represents an electron donating group, R 8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 to 6 alkynyl groups, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 12 carbon atoms, acylamino having 2 to 12 carbon atoms Represents a group, a cyano group or a halogen atom.
  • At least one of R 1 , R 2 , R 3 , R 4 and R 5 represents an electron donating group.
  • one of R 1 , R 3 or R 5 is an electron donating group, and R 3 is more preferably an electron donating group.
  • the electron donating group means one having Hammet's ⁇ p value of O or less
  • Chem. Rev. , 91, 165 (1991) having a Hammett ⁇ p value of O or less is preferably applicable, and more preferably ⁇ 0.85 to 0. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxy group (hydroxyl group).
  • the electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 6 carbon atoms). Having 1 to 4 carbon atoms).
  • R 1 is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), still more preferably an alkyl group having 1 to 4 carbon atoms, a carbon group
  • R 1 is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), still more preferably an alkyl group having 1 to 4 carbon atoms, a carbon group
  • R 2 is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), more preferably a hydrogen atom, an alkyl group, or an alkoxy group, still more preferably a hydrogen atom, an alkyl group ( Preferably 1 to 4 carbon atoms, more preferably a methyl group), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably carbon atoms). 1 to 4 carbon atoms. Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.
  • R 3 is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), and still more preferably an alkyl group or an alkoxy group. Particularly preferably, it is an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group and methoxy group.
  • R 4 is preferably a hydrogen atom or an electron-donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), still more preferably a hydrogen atom or a carbon number of 1 to An alkyl group having 4 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). And particularly preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and most preferably a hydrogen atom, a methyl group and a methoxy group.
  • R 5 is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxy group (hydroxyl group), more preferably a hydrogen atom, an alkyl group, or an alkoxy group, still more preferably a hydrogen atom, an alkyl group ( Preferably it has 1 to 4 carbon atoms, more preferably a methyl group, and an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to carbon atoms). 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.
  • R 6 , R 7 , R 9 and R 10 are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, more preferably a hydrogen atom or a halogen atom. And more preferably a hydrogen atom.
  • R 8 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl having 6 to 12 carbon atoms Represents an oxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group or a halogen atom, and if possible, may have a substituent. Substituent T can be applied. Further, the substituent may be further substituted.
  • R 8 is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxycarbonyl having 2 to 12 carbon atoms.
  • a more preferred compound is a compound represented by the following general formula (HA).
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 have the same meanings as those in general formula (H), The preferred range is also the same.
  • R 11 represents an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group represented by R 11 may be linear or branched, and may further have a substituent, but is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms.
  • a more preferable compound is a compound represented by the following general formula (HB).
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 have the same meanings as those in general formula (H), and the preferred ranges are also the same. It is.
  • R 11 has the same meaning as that in formula (HA), and the preferred range is also the same.
  • X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, carbon Represents an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom.
  • X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group.
  • Group, an aryloxy group, more preferably an alkoxy group preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms).
  • X is preferably an alkynyl group, an aryl group, an alkoxycarbonyl group, or a cyano group, more preferably an aryl group (preferably Is a cyano group or an alkoxycarbonyl group (preferably 2 to 12 carbon atoms), more preferably an aryl group (preferably an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group).
  • a p-cyanophenyl group, and p-methoxyphenyl an alkoxycarbonyl group (preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 6, even more preferably a carbon number of 2 to 4, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl), cyano group, particularly preferably phenyl group, methoxy group A carbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and a cyano group.
  • an alkoxycarbonyl group preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 6, even more preferably a carbon number of 2 to 4, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl
  • cyano group particularly preferably phenyl group, methoxy group A carbonyl group, an ethoxycarbonyl group, an n-propoxycarbony
  • a more preferred compound is a compound represented by the following general formula (HC).
  • R 1 , R 2 , R 4 , R 5 , R 11 and X have the same meanings as those in general formula (HB), and the preferred ranges are also the same.
  • a particularly preferable compound is a compound represented by the following general formula (HD).
  • R 2 , R 4 and R 5 have the same meanings as those in general formula (HC), and the preferred ranges are also the same.
  • R 21 and R 22 each independently represents an alkyl group having 1 to 4 carbon atoms.
  • X 1 represents an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group.
  • R 21 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group or a methyl group.
  • R 22 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.
  • X 1 represents an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxy group having 2 to 6 carbon atoms, or a cyano group. More preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a methoxycarbonyl, an ethoxycarbonyl, an n-propoxycarbonyl, a cyano group, and still more preferably a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group. N-propoxycarbonyl group, cyano group.
  • the most preferred compound is a compound represented by the following general formula (HE).
  • R 2 , R 4 and R 5 have the same meanings as those in general formula (HD), and the preferred ranges are also the same.
  • any one is a group represented by —OR 13 .
  • R 13 is an alkyl group having 1 to 4 carbon atoms.
  • R 21 , R 22 and X 1 have the same meanings as those in formula (HD), and preferred ranges are also the same.
  • R 4 and R 5 are a group represented by —OR 13 , and more preferably, R 4 is a group represented by —OR 13 .
  • R 13 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.
  • substituent T examples include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number).
  • alkyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl,
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably carbon number
  • aryl group preferably having 6 to 3 carbon atoms
  • a substituted or unsubstituted amino group preferably having 0 carbon atoms.
  • carbon atoms particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.
  • an alkoxy group preferably carbon 1 to 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.
  • an aryloxy group preferably having 6 to 20 carbon atoms, More preferably, it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy and the like.
  • An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl).
  • An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (Preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl), acyloxy group (preferably having 2 to 20 carbon atoms) More preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, Examples include benzoyloxy.
  • An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms.
  • sulfamoyl groups preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl) , Dimethylsulfamoyl, phenylsulfamoyl, etc.
  • a carbamoyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • carbamoyl Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.
  • an alkylthio group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, Ethylthio etc.
  • arylthio group preferably Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like
  • a sulfonyl group preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.
  • sulfinyl group preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably Has 1 to 12 carbon atoms, such as
  • ureido, methylureido, phenylureido, etc. phosphoric acid amide groups (preferably having 1 to 20 carbon atoms, More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide.
  • Hydroxy group mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms).
  • halogen atom eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • cyano group eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • sulfo group carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms).
  • hetero atom examples include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl, triphenylsilyl, etc.)These substituents may be further substituted.
  • substituents when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.
  • the compound represented by the general formula (H) used in the present invention can be synthesized by a general ester reaction of a substituted benzoic acid and a phenol derivative, and any reaction may be used as long as it is an ester bond forming reaction.
  • Examples thereof include a method of converting a substituted benzoic acid to an acid halide and then condensing with phenol, a method of dehydrating condensation of a substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, and the like.
  • reaction solvent examples include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane and the like), ketone solvents, ester solvents, acetonitrile and dimethyl.
  • hydrocarbon solvents preferably toluene and xylene
  • ether solvents preferably dimethyl ether, tetrahydrofuran, dioxane and the like
  • ketone solvents preferably dimethyl ether, tetrahydrofuran, dioxane and the like
  • ester solvents acetonitrile and dimethyl.
  • the reaction temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 0 to 100 ° C, still more preferably in the range of 0 to 90 ° C, particularly preferably in the range of 20 ° C to 90 ° C.
  • a base either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).
  • organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).
  • the ⁇ / 4 retardation film according to the present invention preferably contains a rod-like compound having a maximum absorption wavelength ( ⁇ max) of the ultraviolet absorption spectrum of the solution shorter than 250 nm as a retardation adjusting agent.
  • the rod-like compound preferably has at least one aromatic ring, and more preferably has at least two aromatic rings.
  • the rod-like compound preferably has a linear molecular structure.
  • the linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure.
  • the most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation.
  • molecular orbital calculation can be performed using molecular orbital calculation software (eg, WinMOPAC2000, manufactured by Fujitsu Limited) to obtain a molecular structure that minimizes the heat of formation of a compound.
  • the molecular structure being linear means that the angle of the molecular structure is 140 degrees or more in the thermodynamically most stable structure obtained by calculation as described above.
  • the rod-shaped compound preferably exhibits liquid crystallinity. More preferably, the rod-like compound exhibits liquid crystallinity upon heating (has thermotropic liquid crystallinity).
  • the liquid crystal phase is preferably a nematic phase or a smectic phase.
  • the rod-like compound is preferably a trans-1,4-cyclohexanedicarboxylic acid ester compound represented by the following general formula (T).
  • Ar 1 and Ar 2 are each independently an aromatic group.
  • the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.
  • An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group.
  • the heterocyclic ring of the aromatic heterocyclic group is generally unsaturated.
  • the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
  • Aromatic heterocycles generally have the most double bonds. As a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable.
  • aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring, and 1,3,5-triazine ring.
  • a benzene ring As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .
  • substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), hydroxy, carboxy, cyano, amino, alkylamino group (eg, methylamino, ethylamino).
  • substituent of the substituted aryl group and the substituted aromatic heterocyclic group examples include a halogen atom, cyano, carboxy, hydroxy, amino, alkyl-substituted amino group, acyl group, acyloxy group, amide group, alkoxycarbonyl group, alkoxy group, alkylthio And groups and alkyl groups are preferred.
  • the alkyl moiety of the alkylamino group, alkoxycarbonyl group, alkoxy group, and alkylthio group and the alkyl group may further have a substituent.
