WO2017006938A1 - Plaque polarisante, et dispositif d'affichage à cristaux liquides - Google Patents

Plaque polarisante, et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2017006938A1
WO2017006938A1 PCT/JP2016/069925 JP2016069925W WO2017006938A1 WO 2017006938 A1 WO2017006938 A1 WO 2017006938A1 JP 2016069925 W JP2016069925 W JP 2016069925W WO 2017006938 A1 WO2017006938 A1 WO 2017006938A1
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Prior art keywords
film
polarizing plate
protective film
polarizer
mass
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PCT/JP2016/069925
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English (en)
Japanese (ja)
Inventor
秀典 林
孝浩 大場
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富士フイルム株式会社
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Priority to JP2017527467A priority Critical patent/JPWO2017006938A1/ja
Publication of WO2017006938A1 publication Critical patent/WO2017006938A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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

Definitions

  • the present invention relates to a polarizing plate and a liquid crystal display device.
  • polarizing plates used in liquid crystal display devices water-based adhesives such as aqueous polyvinyl alcohol solutions have been used for pasting polarizers and optical films (polarizing plate protective films).
  • actinic radiation curable adhesives have been used.
  • Patent Document 1 describes a polarizing plate in which a polarizer is sandwiched between an acrylic film and a cellulose acetate film that satisfy a specific dimensional change rate through an active ray curable adhesive layer.
  • Patent Document 2 describes a polarizing plate in which a polarizer is sandwiched by a cellulose acetate film containing a specific additive via an actinic radiation curable adhesive layer.
  • Patent Documents 1 and 2 are insufficient from the viewpoint of curling, and when used in a liquid crystal display device, display quality may be deteriorated. Moreover, the polarizing plate of patent document 2 had various restrictions about an additive, and was inferior to manufacture suitability.
  • the problem to be solved by the present invention is a polarizing plate in which an actinic radiation curable adhesive is used, which is excellent from the viewpoint of curling and excellent in display quality when used in a liquid crystal display device, and the polarizing plate A liquid crystal display device having the above is provided.
  • the two protective films bonded to both sides of the polarizer each have a creep deformation amount in a direction parallel to the absorption axis of the polarizer,
  • the relationship between the elastic modulus and the creep moment calculated by the product of the film thickness is important, and the above problem can be solved by designing the ratio of the creep moments of the two protective films within a specific numerical range. I understood. That is, the above problem can be solved by the following configuration.
  • Ratio A1 of the creep moment value A1 in the direction parallel to the absorption axis of the polarizer of the first protective film to the value A2 of the creep moment in the direction parallel to the absorption axis of the polarizer of the second protection film / A2 is 1.1 or more and 3.5 or less polarizing plate.
  • said A1 and said A2 are calculated by the following formula.
  • A1 creep amount (%) in the direction parallel to the absorption axis of the polarizer of the first protective film ⁇ elastic modulus (GPa) in the direction parallel to the absorption axis of the polarizer of the first protective film ⁇ Film thickness ( ⁇ m) of the first protective film
  • A2 creep amount (%) in the direction parallel to the absorption axis of the polarizer of the second protective film ⁇ elastic modulus (GPa) in the direction parallel to the absorption axis of the polarizer of the second protective film ⁇ Film thickness ( ⁇ m) of the second protective film ⁇ 2>
  • ⁇ 3> The polarizing plate according to ⁇ 1> or ⁇ 2>, wherein the A1 / A2 is 1.1 or more and 2.3 or less.
  • ⁇ 4> The polarizing plate according to any one of ⁇ 1> to ⁇ 3>, wherein the second protective film is a film containing a cycloolefin resin.
  • ⁇ 5> When the polarizing plate is placed on a flat plate with the second protective film surface side disposed on the flat plate side, at least the central portion of the polarizing plate is in contact with the flat plate, ⁇ 1> to ⁇ 4 > The polarizing plate in any one of.
