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WO2015128995A1 - Film de protection de polariseur, son procédé de fabrication, polariseur, et dispositif d'affichage à cristaux liquides - Google Patents

Film de protection de polariseur, son procédé de fabrication, polariseur, et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2015128995A1
WO2015128995A1 PCT/JP2014/054914 JP2014054914W WO2015128995A1 WO 2015128995 A1 WO2015128995 A1 WO 2015128995A1 JP 2014054914 W JP2014054914 W JP 2014054914W WO 2015128995 A1 WO2015128995 A1 WO 2015128995A1
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WIPO (PCT)
Prior art keywords
polarizing plate
protective film
plate protective
copolymer
film
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.)
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PCT/JP2014/054914
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English (en)
Japanese (ja)
Inventor
美典 玉川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
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Konica Minolta Inc
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Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to PCT/JP2014/054914 priority Critical patent/WO2015128995A1/fr
Priority to KR1020167023175A priority patent/KR20160113660A/ko
Priority to JP2016504939A priority patent/JPWO2015128995A1/ja
Publication of WO2015128995A1 publication Critical patent/WO2015128995A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/54—Arrangements for reducing warping-twist

Definitions

  • the polarizing plate protective film has high water resistance, suppresses the occurrence of display unevenness (bend unevenness) in the liquid crystal display device, and has high heat resistance and toughness, and heat after the functional layer is applied.
  • a polarizing plate protective film that can suppress shrinkage variation.
  • the present invention has been made in view of the above problems and circumstances, and the solution is to have high water resistance, heat resistance and toughness, and suppress the occurrence of display unevenness (bend unevenness) in a liquid crystal display device.
  • the polarizing plate protective film which can suppress the thermal contraction dispersion
  • the polarizing plate protective film of the present invention preferably has a haze of 1% or less and a yellow index (YI) of 1.0 or less for optical film applications requiring transparency. .
  • ⁇ 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 polarizing plate protective film of the present invention contains the copolymer (A) and the copolymer (B) as main components of a thermoplastic resin used in the film.
  • the “main component” as used herein means that 60% by mass or more of the thermoplastic resin constituting the polarizing plate protective film is the total amount of the copolymer (A) and the copolymer (B). Preferably it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 95 mass% or more.
  • the polarizing plate protective film of the present invention is preferably bonded to a polarizer using an active energy ray-curable adhesive.
  • the adhesive on both sides used for the polarizer is the same type of adhesive. This is preferable because the bonding process does not become complicated and is advantageous in terms of cost.
  • Alkyl (meth) acrylates such as acrylates; (meth) acrylic acids such as acrylic acid and methacrylic acid; ⁇ , ⁇ -unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide And glycidyl group-containing monomers such as glycidyl methacrylate.
  • alkyl (meth) acrylates such as methyl acrylate are preferable.
  • Other monomers (c) may be used alone or in combination of two or more.
  • polymerization initiator a normal peroxide type or azo type can be used, and a redox type can also be used.
  • suspension or emulsion polymerization can be carried out in a temperature range of 30 to 100 ° C.
  • bulk or solution polymerization can be carried out in a temperature range of 80 to 160 ° C.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • the unreacted monomer ratio varies depending on the composition ratio of the copolymer (A).
  • the unreacted acrylonitrile unit is preferably in the range of 0.001 to 0.005%, and the unreacted styrene unit is If it is in the range of 0.05 to 0.1%, the above effect can be exhibited, which is preferable.
  • the unreacted monomer content can be controlled by controlling the polymerization temperature and polymerization time in the polymerization reactor, the heating temperature in the heater, the melting temperature in the devolatilizing extruder, and the unreacted monomer from the vent of the devolatilizing extruder. It can be adjusted by the displacement of volatile components. In order to reduce the content of the unreacted monomer, for example, it is preferable to lengthen the polymerization time in the polymerization reactor or increase the exhaust amount of volatile components from the vent of the devolatilizing extruder.
  • the content of the unreacted monomer contained in the copolymer according to the present invention can be measured by the following method.
  • the content (% by mass) of the unreacted monomer with respect to the total mass of the copolymer contained in the sample solution is measured by GC / MS.
  • the measuring device and measuring conditions of GC / MS are as follows.
  • the weight average molecular weight (Mw) of the copolymer (A) according to the present invention is preferably in the range of 150,000 to 250,000 in terms of styrene equivalent molecular weight.
  • the polarizing plate protective film of the present invention needs to contain a copolymer (B) having a lactone ring structure in the structure from the viewpoint of high heat resistance, high transparency, and the like.
  • the (meth) acrylic copolymer having a lactone ring structure is particularly preferably a (meth) acrylic copolymer having a ring structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • examples of the organic residue represented by R 1 include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group.
  • R 2 is preferably a hydrogen atom.
  • Examples of the organic residue represented by R 2 include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, a hydroxyalkyl group having 1 to 8 carbon atoms, and — (CH 2 ).
  • mNR 11 R 12 , — (CH 2 ) mN (R 11 R 12 R 13 ) + ⁇ M ⁇ , or — (C 2 H 4 O) pR 14 and the like can be mentioned.
  • R 11 , R 12 and R 13 may be the same or different and each is an alkyl group having 1 to 8 carbon atoms
  • R 14 is an alkyl group having 1 to 18 carbon atoms
  • M ⁇ is Cl ⁇ , Br ⁇ , SO 4 2 ⁇ , PO 4 3 ⁇ , CH 3 COO ⁇ or HCOO ⁇
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group.
  • Examples of the organic residue represented by R 3 include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, and a hydroxyalkyl group having 1 to 8 carbon atoms.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a hydroxyalkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom, a methyl group, or a 2-hydroxyethyl group.