  • alkyl moieties and substituents of alkyl groups include halogen atoms, hydroxy, carboxy, cyano, amino, alkylamino groups, nitro, sulfo, carbamoyl, alkylcarbamoyl groups, sulfamoyl, alkylsulfamoyl groups, ureido, alkylureido Group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, alkylsulfonyl group, amide group and non-aromatic An aromatic heterocyclic group is included.
  • a halogen atom hydroxy, amino, alkylamino group, acyl group, acyloxy group, acylamino group, alkoxycarbonyl group and alkoxy group are preferable.
  • L 1 represents a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, a divalent saturated heterocyclic group, —O—, —CO—, and combinations thereof. It is.
  • the alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable.
  • As the chain alkylene group a linear alkylene group is more preferable than a branched alkylene group.
  • the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, and still more preferably 1 to 15. 6 is most preferred.
  • the alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure.
  • the number of carbon atoms in the alkenylene group and alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, and still more preferably 2 to 4. 2 (vinylene or ethynylene) is most preferred.
  • the divalent saturated heterocyclic group preferably has a 3- to 9-membered heterocyclic ring.
  • the hetero atom of the hetero ring is preferably an oxygen atom, a nitrogen atom, a boron atom, a sulfur atom, a silicon atom, a phosphorus atom or a germanium atom.
  • saturated heterocycles include piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, imidazolidine ring, tetrahydrofuran ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, tetrahydrothiophene ring, 1 , 3-thiazolidine ring, 1,3-oxazolidine ring, 1,3-dioxolane ring, 1,3-dithiolane ring and 1,3,2-dioxaborolane.
  • Particularly preferred divalent saturated heterocyclic groups are piperazine-1,4-diylene, 1,3-dioxane-2,5-di
  • Ar 1 -L 2 -XL 3 -Ar 2 Ar 1 and Ar 2 are each independently an aromatic group.
  • the definition and examples of the aromatic group are the same as those of Ar 1 and Ar 2 in the general formula (T).
  • L 2 and L 3 are each independently a divalent linking group selected from the group consisting of an alkylene group, —O—, —CO—, and combinations thereof.
  • the alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure.
  • the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, still more preferably 1 to 4, and 1 or Most preferred is 2 (methylene or ethylene).
  • L 2 and L 3 are particularly preferably —O—CO— or —CO—O—.
  • X is 1,4-cyclohexylene, vinylene or ethynylene.
  • the rod-shaped compound preferably has a linear molecular structure. Therefore, the trans type is preferable to the cis type.
  • Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type.
  • the optical isomer is not particularly superior or inferior, and may be D, L, or a racemate.
  • the central vinylene bond includes a trans type and a cis type. For the same reason as above, the trans type is preferable to the cis type.
  • Two or more rod-like compounds having a maximum absorption wavelength ( ⁇ max) shorter than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination.
  • the rod-like compound can be synthesized with reference to methods described in literature.
  • fine particles can be contained in the ⁇ / 4 retardation film as a matting agent, whereby when the ⁇ / 4 retardation film is a long film, it can be easily conveyed and wound. .
  • the particle size of the matting agent is preferably primary particles or secondary particles of 10 nm to 0.1 ⁇ m.
  • a substantially spherical matting agent having a primary particle acicular ratio of 1.1 or less is preferably used.
  • silicon dioxide is particularly preferable.
  • Preferred fine particles of silicon dioxide for the present invention include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd. What is marketed by a brand name can be mentioned, Aerosil 200V, R972, R972V, R974, R202, R812 can be used preferably.
  • Examples of polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. Examples include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.). Can do.
  • the fine silicon dioxide particles preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more.
  • the average primary particle diameter is more preferably 5 to 16 nm, further preferably 5 to 12 nm. A smaller primary particle average diameter is preferred because haze is low.
  • the apparent specific gravity is preferably 90 to 200 g / L or more, and more preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, which is preferable because no haze or aggregates are generated.
  • the addition amount of the matting agent in the present invention lambda / 4 phase difference film 1 m 2 per 0.01 ⁇ 1.0 g, more preferably 0.03 ⁇ 0.3 g, more preferably 0.08 ⁇ 0.16 g .
  • thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts such as calcium and magnesium may be added.
  • a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent and the like may be added.
  • the long film original fabric used for producing the long stretched film can be obtained by a known method, for example, a solution cast molding method, an extrusion molding method, an inflation molding method, or the like.
  • the solution cast molding method is excellent in the flatness and transparency of the film, and the extrusion molding method makes it easy to reduce the retardation Rt in the thickness direction after oblique stretching, and the amount of residual volatile components is small and the film dimensions are small. It is preferable because it is excellent in stability.
  • This long film original fabric may be a single layer or a laminated film of two or more layers.
  • the laminated film can be obtained by a known method such as a coextrusion molding method, a co-casting molding method, a film lamination method, or a coating method. Of these, the coextrusion molding method and the co-casting molding method are preferable.
  • the thickness unevenness ⁇ m in the flow direction of the long film source supplied for stretching maintains the film take-up tension at the entrance of the oblique stretching tenter, which will be described later, and has optical characteristics such as orientation angle and retardation. From the viewpoint of stabilization, it is preferably less than 0.30 ⁇ m, preferably less than 0.25 ⁇ m, more preferably less than 0.20 ⁇ m.
  • the thickness unevenness ⁇ m in the flow direction of the long film original becomes 0.30 ⁇ m or more, variations in optical properties such as retardation and orientation angle of the long stretched film are remarkably deteriorated.
  • a film having a thickness gradient in the width direction may be supplied as the long film original.
  • the film thickness gradient of the long film so that the film thickness can be made the most uniform at the position where stretching has been completed can be experienced by stretching films with varying thickness gradients experimentally. Can be obtained.
  • the thickness gradient of the long film is adjusted so that, for example, the thickness of the end portion on the thick side is about 0.5 to 3% thicker than the end portion on the thin side. be able to.
  • the width of the long film original fabric is not particularly limited, but may be in the range of 500 to 4000 mm, preferably in the range of 1000 to 3000 mm. Further, the total film thickness of the long original film is not particularly limited, but is preferably in the range of 20 to 400 ⁇ m, preferably in the range of 20 to 200 ⁇ m.
  • a film obtained by a solution cast molding method or an extrusion molding method may be stretched transversely in the width direction or longitudinally stretched in the transport direction.
  • the preferable elastic modulus at the stretching temperature during oblique stretching is expressed in terms of Young's modulus and is from 0.01 MPa to 5000 MPa, more preferably from 0.1 MPa to 500 MPa. If the elastic modulus is too low, the shrinkage rate during stretching and after stretching will be low, and wrinkles will be difficult to disappear. If it is too high, the tension applied during stretching will increase, and the strength of the part holding both side edges of the film will be increased. It is necessary to increase the load, and the load on the tenter in the subsequent process increases.
  • An obliquely stretched tenter is used in order to impart an oblique orientation to an elongated long film original fabric subjected to stretching in the production method according to the present embodiment.
  • the obliquely stretched tenter used in this embodiment can freely set the orientation angle of the film by variously changing the rail pattern and the conveyance speed of the film gripper, and further, the orientation axis of the film across the film width direction. It is preferable that the film stretching apparatus be capable of evenly orienting with high precision on the left and right sides and controlling the film thickness and retardation with high precision.
  • FIGS. 2A and 2B are schematic views of a tenter capable of oblique stretching used in the method for producing a long stretched film according to the present embodiment.
  • this is an example, and the present invention is not limited to this.
  • the long film original 4 whose direction is controlled by the guide roller 12-1 on the tenter entrance side has a gripping tool (clip gripper) at the positions of the outer film holding start point 8-1 and the inner film holding start point 8-2. Part).
  • a gripping tool clip gripper
  • the pair of left and right film grippers are transported and stretched at the same speed in the diagonal direction indicated by the outer film gripping means trajectory 7-1 and the inner film gripping means trajectory 7-2 by the oblique stretching tenter 6.
  • the gripping is released by the outer film gripping end point 9-1 and the inner film gripping end point 9-2, and the conveyance is controlled by the guide roller 12-2 on the tenter outlet side, whereby the obliquely stretched film 5 is formed.
  • the long film original is obliquely stretched at an angle (feeding angle ⁇ i) in the film stretching direction 14-2 with respect to the film feeding direction 14-1.
  • the traveling speed of the gripping tool can be selected as appropriate, but is usually in the range of 1 to 100 m / min.
  • the pair of left and right film grippers having the same speed means that the travel speed of the pair of left and right grippers is substantially 1% or less of the travel speed.
  • FIG. 2C is a schematic view of a tenter capable of oblique stretching used in the method for producing a long stretched film according to the present embodiment.
  • this is an example, and the present invention is not limited to this.
  • the pair of left and right grips that grips both ends of the film at the entrance of the tenter run at the same speed on the left and right rails in a zone where the distance between the left and right rails is constant in the initial stage of the tenter, and then the distance between the left and right rails is In the widening zone, the vehicle travels on the left and right rails at different speeds, and then travels on the left and right rails at a constant speed again in a zone where the distance between the left and right rails becomes equal.
  • the long film original 4 whose direction is controlled by the guide roller 12-1 on the tenter entrance side is gripped by the gripping tool at the position of the outer film gripping start point 8-1 and the inner film gripping start point 8-2.
