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WO2012073692A1 - Film d'ester de cellulose, son procédé de fabrication et plaque polarisante l'utilisant - Google Patents

Film d'ester de cellulose, son procédé de fabrication et plaque polarisante l'utilisant Download PDF

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Publication number
WO2012073692A1
WO2012073692A1 PCT/JP2011/076351 JP2011076351W WO2012073692A1 WO 2012073692 A1 WO2012073692 A1 WO 2012073692A1 JP 2011076351 W JP2011076351 W JP 2011076351W WO 2012073692 A1 WO2012073692 A1 WO 2012073692A1
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Prior art keywords
cellulose ester
ester film
film
cellulose
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/076351
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English (en)
Japanese (ja)
Inventor
崇 南條
真一郎 鈴木
亮太 久木
理英子 れん
浩 居野家
村上　隆
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Priority to KR1020137013596A priority Critical patent/KR101497852B1/ko
Priority to JP2012546761A priority patent/JPWO2012073692A1/ja
Publication of WO2012073692A1 publication Critical patent/WO2012073692A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/08—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates with a particular optical axis orientation

Definitions

  • the present invention relates to a cellulose ester film, a production method thereof, and a polarizing plate provided with the cellulose ester film.
  • liquid crystal display devices (hereinafter also referred to as “LCD”) is strong due to the widespread use of liquid crystal displays mounted on automobiles, large liquid crystal television displays, mobile phones, laptop computers, and the like.
  • various cellulose ester films such as a polarizing film and a retardation film are used.
  • the temperature may increase due to an internal backlight or may be used in a high temperature and high humidity environment.
  • a triacetyl cellulose film used as a polarizing plate protective film has a temperature.
  • the optical performance such as retardation (phase difference) changes depending on the humidity, the optical compensation ability changes, and there is a problem that light leaks during black display or unevenness occurs in the image.
  • Patent Document 1 has not yet fully solved the above problem.
  • the present invention has been made in view of the above-described problems and situations, and the solution is to maintain the optical performance such as transparency and retardation at an appropriate level, weather resistance, and brittleness or elasticity after stretching. It is providing the cellulose-ester film excellent in the, and its manufacturing method. Another object of the present invention is to provide a polarizing plate that includes the cellulose ester film and does not cause color unevenness even when used in a liquid crystal display device.
  • the direction showing the maximum refractive index is the y direction
  • the direction orthogonal to the y direction is the x direction
  • the refractive index in the x direction is nx
  • the refraction in the y direction is nx
  • the rate is ny
  • the elastic modulus in the x direction of the film is Ex
  • the elastic modulus in the y direction is Ey
  • the slow axis is
  • it is a cellulose ester film orthogonal to the direction in which the elastic modulus is maximum and the cellulose ester film is stretched by 15% or more at 160 ° C. or less and the in-plane refractive index is measured nx> ny
  • T 1 When the temperature during stretching in the stretching step is T 1 and the maximum temperature in the step from immediately after peeling the cast cellulose ester-containing dope from the support to before stretching is T 2 , T 1 -T 2 The cellulose ester film according to the first or second item, wherein ⁇ 140 ° C. is satisfied.
  • the ratio of the elastic modulus in the width (TD) direction and the elastic modulus in the longitudinal (MD) direction (TD / MD) of the film is within the range represented by the following formula:
  • the polyester plasticizer uses phthalic acid, terephthalic acid, adipic acid, or 1 as a compound that uses at least one of acetic acid, benzoic acid, or toluic acid as a terminal blocking agent and constitutes the main chain.
  • a polarizing plate comprising the cellulose ester film according to any one of items 1 to 8 above.
  • a cellulose ester film excellent in weather resistance adhesion and brittleness or elasticity after stretching while maintaining optical performance such as transparency and retardation at an appropriate level and a method for producing the same. it can.
  • a polarizing plate that includes the cellulose ester film and does not cause color unevenness even when used in a liquid crystal display device can be provided.
  • the cellulose ester resin used in the cellulose ester film of the present invention has a positive intrinsic birefringence, but as in the present invention.
  • the birefringence relationship is reversed in the film obtained at high temperature and high stretch ratio.
  • the ratio of the elastic modulus in the width (TD) direction and the elastic modulus in the longitudinal (MD) direction (TD / MD) of the film is larger than 1.5.
  • the elastic modulus of the width is large, that is, it is hard and has a slow axis in the coating and conveying direction, the variation in optical performance is less than that in the width direction, and the occurrence of color unevenness can be suppressed. Inferred.
  • the conceptual diagram which shows the manufacturing process of the cellulose-ester film of this invention Schematic diagram showing a state in which glycerin is dropped on a slide glass
  • Schematic diagram showing the state in which glycerin is dropped on the sample film Schematic diagram showing a state where a cover glass is placed on glycerin
  • the direction showing the maximum refractive index in the in-plane refractive index measurement of the film formed through the stretching process is the y direction
  • the direction orthogonal to the y direction is the x direction
  • the refractive index is the x direction.
  • Nx the refractive index in the y direction is ny
  • the elastic modulus in the x direction of the film is Ex
  • the elastic modulus in the y direction is Ey
  • the slow axis is a cellulose ester film orthogonal to the direction in which the elastic modulus is maximum, and the cellulose ester film is stretched by 15% or more at 160 ° C.
  • the temperature during stretching in the stretching step is in the range of 180 to 210 ° C., and the stretching ratio is in the range of 35 to 55%. Is preferred.
  • T 1 the stretching temperature in the stretching step
  • T 2 the maximum temperature in the step from immediately after peeling the cast cellulose ester-containing dope from the support to before stretching
  • the ratio of the elastic modulus in the width (TD) direction and the elastic modulus in the longitudinal (MD) direction (TD / MD) of the film is expressed by the formula: 1.5 ⁇ TD / MD ⁇ 1.7. It is preferable that it exists in the range represented by.
  • the in-plane retardation value Ro is preferably in the range of 1 to 20 nm.
  • the cellulose ester film of the present invention preferably contains a polyester plasticizer having a weight average molecular weight in the range of 300 to 5,000.
  • the polyester plasticizer uses at least one of acetic acid, benzoic acid, or toluic acid as a terminal blocking agent, and phthalic acid, terephthalic acid, adipic acid as a compound constituting the main chain Or a polyester compound synthesized using at least one of 1,2-propanediol. It also contains an ester compound obtained by reacting phthalic acid, adipic acid, benzene monocarboxylic acid, and alkylene glycol having 2 to 12 carbon atoms, and has an acetyl group substitution degree of 2.80 to 2. It is preferable to contain cellulose triacetate which is in the range of 95 and the number average molecular weight is in the range of 125000 or more and less than 155000.