  • the central portion refers to a region having a radius of 10 mm centered on an intersection of a perpendicular that bisects the long side of the polarizing plate and a perpendicular that bisects the short side.
  • the said edge part means the area
  • ⁇ 7> The polarizing plate according to ⁇ 6>, wherein the distance between the long side end of the polarizing plate and the flat plate, and the distance between the short side end and the flat plate are 0 mm or more and less than 10 mm.
  • a liquid crystal display comprising the liquid crystal cell and the polarizing plate according to any one of ⁇ 1> to ⁇ 7>, wherein the liquid crystal display has the second protective film on the liquid crystal cell side rather than the first protective film. apparatus.
  • a polarizing plate in which an actinic radiation curable adhesive is used, which is excellent from the viewpoint of curling and has excellent display quality when used in a liquid crystal display device, and the polarizing plate.
  • a liquid crystal display device can be provided.
  • the molecular weight of the oligomer or polymer was measured as follows.
  • GPC Gel permeation chromatograph apparatus (HLC-8220GPC manufactured by Tosoh Corp., column; Guard column HXL-H manufactured by Tosoh Corp., TSK gel G7000HXL, 2 TSK gel GMHXL, TSK gel G2000HXL, sequentially, eluent; Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8 wt%, sample injection amount: 70 ⁇ L, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard substance: TSK manufactured by Tosoh Corporation Standard polystyrene) was used to measure the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of standard polystyrene. In addition, Mn is the number average molecular weight of standard polystyrene conversion.
  • the present invention is a polarizing plate in which a polarizer is sandwiched between a first protective film and a second protective film via an actinic radiation curable adhesive layer, Having a pressure-sensitive adhesive layer on the surface of the second protective film opposite to the polarizer, Ratio A1 / A2 of the creep moment value A1 in the direction parallel to the absorption axis of the polarizer of the first protective film to the value A2 of the creep moment in the direction parallel to the absorption axis of the polarizer of the second protective film Is a polarizing plate which is 1.1 or more and 3.5 or less.
  • the above A1 and A2 are calculated by the following formula.
  • A1 creep amount (%) in the direction parallel to the absorption axis of the polarizer of the first protective film ⁇ elastic modulus (GPa) in the direction parallel to the absorption axis of the polarizer of the first protective film ⁇ first Film thickness of protective film ( ⁇ m)
  • A2 creep amount (%) in the direction parallel to the absorption axis of the polarizer of the second protective film ⁇ elastic modulus (GPa) in the direction parallel to the absorption axis of the polarizer of the second protective film ⁇ second Film thickness of protective film ( ⁇ m)
  • the direction parallel to the absorption axis of the polarizer is preferably the transport direction (MD (Machine Direction) direction, longitudinal direction) during the production of the protective film, and is parallel to the absorption axis of the polarizer in the present invention. It is preferable that the correct direction matches the MD direction.
  • MD Machine Direction
  • parallel in the present specification includes not only perfect parallelism but also an angle shift that is optically acceptable from perfect parallelism (preferably 15 ° or less, more preferably 10 ° or less. It is also included when there is.
  • Curling that occurs in a polarizing plate using a water-based adhesive is determined by the balance of the shrinkage force of each layer of the polarizing plate (the product of dimensional change, elastic modulus, and film thickness due to elastic deformation caused by the conveyance tension in the bonding process).
  • the balance of shrinkage force of protective films (outer film and inner film) provided on both sides of the polarizer is dominant.
  • the inner film is a film arranged closer to the liquid crystal cell when the polarizing plate is bonded to the liquid crystal cell among the films arranged on both surfaces of the polarizer, and the outer film is the other film.
  • positioned further from a liquid crystal cell) is shown.
  • the polarizing plate is produced by laminating with the residual stress of the polarizer remaining. Therefore, in such a polarizing plate, the dimensional change amount (creep deformation amount) in the direction parallel to the absorption axis of the polarizer (MD direction) due to the residual stress (contraction force) of the polarizer does not become the curl driving force.