  • the traveling speed of the left side gripping tool (hereinafter referred to as the high speed side gripping tool) is the same as the right side gripping tool (hereinafter referred to as the low speed side gripping).
  • the high speed side gripping tool is again equal to the low speed side gripping tool.
  • the pair of left and right gripping tools starts running again at the same speed.
  • the pair of left and right clips travel on the left and right rails at a constant speed, the left gripper releases the film at the left grip end point 9-2, and then the right gripper at the right grip end point 9-1. The film is released and the oblique stretching is finished.
  • FIG. 2D is a schematic view of a tenter capable of oblique stretching used in the method for producing a long stretched film according to the present embodiment.
  • this is an example, and the present invention is not limited to this.
  • a pair of left and right grips that grip both ends of the film at the entrance of the tenter travel on the left and right rails at different speeds in a zone where the distance between the left and right rails is constant in the initial stage of the tenter.
  • the tenter shown in FIG. 2D is a tenter having a portion where the distance between the left and right rails is widened.
  • a pair of left and right grips grip the film at the tenter inlet portions 8-1 and 8-2, and the left and right grips travel on the left and right rails at different speeds.
  • the high-speed side gripping tool of the pair of left and right grips reaches the grip release point 9-2 at the tenter outlet, the paired low-speed side clips are positioned at 11-1, so The film held by the holding tool is stretched obliquely.
  • the tenter shown in FIG. 2D is a tenter having a portion where the distance between the left and right rails is widened, but may not necessarily have a portion where the distance between the left and right rails is widened.
  • the traveling speed of the gripper can be selected as appropriate, but is usually in the range of 1 to 100 m / min.
  • the fact that the pair of left and right film grippers travel at different speeds means that the difference in travel speed between the pair of left and right grippers substantially exceeds 1% of the travel speed.
  • the difference in travel speed between the pair of left and right grippers is preferably more than 1% of the travel speed and 50% or less, more preferably more than 1% of the travel speed and 30% or less, and more than 1% of the travel speed. 10% or less is more preferable.
  • FIG. 2C a known tenter having a mechanism that changes the traveling speed of the gripping tool in the middle of the tenter can be used.
  • the manufacturing method of the elongate stretched film which concerns on embodiment of this invention is performed using the tenter which can be diagonally stretched.
  • This tenter is an apparatus that widens a long film original fabric in an oblique direction with respect to its traveling direction (moving direction of the middle point in the film width direction) in an environment heated by an oven.
  • the tenter includes an oven, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails. Both ends of the film fed out from the film roll and sequentially supplied to the entrance portion of the tenter are gripped by a gripping tool, the film is guided into the oven, and the film is released from the gripping tool at the exit portion of the tenter.
  • the film released from the gripping tool is wound around the core.
  • Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the exit portion of the tenter travels outside and is sequentially returned
  • the tenter rail shape is asymmetrical or bilaterally symmetric depending on the orientation angle ⁇ , the draw ratio, etc. given to the long stretched film to be manufactured. Therefore, fine adjustment can be made manually or automatically.
  • a long thermoplastic resin film is stretched, and the orientation angle ⁇ can be set to an arbitrary angle within a range of preferably 10 to 80 ° with respect to the winding direction after stretching. Yes.
  • the traveling speed difference between the left and right gripping tools is appropriately selected according to the tenter stretching method.
  • the diagonal stretch store can set the draw ratio according to this by setting arbitrary entrance width and exit width (below, the circled part of Drawing 2 is an example of a connection part).
  • the traveling direction 14-1 at the tenter entrance of the long film original is different from the traveling direction 14-2 at the tenter exit side of the stretched film.
  • the feeding angle ⁇ i is an angle formed by the traveling direction 14-1 at the tenter entrance and the traveling direction 14-2 on the tenter exit side of the stretched film.
  • the traveling direction 14-1 at the tenter inlet of the long film is changed to a direction different from the traveling direction at the feeding angle ⁇ i in the tenter and conveyed. Is done. Thereafter, the transport direction is further changed, and finally, a trajectory that matches the traveling direction on the tenter exit side of the stretched film is taken.
  • the feeding angle ⁇ i is 10 ° ⁇ i ⁇ 60 °, preferably 15 ° ⁇ i ⁇ 50 °. Is set. By setting the feeding angle ⁇ i in the above range, the variation in the optical characteristics in the width direction of the obtained film becomes good (smaller).
  • the left and right gripping tools of the tenter are configured to travel at a constant speed with a constant distance from the front and rear gripping tools.
  • the traveling direction of the long film original at the tenter entrance matches the angle at which the film is fed out from the tenter.
  • the right and left gripping tools of the tenter run at different speeds.
  • 3A to 3D are schematic diagrams showing the stretching direction in the oblique stretching tenter shown in FIGS. 2A to 2D of the present invention.
  • the both ends of the transport film are gripped by the gripping tool for the first time, that is, from the grip start points A1 and A1 and pulled substantially perpendicular to the center line of the transport film on the introduction side.
  • the straight line crosses the trajectory of the gripping means on the opposite side and starts at two points B1 (that is, the film grip start point on the opposite side) and the gripping tools at both ends are conveyed at a substantially constant speed
  • A1 moves from A1 to A2 and A3 to the drawing end point An
  • B1 similarly moves from B1 to B2 and B3 to the drawing end point Bn.
  • the gripping portion An is gradually delayed with respect to Bn, so that the stretching direction is gradually inclined from the width direction.
  • the substantial gripping end point of the present invention (the point that is released from the gripping tool that the gripped transport film was gripping) is the point at which either or both ends of the transport film are released from the gripping tool, That is, the grip end point Bx and a straight line drawn substantially perpendicularly to the center line of the transport film sent from Bx to the next process are defined as two points Ay that intersect the trajectory of the gripping means on the opposite side.
  • the final film stretching direction angle is determined by the distance W (the distance between Bx and Ay) and the ratio of Ax and Ay.
  • substantially vertical means within 90 ⁇ 1 °.
  • LA is the travel distance from the grip start point to the grip end point on the tenter rail on the large turn side
  • LB is the grip point from the grip start point to the grip end point on the small tenter rail path.
  • LA ⁇ LB is the difference in distance that the pair of left and right grips travels on the tenter rail at the grip end point.
  • the both ends of the transport film are gripped by the gripping tool for the first time, that is, from the grip start points C1 and C1 to be drawn substantially perpendicular to the center line of the transport film on the introduction side.
  • the starting point is the point D1 where the straight line intersects the trajectory of the opposite gripping means (that is, the film grip start point on the opposite side), and the gripping tools at both ends grip different speeds, for example, the traveling speed of the gripping tool C.
  • the drawing end point Cn moves from C1 to C2 and C3 every unit time, and D1 similarly moves from D1 to D2 and D3 to the drawing end point Dn.
  • the gripping portion Dn is gradually delayed with respect to Cn, so that the stretching direction is gradually inclined from the width direction.
  • the substantial grip end point of the present invention (the point released from the gripping tool held by the gripped transport film) is the end of the transport film gripped by the high-speed side gripping tool being released from the gripping tool.
  • a point, that is, a grip end point Cx and a straight line drawn substantially perpendicularly to the center line of the transport film sent from Cx to the next process are defined as two points Dy intersecting the trajectory of the gripping means on the opposite side.
  • the final film stretching direction angle is determined by the distance W between the grip end points (the distance between Cx and Dy) and the ratio between Dx and Dy.
  • substantially vertical means within 90 ⁇ 1 °.
  • LC is the travel distance from the grip start point to the grip end point on the high speed side tenter rail
  • LD is the grip point on the low speed side tenter rail path from the grip start point to the grip end point.
  • LC ⁇ LD is the difference in distance that the pair of left and right grips travels on the tenter rail at the grip end point.
  • a linear distance from the grip start point A1 to B1 at which the transport film is first gripped by the gripping tool in the oblique stretching tenter is Lo, and the gripping tool when both of the gripping tools have passed through all stretching zones in the oblique stretching tenter.
  • the draw ratio R is preferably in the range of 1.3 to 3.0, more preferably in the range of 1.5 to 2.5.
  • the draw ratio is within this range, thickness unevenness in the width direction is reduced, which is preferable.
  • the stretching zone of the oblique stretching tenter if the stretching temperature is differentiated in the width direction, the thickness unevenness in the width direction can be further improved.
  • the film traveling in the oblique stretching tenter passes through an oven divided into a preheating zone, a lateral stretching zone, an oblique stretching zone, a holding zone, a cooling zone and the like in the tenter according to the rail pattern on which the film travels.
  • only a part of the above zones is used, or any zone among the above zones is used several times. Or you may.
  • Preheating zone / oblique stretching zone / holding zone / cooling zone Preheating zone / lateral stretching zone / oblique stretching zone / holding zone / cooling zone
  • Preheating zone / oblique stretching zone / lateral stretching zone / holding zone / cooling zone Preheating zone / lateral stretching zone 1 / oblique stretching zone / transverse stretching zone 2 / holding zone / cooling zone preheating zone / transverse stretching zone 1 / oblique stretching zone 1 / transverse stretching zone 2 / oblique stretching zone 2 / holding zone / cooling zone
  • In the entrance it refers to a section where the gripping tool that grips both ends of the film travels while maintaining a constant spacing.
  • the transverse stretching zone refers to a section where the gap between the gripping tools that grip both ends of the film starts to reach a predetermined interval.