  • the method for producing a cellulose ester film for producing the cellulose ester film of the present invention is preferably a production method of an embodiment produced by a solution casting method.
  • the cellulose ester film of the present invention can be suitably used for a polarizing plate.
  • ⁇ 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 cellulose ester that can be used in the present invention is preferably a cellulose ester having an aliphatic acyl group having 2 or more carbon atoms, and more preferably, the total acyl substitution degree of the cellulose ester is 1.0 to 2.95. And an acyl group having a total carbon number of 2.0 to 9.5.
  • the total number of acyl groups in the cellulose ester is preferably 4.0 to 9.0, more preferably 5.0 to 8.5.
  • the acyl group total carbon number is the sum total of the products of the substitution degree and the carbon number of each acyl group substituted in the glucose unit of the cellulose ester.
  • the number of carbon atoms of the aliphatic acyl group is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, from the viewpoint of productivity and cost of cellulose synthesis.
  • the portion not substituted with an acyl group usually exists as a hydroxy group (hydroxyl group).
  • the glucose unit constituting cellulose with ⁇ -1,4-glycoside bonds has free hydroxy groups (hydroxyl groups) at the 2nd, 3rd and 6th positions.
  • the cellulose ester in the present invention is a polymer (polymer) obtained by esterifying some or all of these hydroxy groups (hydroxyl groups) with an acyl group.
  • the degree of acyl group substitution represents the total ratio of cellulose esterified at the 2nd, 3rd and 6th positions of the repeating unit. Specifically, the substitution degree is 1 when the hydroxy groups (hydroxyl groups) at the 2-position, 3-position and 6-position of cellulose are esterified 100%. Therefore, when all of the 2nd, 3rd and 6th positions of the cellulose are 100% esterified, the degree of substitution is 3 at the maximum.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, a pentanate group, and a hexanate group.
  • cellulose ester examples include cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, A cellulose pentanate etc. are mentioned. Further, mixed fatty acid esters such as cellulose acetate, cellulose acetate propionate, cellulose propionate, cellulose acetate butyrate, and cellulose acetate pentanate may be used as long as the above-mentioned side chain carbon number is satisfied. Among these, cellulose triacetate is particularly preferable.
  • the cellulose ester that can be suitably used is cellulose triacetate having an acetyl group substitution degree of 2.80 to 2.95 and a number average molecular weight in the range of 125000 or more and less than 155000.
  • the measuring method of the substitution degree of an acetyl group can be measured according to ASTM-D817-96.
  • the cellulose triacetate according to the present invention has an acetyl group substitution degree of 2.80 to 2.95, and preferably 2.84 to 2.94.
  • the number average molecular weight (Mn) is in the range of 125000 or more and less than 155000, and preferably 129000-152000. Further, the weight average molecular weight (Mw) is preferably 265,000 to 310000. Mw / Mn is preferably 1.9 to 2.1.
  • the average molecular weight (Mn, Mw) and molecular weight distribution of the cellulose triacetate according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the cellulose ester according to the present invention can be synthesized with reference to the methods described in JP-A-10-45804 and JP-A-2005-281645.
  • the trace metal component in the cellulose ester is preferably 1 ppm or less with respect to the iron (Fe) component.
  • the calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm.
  • the magnesium (Mg) component is preferably 0 to 70 ppm, particularly preferably 0 to 20 ppm.
  • Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After being performed, it can be analyzed using ICP-AES (Inductively Coupled Plasma Emission Spectroscopy).
  • the cellulose triacetate according to the present invention may be mixed with a third cellulose ester, for example, a cellulose ester such as cellulose acetate propionate, within a range not impeding the performance of the present invention (10% by mass or less).
  • a third cellulose ester for example, a cellulose ester such as cellulose acetate propionate
  • 2% to 20% of cellulose obtained by graft polymerization of substituents may be mixed in the total cellulose ester, or cellulose diacetate may be mixed so that the average degree of substitution of cellulose is 2.75 to 2.85. It is preferable for increasing retardation and preventing brittle deterioration of the stretched film.
  • the cellulose graft-polymerized with a substituent is preferably a cellulose ester having a repeating unit represented by the following general formula (1) or (2).
  • A-1 —CH 2 CH 2 — A-2 —CH 2 CH 2 CH 2 — A-3 -CH CH- A-4 A-5 A-6 —CH 2 C (CH 3 ) 2 —
  • the cellulose ester having a repeating unit represented by the general formula (1) or (2) in the present invention is a cellulose having an unsubstituted hydroxy group (hydroxyl group), an acetyl group, a propionyl group, a butyryl group, a phthalyl group, or the like.
  • An esterification reaction of a polybasic acid or an anhydride thereof with a polyhydric alcohol in the presence of a cellulose ester in which a part of the hydroxy group (hydroxyl group) has already been substituted with an acyl group of L-lactide or D-lactide Can be obtained by ring-opening polymerization of L-lactic acid and self-condensation of L-lactic acid and D-lactic acid.
  • polybasic acid anhydride used in the esterification reaction examples include, but are not limited to, maleic anhydride, phthalic anhydride, and fumaric anhydride.
  • polyhydric alcohol examples include glycerin, ethylene glycol, and propylene glycol, but are not particularly limited.
  • the esterification reaction can be performed without a catalyst, but a known Lewis acid catalyst or the like can be used.
  • catalysts that can be used include metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, sodium, potassium, and aluminum, and derivatives thereof.
  • the derivatives include metal organic compounds, carbonates, oxides, halides. Is preferred. Specific examples include octyl tin, tin chloride, zinc chloride, titanium chloride, alkoxy titanium, germanium oxide, zirconium oxide, antimony trioxide, and alkyl aluminum.
  • an acid catalyst typified by p-toluenesulfonic acid can also be used as the catalyst.
  • stimulate the dehydration reaction of carboxylic acid and alcohol you may add well-known compounds, such as carbodiimide and dimethylaminopyridine.
  • Such a reaction may be a reaction in an organic solvent capable of dissolving cellulose ester and other compounds to be reacted, or a reaction using a batch kneader capable of heating and stirring while applying a shearing force. It may be by reaction using a uniaxial or biaxial extruder.
  • the repeating unit can be appropriately contained in the range of 0.5 to 190% by mass with respect to the cellulose in the part.
  • the degree of substitution of the cellulose ester can be appropriately selected, but is preferably 2.2 to 3 from the viewpoints of thermoplasticity and thermal workability.
  • the hydrogen atom of the hydroxy group (hydroxyl group) part of cellulose is a fatty acid ester with an aliphatic acyl group
  • the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl Propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like.
  • the repeating unit has a number average molecular weight of 300 to 10000, preferably 500 to 8000, from the viewpoint of thermal workability.