  • the present inventors thought. Therefore, referring to the curl model with an aqueous adhesive, the curl in the polarizing plate using the actinic radiation curable adhesive is the contraction force between the outer film and the inner film (direction parallel to the absorption axis of the polarizer (MD direction)).
  • Creep deformation amount elastic modulus in the same direction, product of film thickness, hereinafter referred to as creep moment).
  • the polarizing plate preferably has a smaller curl and a more flat shape in order to prevent deterioration in display performance due to air bubble mixing when pasted to the liquid crystal cell.
  • the polarizing plate curl may touch the negative side due to variations in the A1 and A2 films that each protective film may have.
  • A1 / A2 is preferably suppressed to 3.5 or less. Therefore, in the present invention, A1 / A2 is 1.1 to 3.5. A1 / A2 is more preferably 1.1 to 2.3, and particularly preferably 1.3 to 2.3. A1 / A2 can be adjusted to 1.1 to 3.5 by changing the draw ratio and film thickness of the first and second protective films and adjusting the composition.
  • the creep moment A2 of the second protective film is preferably 0 to 40, more preferably 0 to 34, and still more preferably 0 to 20.
  • the polarizing plate of the present invention is preferably arranged with the second protective film as the inner film, and by making A2 in the above range, the deformation of the inner film due to the polarizer contraction force can be reduced, and the deformation can be reduced. The accompanying phase difference change can be reduced, the optical compensation of the inner film is easily performed, and light leakage is hardly generated in black display.
  • the creep amount in the direction parallel to the absorption axis of the polarizer of the first protective film is preferably 0.0 to 4% from the viewpoint of work stability during processing of the polarizing plate, and preferably 0.01 to 2 % Is more preferable, and 0.02 to 1% is still more preferable.
  • the creep amount in the direction parallel to the absorption axis of the polarizer of the second protective film is preferably 0.05 to 4% from the viewpoint of both work stability during polarizing plate processing and optical characteristics. 10 to 2% is more preferable, and 0.15 to 1% is still more preferable.
  • the amount of creep was 10 mm wide slits, and the film was pulled with a tension of 20 N / 10 mm in the tensile mode of the tensile tester. After the tension reached 20 N, the amount of deformation for 10 minutes (creep amount (%)) was obtained by reading.
  • the elastic modulus in the direction parallel to the absorption axis of the polarizer of the first and second protective films is not particularly limited, but is preferably 2 GPa or more and 8 GPa or less, more preferably 2.2 GPa or more and 6 GPa or less, More preferably, it is 2.3 GPa or more and 6 GPa or less.
  • the elastic modulus of the film depends on the type and amount of resin of the protective film material, the selection of additives (particularly, the particle size, refractive index, and amount of addition of the matting agent particles), and further the film production conditions (stretch ratio, etc.) Can be adjusted.
  • the elastic modulus is 200 mm in length in the measuring direction and 10 mm in width.
  • the sample shape was measured using the Toyo Seiki Strograph V10-C. was measured with a width of 10 mm and a length between chucks of 100 mm.
  • a polarizer Even if it is a case where any one or both of a polarizer, a 1st protective film, and a 2nd protective film is stuck, it can take out and measure a film single-piece
  • a method of taking out the single film for example, it is possible to measure the elastic modulus of the single film by immersing it in warm water or the like to soften and remove the polyvinyl alcohol as the polarizer, or by removing it.
  • the thickness of the first and second protective films is preferably 10 ⁇ m to 100 ⁇ m, more preferably 15 ⁇ m to 80 ⁇ m, still more preferably 25 ⁇ m to 60 ⁇ m, and particularly preferably 35 ⁇ m to 50 ⁇ m.
  • the film thickness of a 1st and 2nd protective film can be measured with a commercially available film thickness meter.
  • the material which comprises the 1st and 2nd protective film is not specifically limited.
