WO2017110400A1 - 偏光板保護フィルム、その製造方法及び偏光板 - Google Patents

偏光板保護フィルム、その製造方法及び偏光板 Download PDF

Info

Publication number
WO2017110400A1
WO2017110400A1 PCT/JP2016/085677 JP2016085677W WO2017110400A1 WO 2017110400 A1 WO2017110400 A1 WO 2017110400A1 JP 2016085677 W JP2016085677 W JP 2016085677W WO 2017110400 A1 WO2017110400 A1 WO 2017110400A1
Authority
WO
WIPO (PCT)
Prior art keywords
polarizing plate
protective film
plate protective
film
fine particles
Prior art date
Application number
PCT/JP2016/085677
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
高木　隆裕
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2017557826A priority Critical patent/JP6859958B2/ja
Priority to CN201680075187.9A priority patent/CN108369310B/zh
Publication of WO2017110400A1 publication Critical patent/WO2017110400A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a polarizing plate protective film and a method for producing the same.
  • the present invention also relates to a polarizing plate having a polarizing plate protective film. More specifically, the present invention relates to a polarizing plate protective film having improved slip properties and a method for producing the same.
  • organic EL organic electroluminescence
  • various resin films are used for a support or a protective film.
  • a film formed from a hydrogenated (hereinafter referred to as “hydrogenated”) norbornene-based resin has high heat resistance and low water absorption. Accordingly, a film formed from a hydrogenated norbornene resin is preferably used because it is excellent in dimensional stability and humidity fluctuation resistance.
  • hydrogenated norbornene-based resin has a small photoelastic coefficient, intrinsic birefringence can be kept low. For this reason, it is a material excellent in optical properties as a polarizing plate protective film for applications requiring optical isotropy.
  • the hydrogenated norbornene-based resin has the above-mentioned advantage, but has a problem that it is inferior in slipperiness. Due to the poor slidability between films, problems are likely to occur during the production of the film. In particular, when the film is wound, if the slipping property between the films is poor, there is a problem that the film is broken or scratched during winding.
  • the hydrogenated norbornene-based resin film is difficult to handle because of insufficient sliding properties, and its application is limited.
  • Patent Document 1 discloses a film coated with an antistatic agent having a nitrogen atom amount of 0.5 to 10 mol% on the surface of the coating layer. By reducing the surface chargeability, both smoothness and slipperiness are achieved.
  • Patent Document 2 proposes a technique for imparting a chemical resistance effect by applying an antistatic layer containing a conductive compound having hydrophilicity.
  • Patent Document 3 discloses that the slipperiness is improved by forming a fine convex structure on the film surface by an ink jet method.
  • Patent Document 4 discloses that the surface is improved by bonding a protective film having a constant Ra (arithmetic mean roughness) or Sm (average interval of unevenness) on the surface.
  • Patent Document 5 proposes a technique for adding matting agent fine particles to a cyclic olefin resin film.
  • the present invention has been made in view of the above problems, and a solution to the problem is to provide a polarizing plate protective film containing a hydrogenated norbornene resin and having improved slipperiness without increasing haze. It is. Moreover, it is providing the polarizing plate provided with the manufacturing method of the said polarizing plate protective film, and the said polarizing plate protective film.
  • a polarizing plate protective film containing a hydrogenated norbornene-based resin and fine particles, the surface peak of the polarizing plate protective film When the density is within a specific range, slipperiness is improved, and a film containing a hydrogenated norbornene resin and fine particles and a hydrogenated norbornene resin are mixed to provide a solution in the dope. It has been found that the growth of the fine particles is promoted and the slipperiness of the polarizing plate protective film is improved, and the present invention has been achieved.
  • the relative standard deviation of the particle diameter of the secondary particles is in the range of 5 to 20%, and the peak density of the surface of the polarizing plate protective film is in the range of 1000 to 5000 (pieces / mm 2 ).
  • a film containing at least a hydrogenated norbornene resin and fine particles and a hydrogenated norbornene resin are mixed, and the mixing ratio defined by the following formula is in the range of 20 to 80 (%).
  • Mixing rate (%) ⁇ a / (a + b) ⁇ ⁇ 100 (Here, a represents the mass (g) of the film containing the hydrogenated norbornene resin and fine particles, and b represents the mass (g) of the hydrogenated norbornene resin.)
  • the polarizing plate protective film has a moisture permeability of 100 to 400 g / m 2 ⁇ 24 h when measured according to JIS Z 0208 in an environment of a temperature of 40 ° C. and a relative humidity of 90%.
  • the polarizing plate protective film according to any one of Items 1 to 3.
  • Ro (n x -n y) ⁇ d
  • Rt ⁇ (n x + n y ) / 2 ⁇ n z ⁇ ⁇ d
  • ⁇ 10 nm
  • n x of the polarizing plate protective film the refractive index in the slow axis direction in the film plane.
  • ny is the refractive index in the fast axis direction in the film plane of the polarizing plate protective film.
  • nz is the refractive index in the film thickness direction of the optical film.
  • d is the film thickness (nm) of the polarizing plate protective film.
  • a polarizing plate comprising the polarizing plate protective film according to any one of items 1 to 6.
  • the polarizing plate protective film of this invention can be preferably used as a film for a display device or a touch panel.
  • the hydrogenated norbornene resin is a resin having a low polarity
  • the interaction with fine particles is weak as compared with a resin having a high polarity, such as a cellulose ester resin.
  • a resin having a high polarity such as a cellulose ester resin.
  • the present inventor re-dissolved a film once formed (a polarizing protective film containing a hydrogenated norbornene resin and fine particles) in an organic solvent.
  • a film once formed a polarizing protective film containing a hydrogenated norbornene resin and fine particles
  • an aggregate of fine particles is introduced into the dope, and the fine particles can be grown.
  • secondary particles (aggregates) of a desired size can be prepared, which makes it a hydrogenated norbornene resin. It is presumed that the peak density on the film surface could be made within the range of 1000 to 5000 (pieces / mm 2 ) for the first time.
  • the polarizing plate protective film of the present invention is a polarizing plate protective film containing a norbornene-based resin and fine particles, wherein the norbornene-based resin is a hydrogenated norbornene-based resin, and the average particle diameter of secondary particles of the fine particles is It is in the range of 0.05 to 0.20 ⁇ m, the relative standard deviation of the secondary average particle diameter of the particles is in the range of 5 to 20%, and the peak density of the surface of the polarizing plate protective film is 1000 It is characterized by being within a range of ⁇ 5000 (pieces / mm 2 ). This feature is a technical feature common to the claimed invention.
  • the polarizing plate protective film has a haze value of 2.0% or less from the viewpoint of the effect of the present invention. Thereby, the polarizing plate protective film which maintained transparency without deterioration of haze can be obtained.