  • the content of the lactone ring structure represented by the general formula (1) in the structure of the (meth) acrylic copolymer having a lactone ring structure is preferably within the range of 5 to 90% by mass, more preferably 10 to It is within the range of 70% by mass, more preferably within the range of 10 to 60% by mass, and particularly preferably within the range of 10 to 50% by mass.
  • the content of the lactone ring structure represented by the general formula (1) in the structure of the copolymer having a lactone ring structure is 5% by mass or more, sufficient heat resistance, solvent resistance, and surface hardness can be obtained. Can do.
  • the lactone ring-containing (meth) acrylic copolymer is prepared from a (meth) acrylic acid ester, a hydroxy group-containing monomer, an unsaturated carboxylic acid, a monomer having a vinyl group, and the like.
  • a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, The content is preferably 0 to 10% by mass.
  • a polymer structural unit (repeating structural unit) constructed by polymerizing a monomer having a vinyl group it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, Particularly preferred is 0 to 10% by mass.
  • the method for producing the (meth) acrylic copolymer having a lactone ring structure is not particularly limited, but preferably, after obtaining a polymer having a hydroxy group and an ester group in the molecular chain by a polymerization step, It is obtained by performing a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat-treating the obtained polymer.
  • the (meth) acrylic acid ester that is a monomer used in the copolymer (B) having a lactone ring structure is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, and isobutyl acrylate.
  • Acrylates such as t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid Methacrylic acid esters such as cyclohexyl and benzyl methacrylate; and the like. These may be used alone or in combination of two or more. Among these, methyl methacrylate is particularly preferable from the viewpoint of excellent heat resistance and transparency.
  • Examples of the copolymerized hydroxy group-containing monomer include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and 2- (hydroxymethyl).
  • Examples thereof include normal butyl acrylate, tertiary butyl 2- (hydroxymethyl) acrylate, and 2- (hydroxyethyl) acrylic acid.
  • methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred, and methyl 2- (hydroxymethyl) acrylate is particularly preferred from the viewpoint of high heat resistance improvement effect. These may be used alone or in combination of two or more.
  • the unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, crotonic acid, ⁇ -substituted acrylic acid, ⁇ -substituted methacrylic acid and the like. These may be used alone or in combination of two or more. You may do it.
  • the monomer having a vinyl group styrene, vinyl toluene, ⁇ -methyl styrene, acrylonitrile, acryloyl morpholine, methyl vinyl ketone, ethylene, propylene, vinyl acetate, N-vinyl pyrrolidone, and the like can be used. Only 1 type may be used and 2 or more types may be used together. Of these, styrene and ⁇ -methylstyrene are particularly preferable in that the effects of the present invention are sufficiently exhibited.
  • the cyclic structural unit represented by the general formula (1) is, for example, a polymer containing a methyl (meth) acrylate unit such as methyl methacrylate as a main constituent unit as described in US Pat. No. 2,146,209.
  • the polymerization temperature and polymerization time vary depending on the type of monomer used, the usage ratio, etc., but preferably the polymerization temperature is in the range of 0 to 150 ° C., the polymerization time is in the range of 0.5 to 20 hours, Preferably, the polymerization temperature is in the range of 80 to 140 ° C., and the polymerization time is in the range of 1 to 10 hours.
  • the polymerization solvent is not particularly limited.
  • aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • ether solvents such as tetrahydrofuran Etc., and only one of these may be used, or two or more may be used in combination.
  • the boiling point of the solvent used is too high, the residual volatile content of the finally obtained acrylic polymer increases, so that the boiling point is in the range of 50 to 200 ° C. is preferable.
  • a polymerization initiator may be added as necessary.
  • the polymerization initiator is not particularly limited.
  • the amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers used, reaction conditions, and the like.
  • the reaction for introducing a lactone ring structure into a polymer is a reaction in which a hydroxy group and an ester group present in the polymer molecular chain are cyclized and condensed to form a lactone ring structure by heating the polymer. is there.
  • the reaction temperature when using the devolatilizer is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C.
  • the reaction treatment temperature is higher than 150 ° C., the cyclization condensation reaction becomes sufficient and the residual volatile matter is small.
  • Copolymers (A) and (B) according to the present invention can be used in combination with other resins as long as the effects of the present invention are not impaired.
  • other resins other styrene resins and (meth) acrylic resins can be preferably used.
  • (Meth) acrylic resin includes structural units derived from (meth) acrylic acid esters.
  • (meth) acrylic acid esters include acrylic acid alkyl esters having 4 to 18 carbon atoms such as methyl acrylate, ethyl acrylate, and butyl acrylate; and carbon atoms having 5 to 18 carbon atoms such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
  • Methacrylic acid alkyl esters Of these, methyl methacrylate is preferable because it is easily polymerized. Another monomer may be used by 1 type and may use 2 or more types together.
  • peeling aid antistatic agent Since the film-like material containing the aromatic vinyl resin according to the present invention has high adhesion to the metal support, it is easy to peel from the metal support, and the thickness of the film obtained by suppressing the elongation at the time of peeling. In order to make the thickness uniform, it is preferable to contain a peeling aid or an antistatic agent.
  • non-reactive quaternary ammonium salt type surfactant as a peeling aid, and among them, a non-reactive quaternary ammonium salt type surfactant having 2 or less methyl groups is useful.
  • the surfactant is not particularly limited, and examples of the non-reactive quaternary ammonium salt type surfactant having one methyl group include polyoxypropylene methyldiethylammonium chloride, methyldiethyl (2-methoxyethyl).
  • the surfactant preferably contains an alkylene oxide (AO) group.
  • Antioxidant in this invention, what is generally known can be used as an antioxidant.
  • lactone, sulfur, phenol, double bond, hindered amine, and phosphorus compounds can be preferably used.