  • the opening angle of the rail on which the gripping tools at both ends run may be opened at the same angle for both rails, or may be opened at different angles.
  • the diagonally stretched zone refers to a gripping tool that grips both ends of the film, while the gripping tool spacing is kept constant or spreads, and then both gripping tools travel on the straight rail again after starting to run on the bending rail. Refers to the section until the beginning.
  • the holding zone refers to a section in which the gripping tools at both ends travel while being parallel to each other during a period in which the interval between the gripping tools after the transverse stretching zone or the oblique stretching zone becomes constant again.
  • the cooling zone refers to a section where the temperature in the zone is set to the glass transition temperature Tg ° C. or lower of the thermoplastic resin constituting the film in the section after the holding zone.
  • a rail pattern that narrows the gap between the opposing grippers in advance may be used.
  • the temperature of each zone is the glass transition temperature Tg of the thermoplastic resin
  • the temperature of the preheating zone is in the range of Tg to Tg + 30 ° C
  • the temperature of the stretching zone is in the range of Tg to Tg + 30 ° C
  • the temperature of the cooling zone is Tg-30 to It is preferable to set in the range of Tg ° C.
  • a temperature difference may be given in the width direction in the stretching zone.
  • a method of adjusting the opening degree of the nozzle for sending warm air into the temperature-controlled room so as to make a difference in the width direction, or controlling the heating by arranging the heaters in the width direction is known. Can be used.
  • the film is supported while being stretched, stretched in a state where the volatile content is 5% by volume or more, and then volatilized while shrinking. It is also preferable to reduce the fraction.
  • To maintain the support of the film means to grip both side edges without impairing the film property of the film.
  • the volatile content the state of 5% by volume or more may always be maintained in the stretching operation process, and the state of the volatile content is maintained at 5% by volume or more only in a part of the stretching operation process. May be. In the latter case, it is preferable that the entrance position is a starting point, and that the section of 50% or more of the entire stretching section and the volatile content rate are 12% by volume or more.
  • the volatile fraction represents the volume of the volatile component contained per unit volume of the film, and is a value obtained by dividing the volatile component volume by the film volume.
  • the guide roller closest to the entrance of the tenter is a driven roller that guides the running of the film, and is rotatably supported by bearings (not shown).
  • Known materials can be used for the roller, but it is preferable to reduce the weight by applying a ceramic coat to prevent the film from being scratched or by applying chrome plating to a light metal such as aluminum. is there. This roller is provided to stabilize the track when the film travels.
  • one of the rollers on the upstream side of this roller is nipped by pressing a rubber roller. This is because by using such a nip roller, it is possible to suppress fluctuations in the drawing tension in the film flow direction.
  • a pair of bearing portions at both ends (left and right) of the guide roller closest to the entrance of the tenter are provided with a first tension detecting device and a second film tension detecting device for detecting the tension generated in the film in the roller.
  • a load cell can be used as the film tension detection device.
  • the load cell a known tensile or compression type can be used.
  • a load cell is a device that detects a load acting on an applied point by converting it into an electrical signal using a strain gauge attached to the strain generating body.
  • the load cell is installed on the left and right bearings of the guide roller closest to the entrance of the diagonally stretched tenter, so that the force that the running film exerts on the roller, i.e., the tension in the film traveling direction that is generated near both side edges of the film. It is detected independently on the left and right.
  • a strain gauge may be directly attached to the support that constitutes the roller bearing portion, and the load, that is, the film tension may be detected based on the strain generated in the support. The relationship between the generated strain and the film tension is measured in advance and is known.
  • the film tension detection device as described above is provided so that the tension in the vicinity of both side edges of the film in the guide roller closest to the entrance of the oblique stretching tenter is detected because the position and direction of the film is the same as that of the film stretching device.
  • the position and direction of the entrance depending on the amount of deviation, there will be a difference in the tension near the side edges of the film in the guide roller closest to the entrance of the obliquely stretched tenter. This is because the degree of deviation is determined by detecting this tension difference.
  • the load acting on the rollers will be roughly equal on the left and right, and if the positions are misaligned, the left and right films There is a difference in tension.
  • a method for changing the film transport direction is required.
  • a device for changing the film conveyance direction a known method such as an air flow roller can be used. It is preferable that a device (winding device, accumulator device, drive device, etc.) after the obliquely extending tenter exit is slidable in the lateral direction.
  • FIG. 4 shows a pattern in which a long film original film once wound up in a roll shape is drawn out and obliquely stretched.
  • FIG. 5 shows a pattern in which an oblique stretching process is continuously performed without winding a long film original.
  • a film feeding device 16 In the figure, a film feeding device 16, a conveying direction changing device 17, a winding device 18, and a film forming device 19 are shown. In each figure, symbols indicating the same thing may be omitted.
  • the film feeding device 16 is slidable and pivotable so that the film can be fed at a predetermined angle with respect to the obliquely stretched tenter inlet, or the film feeding device 16 is slidable, and the transport direction changing device It is preferable that the film can be sent out to the entrance of the obliquely stretched tenter by 17.
  • the film feeding device 16 and the conveyance direction changing device 17 By configuring the film feeding device 16 and the conveyance direction changing device 17 in such a configuration, the width of the entire manufacturing apparatus can be further reduced, and the film feeding position and angle can be finely controlled. This makes it possible to obtain a long stretched film with small variations in film thickness and optical value.
  • the film feeding device 16 and the transport direction changing device 17 movable, it is possible to effectively prevent the left and right clips from being caught in the film.
  • the take-up tension T (N / m) of the stretched film is preferably adjusted between 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m. .
  • the take-up tension is 100 N / m or less, sagging and wrinkles of the film are easily generated, and the retardation and the profile in the width direction of the orientation axis are also deteriorated.
  • the take-up tension is 300 N / m or more, the variation in the orientation angle in the width direction is deteriorated, and the width yield (taking efficiency in the width direction) is deteriorated.
  • the fluctuation of the take-up tension T it is preferable to control the fluctuation of the take-up tension T with an accuracy of less than ⁇ 5%, preferably less than ⁇ 3%.
  • the fluctuation of the take-up tension T is ⁇ 5% or more, the variation in the optical characteristics in the width direction and the flow direction becomes large.
  • general PID control is performed so that the load applied to the first roller at the tenter outlet, that is, the film tension is measured and the value is kept constant.
  • a method of controlling the rotation speed of the take-up roller by a method is mentioned.
  • Examples of the method for measuring the load include a method in which a load cell is attached to a bearing portion of a roller and a load applied to the roller, that is, a film tension is measured.
  • a load cell a known tensile type or compression type can be used.
  • the stretched film is released from the tenter outlet after being gripped by the gripper, trimmed at both ends (both sides) of the film, and then wound around a winding core (winding roller) in order to produce a long stretched film.
  • the wound body can be made.
  • both ends of the film held by the tenter holding tool may be trimmed before being wound on the winding roller.
  • the masking film may be overlapped and wound up at the same time, or at least one of the long stretched films, preferably while winding tape or the like on both ends. You may take it.
  • the masking film is not particularly limited as long as it can protect the film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.
  • the long stretched film obtained by the production method according to the embodiment of the present invention has an orientation angle ⁇ that is inclined in the range of, for example, 10 to 80 ° with respect to the winding direction, and has a width of at least 1300 mm.
  • the variation of the in-plane retardation Ro in the direction is preferably 4 nm or less, and the variation of the orientation angle ⁇ is preferably 1.0 ° or less.
  • the dispersion of the in-plane retardation Ro of the long stretched film obtained by the production method according to the embodiment of the present invention is 4 nm or less, preferably 3 nm or less, at least at 1300 mm in the width direction.
  • the variation of the orientation angle ⁇ of the long stretched film obtained by the production method according to the embodiment of the present invention is 1.0 ° or less, preferably 0.80 ° or less, at least 1300 mm in the width direction. .
  • a long stretched film with a variation in the orientation angle ⁇ exceeding 1.0 ° is bonded to a polarizer to obtain a circularly polarizing plate, and when this is installed in a liquid crystal display device, light leakage may occur and the contrast may be lowered. .
  • the average thickness of the long stretched film obtained by the production method according to the embodiment of the present invention is preferably in the range of 20 to 80 ⁇ m, more preferably in the range of 30 to 60 ⁇ m, particularly preferably from the viewpoint of mechanical strength and the like. Is in the range of 30-40 ⁇ m.
  • the thickness unevenness in the width direction affects the availability of winding, and is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • Hard coat layer It is preferable that a hard coat layer is provided on the ⁇ / 4 retardation film according to the present invention.
  • the hard coat layer is preferably either a clear hard coat layer or an antiglare hard coat layer.
  • the hard coat layer used in the present invention is provided on at least one surface of the ⁇ / 4 retardation film.
  • an antireflection layer including at least a low refractive index layer is preferably provided on the hard coat layer.
  • the antiglare hard coat layer used in the present invention preferably contains an antistatic agent, and examples of the antistatic agent include Sn, Ti, In, Al, Zn, Si, Mg, Ba, Mo, and W. And a conductive material containing at least one element selected from the group consisting of V and V as a main component and having a volume resistivity of 10 7 ⁇ ⁇ cm or less.
  • antistatic agent examples include metal oxides and composite oxides having the above elements.