  • a film containing at least a hydrogenated norbornene resin and fine particles and a hydrogenated norbornene resin are mixed, and the mixing ratio is in the range of 20 to 80 (%). Is preferred. As a result, the effect of improving the slipperiness by growing the secondary particles of the fine particles is increased.
  • the moisture permeability of the polarizing plate protective film is preferably in the range of 100 to 400 g / m 2 ⁇ 24 h. Thereby, the effect that the humidity fluctuation tolerance of a polarizing plate protective film is small is acquired.
  • the thickness of the polarizing plate protective film is preferably in the range of 5 to 40 ⁇ m. Accordingly, the polarizing plate and the display device can be thinned.
  • the viewing angle can be expanded in a liquid crystal display device that requires isotropic properties.
  • the retardation value Rt in the thickness direction it is possible to suppress the occurrence of rainbow unevenness when the polarizing plate protective film is used in a display device.
  • the polarizing plate protective film which manufactures the polarizing plate protective film of this invention, it may have the process of casting the polymer solution containing the said hydrogenated norbornene-type resin and a solvent on a support body, and forming a film. From the viewpoint of easy manufacturing of a thin polarizing plate protective film and good surface quality.
  • the polarizing plate protective film of the present invention from the viewpoint of easy production of a thin film polarizing plate.
  • the polarizing plate protective film of the present invention is a polarizing plate protective film containing a hydrogenated norbornene-based resin and fine particles, and the average particle diameter of secondary particles of the fine particles is in the range of 0.05 to 0.20 ⁇ m.
  • the relative standard deviation of the particle diameter of the secondary particles is in the range of 5 to 20%, and the peak density on the surface of the polarizing plate protective film is in the range of 1000 to 5000 (pieces / mm 2 ). It is characterized by that.
  • the polarizing plate protective film of the present invention is characterized by containing a hydrogenated norbornene resin.
  • the “hydrogenated norbornene-based resin” used in the present invention refers to a norbornene derivative (monomer) alone, or the norbornene derivative and an unsaturated cyclic compound copolymerizable therewith, using a metathesis polymerization catalyst.
  • the hydrogenated norbornene resin is preferably a resin derived from a monomer having a chemical structure represented by the following general formula (I).
  • the resin derived from the norbornene monomer having the chemical structure represented by the general formula (I) is polymerized using the norbornene monomer having the chemical structure represented by the general formula (I) as a component. It represents that the resin is derived.
  • A, B, X and Y are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amide group, an imide group
  • the copolymerizable monomer copolymerizable with the norbornene monomer represented by the general formula (I) is not particularly limited, and examples thereof include cyclic olefin monomers having no norbornene skeleton.
  • Examples of the cyclic olefin monomer having no norbornene skeleton include cyclooctadiene, cyclooctene, cyclohexene, cyclododecene, and cyclododecatriene.
  • the monomer structure has a polar group other than a halogen atom in order to give the polarizing plate protective film a certain moisture permeability.
  • a method for polymerizing a norbornene monomer represented by the general formula (I) or a norbornene monomer represented by the general formula (I) and a copolymerizable monomer copolymerizable therewith for example, conventionally known methods such as ring-opening metathesis polymerization and addition polymerization can be employed.
  • the hydrogenated norbornene-based resin When the hydrogenated norbornene-based resin has an unsaturated bond in the molecule, it is preferably saturated by hydrogenation, and the hydrogenation rate is preferably 95% or more, more preferably 99% or more. . When the hydrogenation rate is less than 95%, the obtained polarizing plate protective film is inferior in light resistance and heat deterioration resistance.
  • the number average molecular weight in terms of polystyrene of the hydrogenated norbornene resin is preferably 10,000 to 1,000,000. If it is less than 10,000, the mechanical strength of the resulting polarizing plate protective film may be insufficient. Conversely, if it exceeds 1,000,000, melt extrusion moldability may be significantly reduced. More preferably, it is 15,000 to 700,000.
  • Examples of commercially available hydrogenated norbornene resins include, for example, “ZEONOR” series, “ZEONEX” series manufactured by ZEON Corporation, “Optretz” series manufactured by Hitachi Chemical Co., Ltd., “ARTON” series manufactured by JSR Corporation, etc. Is mentioned.
  • the “Arton” series having an appropriate moisture permeability, which is necessary when producing a polarizing plate using water glue, is particularly preferable because it has a polar group in the molecular skeleton.
  • the polarizing plate protective film of the present invention contains fine particles, the average particle size of secondary particles of the fine particles is in the range of 0.05 to 0.20 ⁇ m, and the particle size of the secondary particles Relative standard deviation of 5 to 20%.
  • the particle size of the secondary particles is preferably in the range of 0.10 to 0.15 ⁇ m as the equivalent circle diameter.
  • the “equivalent circle diameter” herein refers to the diameter of a circle having an area equal to the area of the particles.
  • This range is preferable since the average particle diameter of the secondary particles (aggregates) of the fine particles is larger when the average particle diameter is better and the smaller one is excellent in transparency.
  • the relative standard deviation of the particle diameter of the primary particles is 5 to 20%, preferably 5 to 10%.
  • the “average particle diameter of secondary particles” in the present invention is a value obtained by measuring the average particle diameter of fine particles in the polarizing plate protective film by the following method.
  • a sample of a polarizing plate protective film containing a hydrogenated norbornene resin and fine particles was embedded in an epoxy resin, and then an ultrathin section having a thickness of about 100 nm was prepared by an ultramicrotome, and a transmission electron microscope 2000FX (acceleration voltage) manufactured by JEOL Ltd. : 200 kV), a TEM image of 2500 to 10,000 times was taken.
  • the obtained image was converted into electronic data using a flat head scanner Sitios 9231 manufactured by Konica Minolta, and the average particle diameter in the film was measured using image analysis software ImagePro Plus.
  • the average particle diameter in the film was calculated as an equivalent circle diameter represented by the diameter of a circle having an area equal to the projected area of the particles. This value is defined as “average particle diameter of secondary particles”.
  • filter processing is performed so that the image analysis software can recognize the fine particles by enhancing the contrast of the fine particle image. Furthermore, the contrast is optimized by changing the filter condition.
  • median 3 ⁇ 3 then flattened 20 pixels, then high pass 3 ⁇ 3, then median 3 ⁇ 3 are used for filtering.
  • particles are extracted from the above image with optimized contrast, and the shape of each particle is measured with image analysis software to measure the average particle size.
  • the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Etc.