  • Examples of the phosphorus compound include “Sumizer GP” commercially available from Sumitomo Chemical Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36”, and “ADK STAB 3010” commercially available from ADEKA Corporation. “IRGAFOS P-EPQ” commercially available from BASF Japan Ltd. and “GSY-P101” commercially available from Sakai Chemical Industry Ltd.
  • the polarizing plate protective film according to the present invention preferably contains an ultraviolet absorber, and applicable ultraviolet absorbers include ultraviolet absorbers such as benzotriazole, 2-hydroxybenzophenone, salicylic acid phenyl ester, and triazine. Agents.
  • UV absorbers Commercially available products of these ultraviolet absorbers may be used, for example, Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928, etc. manufactured by BASF Japan, or 2,2 '-Methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercially available products are manufactured by ADEKA Corporation LA31) can be preferably used.
  • silicon dioxide is particularly preferably used from the viewpoint of excellent transparency (haze).
  • the shape of the matting agent particles can be used without particular limitation, such as indefinite shape, needle shape, flat shape, and spherical shape.
  • the use of spherical particles is particularly preferable because the resulting film can have good transparency.
  • Metabrene C-140A C-215A (manufactured by Mitsubishi Rayon Co., Ltd.), Toughprene 126, Asaflex 800, Asaflex 825 (manufactured by Asahi Kasei Chemicals Corporation), TR2000, TR2250. (Above, manufactured by JSR Corporation).
  • methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
  • methylene chloride, methyl acetate, ethyl acetate, and acetone can be preferably used as the main solvent. Particularly preferably
  • the dope preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in the range of 1 to 40% by mass.
  • the web gels, and peeling from the metal support becomes easy.
  • the proportion of alcohol is small, the resin and other compounds can be dissolved in a non-chlorine organic solvent system.
  • the dope having an alcohol concentration in the range of 0.5 to 15.0% by mass is formed from the viewpoint of improving the flatness of the obtained polarizing plate protective film. The method to do can be applied.
  • a dope composition in which a resin and other compounds are dissolved in a total amount of 15 to 45% by mass in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
  • a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms Preferably there is.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and normal filter media can be used. However, plastic fiber filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel fibers are used to remove fibers. This is preferable.
  • the main dope is filtered by the main filter 3, and a matting agent dispersion liquid, an ultraviolet absorber additive liquid, and the like are added in-line through the conduit 16.
  • the polarizing plate protective film of the present invention has a retardation value (Ro) defined by the following formula (i) in the range of 0 to 70 nm, and the retardation value (Rt) defined by the following formula (ii)
  • Ro retardation value
  • Rt retardation value
  • a thickness in the range of ⁇ 50 to 10 nm is particularly preferable when the polarizing plate protective film does not require retardation.
  • the polarizing plate protective film can be stretched while adjusting the stretching ratio at least in the MD direction or the TD direction.
  • the knurling process is preferably provided after the drying in the film forming process and before winding.
  • the moisture permeability of the polarizing plate protective film can be adjusted by, for example, the content ratio of the structural unit derived from the aromatic vinyl monomer in the copolymer. In order to reduce the moisture permeability, for example, the content ratio of the structural unit derived from the aromatic vinyl monomer in these polymers may be increased.
  • the tear strength of the polarizing plate protective film at 23 ° C. and 55% RH is preferably 15 mN or more, more preferably 20 mN or more, and further preferably 30 mN or more.
  • the upper limit of the tear strength is, for example, about 50 mN.
  • the tear strength of the polarizing plate protective film can be adjusted by, for example, the molecular weight of a copolymer or other resin.
  • the molecular weight of the copolymer or other resin may be increased.
  • the polarizing plate protective film of the present invention can also have a functional layer on at least one surface of the film, such as a hard coat layer, an antistatic layer, a back coat layer, an antireflection layer, a slippery layer, and an adhesive layer. It is preferable to provide functional layers such as an antiglare layer and a barrier layer.
  • the content ratio of the fine particles is desirably blended so as to be in the range of 10 to 400 parts by mass, more preferably in the range of 50 to 200 parts by mass with respect to 100 parts by mass of the ultraviolet curable compound.
  • the dry film thickness of the hard coat layer is in the range of an average film thickness of 0.1 to 30 ⁇ m, preferably 1 to 20 ⁇ m, particularly preferably 6 to 15 ⁇ m.
  • any light source that generates ultraviolet rays can be used without limitation.
  • 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.
  • Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually within a range of 5 to 500 mJ / cm 2 , preferably within a range of 5 to 200 mJ / cm 2 .
  • the polarizing plate protective film of the present invention may further have an antireflection layer on the hard coat layer. Thereby, the polarizing plate protective film of the present invention can be used as an antireflection film having an external light antireflection function.
  • the film thickness of the low refractive index layer is preferably 5 nm to 0.5 ⁇ m, more preferably 10 nm to 0.3 ⁇ m, and most preferably 30 nm to 0.2 ⁇ m.
  • the coating solution for the low refractive index layer may further contain a solvent, a silane coupling agent, a curing agent, a surfactant and the like as necessary.
  • the polarizing plate protective film on the viewing side is an antiglare layer or a clear hard coat layer, an antireflection layer, an antistatic layer, an antifouling layer, etc. It is preferable to provide a functional layer.
  • the polarizing plate protective film of the present invention has a particularly high effect of suppressing variation in heat shrinkage after coating. Therefore, even if the functional layer is formed by coating and then heated and dried and then irradiated with ultraviolet rays, heat shrinkage due to drying. And the generation of wrinkles in the film and the occurrence of cracks in the functional layer can be suppressed.