  • the number average molecular weight of only the repeating unit of the cellulose ester is GPC data obtained by polystyrene conversion of the cellulose ester before the esterification reaction and the cellulose ester after the reaction, or 1 H-NMR (JNM-EX- manufactured by JEOL Ltd.). 270: solvent: methylene dichloride).
  • an oligomer or polyester having a repeating unit represented by formula (1) or (2) may be produced as a side reaction, but these compounds act as a plasticizer. However, it is not always necessary to completely remove the cellulose ester by purification. If content is 30 mass% or less with respect to a cellulose ester, there will be little change in the property of a cellulose ester. From the viewpoint of plasticity, it is preferably 0.5 to 20% by mass.
  • oligomers and polyesters have a number average molecular weight of 300 to 10,000, preferably 500 to 8,000 from the viewpoint of plasticity.
  • the cellulose ester film of the present invention can contain conventionally known various plasticizers.
  • polyester plasticizer having a weight average molecular weight in the range of 300 to 5,000.
  • polyester-based plasticizer a child using various plasticizers described later can be used, but as the end-capping agent, at least one of acetic acid, benzoic acid, or toluic acid is used, and the main chain is constituted.
  • the compound to be synthesized is preferably a polyester compound synthesized using at least one of phthalic acid, terephthalic acid, adipic acid, or 1,2-propanediol. Further, ester compounds obtained by reacting phthalic acid, adipic acid, benzene monocarboxylic acid, and alkylene glycol having 2 to 12 carbon atoms are preferable.
  • An ester plasticizer that can be suitably used in the present invention is an aromatic terminal ester plasticizer.
  • Examples of the benzene monocarboxylic acid component in the aromatic terminal ester plasticizer according to the present invention include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal There are propylbenzoic 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. Most preferred is benzoic acid.
  • alkylene glycol component having 2 to 12 carbon atoms examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2 -Propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2 -Diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1, 5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-
  • the ester compound according to the present invention has only to have an adipic acid residue and a phthalic acid residue as the final compound structure.
  • an acid anhydride or esterified product of a dicarboxylic acid You may make it react.
  • the ester plasticizer used in the present invention has a number average molecular weight of preferably 300 to 1500, more preferably 400 to 1000.
  • the acid value is 1.5 mgKOH / g or less, the hydroxy (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.5 mgKOH / g or less, and the hydroxy (hydroxyl group) value is 15 mgKOH / g or less. is there.
  • the ester compound according to the present invention can be synthesized with reference to Patent Documents 1 to 3.
  • an ester compound having both an adipic acid residue and a phthalic acid residue is preferable, and can be obtained by synthesizing in the presence of adipic acid and phthalic acid simultaneously as dicarboxylic acid components.
  • the ester compound according to the present invention is a mixture having a distribution in molecular weight and molecular structure at the time of its synthesis, and among them, an ester having a phthalic acid residue and an adipic acid residue as a structure, which is a preferred component of the present invention. It suffices to have at least one compound.
  • the cellulose ester film using the ester compound according to the present invention is more effective than the mixture of ester compounds synthesized with adipic acid alone or phthalic acid alone as the dicarboxylic acid component.
  • the above compound is preferably contained in the cellulose ester film in an amount of 1 to 35% by mass, particularly 5 to 30% by mass. If it is in this range, there is no bleed out and it is preferable.
  • the cellulose ester film of the present invention can contain other plasticizers as necessary for obtaining the effects of the present invention.
  • a polyhydric alcohol ester plasticizer 2, a polycarboxylic acid ester plasticizer, 3) a glycolate plasticizer, 4) a phthalate plasticizer, 5) a fatty acid ester plasticizer, 6
  • phosphate plasticizers and the like.
  • the polyhydric alcohol ester plasticizer is an ester compound of a polyhydric alcohol represented by the following general formula (3).
  • R 1- (OH) n (Wherein R 1 represents an n-valent organic group, and n represents a positive integer of 2 or more)
  • Preferred examples of the polyhydric alcohol include ethylene glycol, propylene glycol, trimethylolpropane, and pentaerythritol.
  • monocarboxylic acid used in the polyhydric alcohol ester known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, and the like can be used.
  • a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • 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 which has, or derivatives thereof can be mentioned.
  • benzoic acid is preferred.
  • the molecular weight of the polyhydric alcohol ester is preferably in the range of 300 to 1500, more preferably in the range of 350 to 750.
  • 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 them may be left as OH groups.
  • ester compound (A) represented by the general formula (I) described in JP-A-2008-88292.
  • the polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20-valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably divalent to 20-valent.
  • the polyvalent carboxylic acid is represented by the following general formula (4).
  • R 2 (COOH) m (OH) n
  • R 2 is an (m + n) -valent organic group
  • m is a positive integer of 2 or more
  • n is an integer of 0 or more
  • a COOH group is a carboxy group
  • an OH group is an alcoholic or phenolic hydroxy group (hydroxyl group).
  • preferable polyvalent carboxylic acids include the following.
  • Divalent or higher aromatic polyvalent carboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid
  • Aliphatic polycarboxylic acids such as fumaric acid, maleic acid and tetrahydrophthalic acid, and oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • alcohol used in the polyvalent carboxylic acid ester compound that can be used in the present invention known alcohols and phenols can be used.
  • an aliphatic saturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • phenol examples include phenol, paracresol, dimethyl Phenol etc. can be used individually or in combination of 2 or more types.
  • ester compound (B) represented by the general formula (II) described in JP-A-2008-88292.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, more preferably in the range of 350 to 750.
  • the alcohol used for the polyvalent carboxylic acid ester may be one kind or a mixture of two or more kinds.
  • the acid value of the polycarboxylic acid ester compound is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g 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 glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkylphthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate and the like.
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizers examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • the cellulose ester film of the present invention preferably contains an ultraviolet absorber.
  • the ultraviolet absorber is intended to improve durability by absorbing ultraviolet light having a wavelength of 400 nm or less.
  • the transmittance at a wavelength of 370 nm is preferably 10% or less, and more preferably 5% or less. is there.
  • the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
  • the amount of the UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but when the dry film thickness of the cellulose ester film is 30 to 200 ⁇ m, it is 0.5 to 10 with respect to the cellulose ester film. % By mass is preferable, and 0.6 to 4% by mass is more preferable.
  • the cellulose ester film of the present invention preferably contains fine particles from the viewpoint of slipperiness and storage stability.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • Silicon dioxide that has been subjected to a hydrophobization treatment is preferable for achieving both slipperiness and haze.
  • silanol groups those in which two or more are substituted with a hydrophobic substituent are preferred, and those in which three or more are substituted are more preferred.
  • the hydrophobic substituent is preferably a methyl group.