  • these matting agent fine particles those containing silicon are preferable in terms of low turbidity (haze), and silicon dioxide is particularly preferable.
  • the apparent specific gravity is preferably in the range of 90 to 200 g / liter, and particularly preferably in the range of 100 to 200 g / liter. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
  • Silicon dioxide fine particles are commercially available, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above, Nippon Aerosil Co., Ltd., trade name (Aerosil is a registered trademark)). Goods can be used.
  • Zirconium oxide fine particles are commercially available, for example, as Aerosil R976 and R811 (above, trade name, manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Aerosil 200V and Aerosil R812V are fine particles of silicon dioxide having a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and while keeping the haze of the polarizing plate protective film low, friction This is particularly preferable because the effect of lowering the coefficient is great.
  • a polarizing plate protective film is prepared by mixing a film containing at least a hydrogenated norbornene-based resin and fine particles and a hydrogenated norbornene-based resin within a range of 20 to 80 (%).
  • the peak density can be increased.
  • the film containing at least a hydrogenated norbornene-based resin and fine particles has been produced once, and a part of the film is added together with a new hydrogenated norbornene-based resin during the dope preparation.
  • Mixing of a film containing at least a hydrogenated norbornene-based resin and fine particles may be added before the dope preparation, or may be added during the dope preparation.
  • a part of the fine particles can be prepared by the following method and applied to the protective film. That is, a matting agent fine particle dispersion prepared by stirring and mixing a solvent and matting agent fine particles is prepared in advance, and this matting agent fine particle dispersion is added to various additive solutions having a separately prepared hydrogenated norbornene resin concentration of less than 5% by mass. A method of mixing with the main hydrogenated norbornene resin dope after adding and dissolving with stirring is preferred.
  • the additive Since the surface of the fine particles has been subjected to a hydrophobic treatment, when a hydrophobic additive is added, the additive is adsorbed on the surface of the matting agent fine particle, and aggregates of the additive are generated using this as a nucleus. It may be easier. Therefore, by mixing a relatively hydrophilic additive in advance with the fine particle dispersion and then mixing the hydrophobic additive, aggregation of the additive on the surface of the fine particles can be suppressed, and the haze is low. A protective film with less light leakage in black display when incorporated in a liquid crystal display device can be produced, which is preferable.
  • an in-line mixer for mixing the matting agent fine particle dispersant with the additive solution and mixing with the hydrogenated norbornene resin dope.
  • concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably in the range of 5 to 30% by mass, and is preferably 10 to 25% by mass. It is more preferable that it be within the range, and it is particularly preferable that it be within the range of 15 to 20% by mass.
  • a higher dispersion concentration is preferable because turbidity with respect to the same amount of addition is reduced, and generation of haze and aggregates can be suppressed.
  • the amount of fine particles added in the final dope of the hydrogenated norbornene resin is preferably in the range of 0.01 to 1.0% by mass, and in the range of 0.05 to 0.5% by mass. More preferably, it is particularly preferably in the range of 0.05 to 0.3% by mass.
  • the polarizing plate protective film of the present invention is characterized in that the peak density on the surface of the polarizing plate protective film is in the range of 1000 to 5000 (pieces / mm 2 ). More preferably, the peak density is 2000 to 4000 (pieces / mm 2 ). This range is preferable because the higher peak density is excellent in slipperiness and the smaller peak density is excellent in transparency.
  • the unit of peak density (pieces / mm 2 ) represents the number of peaks per 1 mm 2 .
  • the surface peak density at a temperature of 23 ° C. and a humidity of 50% ⁇ 5% using a three-dimensional surface structure analysis microscope zygo New View 5000 manufactured by Canon Sales Co., Ltd., with an objective lens of 50 ⁇ and an image zoom of 1.0 ⁇ , It can be obtained by measuring the number of peaks of 3 nm or more, dividing by the measurement area, and calculating the number of peaks per unit area.
  • the average line that serves as a reference for peak height is the sum of the areas of the mountains that can be formed above and below the line within the measurement length when the average line is drawn on the roughness curve. It was drawn to be equal.
  • the portion above the average line is the “profile peak”. " In “profile peak”, a portion higher than the average line by 3 nm or more was defined as a peak in the present invention.
  • the peak density on the surface of the polarizing plate protective film can be in the range of 1000 to 5000 (pieces / mm 2 ).
  • a hydrogenated norbornene resin, a film containing fine particles, and a hydrogenated norbornene resin are mixed at 20 to 80% by mass.
  • the peak density of the surface of the polarizing plate protective film can be set within the range of 1000 to 5000 (pieces / mm 2 ).
  • the amount of the fine particles added is preferably 0.02 to 1.0 g, more preferably 0.03 to 0.3 g, and most preferably 0.08 to 0.2 g per 1 m 2 .
  • the content ratio of the film to the hydrogenated norbornene resin is preferably 20 to 80% by mass, and more preferably 50 to 80% by mass.
  • the polarizing plate protective film of the present invention preferably has a haze value of 1.0% or less, more preferably 0.30 or less, and further preferably 0.20 or less. A smaller haze value is preferable because of better transparency. The haze value is adjusted by the secondary particle and primary particle diameter of the fine particles, the amount of fine particles added, and the like.
  • the haze value was measured using T-260DA manufactured by Tokyo Denshoku Industries Co., Ltd. according to ASTM-D1003-52 (ASTM standard) with three polarizing plate protective films superimposed.
  • the polarizing plate protective film of the present invention preferably has a moisture permeability in the range of 100 to 400 g / m 2 ⁇ 24 h.
  • the moisture permeability is a value when measured according to JIS Z 0208 in an environment of a temperature of 40 ° C. and a relative humidity of 90%.
  • the polarizing plate protective film of the present invention is an in-plane retardation value R O (nm) defined by the following formula (I) and a thickness direction defined by the following formula (II) of the polarizing plate protective film. It is preferable that the phase difference value Rt (nm) satisfies the following formula (III) and the following formula (IV).
  • n x of the polarizing plate protective film the refractive index in the slow axis direction in the film plane.
  • ny is the refractive index in the fast axis direction in the film plane of the polarizing plate protective film.
  • nz is the refractive index in the film thickness direction of the optical film.
  • d is the film thickness (nm) of the polarizing plate protective film.
  • the retardation value (R O ) in the in-plane direction of the film and the retardation value (Rt) in the thickness direction were determined using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics). It can be calculated from the obtained refractive indexes nx, ny, and nz by performing a three-dimensional refractive index measurement at a wavelength of 590 nm in an environment of ° C and 55% RH.