  • the first and second protective films preferably contain a resin.
  • a resin a known resin can be used, and is not particularly limited as long as it does not contradict the gist of the present invention, but cellulose acylate. Examples thereof include resins, (meth) acrylic resins, cycloolefin resins, and polyester resins.
  • a 2nd protective film it is preferable to use a cycloolefin resin from a viewpoint that the gap
  • the degree of substitution of cellulose acylate means the ratio of acylation of three hydroxyl groups present in the structural unit of cellulose (glucose having a ( ⁇ ) 1,4-glycoside bond).
  • the degree of substitution can be calculated by measuring the amount of bound fatty acid per unit mass of cellulose.
  • the degree of substitution of the cellulose body is determined by dissolving the cellulose body in a solvent such as dimethyl sulfoxide substituted with deuterium and measuring a 13 C-NMR (nuclear magnetic resonance) spectrum, and measuring the carbonyl carbon in the acyl group.
  • the total acyl substitution degree of the cellulose acylate is preferably 2.0 to 2.97, more preferably 2.2 to 2.95, and particularly preferably 2.3 to 2.95.
  • As the acyl group of cellulose acylate an acetyl group, a propionyl group, and a butyryl group are particularly preferable, and an acetyl group is particularly preferable.
  • a mixed fatty acid ester composed of two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the present invention.
  • the acyl group is preferably an acetyl group and an acyl group having 3 to 4 carbon atoms.
  • the substitution degree of an acetyl group is preferably less than 2.5, and more preferably less than 1.9.
  • the substitution degree of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, and 0.5 to 1.1. It is particularly preferred.
  • two types of cellulose acylates having different substituents and / or degree of substitution may be used in combination, mixed, or a film comprising a plurality of layers composed of different cellulose acylates by a co-casting method or the like. May be formed.
  • mixed acid esters having a fatty acyl group and a substituted or unsubstituted aromatic acyl group described in [0023] to [0038] of JP-A-2008-20896 can also be preferably used in the present invention.
  • the cellulose acylate preferably has a mass average degree of polymerization of 250 to 800, more preferably 300 to 600.
  • the cellulose acylate preferably has a number average molecular weight of 70000 to 230,000, more preferably a number average molecular weight of 75000 to 230,000, and most preferably a number average molecular weight of 78000 to 120,000.
  • Cellulose acylate can be synthesized using an acid anhydride or acid chloride as an acylating agent.
  • an organic acid for example, acetic acid
  • methylene chloride is used as a reaction solvent.
  • a protic catalyst such as sulfuric acid can be used as the catalyst.
  • the acylating agent is an acid chloride
  • a basic compound can be used as a catalyst.
  • cellulose is an organic acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, butyric acid) or acid anhydrides thereof (acetic anhydride, propionic anhydride, butyric anhydride).
  • a cellulose ester is synthesized by esterification with a mixed organic acid component containing.
  • cellulose such as cotton linter and wood pulp is activated with an organic acid such as acetic acid, and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst.
  • the organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in the cellulose.
  • a hydrolysis reaction depolymerization reaction
  • the cellulose main chain ⁇
  • 1,4-glycoside bond proceeds in addition to the esterification reaction.
  • the reaction conditions such as the reaction temperature are preferably determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.
  • (Meth) acrylic resin is a concept that includes both methacrylic resin and acrylic resin, and is an acrylate / methacrylate derivative, particularly an acrylate ester / methacrylate ester (co) polymer. Is also included. Furthermore, the (meth) acrylic resin includes, in addition to the methacrylic resin and acrylic resin, a (meth) acrylic polymer having a ring structure in the main chain, a polymer having a lactone ring, and a succinic anhydride ring. A maleic anhydride-based polymer having, a polymer having a glutaric anhydride ring, and a glutarimide ring-containing polymer.
  • the repeating structural unit of the (meth) acrylic polymer is not particularly limited.