  • polarizer a polarizer obtained by forming a polyvinyl alcohol aqueous solution into a film and dyeing it by uniaxial stretching or dyeing and then uniaxially stretching and then preferably performing a durability treatment with a boron compound may be used.
  • the film thickness of the polarizer is in the range of 5 to 15 ⁇ m, and particularly preferably in the range of 5 to 10 ⁇ m.
  • the polarizing plate of the present invention can be produced by a general method.
  • the polarizer side of the polarizing plate protective film of the present invention is subjected to surface treatment such as corona treatment, plasma treatment or excimer light treatment, and is immersed in an iodine solution and stretched on at least one surface of the polarizer. It can be bonded using a wire curable adhesive.
  • the following retardation film and polarizer are similarly bonded with an active energy ray-curable adhesive.
  • the retardation film is a cellulose ester film
  • the surface may be saponified.
  • the cellulose ester preferably has a total acyl group substitution degree in the range of 1.5 to 2.5, and more preferably satisfies the following formulas (a) and (b).
  • the active energy ray-curable adhesive to the bonding of the polarizing plate protective film and the polarizer of the present invention, or the bonding of the retardation film and the polarizer, with high productivity, It is easy to suppress the deformation of the polarizing plate, and it is possible to obtain characteristics with excellent flatness.
  • the radical photopolymerizable composition includes a radically polymerizable compound containing a polar group such as a hydroxy group and a carboxy group described in JP-A-2008-009329 and a radically polymerizable compound not containing a polar group at a specific ratio.
  • Composition) and the like are known.
  • the radical polymerizable compound is preferably a compound having a radical polymerizable ethylenically unsaturated bond.
  • the compound having an ethylenically unsaturated bond capable of radical polymerization include a compound having a (meth) acryloyl group.
  • Examples of the compound having a (meth) acryloyl group include an N-substituted (meth) acrylamide compound and a (meth) acrylate compound.
  • (Meth) acrylamide means acrylamide or methacrylamide.
  • Adhesive application step of applying the following active energy ray-curable adhesive to at least one of the adhesive surfaces of the polarizer and the polarizing plate protective film of the present invention; 2) Adhering a polarizer and a polarizing plate protective film via an adhesive layer, and a laminating step for bonding, 3) A curing step of curing the adhesive layer in a state where the polarizer and the polarizing plate protective film are bonded via the adhesive layer, Can be mentioned. Moreover, you may have the following pre-processing process of carrying out an easy adhesion process with respect to the surface which adhere
  • Pretreatment process an easy adhesion treatment is performed on the surface of the polarizing plate protective film adhered to the polarizer.
  • the polarizing plate protective film 102 and the retardation film 105 are bonded to both surfaces of the polarizer 104 via the active energy ray curable adhesives 103 ⁇ / b> A and 103 ⁇ / b> B, the respective polarizing plates are used.
  • the adhesion surface of the protective film 102 and the retardation film 105 is subjected to easy adhesion treatment.
  • the surface subjected to the easy adhesion treatment is treated as a bonding surface with the polarizer, and therefore the active energy ray-curable resin layer 103A is bonded to both surfaces of the polarizing plate protective film.
  • the surface to be treated is subjected to an easy adhesion treatment.
  • Examples of the easy adhesion treatment include corona treatment, plasma treatment, and excimer light treatment.
  • Bonding process After apply
  • this bonding step for example, when an active energy ray-curable adhesive is applied to the surface of the polarizer in the previous application step, a polarizing plate protective film is superimposed there.
  • a polarizer is superimposed thereon.
  • an active energy ray hardening-type adhesive agent is cast between a polarizer and a polarizing plate protective film, a polarizer and a polarizing plate protective film are piled up in that state.
  • both sides When a polarizing plate protective film and a retardation film are bonded to both sides of a polarizer, and both surfaces use an active energy ray-curable adhesive, an active energy ray-curable adhesive is applied to both sides of the polarizer.
  • a polarizing plate protective film and a retardation film are superimposed on each other.
  • both sides when a polarizing plate protective film is superimposed on one side of the polarizer, the polarizing plate protective film and the retardation film are provided on both sides of the polarizer and the polarizing plate protective film side.
  • pressure is applied between the polarizing plate protective film and the retardation film side of both surfaces with a roller or the like.
  • the material of the roller metal, rubber or the like can be used.
  • the rollers arranged on both sides may be made of the same material or different materials.
  • the acceleration voltage is preferably in the range of 5 to 300 kV, more preferably in the range of 10 to 250 kV. If the acceleration voltage is 5 kV or more, the electron beam can reach the adhesive sufficiently to obtain the desired curing conditions, and if the acceleration voltage is 300 kV or less, the penetration force through the bonding unit becomes excessively strong. It can suppress that a transparent polarizing plate protective film and a polarizer are damaged.
  • the irradiation dose is in the range of 5 to 100 kGy, more preferably in the range of 10 to 75 kGy.
  • the active energy ray-curable adhesive is sufficiently cured.
  • the irradiation dose is 100 kGy or less, the polarizing plate protective film and the polarizer are not damaged, and the mechanical strength is reduced. Changes can be prevented, and predetermined optical characteristics can be obtained.
  • the dose of ultraviolet rays is preferably in accumulated light amount is within the range of 50 ⁇ 1500mJ / cm 2, and even more preferably in the range of 100 ⁇ 500mJ / cm 2.
  • the line speed depends on the curing time of the active energy ray-curable adhesive, but is preferably in the range of 1 to 500 m / min, more preferably 5 to 300 m / min, and further Preferably, it is within the range of 10 to 100 m / min.
  • the line speed is 1 m / min or more, appropriate productivity can be secured, damage to the transparent polarizing plate protective film can be suppressed, and a polarizing plate that can withstand a durability test can be produced.
  • the line speed is 500 m / min or less, the resulting adhesive is sufficiently cured, and the desired adhesiveness can be obtained.