  • the film thickness of the polarizing plate protective film of the present invention is preferably 5 to 40 ⁇ m. It is more preferably 5 to 30 ⁇ m or less, and further preferably 5 to 20 ⁇ m or less. Thus, the polarizing plate protective film of the present invention can be thinned.
  • the film thickness of the polarizing plate protective film means the average film thickness of the film.
  • the polarizing plate protective film of the present invention can contain various additives for the purpose of imparting various functions.
  • Additives that can be applied to the present invention are not particularly limited, and are, for example, ultraviolet absorbers, plasticizers, deterioration inhibitors, matting agents, retardation increasing agents, and chromatic dispersion improvement within the range that does not impair the object effects of the present invention.
  • An agent or the like can be used.
  • the polarizing plate protective film of the present invention can contain an ultraviolet absorber.
  • ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used. As an ultraviolet absorber, from the viewpoint of preventing deterioration of a polarizer and an organic EL element, it has an excellent ability to absorb ultraviolet light having a wavelength of 370 nm or less, and from the viewpoint of display properties of the organic EL element, it absorbs visible light having a wavelength of 400 nm or more. It is preferable to have few characteristics.
  • benzotriazole-based ultraviolet absorber examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2 -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy- '-T-butyl-5'-methylphenyl) -5-
  • TINUVIN 109 can be preferably used as a commercial product.
  • TINUVIN 171 can be preferably used as a commercial product.
  • TINUVIN 326 can be preferably used as a commercial product.
  • TINUVIN 328 can be preferably used as a commercial product.
  • the addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5.0% by mass, more preferably in the range of 0.5 to 5.0% by mass with respect to the hydrogenated norbornene resin. Further preferred. *
  • a polarizing plate protective film is poor in flexibility, and when the film is subjected to bending stress or shear stress, the film is likely to be cracked. Moreover, when processing as a polarizing plate protective film, a crack is easy to enter into a cut part and it is easy to generate
  • plasticizer examples include, for example, phthalic acid ester compounds, trimellitic acid ester compounds, aliphatic dibasic acid ester compounds, sugar ester compounds, normal phosphate ester compounds, acetate ester compounds, Examples include polyester / epoxidized ester compounds, ricinoleic acid ester compounds, polyolefin compounds, polyethylene glycol compounds, and the like.
  • a compound that is normal temperature, normal pressure, liquid and has a boiling point of 200 ° C. or higher specifically examples include aliphatic dibasic acid ester, phthalic acid ester, and polyolefin compounds.
  • an aliphatic dibasic acid ester compound and a sugar ester compound are contained in the polarizing plate protective film from the viewpoint of relaxing the orientation of the hydrogenated norbornene resin and reducing the retardation value.
  • the addition amount of the plasticizer is preferably in the range of 0.5 to 40.0% by mass, and in the range of 1.0 to 30.0% by mass with respect to the hydrogenated norbornene resin. Is more preferable, and it is particularly preferably in the range of 3.0 to 20.0% by mass.
  • the added amount of the plasticizer is 0.5% by mass or more, the plasticizing effect is sufficient and the processability is improved. Further, when the content is 40% by mass or less, separation and elution of the plasticizer can be suppressed when it is aged for a long time, and optical unevenness, contamination to other parts, and the like can be more reliably suppressed.
  • the protective film of the present invention may contain a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines.
  • a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines.
  • Examples of the deterioration preventing agent are described in JP-A-3-199201, JP-A-5-97073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, and the like.
  • the addition amount of the deterioration preventing agent is effective for the addition of the deterioration preventing agent, and the dope (water) used for the production of the polarizing plate protective film from the viewpoint of suppressing the bleeding out of the deterioration preventing agent to the film surface.
  • the added norbornene resin solution is preferably in the range of 0.01 to 1% by mass, and more preferably in the range of 0.01 to 0.2% by mass.
  • BHT butylated hydroxytoluene
  • TBA tribenzylamine
  • the polarizing plate protective film of the present invention is produced by a solution casting method or a melt casting method. However, it is easy to produce a thin film polarizing plate protective film by the solution flow knitting method, and the surface quality is good. To preferred.
  • Production of the polarizing plate protective film of the present invention is a hydrogenated norbornene resin, a step of preparing a dope by dissolving the polymerizable compound in a solvent, a step of casting on an endless metal support that moves the dope indefinitely , The process of drying the cast dope as a web, the process of peeling from the metal support, the process of stretching or maintaining the width, the process of further drying, and the process of winding up the finished film.
  • the process for preparing the dope will be described.
  • the concentration of the dissolved hydrogenated norbornene resin and the polymerizable compound in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration is too high, the load during filtration increases. Thus, the filtration accuracy is deteriorated.
  • the concentration at which these are compatible is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the hydrogenated norbornene resin.
  • a preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as dichloromethane, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is dichloromethane or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2% by mass of water.
  • the solvent used for dissolving the hydrogenated norbornene-based resin, the polymerizable compound, and the additive may be used by collecting the solvent removed from the film by drying in the film forming process and reusing it.
  • a general method for dissolving the hydrogenated norbornene resin when preparing the dope described above a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
  • the hydrogenated norbornene resin, the polymerizable compound, and the additive solution are filtered using an appropriate filter medium such as filter paper.
  • the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged.
  • a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
  • the bright spot foreign matter was placed in a crossed Nicols state with two polarizing plates, a rolled cellulose ester was placed between them, and light was applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side sometimes leaks, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less.
  • it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, still more preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small and preferable.
  • the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 to 4 m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
  • the support temperature is preferably 0 to 40 ° C. ⁇ 0 to 50 ° C., more preferably 5 to 30 ° C.
  • the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is preferably peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0.1% by mass.