  • the (meth) acrylic polymer preferably has a repeating structural unit derived from a (meth) acrylic acid ester monomer as a repeating structural unit.
  • the (meth) acrylic acid ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate.
  • Acrylic acid esters; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate; These may be used alone or in combination of two or more.
  • the content ratio in the monomer component to be subjected to the polymerization step is preferably 50 to 100% by mass in order to sufficiently exhibit the effects of the present invention.
  • the amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
  • the glass transition temperature Tg of the resin mainly composed of the (meth) acrylic acid ester is preferably in the range of 80 to 120 ° C.
  • the weight average molecular weight of the resin mainly composed of the (meth) acrylic acid ester is preferably in the range of 50,000 to 500,000.
  • rubber elastic particles are preferably blended with the (meth) acrylic resin.
  • the rubber elastic particle is a particle containing a rubber elastic body, and may be a particle made of only a rubber elastic body, or may be a multi-layered particle having a rubber elastic body layer, and may be a film surface. From the viewpoint of hardness, light resistance and transparency, an acrylic elastic polymer is preferably used.
  • Rubber elastic particles containing an acrylic elastic polymer can be obtained with reference to JP 2012-180422 A, JP 2012-032773 A, and JP 2012-180423 A.
  • the number average particle diameter of the rubber elastic particles is preferably in the range of 10 to 300 nm, more preferably in the range of 50 to 250 nm.
  • the (meth) acrylic resin composition forming the (meth) acrylic resin film 25 to 45% by mass of rubber elastic particles having a number average particle diameter of 10 to 300 nm are blended in a transparent acrylic resin. preferable.
  • (meth) acrylic polymers those having a ring structure in the main chain are preferred.
  • the rigidity of the main chain can be improved and the heat resistance can be improved.
  • (meth) acrylic polymers having a ring structure in the main chain a polymer having a lactone ring structure in the main chain, a maleic anhydride polymer having a succinic anhydride ring in the main chain, and an anhydride in the main chain
  • a polymer having a lactone ring structure in the main chain and a polymer having a glutarimide ring structure in the main chain are more preferable.
  • the following polymers having a ring structure in these main chains will be described in order.
  • R 101 , R 102 and R 103 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain an oxygen atom.
  • the organic residue having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like.
  • the content of the lactone ring structure represented by the general formula (100) in the structure of the lactone ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60% by mass. %, Particularly preferably 10 to 50% by weight.
  • the lactone cyclization rate can be determined by removing the theoretical weight loss from 150 ° C. before the weight reduction starts to 300 ° C. before the polymer decomposition starts. It can be calculated from the weight loss heating weight loss rate due to the alcohol reaction.
  • the method for producing the (meth) acrylic resin having a lactone ring structure is not particularly limited.
  • the (meth) acrylic resin having a lactone ring structure is obtained by polymerizing the following predetermined monomer to obtain a polymer (p) having a hydroxyl group and an ester group in the molecular chain.
  • the obtained polymer (p) is heat-treated at a temperature in the range of 75 ° C. to 120 ° C. to perform lactone cyclization condensation for introducing a lactone ring structure into the polymer.
  • a polymer having a hydroxyl group and an ester group in the molecular chain is obtained by performing a polymerization reaction of a monomer component containing a monomer represented by the following general formula (101).
  • R 1a and R 2a each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • Examples of the monomer represented by the general formula (101) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- ( Hydroxymethyl) normal butyl acrylate, t-butyl 2- (hydroxymethyl) acrylate, and the like. Among these, 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. As for the monomer represented by the general formula (101), only one type may be used, or two or more types may be used in combination.
  • the content ratio of the monomer represented by the general formula (101) in the monomer component used in the polymerization step has a lower limit value in a preferable range in terms of heat resistance, solvent resistance, and surface hardness, and was obtained. From the viewpoint of molding processability of the polymer, there is an upper limit value of a preferable range. In view of these viewpoints, it is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 10 to 60% by mass, and particularly preferably. Is 10 to 50% by mass.