  • the primary particle diameter of silicon dioxide is preferably 20 nm or less, and more preferably 10 nm or less.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferable because they have a large effect of reducing the friction coefficient while keeping the haze of the cellulose ester film low, and Aerosil R812 is most preferably used in the present invention.
  • the dynamic friction coefficient of at least one surface is preferably 0.2 to 1.0.
  • a dye may be added to the cellulose ester film of the present invention for color adjustment.
  • a blue dye may be added to suppress the yellowness of the film.
  • Preferred examples of the dye include anthraquinone dyes.
  • the cellulose ester film of the present invention can be produced by either a normal solution casting method or a melt casting method.
  • Production of the cellulose ester film of the present invention by the solution casting method is a step of preparing a dope by dissolving the cellulose ester and the additive in a solvent, a step of casting the dope on an endless metal support that moves infinitely , 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 drying, and the process of winding up the finished film.
  • the concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • Solvents used in dope may be used alone or in combination of two or more. It is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester from the viewpoint of production efficiency.
  • the good solvent is particularly preferably methylene chloride or methyl acetate.
  • Examples of the poor solvent include methanol, ethanol, n- Butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope contains 0.01 to 2% by mass of water.
  • 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 cellulose ester solution is filtered using an appropriate filter medium such as filter paper.
  • 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 more preferable.
  • the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel are preferable because they do not drop off fibers. .
  • 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 the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even 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 a temperature lower than the boiling point of the solvent, and the preferable support temperature is 0 to 40 ° C., more preferably 5 to 30 ° C.
  • the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% 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 peeled off from the metal support and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferably, it is 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 for drying) or a tenter method for drying while transporting the web is employed.
  • the web is stretched in the longitudinal direction (MD direction) where there is a large amount of residual solvent of the web immediately after peeling from the metal support, and both ends of the web are gripped with clips or the like. It is preferable to perform stretching in the width direction (TD direction) by the tenter method.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity.
  • the drying temperature in the web drying step is preferably 90 to 200 ° C, more preferably 110 ° C to 190 ° C.
  • the drying temperature is preferably increased stepwise.
  • the preferable drying time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes, although it depends on the drying temperature.
  • the film thickness of the cellulose ester film is not particularly limited, but 10 to 200 ⁇ m is used.
  • the film thickness is particularly preferably 10 to 100 ⁇ m. More preferably, it is 20 to 60 ⁇ m.
  • the cellulose ester film of the present invention has a width of 1 to 4 m. From the viewpoint of productivity, those having a width of 1.6 to 4 m are preferably used, and particularly preferably 1.8 to 3.6 m. If it exceeds 4 m, conveyance becomes difficult.
  • the stretching operation can be performed sequentially or simultaneously with respect to the longitudinal direction (MD direction) and the width direction (TD direction) of the film.
  • the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively. It is preferably performed in the range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction.
  • a method of stretching in the MD direction a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching in the MD / TD direction simultaneously and stretching in both the MD / TD directions, and the like.
  • a tenter it may be a pin tenter or a clip tenter.
  • the film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 to 200 N / m, more preferably 140 to 200 N / m. 140 to 160 N / m is most preferable.
  • the glass transition temperature of the film of the present invention is Tg (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (Tg + 20) ° C.
  • the Tg of the cellulose ester film can be controlled by the material type constituting the film and the ratio of the constituting materials.
  • the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.
  • the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower.
  • the Tg of the film can be determined by the method described in JIS K7121.
  • the temperature during stretching is 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened.
  • Roughening the film surface is preferable because it improves not only the slipperiness but also the surface processability, particularly the adhesion of the clear hard coat.
  • the average surface roughness Ra is preferably 2.0 to 4.0 nm, more preferably 2.5 to 3.5 nm.
  • the film preferably contains the above-mentioned hydrophobized silicon dioxide fine particles, and R972V and R812 are particularly preferred for improving haze stability.
  • the cellulose ester film is preferably heat-set after stretching.
  • the heat-setting is usually performed at a temperature higher than the final TD direction stretching temperature and within a temperature range of Tg-20 ° C or lower, usually for 0.5 to 300 seconds. Is preferred. At this time, it is preferable to perform heat setting while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more.
  • the heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the TD direction and / or MD direction within a temperature range not higher than the final heat setting temperature and not lower than Tg.
  • the cooling is preferably performed by gradually cooling from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second.
  • Means for cooling and relaxation treatment are not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to carry out these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film.
  • the cooling rate is a value obtained by (T 1 ⁇ Tg) / t, where T 1 is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
  • More optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions vary depending on the type of additives such as cellulose ester and plasticizer constituting the film, so the physical properties of the obtained biaxially stretched film are measured and preferable characteristics are obtained. What is necessary is just to determine by adjusting suitably so that it may have.
  • the slow axis or fast axis of the cellulose ester film of the present invention exists in the film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is ⁇ 1. More preferably, it is 5 ° or more and + 0.5 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • KOBRA-21ADH Oji Scientific Instruments
  • the moisture permeability of the cellulose ester film according to the present invention is preferably 10 to 1200 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH, more preferably 20 to 1000 g / m 2 ⁇ 24 h, and 20 to 850 g / m 2 ⁇ 24 h. Is particularly preferred.
  • the moisture permeability can be measured according to the method described in JIS Z 0208.
  • the cellulose ester film according to the present invention has a storage elastic modulus at 30 ° C. of 3.2 to 4.7 GPa in the MD direction and 4.7 to 7.0 GPa in the TD direction. preferable.
  • the storage elastic modulus can be obtained by the same measurement as tan ⁇ .
  • the cellulose ester film according to the present invention preferably has a tear strength that is a brittleness index of 35 mN or more, and more preferably 50 mN or more.
  • the cellulose ester film according to the present invention has a breaking elongation of preferably 5 to 80%, more preferably 8 to 50%.
  • the visible light transmittance of the cellulose ester film according to the present invention is preferably 90% or more, and more preferably 93% or more.
  • the haze of the cellulose ester film according to the present invention is preferably less than 1%, particularly preferably 0 to 0.4%.
  • the cellulose ester film of the present invention preferably has a retardation value Ro represented by the following formula of 0 to 150 nm and Rt of ⁇ 100 to 300 nm, particularly preferably Ro within the range of 1 to 20 nm and Rt of 0. Within the range of ⁇ 100 nm.
  • Ro (nx ⁇ ny) ⁇ d
  • Rt ((nx + ny) / 2 ⁇ nz) ⁇ d
  • Ro is the retardation value in the film plane
  • Rt is the retardation value in the film thickness direction
  • nx is 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
  • nz represents the refractive index in the thickness direction of the film
  • d represents the thickness (nm) of the film.