  • the content is particularly preferably 0 to 0.01% by mass or less.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web to dry) or a tenter method is used while drying the web.
  • any appropriate surface treatment may be applied to the surface of the protective film (outer protective film) disposed outside the protective film.
  • a commercially available polymer film subjected to surface treatment can be used as it is.
  • a commercially available polymer film can be used after any surface treatment.
  • the surface treatment include an antiglare treatment, a diffusion treatment (antiglare treatment), an antireflection treatment (antireflection treatment), a hard coat treatment, and an antistatic treatment.
  • Any appropriate method can be used as the anti-glare treatment method.
  • the surface reflection light can be formed by an appropriate method such as embossing, sand blasting, etching, or the like by providing a fine uneven structure on the surface.
  • polarizing plate protective film of the present invention a film containing a hydrogenated norbornene resin is used.
  • an unstretched film or a uniaxially stretched film may be used.
  • polarizer any appropriate polarizer can be used as the polarizer used in the present invention.
  • dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product.
  • a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio.
  • the thickness of these polarizers is not particularly limited and is generally about 1 to 80 ⁇ m.
  • a polarizer uniaxially stretched by adsorbing iodine to a polyvinyl alcohol film can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. . If necessary, it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. *
  • Stretching may be performed after dyeing with iodine, or may be performed while dyeing. Further, it may be dyed with iodine after stretching.
  • the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the polarizer used in the present invention preferably satisfies 0.030 ⁇ Rpva ⁇ 0.040.
  • Rpva nx ⁇ ny.
  • Rpva is more preferably 0.030 ⁇ Rpva ⁇ 0.039, and particularly preferably 0.030 ⁇ Rpva ⁇ 0.035. It is estimated that such characteristics are satisfied by increasing the amount of crystals that do not contribute to orientation in the polarizer (typically, low orientation).
  • Rpva is a polarizer in such a range, it can have excellent dimensional stability and optical durability in a high temperature and high humidity environment. As a result, even when the polarizer is used for a polarizing plate provided with a polarizing plate protective film only on one side of the polarizer, the dimensional change and the deterioration of the optical characteristics are unlikely to occur, and the practically acceptable dimensional stability and optical Durability can be achieved.
  • the polarizer used in the present invention has a dichroic ratio DR of preferably 160 or more, more preferably 160 to 220, particularly preferably 170 to 210, and most preferably 175 to 185.
  • a liquid crystal panel and a liquid crystal display device with high front contrast can be obtained by using the polarizing plate of the present invention.
  • Such a liquid crystal panel and a liquid crystal display device are suitable for television applications, for example.
  • the dichroic ratio DR can be obtained from the following equation.
  • Dichroic ratio DR log (0.919 / k 2 ) / log (0.919 / k 1 )
  • k 1 is the transmission axis of the transmittance of the polarizer
  • k 2 is the absorption axis direction of the transmittance of the polarizer
  • the constant 0.919 is the interfacial reflectance.
  • the polarizer used in the present invention has a transmittance (single transmittance) Ts of preferably 42% or more, more preferably 42. It is in the range of -44.0%, particularly preferably in the range of 42.5-43.0%.
  • Ts a transmittance (single transmittance) Ts of preferably 42% or more, more preferably 42. It is in the range of -44.0%, particularly preferably in the range of 42.5-43.0%.
  • the transmittance Ts is in such a range, a liquid crystal panel or a liquid crystal display device with high luminance can be obtained by using the polarizing plate of the present invention.
  • Such a liquid crystal panel and a liquid crystal display device are suitable for television applications, for example.
  • permeability of a polarizing plate can be calculated
  • Transmittance ⁇ (k 1 + k 2 ) / 2 ⁇ ⁇ 100 [%]
  • k 1 is the transmittance in the transmission axis direction of the polarizer
  • k 2 is the transmittance in the absorption axis direction of the polarizer.
  • the polarizer used in the present invention may be a polarizer mainly composed of a polyvinyl alcohol (PVA) resin containing a dichroic substance such as iodine or a dichroic dye.
  • PVA polyvinyl alcohol
  • the iodine content of the polarizer used in the present invention is preferably 1.8 to 5.0 mass%, more preferably 2.0 to 4.0 mass%.
  • the boric acid content of the polarizer used in the present invention is preferably 0.5 to 3.0% by mass, more preferably 1.0 to 2.8% by mass, particularly preferably 1 in terms of boron. 0.5 to 2.6% by mass.
  • a polarizer having excellent dimensional stability and optical durability in a humidified environment can be obtained without increasing the amount of boric acid.
  • the polarizer used in the present invention may preferably further contain potassium.
  • the potassium content is preferably 0.2 to 1.0% by mass, more preferably 0.3 to 0.9% by mass, and particularly preferably 0.4 to 0.8% by mass.
  • the linear expansion coefficient in the transmission axis direction of the polarizer is not particularly limited and can take any appropriate value.
  • the linear expansion coefficient in the transmission axis direction of the polarizer is 4.0 ⁇ 10 ⁇ 5 to 5.0. It can be ⁇ 10 ⁇ 5 / ° C.
  • the polarizing plate protective film of the present invention may be combined with a polarizer to form a polarizing plate.
  • the polarizing plate has a polarizer and polarizing plate protective films provided on both sides of the polarizer, and at least one of the polarizing plate protective films is the polarizing plate protective film of the present invention.
  • the polarizing plate protective film has a contact angle with water on the surface of the transparent support opposite to the side having the light scattering layer or antireflection layer, that is, the surface to be bonded to the polarizer, in the range of 10 to 50 degrees. It is preferable.
  • an adhesive layer may be provided on one side of the polarizing plate protective film of the present invention and disposed on the outermost surface of the display.
  • FIG. 1 is a schematic sectional view of a polarizing plate according to a preferred embodiment of the present invention.
  • the polarizing plate 101 includes a polarizer 10 and polarizing plate protective films 20 and 30 disposed on both surfaces of the polarizer 10.
  • the polarizer 10 and the polarizing plate protective films 20 and 30 are bonded to each other through an arbitrary adhesive layer (not shown).
  • the polarizing plate of the present invention may further have other layers.
  • the other layers include an antireflection layer, an antistatic layer, a retardation layer, a brightness enhancement film layer, and an adhesive layer.
  • the polarizing plate of the present invention is bonded to a liquid crystal cell via the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer preferably has a storage elastic modulus at 23 ° C. of 8.0 ⁇ 10 4 or more and less than 1.0 ⁇ 10 7 , and is 1.0 ⁇ 10 5 to 8.0 ⁇ 10 6. More preferred. Any other appropriate layer may be selected depending on the purpose and application, the configuration of the liquid crystal display device in which the polarizing plate of the present invention is used, and the number, type, position, arrangement, and the like are appropriately set. obtain.