  • the monomer component provided in the polymerization step may contain a monomer other than the monomer represented by the general formula (101).
  • a monomer is not particularly limited.
  • (meth) acrylic acid ester, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer represented by the following general formula (102) are preferable. It is done. Only one type of monomer other than the monomer represented by formula (101) may be used, or two or more types may be used in combination.
  • the weight average molecular weight of the lactone ring-containing polymer is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and particularly preferably 50,000 to 500,000.
  • the lactone ring-containing polymer has a mass reduction rate in the range of 150 to 300 ° C. in dynamic TG measurement, preferably 1% or less, more preferably 0.5% or less, and still more preferably 0.3% or less. It is good.
  • a method for measuring dynamic TG the method described in JP-A-2002-138106 can be used.
  • the lactone ring-containing polymer Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, there is little dealcoholization reaction in the production process of the molded product, and bubbles and silver stripes (silver streak) are formed in the molded product after molding due to the alcohol. The disadvantage of entering can be avoided. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to a high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has high heat resistance.
  • the coloration degree (YI) is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less. . If the degree of coloring (YI) is 6 or less, problems such as loss of transparency due to coloring are unlikely to occur, and therefore, it can be preferably used in the present invention.
  • the lactone ring-containing polymer has a 5% mass reduction temperature in thermal mass spectrometry (TG) of preferably 330 ° C. or higher, more preferably 350 ° C. or higher, and still more preferably 360 ° C. or higher.
  • TG thermal mass spectrometry
  • the 5% mass reduction temperature in thermal mass spectrometry (TG) is an indicator of thermal stability, and by setting it to 330 ° C. or higher, sufficient thermal stability tends to be exhibited.
  • the thermal mass spectrometry can use the apparatus for measuring the dynamic TG.
  • the glass transition temperature (Tg) of the lactone ring-containing polymer is preferably 115 ° C to 180 ° C, more preferably 120 ° C to 170 ° C, and still more preferably 125 ° C to 160 ° C.
  • (2-2) Maleic anhydride polymer having a succinic anhydride ring in the main chain By forming a succinic anhydride structure in the main chain in the molecular chain of the polymer (in the main skeleton of the polymer), High heat resistance is imparted to the (meth) acrylic resin that is a polymer, and the glass transition temperature (Tg) is also high, which is preferable.
  • the glass transition temperature (Tg) of the maleic anhydride polymer having a succinic anhydride ring in the main chain is preferably 110 ° C. to 160 ° C., more preferably 115 ° C. to 160 ° C., still more preferably 120 ° C. to 160 ° C. is there.
  • the weight average molecular weight of the maleic anhydride polymer having a succinic anhydride ring in the main chain is preferably in the range of 50,000 to 500,000.
  • the maleic anhydride unit used for the copolymerization with the (meth) acrylic resin is not particularly limited, but JP-A-2008-216586, JP-A-2009-052021, JP-A-2009-196151, Mention may be made of maleic acid-modified resins described in Tables 2012-504783. In addition, these do not limit this invention.
  • As a commercially available maleic acid-modified resin Delpet 980N manufactured by Asahi Kasei Chemicals Corporation, which is a maleic acid-modified MAS resin (methyl methacrylate-acrylonitrile-styrene copolymer), can be preferably used.
  • the method for producing the (meth) acrylic resin containing maleic anhydride units is not particularly limited, and a known method can be used.
  • polymer having a glutaric anhydride ring structure in the main chain is a polymer having a glutaric anhydride unit.
  • the polymer having a glutaric anhydride unit preferably has a glutaric anhydride unit represented by the following general formula (300) (hereinafter referred to as a glutaric anhydride unit).
  • R 31 and R 32 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • R 31 and R 32 particularly preferably represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
  • the polymer having a glutaric anhydride unit is preferably a (meth) acrylic polymer containing a glutaric anhydride unit.