  • the film thickness of the clear hard coat layer or the antiglare hard coat layer is preferably in the range of 0.5 ⁇ m to 15 ⁇ m, more preferably in the range of 1.0 ⁇ m to 7 ⁇ m. It is.
  • the hard coat layer used in the present invention preferably contains an active energy ray-curable resin that is cured by irradiation with active energy rays such as ultraviolet rays.
  • 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.
  • an active energy ray such as an ultraviolet ray or an electron beam.
  • Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an active energy ray other than an ultraviolet ray or an electron beam may be used.
  • Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.
  • the active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, ⁇ ray, etc., but ultraviolet ray and electron beam are preferable, especially easy handling and high energy. UV rays are preferred in that they can be easily obtained.
  • the ultraviolet light source for photopolymerizing the ultraviolet reactive compound any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.
  • the irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably 20 mJ / cm 2 or more, more preferably in the range of 50 ⁇ 10000mJ / cm 2, particularly preferably in the range of 50 ⁇ 2000mJ / cm 2 .
  • the active energy ray-reactive compound used in the present invention In order to initiate the photopolymerization or photocrosslinking reaction of the active energy ray-reactive compound used in the present invention, the active energy ray-reactive compound alone is initiated, but the polymerization induction period is long or the polymerization initiation is slow. Therefore, it is preferable to use a photosensitizer or a photoinitiator, which can accelerate the polymerization.
  • the hard coat layer used in the present invention contains an active energy ray-curable resin
  • a photoreaction initiator and a photosensitizer can be used at the time of irradiation with active energy rays.
  • Examples of the ultraviolet curable resin include ADEKA OPTMER KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Dainichi Chemical Industries) Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131
  • the antireflection layer used in the present invention may have a single-layer structure consisting of only a low refractive index layer, but it is also preferable to provide a multilayer refractive index layer.
  • a hard coat layer is provided on the ⁇ / 4 retardation film, and can be laminated on the surface in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference.
  • the antireflection layer is composed of a combination of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support, and particularly preferably from three or more refractive index layers.
  • An anti-reflection layer comprising three layers having different refractive indexes from the support side, a medium refractive index layer (having a higher refractive index than the support or anti-glare hard coat layer, and having a higher refractive index than the high refractive index layer). It is preferable that the layers are laminated in the order of (low layer) / high refractive index layer / low refractive index layer.
  • an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.
  • Examples of preferred layer configurations of the antireflection layer used in the present invention are shown below. Here, / indicates that the layers are arranged in layers.
  • an antifouling layer may be further provided on the outermost low refractive index layer.
  • the antifouling layer fluorine-containing organic compounds are preferably used.
  • an intermediate layer may be provided as appropriate.
  • an antistatic layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO 2 , ITO) is preferable.
  • ⁇ Low refractive index layer> In the low refractive index layer used in the present invention, the following hollow spherical silica-based fine particles are preferably used.
  • the hollow spherical fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.
  • the cavity particles are particles having a cavity inside, and the cavity is surrounded by a particle wall.
  • the cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation.
  • the average particle diameter of such hollow spherical fine particles is desirably in the range of 5 to 300 nm, preferably in the range of 10 to 200 nm.
  • the hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable.
  • These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer.
  • an appropriate medium for example, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.
  • the refractive index of the inorganic fine particles thus obtained is as low as less than 1.42.
  • Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.
  • the refractive index of the low refractive index layer used in the present invention is preferably in the range of 1.30 to 1.50, and more preferably in the range of 1.35 to 1.44.
  • the commercially available SiO 2 fine particles can be used.
  • Specific examples of commercially available particles include P-4 manufactured by Catalyst Chemical Industry Co., Ltd.
  • the content (mass) of the hollow spherical silica-based fine particles having an outer shell layer and porous or hollow inside in the low refractive index layer coating solution is preferably in the range of 10 to 80% by mass, more preferably 20 to 20% by mass. The range is 60% by mass.
  • the low refractive index layer used in the present invention is applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). Can be formed. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).
  • the film thickness of the low refractive index layer used in the present invention is preferably in the range of 50 to 200 nm, more preferably 60 to 150 nm.
  • ⁇ High refractive index layer and medium refractive index layer> it is preferable to provide a high refractive index layer between the hard coat layer and the low refractive index layer in order to reduce the reflectance.
  • a middle refractive index layer between the docoat layer and the high refractive index layer.
  • the refractive index of the high refractive index layer is preferably in the range of 1.55 to 2.30, and more preferably in the range of 1.57 to 2.20.
  • the refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the support and the refractive index of the high refractive index layer.
  • the refractive index of the middle refractive index layer is preferably in the range of 1.55 to 1.80.
  • the thickness of the high refractive index layer and the middle refractive index layer is preferably in the range of 5 nm to 1 ⁇ m, more preferably in the range of 10 nm to 0.2 ⁇ m, and most preferably in the range of 30 to 100 nm. .
  • the haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.
  • the strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.
  • a polymer having a relatively high refractive index for the medium refractive index layer and the high refractive index layer.
  • the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. .
  • Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.
  • each layer of the antireflection layer or coating liquid thereof includes a polymerization inhibitor, a leveling agent, a thickener, and an anti-coloring agent.
  • An agent, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.
  • the medium to high refractive index layer and the low refractive index layer used in the present invention it is preferable to irradiate active energy rays in order to promote hydrolysis or curing of the composition containing the metal alkoxide. More preferably, the active energy ray is irradiated every time each layer is coated.
  • the active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, and ⁇ ray, but ultraviolet ray and electron beam are preferable, and handling is particularly simple and high energy. Ultraviolet rays are preferred because they can be easily obtained.
  • the ultraviolet light source for photopolymerizing the ultraviolet reactive compound any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.
  • the irradiation conditions vary depending on individual lamps, but the amount of light irradiated is preferably in the range of 20 ⁇ 10,000 / cm 2, more preferably, a 100mJ / cm 2 ⁇ 2,000mJ / cm 2, particularly preferably 400 to The range is 2,000 mJ / cm 2 .
  • the multilayer antireflection layer may be irradiated one by one or may be irradiated after lamination. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.
  • an electron beam can be used in the same manner.
  • the electron beam 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as cockroft walton type, bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type.
  • An electron beam having an energy of 300 keV can be given.
  • each refractive index layer constituting the antireflection layer is preferably in the range of 1 to 200 nm, and more preferably in the range of 5 to 150 nm. Depending on the refractive index of each layer, an appropriate film is used. It is preferable to select the thickness.
  • the antireflection layer used in the present invention preferably has an average reflectance in the range of 450 to 650 nm of 1% or less, particularly preferably 0.5% or less.
  • the minimum reflectance in this range is particularly preferably in the range of 0.00 to 0.3%.
  • the refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance.
  • the reflective optical characteristic of the produced low reflection film can measure a reflectance on the conditions of a 5-degree regular reflection using a spectrophotometer. In this measurement method, after roughening the substrate surface on which the antireflection layer is not applied, a light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the film and reflectivity. Is measured.
  • the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.
  • the polarizing plate according to the present invention is characterized by satisfying the following (a) to (c).
  • the polarizing plate has a ⁇ / 4 retardation film having the following optical characteristics on both sides of a polarizer drawn out from a long roll, and the long roll is in the same direction as the long direction of the polarizer. It is formed by being drawn out and pasted.
  • a polarizer having an absorption axis or a transmission axis in the long direction and a ⁇ / 4 retardation film having a slow axis in an oblique direction are both in a long roll shape.
  • a long roll-shaped circularly polarizing plate is formed with good productivity by bonding.
  • the slow axis of the ⁇ / 4 retardation film bonded to both surfaces of the polarizer is in a direction between both the longer direction and the width direction of the polarizer, and The slow axes of the ⁇ / 4 retardation films on both sides are bonded in directions orthogonal to each other.
  • the polarizing plate according to the present invention has a ⁇ / 4 retardation film on both sides of the polarizer and has a ⁇ / 4 position in an oblique direction with respect to a polarizer having an absorption axis or a transmission axis in the longitudinal direction.
  • the slow axes of the retardation film By causing the slow axes of the retardation film to be bonded in a direction perpendicular to each other, the occurrence of crosstalk and the change in color are prevented.
  • the ⁇ / 4 retardation films to be bonded to both sides of the polarizer are T1 and T2, respectively, when the retardation values satisfy the following relationship, the occurrence of crosstalk and the prevention of color change It has an effect.
  • the in-plane retardation value Ro and the thickness direction retardation value Rt of the ⁇ / 4 retardation film measured at an optical wavelength of 550 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% are respectively represented by the following formulas ( 1) to (4) are satisfied.
  • Rt (T2) Represents the retardation value Rt in the thickness direction of the retardation film T2 bonded to the light emitting element side of the polarizer of the polarizing plate laminated on the light emitting element.
  • the polarizing plate according to the present invention is required to be used as a polarizing plate on the viewing side with respect to the liquid crystal cell of the liquid crystal display device from the viewpoint of preventing the occurrence of crosstalk and color change.
  • a liquid crystal display device uses two polarizing plates with a liquid crystal cell sandwiched therebetween, but the polarizing plate located on the opposite side with respect to the polarizing plate according to the present invention is particularly limited. Although it is not a thing, it is preferable to use the polarizing plate of the following structures.
  • the ⁇ / 4 retardation film, a polarizer, and an optical film are provided in this order, and the optical film is It is preferable to satisfy the following requirement (1) or (2).