  • the polarizing plate protective film of the present invention and the polarizing plate having the above-described polarizing plate protective film of the present invention include a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device ( It can be used for various display devices such as CRT).
  • the polarizing plate protective film or the polarizing plate of the present invention is preferably disposed on the viewing side of the display screen of the image display device.
  • the polarizing plate protective film or polarizing plate of the present invention is particularly preferably used for the outermost layer of a display such as a liquid crystal display device.
  • the liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates.
  • one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.
  • the liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.
  • the rod-like liquid crystal molecules are substantially horizontally aligned and twisted to 60 to 120 °.
  • TN mode liquid crystal cells are most frequently used as color TFT liquid crystal display devices, and are described in many documents.
  • rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied.
  • the VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of Tech.
  • the OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in substantially opposite directions (symmetrically) at the upper and lower portions of the liquid crystal cell.
  • the bend alignment mode liquid crystal display device has an advantage of high response speed.
  • IPS mode liquid crystal cell is a type of switching by applying a lateral electric field to nematic liquid crystal. For details, see Proc. IDRC (Asia Display 1995), p. 577-580 and p. 707-710.
  • ECB mode liquid crystal cell
  • rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied.
  • the ECB mode is one of liquid crystal display modes having the simplest structure, and is described in detail in, for example, Japanese Patent Laid-Open No. 5-203946.
  • a plasma display panel is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor.
  • Two glass substrates are a front glass substrate and a rear glass substrate.
  • An electrode and an insulating layer are formed on the two glass substrates.
  • a phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.
  • a commercially available plasma display panel (PDP) can be used.
  • the plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.
  • the front plate may be placed in front of the plasma display panel.
  • the front plate preferably has sufficient strength to protect the plasma display panel.
  • the front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.
  • an optical filter can be directly attached to the display surface. Further, when a front plate is provided in front of the display, an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.
  • the polarizing plate protective film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
  • a substrate such as an organic EL element or a protective film.
  • the contents described in each gazette such as issue numbers can be applied. Further, it is preferably used in combination with the contents described in JP-A Nos. 2001-148291, 2001-221916, and 2001-231443.
  • touch panel The above-described transparent conductive film is suitable for touch panel applications.
  • a touch panel can be produced according to the description in paragraphs [0073] to [0075] of JP-A-2009-176608.
  • the touch panel according to the present invention can be used as an input device by being incorporated in a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • a capacitance type input device has an advantage that a light-transmitting conductive film is simply formed on a single substrate.
  • a capacitance type is preferred.
  • a type that detects the input position can be preferably used.
  • descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
  • Example 1 Polarizing plate protective film (hereinafter simply referred to as “protective film”)] ⁇ Preparation of protective film 101> (Preparation of fine particle dispersion a) 90 parts by mass of ethanol was put into an airtight container, and 10 parts by mass of silicon oxide fine particles a shown in Table 1 (manufactured by Nippon Aerosil Co., Ltd.) were added with stirring. Then, after stirring and mixing with a dissolver for 50 minutes, the above 2000 g of the mixed solution was passed through a high-pressure dispersion device (trade name: Super High-Pressure Homogenizer M110-E / H, manufactured by Microfluidics Corporation) and treated once at 175 MPa to disperse the fine particles. Liquid a was prepared.
  • a high-pressure dispersion device trade name: Super High-Pressure Homogenizer M110-E / H, manufactured by Microfluidics Corporation
  • Fine particle additive liquid A (Preparation of fine particle additive liquid A) The obtained fine particle dispersion a was slowly added to a closed container containing dichloromethane with sufficient stirring. Further, dispersion was performed with an attritor. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution A.
  • a main dope having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. A hydrogenated norbornene resin was charged into a pressure dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. 244 was used to prepare the main dope (first main dope preparation).
  • the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 100%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
  • the peeled protective film was stretched 5% in the width direction using a tenter while applying heat at 160 ° C.
  • the residual solvent at the start of stretching was 30%.
  • 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 90 N / m.
  • a second main dope was prepared as follows.
  • (Main dope composition) Dichloromethane 300 parts by weight Ethanol 19 parts by weight Protective film 101A for mixing 80 parts by weight Hydrogenated norbornene-based resin (Resin I below) 20 parts by weight Particulate additive liquid A 0.2 parts by weight A dope was prepared by dissolution. Then, 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 1500 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 100%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
  • the peeled protective film was stretched 5% in the width direction using a tenter while applying heat at 160 ° C.
  • the residual solvent at the start of stretching was 30%.
  • 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 90 N / m.
  • the table below shows the addition rate of the protective film for mixing, the type of hydrogenated norbornene resin, the addition ratio (% by mass) of the fine particle additive to the hydrogenated norbornene resin in the first dope preparation, and the type of plasticizer.
  • Protective films 102 to 123 were produced in the same manner as the protective film 101 except for the changes shown in Table 1 and Table 2.
  • the addition amount (parts by mass) of the fine particle addition liquid in the second main dope adjustment is the total mass of the hydrogenated norbornene resin (the mass of the hydrogenated norbornene resin in the protective film for mixing, and a new addition)
  • the ratio of the mass of the fine particles in the additive solution to the mass of the hydrogenated norbornene resin in the first main dope preparation (mass%) was adjusted to be the same.
  • the plasticizers A, B, and C were added at a ratio of 10 parts by mass of the plasticizer with respect to 100 parts by mass of the hydrogenated norbornene resin.