  • the thickness of the active energy ray-curable adhesive layer is not particularly limited, but is usually in the range of 0.01 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m. Within range.
  • the first polarizing plate A, the liquid crystal cell, and the second polarizing plate B are arranged in this order from the viewing surface side, and the polarizing plate A and the polarizing plate B are Both are polarizing plates of the present invention, and from the viewing surface side, the first polarizing plate A is composed of a polarizing plate protective film T1, a polarizer and a retardation film T2, and the second polarizing plate B is a retardation.
  • polarizing plate protective film T1 and polarizing plate protective film T4 are polarizing plate protective films which consist of a structure prescribed
  • the polarizing plate protective film of the present invention is excellent in water resistance, heat resistance, flatness, etc.
  • the glass substrate constituting the liquid crystal cell is thinned by providing the liquid crystal display device with the polarizing plate of the present invention. As a result, a liquid crystal display device in which thinning is achieved can be obtained.
  • the thickness of the glass substrate of the liquid crystal cell constituting the liquid crystal display device is preferably in the range of 0.4 to 0.6 mm. Such a thickness is preferable in that it can contribute to the formation of a thin liquid crystal display device.
  • Such a glass substrate can also be obtained as a commercial product.
  • non-alkali glass AN100 (thickness 500 ⁇ m) manufactured by Asahi Glass Co., Ltd.
  • glass substrate EAGLE XG (r) Slim (thick manufactured by Corning) 300 ⁇ m, 400 ⁇ m, etc.
  • glass substrates (thickness 100 to 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd.
  • the polarizing plate of the present invention By using the polarizing plate of the present invention, even if the screen using the thin film glass substrate for a liquid crystal cell is a large-screen liquid crystal display device of 30 type or more, display unevenness (bend unevenness) is suppressed and the front surface is suppressed. A liquid crystal display device having excellent visibility such as contrast can be obtained.
  • FIG. 3 is a schematic sectional view showing an example of the configuration of the liquid crystal display device 106 including the polarizing plate 101 of the present invention.
  • a liquid crystal cell 107 is sandwiched between the retardation film 105 constituting the polarizing plate 101A and the retardation film 105 constituting the polarizing plate 101B described in FIG. Yes.
  • a polarizing plate protective film 102 is disposed on the surface portion as an optical film, which is referred to as a polarizing plate protective film T ⁇ b> 1, and further below the polarizer 104.
  • the phase difference film 105 is arrange
  • the mode (driving method) of the liquid crystal display device is not particularly limited, and liquid crystal display devices in various drive modes such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB can be used.
  • a VA (MVA, PVA) type liquid crystal display device is preferable. Note that the direction of bonding of the polarizing plate in the VA mode liquid crystal display device can be performed with reference to JP-A-2005-234431.
  • stearyl phosphate / distearyl phosphate mixture manufactured by Sakai Chemicals, trade name: Phoslex A-18
  • cyclized under reflux about 90 to 110 ° C.
  • a condensation reaction was performed.
  • the polymer solution obtained by the above cyclization condensation reaction was converted into a vent having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of one, and a forevent number of four.
  • copolymer 1 was prepared in the same manner as in the preparation of the copolymer 1, except that the lactone ring-containing acrylic resin prepared above was used as the lactone ring-containing acrylic resin alone (mass ratio 0/100) as shown in Table 1. 5 was prepared.
  • Copolymer 1 was prepared in the same manner as in Table 1, except that the styrene-acrylonitrile copolymer prepared above was used as a styrene-acrylonitrile copolymer alone (mass ratio 100/0) as shown in Table 1. Polymer 6 was prepared.
  • a lactone ring-containing acrylic resin having a methyl acrylate unit content of 20% by mass and a styrene unit content of 10% by mass is prepared and mixed at a mass ratio of 60:40 as shown in Table 1.
  • a copolymer 11 was prepared in the same manner except that.
  • a copolymer 13 was prepared as shown in Table 1 in the same manner as in the preparation of the copolymer 3, except that a lactone ring-containing acrylic resin having a weight average molecular weight adjusted to 150,000 was prepared.
  • ⁇ Preparation of copolymer 14> In the preparation of the copolymer 3, a styrene-acrylonitrile copolymer having a hydroxystyrene unit content of 75% by mass and an acrylonitrile unit content of 25% was prepared. A copolymer 14 was prepared in the same manner except that the mixing was performed at a mass ratio of 50:50.
  • copolymer 15 a styrene-ethacrylonitrile copolymer having a styrene unit content of 75% by mass and an ethacrylonitrile unit content of 25% by mass was prepared.
  • copolymer 15 was prepared in the same manner except that it was mixed at a mass ratio of 50:50.
  • styrene-acrylonitrile copolymer having a styrene unit content of 85% by mass and an acrylonitrile unit content of 15% by mass was prepared.
  • a copolymer 16 was prepared in the same manner except that the mixing was performed at a mass ratio of 50:50.
  • Copolymer 17 a styrene-acrylonitrile copolymer having a styrene unit content of 65% by mass and an acrylonitrile unit content of 35% by mass was prepared.
  • Copolymer 17 was prepared in the same manner except that it was mixed at a mass ratio of 50:50.
  • the content (mass%) of the unreacted monomer with respect to the total mass of the copolymer (A) contained in the sample solution is measured by GC / MS.
  • the measuring device and measuring conditions of GC / MS are as follows.