  • the in-plane retardation value Ro defined by the following formula (I) is in the range of 20 to 150 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) is 70 to 400 nm. Is within the range.
  • the in-plane retardation value Ro defined by the following formula (I) is in the range of 0 to 2 nm, and the retardation value Rt in the thickness direction defined by the following formula (II) is ⁇ 15 to It is in the range of 15 nm.
  • Formula (I): Ro (n x ⁇ n y ) ⁇ d (nm)
  • Formula (II): Rt ⁇ (n x + n y ) / 2 ⁇ n z ⁇ ⁇ d (nm)
  • Ro represents the in-plane retardation value in the film at the measurement wavelength of 590 nm
  • Rt (590) represents the retardation value in the thickness direction in the film at the measurement wavelength of 590 nm.
  • d represents the thickness of the optical film (nm)
  • n x represents the maximum refractive index in the plane of the film at a measurement wavelength of 590 nm, also referred to as a slow axis direction of the refractive index.
  • n y represents a direction perpendicular refractive index to the slow axis in the film plane at a measurement wavelength of 590 nm
  • n z represents the refractive index of the film in the thickness direction of 590 nm.
  • the optical film, the polarizer, and the optical film are provided in this order.
  • optical film for polarizing plate is a cellulose ester, a plasticizer, an ultraviolet absorber, an antioxidant, a retardation adjusting agent, a matting agent, an anti-degradation agent, and a release agent used in the ⁇ / 4 retardation film according to the present invention.
  • Auxiliaries, surfactants and the like can be preferably used.
  • the optical film bonded to the surface opposite to the surface where the ⁇ / 4 retardation film is bonded to the polarizer is the in-plane retardation value Ro defined by the above formula, the retardation in the thickness direction.
  • Ro defined by the above formula
  • the optical films have retardation values Ro and Rt in the range of 20 to 150 nm and 70 to 400 nm, respectively.
  • Ro when used as an optical compensation film of a VA liquid crystal display device having a VA mode liquid crystal cell, Ro When the value is in the range of 30 to 100 nm and the Rt value is in the range of 70 to 250 nm when two optical compensation films are used in the VA liquid crystal display device, and when one optical film is used in the VA liquid crystal display device
  • the Rt value is preferably in the range of 150 to 400 nm.
  • optical film for example, a method of supporting a discotic liquid crystalline compound, which is a compound having negative uniaxiality, on a support (see, for example, JP-A-7-325221), positive optical anisotropy is achieved.
  • a method in which a nematic type polymer liquid crystalline compound having a hybrid orientation in which the pretilt angle of liquid crystal molecules changes in the depth direction is supported on a support see, for example, JP-A-10-186356
  • an optical film provided with an optically anisotropic layer on a support by a method for example, see JP-A-8-15681
  • a conventional TAC film An optical film having a retardation film function by causing a retardation to develop by stretching a roulose derivative film, saponifying the film, and laminating a PVA polarizer (see, for example, JP-A-2003-270442)
  • Examples include, but are not limited to, optical compensation films obtained by adding a retardation adjusting agent to a cellulose ester film to obtain a retardation film (see, for example, JP-A Nos. 2000-275434 and 2003-344655). Is not to be done.
  • optical films are preferably polymer films, and are preferably easy to manufacture, optically uniform, and optically transparent. Any of these may be used, for example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate.
  • Polyester film such as polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin Film, polymethylpentene film, polyetherketone film, Examples include, but are not limited to, ether ketone imide films, polyamide films, fluororesin films, nylon films, cycloolefin polymer films, polyvinyl acetal resin films, polymethyl methacrylate films, and acrylic films. . As these films, films formed by a solution casting method or a melting method are preferably used.
  • cellulose ester film, polycarbonate film, polysulfone (including polyethersulfone) and cycloolefin polymer film are preferred.
  • cellulose ester film and cycloolefin polymer film are particularly advantageous in terms of production, cost and transparency. From the viewpoints of uniformity, adhesion and the like.
  • commercially available cellulose ester films include Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC16UR, KC4UE, KC8UE, KC4F Etc.) are preferably used.
  • the most preferred optical film is a cellulose ester film stretched in the width direction of the film by a tenter device or the like.
  • the optical film used in the present invention can also be used as a polarizing plate protective film used in a transverse electric field switching mode type (also referred to as IPS mode type) liquid crystal display device, in which case the retardation value is 0 nm ⁇
  • IPS mode type transverse electric field switching mode type
  • the optical film preferably contains an acrylic polymer containing a cellulose ester and having a weight average molecular weight in the range of 500 to 30,000.
  • an ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule Polymer X having a weight average molecular weight in the range of 5,000 to 30,000 obtained by copolymerization with ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group, more preferably an aromatic ring in the molecule
  • an ethylenically unsaturated monomer Xa having no hydrophilic group and an ethylenically unsaturated monomer Xb having no hydrophilic ring in the molecule and having a hydrophilic group having a weight average molecular weight of 5,000 to 30,000
  • the polymer X used in the present invention comprises an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group in the molecule.
  • Xa is an acrylic or methacrylic monomer that does not have an aromatic ring and a hydrophilic group in the molecule
  • Xb is an acrylic or methacrylic monomer that does not have an aromatic ring in the molecule and has a hydrophilic group.
  • the polymer X used in the present invention is represented by the following general formula (X).
  • R 1 and R 3 represent H or CH 3.
  • R 2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group.
  • R 4 represents —CH 2 —, —C 2 H 4 —.
  • Xc represents a monomer unit polymerizable to Xa and Xb
  • a hydrophilic group means a group having a hydroxy group (hydroxyl group) or an ethylene oxide chain.
  • Examples of the ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), and butyl acrylate (n-, i- , S-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n- I-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -caprolactone), acrylic acid (2-hydroxyethyl) ), Acrylic acid (2-ethoxyethyl), etc., or those obtained by replacing the above acrylic ester with a methacrylic ester.
  • the ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxy group (hydroxyl group).
  • Acrylic acid (2-hydroxyethyl), methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), and acrylic acid (3-hydroxypropyl) are preferable.
  • Xc is not particularly limited as long as it is an ethylenically unsaturated monomer other than Xa and Xb and copolymerizable, but preferably has no aromatic ring.
  • the molar composition ratio m: n of Xa, Xb and Xc is preferably in the range of 99: 1 to 65:35, more preferably in the range of 95: 5 to 75:25.
  • P of Xc is 0-10.
  • Xc may be a plurality of monomer units.
  • the molecular weight of the polymer X has a weight average molecular weight in the range of 5000 to 30000, and more preferably in the range of 8000 to 25000.
  • the weight average molecular weight be 5000 or more because advantages such as little dimensional change of the optical film under high temperature and high humidity and less curling as a polarizing plate protective film can be obtained.
  • the weight average molecular weight is 30000 or less, the compatibility with the cellulose ester is further improved, and bleeding out under high temperature and high humidity and further haze generation immediately after film formation are suppressed.
  • the weight average molecular weight of the polymer X used in the present invention can be adjusted by a known molecular weight adjusting method.
  • a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
  • the polymerization temperature is usually from room temperature to 130 ° C., preferably from 50 ° C. to 100 ° C., but this temperature or the polymerization reaction time can be adjusted.
  • the method for measuring the weight average molecular weight can be as follows.
  • Weight average molecular weight measurement method The weight average molecular weight Mw was measured using gel permeation chromatography.
  • the measurement conditions are as follows.
  • the polymer Y used in the present invention is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring.
  • a weight average molecular weight of 500 or more is preferable because the residual monomer of the polymer is reduced.
  • Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.
  • the polymer Y used in the present invention is represented by the following general formula (Y).
  • R 5 represents H or CH 3.
  • R 6 represents an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms.
  • Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya.
  • Yb may be plural.
  • k + q 100, q is preferably 0-30.
  • the ethylenically unsaturated monomer Ya constituting the polymer Y obtained by polymerizing an ethylenically unsaturated monomer having no aromatic ring is, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i- , N-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (N-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), cyclohexyl acrylate, acrylic acid (2- Ethyl hexyl), acrylic acid ( ⁇ -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid
  • Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya.
  • vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, and vinyl caproate.
  • Vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl cinnamate and the like are preferred.
  • Yb may be plural.
  • a method that can align the molecular weight as much as possible without increasing the molecular weight examples include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than usual polymerization, and a mercapto compound in addition to the polymerization initiator.
  • a method using a chain transfer agent such as carbon tetrachloride a method using a polymerization terminator such as benzoquinone and dinitrobenzene in addition to the polymerization initiator, and further disclosed in JP 2000-128911 or 2000-344823.
  • Examples include a compound having one thiol group and a secondary hydroxy group (hydroxyl group), or a bulk polymerization method using a polymerization catalyst in which the compound and an organometallic compound are used in combination.
  • the polymer Y has a thiol group and a secondary group in the molecule.
  • the polymerization method of using a compound having a Dorokishi group (hydroxyl group) as a chain transfer agent is preferred.
  • the terminal of the polymer Y has a hydroxy group (hydroxyl group) and a thioether resulting from the polymerization catalyst and the chain transfer agent.
  • the compatibility of Y and cellulose ester can be adjusted by this terminal residue.
  • Polymers X and Y preferably have a hydroxy group (hydroxyl group) value in the range of 30 to 150 [mg KOH / g].