  • plasticizer A 62 g of ethylene glycol, 144 g of adipic acid, 30 g of benzoic acid, and 0.181 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a slow cooling tube, and 230 ° C. in a nitrogen stream. The temperature was gradually raised while stirring until After dehydration condensation reaction for 15 hours, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. after completion of the reaction to obtain a polyester as plasticizer A.
  • the acid value was 0.10 mg KOH / g and the number average molecular weight was 1900.
  • plasticizer B 60 g of 1,6-hexanediol, 101 g of sebacic acid, 122 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a quick cooling tube. The temperature was gradually raised while stirring until it reached 230 ° C in an air stream. After dehydration condensation reaction for 15 hours, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. after completion of the reaction to obtain a polyester as plasticizer B. The acid value was 0.10 mg KOH / g, and the number average molecular weight was 600.
  • the average particle size of the primary and secondary particles was measured as follows. ⁇ Average particle size and relative standard deviation of fine particles (primary particles) in additive solution> The prepared silicon oxide fine particle additive liquid was applied to a glass plate and dried, and the fine particles were photographed with a transmission electron microscope (magnification 10,000 to 100,000 times).
  • the obtained images were converted into electronic data using a flat head scanner Sitios 9231 manufactured by Konica Minolta, and the average primary particle size was measured using image analysis software Image Pro Plus (ImagePro Plus).
  • Image Pro Plus image analysis software
  • As the average primary particle diameter an equivalent circle diameter represented by the diameter of a circle having an area equal to the projected particle area was used. Further, the relative standard deviation was calculated from this data.
  • a filter process was performed so that the image analysis software can recognize the fine particles by enhancing the contrast of the fine particle image. Furthermore, the contrast was optimized by changing the filter conditions.
  • median 3 ⁇ 3 then flattened 20 pixels, then high pass 3 ⁇ 3, then median 3 ⁇ 3 were used for filtering.
  • the obtained images were converted into electronic data using Konica Minolta's flat head scanner Citios 9231, and the average particle diameter in the film was measured using image analysis software ImagePro Plus.
  • the average particle diameter in the film was calculated as an equivalent circle diameter represented by the diameter of a circle having an area equal to the projected area of the particles.
  • a filter process was performed so that the image analysis software can recognize the fine particles by enhancing the contrast of the fine particle image. Furthermore, the contrast was optimized by changing the filter conditions.
  • median 3 ⁇ 3 then flattened 20 pixels, then high pass 3 ⁇ 3, then median 3 ⁇ 3 were used for filtering.
  • ⁇ Dynamic friction coefficient> The coefficient of dynamic friction between the front and back surfaces of the protective film is in accordance with JIS K 7125 (ISO 8295), cut out so that the front and back surfaces of the film are in contact, put a weight of 200 g, have a sample moving speed of 100 mm / min, and a contact area of 80 mm ⁇ 200 mm. The weight was pulled horizontally under the conditions, the average load (F) while the weight was moving was measured, and the dynamic friction coefficient ( ⁇ ) was determined from the following formula. This was taken as a measure of slipperiness.
  • Coefficient of dynamic friction F (gf) / weight of weight (gf) ⁇ Flatness>
  • the wound protective film original fabric sample was stored for 10 days under conditions of 35 ° C. and 80% RH. Unwind 500m sample film, sample 1m long, reflect the fluorescent tube on the surface of the film sample, observe the distortion or fine turbulence, and have the following flatness Ranked.
  • ⁇ When a fluorescent lamp is projected on the surface of the screen, the fluorescent lamp looks beautiful without distortion.
  • ⁇ When a fluorescent lamp is projected on the surface of the screen, the fluorescent lamp appears slightly distorted. Level that is not problematic for use.
  • X When a fluorescent lamp is projected on the surface of the screen, the fluorescent lamp appears to be distorted severely. Level that causes problems in use.
  • the protective film of the present invention has a large coefficient of dynamic friction (good slipperiness) without deterioration of haze.
  • FIG. 2 shows an electron micrograph of polarizing plate protective film number 110 (comparative example).
  • FIG. 3 shows an electron micrograph of the protective film number 101 (present invention).
  • Example 2 ⁇ Preparation of polarizing plates 301 to 326> A protective film 101 is bonded to one surface (surface A) of the polarizer 1 via a PVA adhesive so as to be in a direction parallel to the transmission axis of the polarizer 1, and the other surface (B The following protective film 203 was bonded to the surface) to obtain a polarizing plate 301.
  • polarizing plates 302 to 326 were prepared in the same manner as the polarizing plate 301 except that a protective film and a polarizer were combined.
  • Protective film 201 Polyethylene naphthalate film, Teonex Q83 (trade name) (manufactured by Teijin DuPont), thickness: 40 ⁇ m)
  • Protective film 202 Polyethylene terephthalate film, MRF40 (trade name) (Mitsubishi Resin Co., Ltd.) thickness: 25 ⁇ m)
  • Protective film 203 Triacetylcellulose film, KC4UAW (trade name) manufactured by Konica Minolta, thickness: 40 ⁇ m
  • Protective film 204 Triacetyl cellulose film, KC2UAW (trade name) manufactured by Konica Minolta, thickness: 25 ⁇ m)
  • a PVA resin film having a polymerization degree of 2400, a saponification degree of 99.7 mol%, and a thickness of 75 ⁇ m was prepared.
  • the film was stretched 3 times in the film conveying direction while being dyed in an aqueous iodine solution at 30 ° C., and then the total draw ratio was 4% by weight boric acid at 60 ° C. and 5% by weight potassium iodide aqueous solution.
  • the film was stretched to be 6 times the original length. Furthermore, the stretched film was washed by immersing it in a 2 mass% potassium iodide aqueous solution at 30 ° C. for several seconds.
  • the obtained stretched film was dried at 90 ° C. to obtain a polarizer.
  • Polarization degree is 99.7% or more
  • ⁇ Polarization degree is 99.2% or more and less than 99.7%
  • X Polarization degree is less than 99.2% The above polarization degree was calculated by the following method.
  • the transmittance (single transmittance) of one polarizing plate was measured.
  • the transmittance (orthogonal transmittance: H90) in the case of superposition was measured.
  • the degree of polarization was calculated by applying the parallel transmittance (H 0 ) and the orthogonal transmittance (H 90 ) to the following equation.
  • Polarization degree (%) ⁇ (H 0 ⁇ H 90 ) / (H 0 + H 90 ) ⁇ 1/2 ⁇ 100
  • the single transmittance, the parallel transmittance (H 0 ), and the orthogonal transmittance (H 90 ) are Y values obtained by correcting the visibility with a two-degree field of view (C light source) of JIS Z8701.
  • the polarizing plate of the present invention has good flatness and good wet heat durability of the degree of polarization.
  • the present invention can be used for a polarizing plate protective film with improved slipperiness, production of the polarizing plate protective film, and a polarizing plate provided with the polarizing plate protective film without increasing haze.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2016/085677 2015-12-25 2016-12-01 偏光板保護フィルム、その製造方法及び偏光板 WO2017110400A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2017557826A JP6859958B2 (ja) 2015-12-25 2016-12-01 偏光板保護フィルム、その製造方法及び偏光板
CN201680075187.9A CN108369310B (zh) 2015-12-25 2016-12-01 偏振片保护膜、其制造方法及偏振片