  • the retardation can be determined at a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using, for example, KOBRA-21ADH (Oji Scientific Instruments).
  • Rt ⁇ 0.85 nm / film thickness 1 ⁇ m.
  • the film is a thin film and has a certain Rt or more. It is preferable.
  • Rt relative to the unit film thickness is more preferably 0.9 to 5.0 nm / film thickness 1 ⁇ m, and further preferably 1.0 to 5.0 nm / film thickness 1 ⁇ m.
  • a hard coat layer When producing the cellulose ester film of the present invention, before or after stretching, a hard coat layer, an antistatic layer, a back coat layer, a slippery layer, an adhesive layer, a barrier layer, an antiglare layer, an antireflection layer, an optical compensation layer, etc.
  • the functional layer may be provided.
  • the cellulose ester film of the present invention can be provided with a hard coat layer as described above.
  • the layer thickness (dry layer thickness) of the hard coat layer is 3 to 30 ⁇ m, and more preferably 5 to 15 ⁇ m.
  • High hardness is desired because it is less likely to be scratched during use on the surface of a display device such as an LCD or in a polarizing plate process.
  • High hardness in the present invention means that the pencil hardness, which is an indicator of hardness, is 3H or more. More preferably, it is 4H or more.
  • the pencil hardness is defined by JIS K 5400 using a test pencil specified by JIS S 6006 after the prepared hard coat film is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to the evaluation method.
  • Or Martens hardness of Dokoto is, 400 N / mm 2 or more, and preferably 800 N / mm 2 or less.
  • Martens hardness is a microhardness meter using a Vickers indenter and a triangular pyramid indenter whose angle between ridges is 115 degrees.
  • the hard coat surface of the film is approximately 1 / th of the film thickness of the hard coat layer.
  • Fmax maximum load test force
  • a known hard coat layer according to the present invention can be used as it is.
  • the resin binder that forms the hard coat layer will be described.
  • an active energy ray curable resin is preferable.
  • the active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.
  • the active energy ray curable resin a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed.
  • the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin.
  • the ultraviolet curable resin is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable.
  • polyfunctional acrylate is preferable.
  • the polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate.
  • the polyfunctional acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule. These compounds are used as a mixture of at least each alone or in combination.
  • the amount of the energy active ray curable resin added is preferably 15% by mass or more and less than 70% by mass in the solid content.
  • the docoat layer preferably contains a photopolymerization initiator in order to accelerate the curing of the energy active ray curable resin.
  • photopolymerization initiator examples include acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, ⁇ -amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.
  • a binder such as a thermoplastic resin, a thermosetting resin, or a hydrophilic resin such as gelatin can also be used.
  • the docoat layer may contain particles of an inorganic compound or an organic compound in order to adjust slipperiness and refractive index.
  • the average particle size of these fine particle powders is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 5.0 ⁇ m, and particularly preferably 0.1 to 4.0 ⁇ m. Moreover, it is preferable to contain two or more kinds of fine particles having different particle diameters. It is desirable that the ratio of the curable resin composition to the fine particles is 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable resin composition.
  • the hard coat layer preferably contains reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group.
  • reactive silica particles (Xa) surface-treated with an organic compound having a polymerizable unsaturated group will be described.
  • silica particles can be used. Further, the shape may be spherical or irregular, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core / shell particles, or the like.
  • the number average particle diameter of the silica particles determined by the dynamic light scattering method is preferably 30 nm or more, more preferably 30 to 200 nm, and particularly preferably 40 to 80 nm.
  • Examples of commercially available products include MEK-ST-L, IPA-ST-L, and IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. as colloidal silica.
  • the reactive silica particles (Xa) are obtained by surface treatment with an organic compound having a polymerizable unsaturated group (hereinafter referred to as “organic compound (X)”).
  • organic compound (X) used for the production of the reactive silica particles (Xa) is a compound having a polymerizable unsaturated group, preferably an ethylenically unsaturated group, and further has a group represented by the following general formula (a). It is preferable that it is an organic compound to contain.
  • the organic compound is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
  • This ethylenically unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
  • Group represented by the general formula (a) The group [—UC ( ⁇ V) —NH—] represented by the formula (a) contained in the organic compound is specifically represented by [—O—C ( ⁇ O) —NH—], [—O—C ( ⁇ S) —NH—], [—S—C ( ⁇ O) —NH—], [—NH—C ( ⁇ O) —NH—] , [—NH—C ( ⁇ S) —NH—], and [—S—C ( ⁇ S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types.
  • the group [—UC ( ⁇ V) —NH—] represented by the formula (a) generates an appropriate cohesive force due to hydrogen bonds between molecules, and has excellent mechanical strength and group when cured. Excellent adhesion to materials and adjacent layers.
  • Silanol groups or compounds that generate silanol groups by hydrolysis Examples of compounds that generate silanol groups include compounds in which an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, or the like is bonded to a silicon atom. However, a compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • Preferred embodiment As a preferred specific example, for example, a compound represented by the following general formula (b) can be mentioned.
  • R 21 and R 22 may be the same or different and each represents a hydrogen atom or an alkyl or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl , Phenyl, xylyl group and the like.
  • j is an integer of 1 to 3.
  • Examples of the group represented by [(R 21 O) j R 22 3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
  • R 23 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
  • R 24 is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 1000, preferably a molecular weight of 76 to 500.
  • divalent organic groups having a molecular weight of 14 to 1000, preferably a molecular weight of 76 to 500.
  • Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products.
  • These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
  • R 25 is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
  • Specific examples of the compound represented by the general formula (b) include compounds represented by the following (b-1) or the following (b-2).
  • ⁇ (Xa) reactive silica particles The organic compound (X) is mixed with silica particles, hydrolyzed, and bonded together.
  • the binding amount of the organic compound (X) to the silica particles is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the reactive silica particles (Xa). Especially preferably, it is 1 mass% or more. Within the above range, the dispersibility is excellent, and the mechanical strength of the obtained cured product is also excellent.
  • the blending ratio of the silica particles in the raw material during the production of the reactive silica particles (Xa) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass.
  • the content of the silica particles constituting the reactive silica particles (Xa) is preferably 65 to 95% by mass.
  • the content of the reactive silica particles (Xa) in the coating composition for the hard coat layer is preferably 5 to 80% by mass when the total solid content in the composition is 100% by mass, and preferably 10 to 80% by mass. % Is more preferable. By using it in the ratio of this range, it exists stably in a composition and it is easy to exhibit the target effect of this invention.
  • an antioxidant that does not inhibit the photocuring reaction can be selected and used.
  • examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like.
  • the hard coat layer forming composition may contain a solvent, or may be appropriately contained and diluted as necessary.