  • Stripping aid (Compound 1) 1-1: ELECUT S-412-2 (manufactured by Takemoto Yushi Co., Ltd.): sodium dodecylbenzenesulfonate 1-2: Epan 750 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): nonionic surfactant 1-3 : Stearyl alcohol (3) Rubber particles (Compound 2) 2-1: Tufprene 126S (Asahi Kasei Chemicals Corporation) styrene-butadiene copolymer 2-2: TR2003 (JSR Corporation) styrene-butadiene copolymer 2-3: The following particles 1 2-4: Particle 2 below ⁇ Particle 1: Acrylic particles synthesized by the following method> (Acrylic particles C1) A reactor with a reflux condenser with an internal volume of 60 liters is charged with 38.2 liters of ion-exchanged water and 111.6 g of sodium diocty
  • n-OM n-octyl mercaptan
  • ⁇ Particle 2 Elastic organic fine particles synthesized by the following method> (Elastic organic fine particles (B1) In a pressure-resistant reaction vessel equipped with a stirrer, 70 parts of deionized water, 0.5 part of sodium pyrophosphate, 0.2 part of potassium oleate, 0.005 part of ferrous sulfate, 0.2 part of dextrose, p-menthane A mixture comprising 0.1 part of hydroperoxide and 28 parts of 1,3-butadiene was added, the temperature was raised to 65 ° C., and a polymerization reaction was carried out for 2 hours.
  • Elastic organic fine particles (B1) In a pressure-resistant reaction vessel equipped with a stirrer, 70 parts of deionized water, 0.5 part of sodium pyrophosphate, 0.2 part of potassium oleate, 0.005 part of ferrous sulfate, 0.2 part of dextrose, p-menthane A mixture comprising 0.1 part of hydroperoxide and 28 parts of 1,3
  • the internal temperature was raised to 80 ° C. and polymerization was continued for 2 hours.
  • the mixture was passed through a 300 mesh wire net to obtain an emulsion polymerization liquid of elastic organic fine particles.
  • the obtained emulsion polymerization liquid of elastic organic fine particles was salted out and solidified with calcium chloride, washed with water and dried to obtain powdery elastic organic fine particles.
  • the volume average particle diameter of the elastic organic fine particles was 0.260 ⁇ m.
  • composition of dope 1 100 parts by mass UV absorber 2- (2H-benzotriazol-2-yl) -6- (1 -Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol] (Ti928 manufactured by BASF Japan) 3.0 parts by weight Matting agent R812 (manufactured by Nippon Aerosil Co., Ltd., silica particles) 0.30 part by weight Release aid ELECUT S-412-2 (sodium dodecylbenzenesulfonate, manufactured by Takemoto Yushi Co., Ltd.) 0.20 part by weight Rubber particle 1 part by weight of styrene-butadiene copolymer Dichloromethane 150 Part by mass Ethanol 5 parts by mass The prepared dope 1 was uniformly cast on a stainless steel band support at a temperature of 22 ° C.
  • the obtained film was slit to a width of 1.5 m, a knurling process having a width of 10 mm and a height of 5 ⁇ m was applied to both ends of the film, and then wound around a core to prepare a polarizing plate protective film 101.
  • the produced protective film 101 had a thickness of 40 ⁇ m and a winding length of 4000 m.
  • the obtained pellets were put into a single screw extruder and melt kneaded at 250 ° C. in a nitrogen atmosphere. Then, it extruded from the die
  • polarizing plate protective film 122 (Preparation of polarizing plate protective film 122)
  • a polarizing plate protective film 122 having a film thickness of 40 ⁇ m was obtained in the same manner except that the copolymer 4 was used.
  • composition of dope for core layer Cellulose acetate (total substitution degree 2.45, acetyl group substitution degree 2.45, Weight average molecular weight 180,000) 100 parts by mass Compound C (retardation increasing agent) 3 parts by mass Both compounds D (terephthalic acid / succinic acid / ethanediol / propanediol (80/20/50/50 molar ratio) condensate) (Terminal sealed with acetyl ester group) 10 parts by mass Dichloromethane 406 parts by mass Methanol 61 parts by mass
  • composition of dope for skin B layer Cellulose acetate (total substitution degree 2.93, acetyl group substitution degree 2.93, Weight average molecular weight 280,000) 100 parts by mass Compound E (terephthalic acid / succinic acid / ethylene glycol copolymer (50 / 50/100 molar ratio), molecular weight 2000, retardation developer) 4 parts by mass Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd., silicon dioxide fine particles (average particle size 15 nm, matting agent) 0.12 parts by mass Half ethyl citrate Esters (manufactured by Fuso Chemical Industries, exfoliation accelerator) 2 parts by mass Dichloromethane 406 parts by mass Methanol 61 parts by mass (Skin A layer dope composition)
  • the composition of the dope for skin B layer was the same as that described above, except that citric acid partial ethyl ester (exfoliation accelerator) was not included.
  • the obtained core layer dope, skin A layer dope and skin B layer dope were co-cast from a casting die on a traveling casting band (simultaneous multilayer casting).
  • the co-casting was performed so that the dope for the skin B layer was in contact with the casting band.
  • the cast film was peeled off from the cast band, made into a wet film, and then dried with a tenter to obtain a film-like product.
  • the residual solvent amount of the film-like material immediately after peeling off was about 30% by mass.
  • the film-like material is stretched to a stretch ratio of 30% with a tenter and then relaxed at 140 ° C. for 60 seconds to have a three-layer structure of skin B layer / core layer / skin A layer, and a retardation film having a thickness of 40 ⁇ m. A was obtained.
  • Phase difference film B Each material is put into a mixing tank and stirred to dissolve each component, and then filtered through a filter paper having an average pore size of 34 ⁇ m and a sintered metal filter having an average pore size of 10 ⁇ m, and the core layer dope and skin B layer having the following composition A dope for skin and a dope for skin A layer were prepared.
  • Three layers of skin B layer / core layer / skin A layer were prepared in the same manner as in the preparation of the retardation film A except that the obtained core layer dope, skin A layer dope, and skin B layer dope were used.