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-253077 2015-12-25
JP2015253077 2015-12-25

Publications (1)

Publication Number Publication Date
WO2017110400A1 true WO2017110400A1 (ja) 2017-06-29

Family

ID=59090020

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/085677 WO2017110400A1 (ja) 2015-12-25 2016-12-01 偏光板保護フィルム、その製造方法及び偏光板

Country Status (4)

Country Link
JP (1) JP6859958B2 (zh)
CN (1) CN108369310B (zh)
TW (1) TW201730588A (zh)
WO (1) WO2017110400A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111640373B (zh) * 2020-06-09 2023-06-23 京东方科技集团股份有限公司 盖板和显示装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006022306A (ja) * 2004-06-07 2006-01-26 Konica Minolta Opto Inc セルロースエステルフィルム及びその製造方法、光学フィルム、偏光板、液晶表示装置
JP2007112967A (ja) * 2005-10-24 2007-05-10 Fujifilm Corp 環状オレフィン系樹脂フィルムとその製造方法、偏光板、及び液晶表示装置
JP2008304904A (ja) * 2007-05-07 2008-12-18 Jsr Corp 偏光板
JP2009237376A (ja) * 2008-03-27 2009-10-15 Fujifilm Corp 偏光板およびそれを用いた液晶表示装置

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4612166B2 (ja) * 2000-09-28 2011-01-12 山本光学株式会社 光学物品の連続製造方法
EP1710278A4 (en) * 2004-01-26 2011-08-24 Jsr Corp LIQUID COMPOSITION CONTAINING HOLLOW PARTICLES, PROCESS FOR PRODUCING THE SAME, AND OPTICAL ARTICLE
JP2005302088A (ja) * 2004-04-07 2005-10-27 Konica Minolta Opto Inc 対物レンズ及び光ピックアップ装置
CN100453583C (zh) * 2004-06-07 2009-01-21 柯尼卡美能达精密光学株式会社 纤维素酯薄膜及其制备方法,光学薄膜、起偏振片和液晶显示器
CN101052520A (zh) * 2004-10-29 2007-10-10 3M创新有限公司 包含环烯烃共聚物的光学膜
JP4697871B2 (ja) * 2005-10-20 2011-06-08 日東電工株式会社 積層フィルム
TWI387526B (zh) * 2006-06-06 2013-03-01 Fujifilm Corp 熱可塑性樹脂薄膜及其製法、以及偏光板、光學補償薄膜、抗反射薄膜與液晶顯示裝置
JP4050778B2 (ja) * 2006-07-07 2008-02-20 日東電工株式会社 液晶パネルおよび液晶表示装置
JP5487759B2 (ja) * 2009-06-30 2014-05-07 日本ゼオン株式会社 フィルム及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006022306A (ja) * 2004-06-07 2006-01-26 Konica Minolta Opto Inc セルロースエステルフィルム及びその製造方法、光学フィルム、偏光板、液晶表示装置
JP2007112967A (ja) * 2005-10-24 2007-05-10 Fujifilm Corp 環状オレフィン系樹脂フィルムとその製造方法、偏光板、及び液晶表示装置
JP2008304904A (ja) * 2007-05-07 2008-12-18 Jsr Corp 偏光板
JP2009237376A (ja) * 2008-03-27 2009-10-15 Fujifilm Corp 偏光板およびそれを用いた液晶表示装置

Also Published As

Publication number Publication date
TW201730588A (zh) 2017-09-01
JP6859958B2 (ja) 2021-04-14
JPWO2017110400A1 (ja) 2018-10-11
CN108369310B (zh) 2021-03-16
CN108369310A (zh) 2018-08-03

Similar Documents

Publication Publication Date Title
JP5169215B2 (ja) 偏光板用保護フィルム
CN100547466C (zh) 液晶显示装置、光学补偿片、和偏振器以及使用偏振器的液晶显示装置
TWI530717B (zh) 偏振板及其製備方法和包括它的液晶顯示器
JP4622698B2 (ja) 位相差板、偏光板及び液晶表示装置
JP6677722B2 (ja) 水平配向型液晶表示装置
TWI391757B (zh) 光學功能薄膜，相位差薄膜，光學功能層形成用組成物，及光學功能薄膜之製造方法
WO2007046203A1 (ja) 液晶パネルおよび液晶表示装置
JP2006301572A (ja) 偏光板及びこれを用いた液晶表示装置
JP2006330390A (ja) 偏光板及びこれを用いた液晶表示装置
TW200806451A (en) Optical film, its manufacturing method and liquid crystal display device using it
JP2014006505A (ja) 液晶表示装置
JP2006292834A (ja) 偏光板用保護フィルム、偏光板および液晶表示装置
JP6981205B2 (ja) 光学フィルムおよび偏光板
JP5479179B2 (ja) 液晶表示装置
KR20120004466A (ko) 편광판, 편광판의 제조 방법 및 액정 표시 장치
JP4802067B2 (ja) 偏光板及びこれを用いた液晶表示装置
JPWO2018070132A1 (ja) 偏光板および液晶表示装置
JP6303544B2 (ja) 液晶表示装置及び偏光板
CN100443933C (zh) 光学补偿起偏振板、图像显示单元和液晶显示单元
JP2008003188A (ja) 偏光板の製造方法，及び液晶表示装置
WO2006064834A1 (ja) 光学補償シート、その製造方法、偏光板及び液晶表示装置
TWI637850B (zh) 偏光板及液晶顯示裝置
WO2017110400A1 (ja) 偏光板保護フィルム、その製造方法及び偏光板
WO2018074513A1 (ja) 光学フィルム、光学フィルムの製造方法、及び偏光板
JP2018112577A (ja) 光学フィルム及び偏光板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16878293

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017557826

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16878293

Country of ref document: EP

Kind code of ref document: A1