  • the hard coat layer has a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 ⁇ m, or a fine hard particle, Ra is adjusted to 0.1 to 1 ⁇ m.
  • Ra center line average roughness
  • An antiglare hard coat layer may also be used.
  • the center line average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, a non-contact surface fine shape measuring device WYKO NT-2000 manufactured by WYKO.
  • the hard coat layer may contain a fluorine compound or a silicone compound. Moreover, you may contain the surfactant shown below.
  • the hard coat layer further has a vinyl group and a carboxy group in the side chain of the polyurethane resin as a curing aid, has a weight average molecular weight of 10,000 to 30,000, and a double bond equivalent of 500 to 2,000.
  • Commercially available products include Showa Denko Co., Ltd., trade name Karenz MT series, and the like.
  • a fluorine-acrylic copolymer resin may be contained.
  • fluorine-acrylic copolymer resins include Nippon Oil & Fats Co., Ltd., Modiper F-200, Modiper F-600, Modiper F-2020, and the like.
  • the refractive index of the hard coat layer is preferably adjusted to a range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm.
  • the means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like.
  • Metal oxide The metal oxide fine particles used preferably have a refractive index of 1.80 to 2.60, more preferably 1.85 to 2.50.
  • the kind of metal oxide fine particles is at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and zinc antimonate. It is particularly preferable to use as the main component. In particular, it is preferable to contain zinc antimonate particles.
  • the average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 to 200 nm, particularly preferably 10 to 150 nm.
  • the average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like.
  • the metal oxide fine particles may be surface-treated with an organic compound.
  • the clear hard coat layer according to the present invention can be applied by a known method.
  • a solvent for coating the clear hard coat layer for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used. .
  • propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether or propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass or more.
  • the containing solvent is used.
  • any light source that generates ultraviolet rays can be used.
  • 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.
  • the irradiation conditions vary depending on individual lamps, but the amount of light irradiated may if 20 ⁇ 10000mJ / cm 2 degrees, preferably 50 ⁇ 2000mJ / cm 2.
  • the near ultraviolet region to the visible light region it can be used by using a sensitizer having an absorption maximum in that region.
  • the UV curable resin composition is coated and dried and then irradiated with UV light from a light source.
  • the irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 due to the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.
  • the polarizing plate according to the present invention is a polarizing plate formed by sandwiching at least one surface of a polarizer with the cellulose ester film of the present invention.
  • the polarizing plate can be produced by a general method.
  • the cellulose ester film of the present invention is preferably bonded to at least one surface of a polarizer produced by subjecting the polarizer side to alkali saponification treatment and immersion drawing in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution.
  • the cellulose ester film of the present invention may be used or another cellulose ester film may be used.
  • Commercially available cellulose acylate film for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, HAC, UE8, HA8, UE8, 8 KC4UE, KC4HR-1, KC4KR-1, KC4UA, KC6UA or higher, manufactured by Konica Minolta Opto Co., Ltd.) are also preferably used.
  • liquid crystal display device By incorporating the polarizing plate according to the present invention into a liquid crystal display device, various liquid crystal display devices with excellent visibility can be manufactured.
  • the cellulose ester film of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), and IPS. Particularly preferred are VA (MVA, PVA) type and IPS type liquid crystal display devices.
  • Example 1 ⁇ Synthesis of ester compound 1> 251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with thermometer, stirrer, and slow cooling tube The flask is charged and gradually heated with stirring until it reaches 230 ° C. in a nitrogen stream.
  • the ester compound 1 according to the present invention was obtained by performing dehydration condensation reaction for 15 hours, and distilling off unreacted 1,2-propylene glycol under reduced pressure at 200 ° C. after completion of the reaction.
  • the acid value was 0.10 and the number average molecular weight was 450.
  • ester compounds 2 and 3 In the synthesis of the ester compound 1, the same reaction was carried out with the amounts of phthalic anhydride and adipic acid being (185 g, 182 g) and (93 g, 273 g), respectively, and ester compounds 2 and 3 were obtained.
  • the acid value was 0.10
  • the number average molecular weight was 500
  • the acid value was 0.15
  • the number average molecular weight was 600.
  • ester compound 4 205 g 2-methyl-1,3-propanediol, 111 g phthalic anhydride, 37 g adipic acid, 272 g p-toluic acid, 0.08 g tetraisopropyl titanate as an esterification catalyst, equipped with thermometer, stirrer and slow cooling tube Into a 2 L four-necked flask, the temperature is gradually raised while stirring until reaching 230 ° C. in a nitrogen stream.
  • the ester compound 4 according to the present invention was obtained by carrying out a dehydration condensation reaction for 11 hours, and distilling off unreacted 2-methyl-1,3-propanediol at 200 ° C. after completion of the reaction.
  • the acid value was 0.15 and the number average molecular weight was 600.
  • 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 is evaporated at 40 ° C. (maximum temperature in the process from immediately after peeling the cast cellulose ester-containing dope from the support as a web until before stretching), and slit to a width of 1.65 m, The width was maintained with a tenter and dried at a drying temperature of 190 ° C. (also referred to as “heat treatment temperature” or “stretching temperature”).
  • the amount of residual solvent when drying was started was 20%. Thereafter, the film is dried for 15 minutes while being transported in a drying apparatus at 120 ° C. with a number of rolls, 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 cellulose ester film 101. It was.
  • the residual solvent amount of the cellulose ester film was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 6000 m.
  • the average surface roughness Ra of the cellulose ester film 101 is 2.2 nm
  • the storage elastic modulus at 30 ° C. is 5.0 GPa in the MD direction
  • 4.5 GPa in the TD direction the rotational speed of the stainless band support and the operating speed of the tenter.
  • the draw ratio in the MD direction (conveyance direction) calculated from 1 was 1.10 times (10% draw ratio).
  • the cellulose ester film 101 is filtered with the following hard coat layer coating composition 1 through a polypropylene filter having a pore size of 0.4 ⁇ m to prepare a hard coat layer coating solution, which is coated with a die coater, dried at 70 ° C., and then oxygen concentration While applying nitrogen purge so that the atmosphere becomes 1.0 volume% or less, using an ultraviolet lamp, the illuminance of the irradiated part is 300 mW / cm 2 , the irradiation amount is 0.3 J / cm 2 , the coating layer is cured, and further heated In the treatment zone, heat treatment was performed at 130 ° C. for 5 minutes with a conveyance force of 300 N / m to form a hard coat layer having a dry film thickness of 7 ⁇ m, and a hard coat film 101 was produced and wound.
  • Hard coat layer composition 1 The following materials were stirred and mixed to obtain hard coat layer coating composition 1.