  • a retardation film B having a structure and a film thickness of 40 ⁇ m was obtained.
  • Fine particle dispersion 1 Fine particles (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.): 11 parts by mass Ethanol 89 parts by mass The above-prepared fine particle dispersion 1 was sufficiently added to a dissolution tank containing methylene chloride while sufficiently stirring. The resulting solution was dispersed with an attritor so that the secondary particles had a predetermined particle size, and then filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1 did.
  • polarizing plate 101 Production of polarizing plate (Production of polarizing plate 101) 1) Production of polarizer A polyvinyl alcohol film having a thickness of 30 ⁇ m was swollen with water at 35 ° C. The obtained film was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and further immersed in an aqueous solution of 45 ° C. consisting of 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . The obtained film was uniaxially stretched under conditions of a stretching temperature of 55 ° C. and a stretching ratio of 3 times. This uniaxially stretched film was washed with water and dried to obtain a polarizer having a thickness of 5 ⁇ m. Furthermore, polarizers having thicknesses of 10 ⁇ m and 15 ⁇ m were obtained by changing the stretching conditions.
  • 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Epolide GT-301 (alicyclic epoxy resin manufactured by Daicel Chemical Industries) 40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Triarylsulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 parts by mass 1,4-diethoxynaphthalene 2.0 parts by mass 3)
  • the retardation film C was prepared as a retardation film, and the surface thereof was subjected to corona discharge treatment.
  • the corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min.
  • the active energy ray-curable adhesive liquid prepared above is applied to the corona discharge-treated surface of the retardation film C with a bar coater so that the film thickness after curing is about 3 ⁇ m.
  • a mold adhesive layer was formed.
  • the above-produced polarizer having a thickness of 5 ⁇ m was bonded to the obtained active energy ray-curable adhesive layer.
  • a polarizing plate protective film 101 was prepared as a polarizing plate protective film, and the surface of the polarizing plate protective film 101 was subjected to corona discharge treatment.
  • the conditions for the corona discharge treatment were a corona output intensity of 2.0 kW and a line speed of 18 m / min.
  • the active energy ray-curable adhesive liquid prepared above is applied to the corona discharge-treated surface of the polarizing plate protective film 101 with a bar coater so that the cured film thickness is about 3 ⁇ m, and the active energy ray is cured.
  • a mold adhesive layer was formed.
  • the laminate was performed so that the slow axis of the retardation film C and the absorption axis of the polarizer were orthogonal to each other.
  • the polarizing plate protective films 102 to 126 and the thicknesses of the polarizers were appropriately changed to produce the polarizing plates 102 to 126 with the constitution described in Table 3.
  • a VA liquid crystal cell having two glass substrates having a thickness of 0.5 mm and a liquid crystal layer disposed therebetween was prepared. Then, the prepared polarizing plate 101 was bonded to both surfaces of the prepared liquid crystal cell via a 25 ⁇ m-thick double-sided tape (baseless tape MO-3005C) manufactured by Lintec to obtain a liquid crystal display panel. It was. As shown in Table 3, the bonding was performed so that the retardation film C of the polarizing plate 101 was in contact with the glass substrate of the liquid crystal cell.
  • liquid crystal display devices 127 to 129 having the configurations shown in Table 3 were fabricated.
  • Heat resistance Heat resistance is evaluated by the glass transition temperature Tg (° C) of the polarizing plate protective film, and the higher the Tg (° C), the better the heat resistance.
  • the glass transition temperature Tg (° C.) was measured using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. according to JIS K-7121.
  • sample film About 10 mg of sample film is set, and the temperature is raised from room temperature to 250 ° C. at 20 ° C./min under a nitrogen flow rate of 50 ml / min. The temperature was lowered to 30 ° C. and held for 10 minutes (2nd scan), further raised to 250 ° C. at 20 ° C./min (3rd scan), a DSC curve was created, and the glass transition temperature was obtained from the obtained 3rd scan DSC curve Obtain Tg.
  • the glass transition temperature (Tg) of each polarizing plate protective film measured as described above was evaluated according to the following criteria, and used as a heat resistance index.
  • the glass transition temperature is 120 ° C. or higher.
  • ⁇ The glass transition temperature is in the range of 110 ° C. or higher and lower than 120 ° C.
  • ⁇ The glass transition temperature is in the range of 100 ° C. or higher and lower than 110 ° C.
  • ⁇ Glass transition temperature is less than 100 ° C.
  • Haze Haze is a haze meter (turbidimeter) (model: NDH 2000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K-7136. Measured with
  • Yellow index (YI) The yellow index (YI) is obtained by the method described in JIS K-7105-6.3. As a specific method for measuring the yellow index value, the color tristimulus values X, Y, and Z are obtained using a spectrophotometer U-3200 manufactured by Hitachi, Ltd. and the attached saturation calculation program, etc. The yellow index value was determined.
  • Yellow index (YI) 100 (1.28X-1.06Z) / Y (4) Bending resistance [Evaluation of bending strength]
  • a polarizing plate protective film is cut out at 100 mm (TD) ⁇ 10 mm (MD), left for 1 hour in an environment of 23 ° C. and 55% RH, and then once in a mountain fold and a valley fold at the center in the vertical direction. Folded one by one, this evaluation was measured three times and evaluated as follows. In addition, breaking of evaluation here represents having broken into two or more pieces.
  • UV curable monomer 10 parts by mass-UV curable polymer 30 parts by mass-Particle size 8 ⁇ m silica particles 10 parts by mass-Methyl isobutyl ketone 35 parts by mass-Methyl ethyl ketone 15 parts by mass
  • the viscosity of this UV curable monomer at 60 ° C is 300 cp.