  • hydroxy group (hydroxyl group) value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxy group (hydroxyl group) when 1 g of a sample is acetylated.
  • sample Xg about 1 g
  • 20 ml of an acetylating reagent a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml
  • Hydroxyl group (hydroxyl group) value ⁇ (BC) ⁇ f ⁇ 28.05 / X ⁇ + D (Wherein B is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test (ml), and C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the titration (ml).
  • the content of the polymer X and the polymer Y in the optical film is preferably in a range satisfying the following formulas (i) and (ii).
  • a preferred range of formula (i) is in the range of 10 to 25% by weight.
  • the polymer X and the polymer Y have a sufficient effect for reducing the retardation value Rt. Moreover, if it is 35 mass% or less as a total amount, adhesiveness with a polyvinyl alcohol-type polarizer will be favorable.
  • Polymer X and polymer Y can be directly added and dissolved as a material constituting the dope, or can be added to the dope after being previously dissolved in an organic solvent for dissolving the cellulose ester.
  • Examples of the polarizer preferably used in the polarizing plate according to the present invention include a polyvinyl alcohol polarizing film, which includes a polyvinyl alcohol film dyed with iodine and a dichroic dye dyed.
  • a polyvinyl alcohol film a modified polyvinyl alcohol film modified with ethylene is preferably used.
  • a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound. The stretching is preferably performed by uniaxial stretching in the film forming direction, or in the direction of 45 ° obliquely with respect to the film forming direction in the same manner as the ⁇ / 4 retardation film described above.
  • the film thickness of the polarizer is in the range of 5 to 40 ⁇ m, preferably in the range of 5 to 30 ⁇ m, particularly preferably in the range of 5 to 20 ⁇ m.
  • On the surface of the polarizer one side of the ⁇ / 4 retardation film according to the present invention and the polarizing plate protective film B is bonded to form a polarizing plate.
  • the polarizing plate can be produced by a general method.
  • the ⁇ / 4 retardation film according to the present invention which has been subjected to alkali saponification treatment, is bonded to at least one surface of a polarizer prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable to match. On the other surface, the ⁇ / 4 retardation film is bonded.
  • the polarizing plate can be constructed by further bonding a protective film on one side of the polarizing plate and a separate film on the other side.
  • the protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.
  • the polarizing plate according to the present invention is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.
  • the position of the polarizing plate according to the present invention in the liquid crystal display device needs to be arranged on the viewing side with respect to the liquid crystal cell, and the ⁇ / 4 retardation film according to the present invention is arranged on the viewing side. It is possible to greatly improve the visibility when linearly polarized light is converted into circularly polarized light and observed through an optical member having a polarizing action such as polarized sunglasses.
  • the ⁇ / 4 retardation film according to the present invention can be used in various modes in a stereoscopic image display device.
  • a stereoscopic image display device comprising a liquid crystal display device and liquid crystal shutter glasses, wherein the liquid crystal shutter glasses are provided with (1) a ⁇ / 4 retardation film, a liquid crystal cell, and a polarizer in this order.
  • It can be used in a stereoscopic image display device characterized by being liquid crystal shutter glasses in which a ⁇ / 4 retardation film, a polarizer, a liquid crystal cell, and a polarizer are provided in this order.
  • the front polarizing plate of the liquid crystal display device is provided with a ⁇ / 4 retardation film, a polarizer, a ⁇ / 4 retardation film, a liquid crystal cell, and a rear polarizing plate in this order. It is configured.
  • the above aspect and configuration can reduce crosstalk or luminance reduction and color change when tilting the head when viewing stereoscopic (3D) video images, and maintain excellent visibility in the usage environment. Therefore, a stereoscopic image display device with higher durability against the use environment can be obtained.
  • Organic electroluminescence device In the stereoscopic image display device of the present invention, various types of light-emitting elements can be used as the light-emitting elements, but it is preferable to use an organic electroluminescent element from the viewpoint that the effects of the present invention are remarkably exhibited.
  • an organic electroluminescence device (organic EL image display device) can be used as the light emitting element.
  • an organic EL image display device is formed by sequentially laminating a metal electrode 2a, an organic light emitting layer 3a, and a transparent electrode 4a on a transparent substrate 1a such as glass or plastic.
  • Luminous body a transparent substrate 1a such as glass or plastic.
  • the organic light emitting layers 3aR, 3aG, and 3aB are laminates of various organic thin films, which respectively represent a red light emitting layer (3aR), a green light emitting layer (3aG), and a blue light emitting layer (3aB).
  • the organic EL image display device has an insulating film 5a on a transparent electrode 4a, and a circularly polarizing plate 10a is disposed on the insulating film 5a via an adhesive layer 6a.
  • a ⁇ / 4 retardation film 9a and a ⁇ / 4 retardation film 7a on the organic light emitting layer 3a side (illuminator side) of the polarizer 8a are arranged on the viewing side of the polarizer 8a.
  • holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons is reduced by the phosphor material. It emits light on the principle that it is excited and emits light when the excited fluorescent material 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.
  • the organic EL image display device in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and usually a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) is used. Used as the anode.
  • ITO indium tin oxide
  • metal electrodes such as Mg—Ag and Al—Li are used.
  • the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted 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 comprising an organic electroluminescent illuminator comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate (not shown) can be provided 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 mirror surface of the metal electrode can be completely shielded by configuring the retardation plate with a quarter-wave plate and adjusting the angle formed by the polarization direction of the polarizing plate and the retardation plate to ⁇ / 4. .
  • linearly polarized light becomes generally elliptically polarized light by the phase difference plate, but becomes circularly polarized light particularly when the phase difference plate is a quarter wavelength plate and the angle formed by the polarization direction of the polarizing plate and the phase difference plate is ⁇ / 4. .
  • This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, reflected by the metal electrode, is again transmitted through the organic thin film, 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
  • Polyester A has a terminal toluic acid ester because the monocarboxylic acid is used in an amount twice as much as that of the dicarboxylic acid.
  • Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
  • Fine particle additive solution 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
  • a main dope having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. The cellulose ester was added to the pressure dissolution tank containing the solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope was prepared by filtration using 244.
  • ⁇ Composition of main dope> Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose ester (acetyl group substitution degree 1.5, propionyl group substitution degree 0.9, total acyl group substitution degree 2.4, weight average molecular weight Mw 190,000) 100 parts by mass Compound 1-23 represented by the general formula (1) 7 parts by mass Polyester A 2.5 parts by mass UV absorber (Tinuvin 928 (manufactured by BASF Japan Ltd.)) 1.5 parts by mass Particulate additive solution 1 1 part by mass The above was put into a closed container and dissolved while stirring to prepare a dope. Next, using an endless belt casting apparatus, the dope was cast uniformly on a stainless steel belt support at a temperature of 33 ° C. and a width of 2000 mm. The temperature of the stainless steel belt was controlled at 30 ° C.
  • the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
  • the peeled cellulose ester film was stretched in an oblique direction so that the slow axis formed 45 ° with the film width direction under the stretching conditions shown in Table 1 using the apparatus of FIG. .
  • drying was terminated while the drying zone was conveyed by a number of rolls.
  • the drying temperature was 130 ° C. and the transport tension was 100 N / m.
  • a ⁇ / 4 retardation film A-1 having a dry film thickness of 40 ⁇ m and a winding number of 6000 m was obtained.
  • the retardation film A-1 produced above was provided with the following intermediate layer and vertical alignment liquid crystal layer.
  • This coating solution was applied to the retardation film 101 with a wire bar # 3, dried at 80 ° C. for 30 seconds, and then cured by irradiating with ultraviolet rays of 120 mJ / mm for 10 seconds.
  • the film thickness of the intermediate layer after drying was 0.5 ⁇ m
  • UV-polymerizable liquid crystal material UCL-018 manufactured by DIC Corporation
  • PDL-018 manufactured by DIC Corporation
  • Propylene glycol monomethyl ether 80 parts by mass
  • Photopolymerization initiator (Lucirin TPO (manufactured by BASF Japan)) 0.04 parts by mass hindered amine LS-765 (Sankyo Lifetech Co., Ltd.) 0.02 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.10 parts by mass Air interface side vertical alignment agent 1 0.01 parts by mass
  • This anisotropic layer coating solution is subjected to direct orientation by a die coater.
  • the film was applied on the film by adjusting the gap of the die coater so that the film thickness of the coating layer after drying was 0.5 ⁇ m. Thereafter, the film was heated in a constant temperature bath at 100 ° C. for 2 minutes to align the ultraviolet polymerizable liquid crystal material (rod-like liquid crystal compound).
  • the coated film was irradiated with ultraviolet rays of 250 mJ / mm for 10 seconds at an oxygen concentration of 0.2% and a temperature of 28 ° C. to cure the polymerizable liquid crystal composition, thereby producing a retardation film B-1.
  • ⁇ Production of ⁇ / 4 retardation films B-2 to 7> In the coating process of the anisotropic layer coating liquid in the method for producing the retardation film B-1, the total coating thickness after drying is as shown in Tables 1 to 3 (the thickness of the pC layer). Retardation films B-2 to B-7 were prepared in the same manner except that the gap of the die coater was adjusted so that
  • a sodium hydroxide aqueous solution and ion-exchanged water are charged into a reaction apparatus equipped with a stirrer, a thermometer, and a reflux condenser, and bisphenol A and biscresol fluorene are dissolved at a ratio of 36:64 (mol%), and a small amount Of hydrosulfide was added.