  • Radical polymerizable fluororesin (FA) Cefal coat CF-803 (hydroxy (hydroxyl group) value 60, number average molecular weight 15000; manufactured by Central Glass Co., Ltd.)
  • Radical polymerization initiator Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
  • Curing agent Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.) (Synthesis of radical polymerizable fluororesin (FA))
  • a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet was added to cefal coat CF-803 (1554 parts by mass
  • the weight average molecular weight was determined by GPC. Further, the mass% of the fluorine-siloxane graft polymer I was determined by HPLC (liquid chromatography).
  • ⁇ Preparation of cellulose ester film 102> In the production of the cellulose ester film 101, after slitting to a width of 1.7 m, the film is dried at a maximum temperature of 40 ° C. (T 2 ) in the process before stretching, and 1. in the TD direction (the width direction of the film) with a tenter. The film was dried at a drying temperature of 190 ° C. (T 1 ) (also referred to as a heat treatment temperature or a stretching temperature) while being stretched 45 times (a stretching ratio of 45%). At this time, the residual solvent amount (also referred to as residual solution) when starting stretching with a tenter was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C.
  • T 1 also referred to as a heat treatment temperature or a stretching temperature
  • the cellulose ester film 102 was obtained.
  • the residual solvent amount of the cellulose ester film was 0.2%, the film thickness was 40 ⁇ m, and the winding number was 6000 m.
  • the average surface roughness Ra is 3.0 nm
  • the storage elastic modulus at 30 ° C. is 4.1 GPa in the MD direction
  • the MD direction is calculated from the rotational speed of the 5.5 GPa stainless band support in the TD direction and the operating speed of the tenter.
  • the draw ratio of was 1.01 times.
  • the cellulose triacetate resin C1 and the ester compound 1 were changed to the cellulose triacetate resin and the ester compound shown in Table 1, and cellulose ester films 103 to 113 were produced in the same manner as the cellulose ester film 102.
  • a clear hard coat layer was provided on these cellulose ester films in the same manner as the hard coat film 101 to prepare hard coat films 102 to 113.
  • cellulose ester films 202 to 204 were produced using cellulose diacetate resin B having a degree of acetyl substitution of 2.42 and a number average molecular weight of 50000, ester compound 1, and comparative ester compound A. .
  • These cellulose ester films were provided with a clear hard coat layer in the same manner as the hard coat film 101 to prepare hard coat films 202 to 204.
  • a methacrylic resin film 205 was produced from a resin A having negative intrinsic birefringence in accordance with Production Example 1 described in JP 2010-11745 A.
  • a hard coat film 205 was produced in the same manner as described above.
  • the polymerization solution thus obtained was dried at 240 ° C. under reduced pressure for 1 hour to obtain a transparent resin A composed of N-PII units and MMA units.
  • Resin A had a Tg of 128 ° C., a weight average molecular weight of 110,000, and a 5% mass reduction temperature of 298 ° C.
  • the internal haze was measured according to JIS K-7136.
  • the internal haze is a haze generated by a scattering factor inside the film, and the internal is a portion of 5 ⁇ m or more from the film surface.
  • This internal haze is measured by a haze meter by dropping a solvent having a refractive index of ⁇ 0.05 on the film interface to make the haze on the film surface negligible as much as possible.
  • Haze meter (turbidity meter): Model NDH 2000, manufactured by Nippon Denshoku Industries Co., Ltd.
  • Light source 5V9W halogen bulb
  • light receiving part is a silicon photocell (with a relative sensitivity filter)
  • the internal haze measurement is performed as follows. This will be described with reference to FIGS.
  • the blank haze 1 of a measuring instrument other than the film is measured.
  • each sample had a width of 10 mm ⁇ length so that the MD direction and the TD direction were respectively longer. Cut into strips of 200 mm.
  • the above strip-shaped sample was set at a chucking pressure of 0.25 MPa and a distance between marked lines of 100 ⁇ 10 mm, and the pulling speed was 100 ⁇ 10 mm / min. Pulled on.
  • the elastic modulus calculation start point was 10 N
  • the end point was 30 N
  • the tangent line drawn between them was extrapolated to obtain the elastic modulus in the MD direction and the TD direction.
  • the average value of the obtained elastic modulus in the MD direction and the TD direction was regarded as the elastic modulus of the transparent film, and evaluated by a relative ratio.
  • the prepared hard coat film was irradiated with light for 250 hours with a weather resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.) with the hard coat surface facing up.
  • a weather resistance tester eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.
  • Evaluation criteria a: Not peeled at all. b: The peeled area ratio was less than 5%. c: The peeled area ratio was less than 10%. d: The peeled area ratio was 10% or more.
  • the above measurement / evaluation results are shown in Tables 1 and 2.
  • the slow axis before redrawing of the cellulose ester film according to the present invention is orthogonal to the direction in which the elastic modulus is maximum, and the cellulose ester film
  • the refractive index in the film plane is measured by stretching 20% at 160 ° C., nx> ny and the slow axis is parallel to the direction in which the elastic modulus is maximum.
  • the prepared hard coat film 102 was alkali-treated with a 2.5 mol / L aqueous sodium hydroxide solution at 40 ° C. for 90 seconds, washed with water for 45 seconds, neutralized with 10% by mass HCl at 30 ° C. for 45 seconds, and then 30 Washing with water at 45 ° C. for saponification treatment gave an alkali treated film.
  • a 120 ⁇ m thick polyvinyl alcohol film was uniaxially stretched (temperature 110 ° C., stretch ratio 6 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a 3.0 m wide polarizer.
  • the alkali-treated film was bonded to one side of a polarizer using a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive.
  • a polarizing plate 101 is bonded to the polarizing plate 101 on the opposite surface (back surface) side of the polarizer using a commercially available cellulose ester film (KC4KR-1, manufactured by Konica Minolta Opto) as a polarizer protective film in the same manner as described above.
  • a commercially available cellulose ester film (KC4KR-1, manufactured by Konica Minolta Opto) as a polarizer protective film in the same manner as described above.
  • polarizing plates 102 to 119 shown in Table 3 were produced in the same manner as described above.
  • the liquid crystal display device using the polarizing plate provided with the cellulose ester film (hard coat film) of the present invention has excellent color unevenness prevention properties.
  • Example 2 In the production method of the cellulose ester film 102 of Example 1, cellulose ester resin D1 and cellulose ester resin D2 were used in place of 90 parts by mass of cellulose triacetate resin C1, and the others were similarly performed. 405 was produced. Furthermore, it mixed by the mass ratio of Table 4, and produced the cellulose-ester film 406.
  • hard coat films 402 to 406 were produced in the same manner as described above.
  • the cellulose ester resins D1 and D2 were produced as follows.