  • the viscosity is measured with an SV type (tuning fork vibration type) viscometer in a state where the UV curable monomer is kept at 60 ° C.
  • the first 15 seconds after coating is applied with a drying air with an air speed of 0.3 m / s and an air temperature of 28 ° C., and the next 10 seconds with a drying air with an air speed of 1.0 m / s and an air temperature of 37 ° C. I guessed.
  • the coating film viscosity is 50 to 60 cp.
  • the first 15 s was applied with a dry air having a wind speed of 1.5 m / s and an air temperature of 60 ° C.
  • the next 15 s was applied with a dry air having an air speed of 1.3 m / s and an air temperature of 60 ° C.
  • the film obtained by UV curing with a high-pressure mercury lamp (film thickness: 11 ⁇ m) was visually evaluated for unevenness of drying and wrinkles due to UV irradiation.
  • the evaluation criteria are as follows.
  • the polarizing plate protective films 101 to 103 and 107 to 126 of the present invention are excellent in heat resistance, haze, yellow index (YI), bending, and heat shrinkage unevenness after coating.
  • the evaluation results of the liquid crystal display devices 101 to 103 and 107 to 126 show that the bend unevenness is superior to the comparative example.
  • the polarizing plate protective film 121 of the present invention produced by the melt casting method has a slightly high haze and yellow index (YI) value, and coloration is observed, and the solution casting method is a method for producing the polarizing plate protective film of the present invention. It has been found preferable to adopt
  • the polarizing plate protective films 104, 105, and 122 as comparative examples have a high content ratio of the copolymer (B), they are excellent in heat resistance, but the bend unevenness is inferior.
  • the polarizing plate protective film 106 which is a comparative example has a high content ratio of a copolymer (A), it turns out that it is inferior to heat resistance and heat shrink nonuniformity.
  • the polarizing plate 103HC and 119HC in which the hard coat layer is applied to the polarizing plate protective film of the present invention the occurrence of heat shrinkage unevenness after coating is effectively suppressed by the configuration of the present invention. Therefore, the liquid crystal display devices 127 and 129 provided with them were excellent in bend unevenness and excellent in visibility without display unevenness by visual observation. In contrast, the liquid crystal display device 128 using the polarizing plate 105HC in which the hard coat layer is applied to the polarizing plate protective film of the comparative example is inferior in bend unevenness.
  • the polarizing plate protective film of the present invention is excellent in overall heat resistance, haze, yellow index (YI), bending, heat shrinkage unevenness after coating, and bend unevenness of liquid crystal display devices. It was found that a protective film was obtained.
  • the polarizing plate protective film of the present invention has high water resistance, heat resistance, and toughness, suppresses the occurrence of display unevenness (bend unevenness) in the liquid crystal display device, and the thermal shrinkage variation after the functional layer is applied. Can be suitably used for polarizing plates and liquid crystal display devices.

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Abstract

La présente invention vise à fournir ce qui suit : un film de protection de polariseur tenace, qui est hautement résistant à l'eau et à la chaleur, réduit à un minimum des artefacts d'affichage (artefacts de gauchissement) sur un dispositif d'affichage à cristaux liquides, et réduit à un minimum les non-uniformités de contraction thermique après l'application d'une couche fonctionnelle ; un procédé de fabrication dudit film de protection de polariseur ; un polariseur ; et un dispositif d'affichage à cristaux liquides. Ce film de protection de polariseur est caractérisé par le fait qu'il contient, comme constituants principaux d'une résine thermoplastique, un copolymère (A) obtenu par polymérisation d'un monomère vinylique aromatique conjointement avec un monomère de nitrile insaturé, et un copolymère (B) qui a une structure d'anneau de lactone, le rapport de masse entre eux (A:B) étant compris entre 95:5 et 50:50, inclus.
PCT/JP2014/054914 2014-02-27 2014-02-27 Film de protection de polariseur, son procédé de fabrication, polariseur, et dispositif d'affichage à cristaux liquides Ceased WO2015128995A1 (fr)

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PCT/JP2014/054914 WO2015128995A1 (fr) 2014-02-27 2014-02-27 Film de protection de polariseur, son procédé de fabrication, polariseur, et dispositif d'affichage à cristaux liquides
KR1020167023175A KR20160113660A (ko) 2014-02-27 2014-02-27 편광판 보호 필름, 그 제조 방법, 편광판 및 액정 표시 장치
JP2016504939A JPWO2015128995A1 (ja) 2014-02-27 2014-02-27 偏光板保護フィルム、その製造方法、偏光板及び液晶表示装置

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PCT/JP2014/054914 WO2015128995A1 (fr) 2014-02-27 2014-02-27 Film de protection de polariseur, son procédé de fabrication, polariseur, et dispositif d'affichage à cristaux liquides

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KR20190075582A (ko) * 2017-12-21 2019-07-01 주식회사 엘지화학 광학 필름의 제조방법, 광학 필름 및 이를 포함하는 편광판
WO2020027078A1 (fr) * 2018-07-31 2020-02-06 コニカミノルタ株式会社 Film de résine (méth)acrylique, film optique et procédé de production de film de résine (méth)acrylique
JP2023113617A (ja) * 2019-12-23 2023-08-16 コニカミノルタ株式会社 保護フィルムおよびその製造方法
JP2023151103A (ja) * 2022-03-31 2023-10-16 株式会社日本触媒 フィルムの製造方法及びドープ液
WO2024135551A1 (fr) * 2022-12-20 2024-06-27 三菱瓦斯化学株式会社 Composition de résine, objet moulé en forme de plaque, objet multicouche et article moulé

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US12421414B2 (en) 2022-03-03 2025-09-23 Lg Chem, Ltd. Optical film, composition for forming coating layer, and electronic device

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