  • this polymer had a glass transition temperature (Tg) of 223 ° C. and a photoelastic constant of 43 Brewster.
  • This copolymerized polycarbonate was dissolved in methylene chloride to prepare an 18% by mass dope solution.
  • This dope solution was cast on a steel drum, which was continuously peeled off and dried, and this was obliquely stretched at a stretching temperature of 230 ° C. and a stretching ratio of 2.2 times with an oblique stretching machine.
  • the obtained stretched polycarbonate film had a thickness of 50 ⁇ m, a winding number of 6000 m, and the residual solvent amount was 0.2% by mass.
  • thermoplastic resin P1 (trade name “ZEONOR 1420”, manufactured by Nippon Zeon Co., Ltd., norbornene resin) were melted by an extruder and supplied to an extrusion die to produce an original film.
  • the original film was stretched obliquely at a stretching temperature of 147 ° C. and a stretching ratio of 2.1 times so that the slow axis was inclined by 45 ° with respect to the longitudinal direction with a tenter stretching machine, and the number of windings was 6000 m.
  • a cycloolefin polymer film was obtained.
  • the ester compound 1 was obtained by making it dehydrate-condense for 15 hours, and distilling off unreacted propylene glycol under reduced pressure at 200 degreeC after completion
  • the above ester compound 1 10 parts by mass Tinuvin 928 (manufactured by BASF Japan Ltd.) 2.5 parts by mass Methylene chloride 432 parts by mass Ethanol 38 parts by mass Azumi Filter Paper No. manufactured by Azumi Filter Paper Co., Ltd. 24 was used to prepare a dope.
  • the belt was cast evenly 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.
  • the solvent of the cellulose ester film web was evaporated at 35 ° C., slit to a width of 1.65 m, the width was held with a tenter, and the film was stretched obliquely at a stretching temperature of 170 ° C. and a stretching ratio of 1.3 times.
  • the residual solvent amount at the start of drying was 20%.
  • the film is dried for 15 minutes while being transported in a drying apparatus at 120 ° C. by a number of rolls, and then subjected to knurling with a width of 15 mm and a height of 10 ⁇ m at both ends of the film, and wound on a core to obtain a retardation film E. It was.
  • the residual solvent amount of the retardation film E was 0.2%, the film thickness was 40 ⁇ m, and the number of turns was 6000 m.
  • the draw ratio in the MD direction (conveyance direction) calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.10 times (10% draw ratio).
  • the retardation value Rt in the film thickness direction was calculated using the following formula.
  • Formula (I): Ro (n x ⁇ n y ) ⁇ d
  • Rt ⁇ (n x + n y ) / 2 ⁇ n z ⁇ ⁇ d
  • n x, n y, n z is, 23 °C ⁇ 55% RH
  • the refractive indices n x at 590 nm maximum refractive index in the plane of the film, also referred to as a slow axis direction of the refractive index.)
  • N y reffractive index in the direction perpendicular to the slow axis in the film plane
  • nz is the refractive index in the film thickness direction
  • d is the thickness (nm) of the film.
  • the in-plane slow axis direction is the direction of the refractive index n x.
  • Each of the films prepared above was bonded to both sides of the polarizer using a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive. At that time, bonding was performed such that the transmission axis of the polarizer and the slow axis of the ⁇ / 4 retardation film were 45 degrees.
  • Table 4 shows combinations of retardation films to be attached to both sides of the polarizer. A retardation film was bonded to both sides with a roll-to-roll to produce a polarizing plate.
  • a reflective electrode made of chromium having a thickness of 80 nm is formed on a glass substrate by sputtering, ITO is formed on the reflective electrode as an anode by sputtering to a thickness of 40 nm, and the positive electrode is formed on the anode.
  • Poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT: PSS) is used as the hole transport layer by sputtering to a thickness of 80 nm, and a shadow mask is used on the hole transport layer to form each of the RGB light-emitting layers to 100 nm. The film thickness was formed.
  • red light emitting layer tris (8-hydroxyquinolinate) aluminum (Alq 3 ) as a host and a light emitting compound [4- (dicyanomethylene) -2-methyl-6 (p-dimethylaminostyryl) -4H-pyran] (DCM ) Were co-evaporated (mass ratio 99: 1) to form a thickness of 100 nm.
  • Alq 3 as a host and the light emitting compound coumarin 6 (Coumarin 6) were co-evaporated (mass ratio 99: 1) and formed to a thickness of 100 nm.
  • the blue light-emitting layer was formed with a thickness of 100 nm by co-evaporating BAlq and a light-emitting compound Perylene as a host (mass ratio 90:10). Further, calcium is deposited to a thickness of 4 nm by vacuum deposition as a first cathode having a low work function so that electrons can be efficiently injected onto the light emitting layer, and a second cathode is formed on the first cathode. Aluminum was deposited to a thickness of 2 nm. Here, the aluminum used as the second cathode has a role to prevent calcium as the first cathode from being chemically altered when the transparent electrode formed thereon is formed by sputtering.
  • an organic light emitting layer was obtained.
  • a transparent conductive film was formed to a thickness of 80 nm on the cathode by sputtering.
  • ITO was used as the transparent conductive film.
  • an insulating film was formed by depositing 200 nm of silicon nitride on the transparent conductive film by a CVD method.
  • the organic EL display device manufactured as described above was manufactured.
  • the organic EL display device was produced by pasting so that the arrangement of T1 and T2 was matched.
  • the produced 3D-organic EL display device was evaluated for crosstalk when the head was tilted when viewing 3D video, crosstalk when the head was not tilted after continuous lighting, antireflection function, and hue (color) variation. .
  • the front antireflection function was evaluated based on the following criteria. ⁇ : When the produced EL display device is viewed, the image of itself and the background are not so visible. (Triangle
  • Comparative Example 1 since the slow axes of the retardation films of T1 and T2 are arranged in parallel, the change in color when the display device is observed from an oblique direction cannot be suppressed, so that the color variation is remarkable. appear.
  • Rt (T2) / Rt (T1) exceeds 1.7. This is because Rt of the retardation film A-4 of T2 exceeds 100 nm. When Rt of the retardation film of T2 exceeds 100 nm, the antireflection function is deteriorated.
  • Rt (T2) / Rt (T1) exceeds 1.7. This is because Rt of the retardation film B-4 of T1 is less than 20 nm. If Rt of the T1 retardation film is less than 20 nm, crosstalk of the stereoscopic display image occurs. In particular, when the display device is viewed from an oblique direction, crosstalk is intensely seen.
  • Rt (T2) / Rt (T1) is a negative value. This is because Rt of the retardation film A-4 of T2 has a negative value. If Rt of the retardation film of T2 has a negative value, the hue (hue) variation increases and the antireflection function also decreases.
  • Rt of the retardation film A-5 of T1 exceeds 250 nm. If Rt of the retardation film of T1 exceeds 250 nm, crosstalk of the stereoscopic display image will occur remarkably. In particular, when the display device is viewed from an oblique direction, crosstalk is intensely seen.
  • Rt of each of the retardation films of T1 and T2 is within the range described in claim 1, but the value of Rt (T2) / Rt (T1) exceeds 1.7. Yes. If the value of Rt (T2) / Rt (T1) exceeds 1.7, the hue (color) variation will increase.
  • the stereoscopic image display system of the present invention is a stereoscopic image display system with improved hue (color) change and crosstalk in an oblique direction, and is particularly suitable for a stereoscopic image display system provided with an organic electroluminescence element.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Stereoscopic And Panoramic Photography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention vise à résoudre le problème de fourniture d'un système d'affichage d'image stéréoscopique ayant un changement de teinte (couleur) diagonal et un brouillage améliorés. Ce système d'affichage d'image stéréoscopique est un système d'affichage d'image stéréoscopique constitué par un dispositif d'affichage d'image ayant au moins une plaque polarisante (f, g, h) et un élément électroluminescent (c) et des lunettes ayant au moins un polariseur, la plaque polarisante (f, g, h) comprenant un polariseur (g), un film à différence de phase T1 (h) lié au côté d'observation du polariseur (g) et un film à différence de phase T2 (f) lié au côté élément électroluminescent du polariseur (g), les axes lents de chacun des films à différence de phase (f, h) étant orthogonaux les uns par rapport aux autres et la valeur de différence de phase dans le plan Ro et la valeur de différence de phase de direction d'épaisseur Rt des films à différence de phase satisfaisant la formule (1) (108 nm≤Ro≤168 nm), la formule (2) (20 nm≤Rt(T1)≤250 nm), la formule (3) (0 nm≤Rt(T2)≤100 nm), et la formule (4) (0≤Rt(T2)/Rt(T1)≤1.7).
PCT/JP2012/069087 2011-09-28 2012-07-27 Système d'affichage d'image stéréoscopique WO2013046897A1 (fr)

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WO2019059067A1 (fr) * 2017-09-22 2019-03-28 日本ゼオン株式会社 Visualiseur de détermination d'authenticité
WO2021045154A1 (fr) * 2019-09-06 2021-03-11 三菱瓦斯化学株式会社 Composition de résine de polycarbonate
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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
WO2019059067A1 (fr) * 2017-09-22 2019-03-28 日本ゼオン株式会社 Visualiseur de détermination d'authenticité
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