  • reaction product 10 parts was dissolved in 90 parts of chloroform, and then slowly dropped into 900 parts of a large excess of methanol, and the precipitated precipitate was filtered off to remove the homopolymer of ⁇ -caprolactone. .
  • Synthesis Example 2 Synthesis of Cellulose Ester Resin D2 70 parts of cellulose acetate (L-20, substitution degree 2.41 manufactured by Daicel Chemical Industries, Ltd.) and 30 parts of L-lactide were added to a reactor. It was dried under reduced pressure at 4 Torr for 4 hours. Thereafter, purging was performed with dry nitrogen, a reflux condenser was attached, 67 parts of cyclohexanone that had been dried and distilled in advance was added, and the mixture was heated to 160 ° C. and stirred to dissolve cellulose acetate uniformly.
  • reaction product 10 parts was dissolved in 90 parts of chloroform, and then slowly dropped into 900 parts of a large excess of methanol, and the precipitated precipitate was filtered off to remove the L-lactide homopolymer. .
  • the hard coat films 402, 403, and 404 were evaluated in the same manner as the items described in Table 2. The evaluation results are shown in Table 4.
  • polarizing plates 402 to 406 shown in Table 6 were produced in the same manner as described above. Using the produced polarizing plates 402 to 406, display characteristics of the liquid crystal display device were evaluated.
  • the polarizing plate according to the present invention does not cause any color unevenness when used in a liquid crystal display device, or has no practical problem even if some color unevenness occurs. It turns out that it is.
  • Example 3 Using the cellulose triacetate resins E1 to E3 shown in Table 7, the cellulose triacetate resin C1 was changed in the same manner as in the cellulose ester film 102 of Example 1 and the production method thereof, but 90 parts by mass of the cellulose triacetate resin C1 was changed. Films 502 to 507 were produced. Furthermore, it mixed by the mass ratio of Table 7, and produced the cellulose-ester films 508 and 509. Next, hard coat films 502 to 509 were prepared in the same manner as described above, and the same evaluation as the evaluation of the items described in Table 2 was performed. The evaluation results are shown in Table 8.
  • polarizing plates 502 to 509 shown in Table 9 were produced. Using the produced polarizing plates 502 to 509, display characteristics of the liquid crystal display device were evaluated.
  • the polarizing plate according to the present invention has no or no color unevenness when used in a liquid crystal display device, and has a practically no problem level. I understand that there is.

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Abstract

L'invention concerne : un film d'ester de cellulose qui présente une excellente adhérence résistante aux intempéries et une excellente fragilité ou élasticité après étirage, tout en maintenant des propriétés optiques telles qu'une transparence et un retard optique à des niveaux adéquats ; et un procédé de fabrication du film d'ester de cellulose. L'invention concerne également une plaque polarisante qui comporte le film d'ester de cellulose et ne génère pas d'inhomogénéité de couleur dans des cas où la plaque polarisante est utilisée dans un dispositif d'affichage à cristaux liquides. Ce film d'ester de cellulose satisfait les relations suivantes de nx < ny et Ex > Ey lorsque l'indice de réfraction dans la direction x est représenté par nx, l'indice de réfraction dans la direction y est représenté par ny, le module élastique du film dans la direction x est représenté par Ex, et le module élastique dans la direction y est représenté par Ey, et son axe lent est perpendiculaire à la direction où le module élastique est maximal. Ce film d'ester de cellulose est caractérisé en ce que la relation nx > ny est satisfaite et son axe lent est parallèle à la direction où le module élastique est maximal si le film d'ester de cellulose est étiré de 15 % ou plus à une température de 160°C ou moins et l'indice de réfraction dans le plan du film est mesuré.
PCT/JP2011/076351 2010-11-29 2011-11-16 Film d'ester de cellulose, son procédé de fabrication et plaque polarisante l'utilisant Ceased WO2012073692A1 (fr)

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Cited By (2)

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KR20150109341A (ko) * 2013-01-25 2015-10-01 디아이씨 가부시끼가이샤 셀룰로오스에스테르 수지용 폴리에스테르계 개질제 조성물, 셀룰로오스에스테르 광학 필름 및 편광판용 보호 필름
WO2016111316A1 (fr) * 2015-01-09 2016-07-14 コニカミノルタ株式会社 Film protecteur de plaque polarisante, son procédé de fabrication, plaque polarisante et dispositif d'affichage à cristaux liquides

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KR20150123553A (ko) * 2014-04-25 2015-11-04 동우 화인켐 주식회사 편광자의 제조 방법
KR20160033892A (ko) * 2014-09-18 2016-03-29 주식회사 효성 위상차 발현성이 우수한 셀룰로오스 에스테르 필름
JPWO2017104623A1 (ja) * 2015-12-16 2018-10-04 コニカミノルタ株式会社 異形表示装置

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JP2008239919A (ja) * 2007-03-29 2008-10-09 Fujifilm Corp セルロースアシレートフィルムとその製造方法、位相差フィルム、偏光板、および液晶表示装置
WO2010087219A1 (fr) * 2009-01-29 2010-08-05 株式会社Adeka Composition de résine de cellulose et film de résine de cellulose
WO2010106855A1 (fr) * 2009-03-18 2010-09-23 コニカミノルタオプト株式会社 Appareil d'affichage à cristaux liquides de type à alignement vertical

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JP2008239919A (ja) * 2007-03-29 2008-10-09 Fujifilm Corp セルロースアシレートフィルムとその製造方法、位相差フィルム、偏光板、および液晶表示装置
WO2010087219A1 (fr) * 2009-01-29 2010-08-05 株式会社Adeka Composition de résine de cellulose et film de résine de cellulose
WO2010106855A1 (fr) * 2009-03-18 2010-09-23 コニカミノルタオプト株式会社 Appareil d'affichage à cristaux liquides de type à alignement vertical

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KR20150109341A (ko) * 2013-01-25 2015-10-01 디아이씨 가부시끼가이샤 셀룰로오스에스테르 수지용 폴리에스테르계 개질제 조성물, 셀룰로오스에스테르 광학 필름 및 편광판용 보호 필름
US20150368429A1 (en) * 2013-01-25 2015-12-24 Dic Corporation Polyester modifier composition for cellulose ester resin, cellulose ester optical film, and polarizing plate protective film
KR102263372B1 (ko) * 2013-01-25 2021-06-11 디아이씨 가부시끼가이샤 셀룰로오스에스테르 수지용 폴리에스테르계 개질제 조성물, 셀룰로오스에스테르 광학 필름 및 편광판용 보호 필름
WO2016111316A1 (fr) * 2015-01-09 2016-07-14 コニカミノルタ株式会社 Film protecteur de plaque polarisante, son procédé de fabrication, plaque polarisante et dispositif d'affichage à cristaux liquides

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