  • the (meth) acrylic polymer preferably has a glass transition temperature (Tg) of 120 ° C. or higher from the viewpoint of heat resistance.
  • the glass transition temperature (Tg) of the polymer having a glutaric anhydride ring structure in the main chain is preferably 110 ° C. to 160 ° C., more preferably 115 ° C. to 160 ° C., and still more preferably 120 ° C. to 160 ° C.
  • the weight average molecular weight of the polymer having a glutaric anhydride ring structure in the main chain is preferably in the range of 50,000 to 500,000.
  • the content of glutaric anhydride units relative to the (meth) acrylic polymer is preferably 5 to 50% by mass, more preferably 10 to 45% by mass.
  • the content is preferably 5 to 50% by mass, more preferably 10 to 45% by mass.
  • glutarimide resin acrylic polymer having glutarimide ring structure in main chain
  • the (meth) acrylic polymer having a glutarimide ring structure in the main chain is at least the following general formula (400):
  • R 301 , R 302 and R 303 are independently hydrogen or an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and an aryl group. It is preferable to contain a glutarimide resin having 20% by mass or more).
  • R 301 and R 302 are hydrogen or a methyl group
  • R 303 is a methyl group or a cyclohexyl group.
  • the glutarimide unit may be a single type or may include a plurality of types in which R 301 , R 302 , and R 303 are different.
  • Cycloolefin resin As the thermoplastic resin that can be used in the present invention, a cycloolefin resin (hereinafter also referred to as a cyclic polyolefin resin) can be used.
  • the cyclic polyolefin resin represents a polymer resin having a cyclic olefin structure.
  • the cyclic polyolefin resins preferably used in the present invention are listed below.
  • a cyclic polyolefin resin which is an addition (co) polymer containing at least one repeating unit represented by the following general formula (II) and, if necessary, a general A cyclic polyolefin resin which is an addition (co) polymer further comprising at least one repeating unit represented by formula (I).
  • a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III) can also be suitably used.
  • m represents an integer of 0 to 4.
  • R 1 to R 6 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • X 1 to X 3 , Y 1 to Y 3 are hydrogen atoms, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, or a halogen atom.
  • Substituted hydrocarbon group having 1 to 10 carbon atoms — (CH 2 ) nCOOR 11 , — (CH 2 ) nOCOR 12 , — (CH 2 ) nNCO, — (CH 2 ) nNO 2 , — (CH 2 ) nCN , — (CH 2 ) nCONR 13 R 14 , — (CH 2 ) nNR 13 R 14 , — (CH 2 ) nOZ, — (CH 2 ) nW, or X 1 and Y 1 or X 2 and Y 2 or X 3 And (—CO) 2 O, (—CO) 2 NR 15 composed of Y 3 .
  • R 11 , R 12 , R 13 , R 14 , and R 15 are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, Z is a hydrocarbon group or a hydrocarbon group substituted with halogen, and W is SiR 16 pD.
  • 3- p R 16 is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR 16 or —OR 16 , p is an integer of 0 to 3), and n is an integer of 0 to 10 .
  • Norbornene polymer hydrides can also be preferably used. JP-A-1-240517, JP-A-7-196636, JP-A-60-26024, JP-A-62-19801, JP-A-2003-1159767. As disclosed in Japanese Patent Application Laid-Open No. 2004-309979 or the like, the polycyclic unsaturated compound is hydrogenated after addition polymerization or metathesis ring-opening polymerization.
  • R 5 to R 6 are preferably a hydrogen atom or —CH 3
  • X 3 and Y 3 are preferably a hydrogen atom, Cl, —COOCH 3 , and other groups are appropriately selected.
  • This norbornene-based resin is sold under the trade name Arton G or Arton F by JSR Corporation, and from Zeon Corporation, Zeonor ZF14, ZF16, Zeonex 250 or Zeonex. They are commercially available under the trade name 280 and can be used.
  • norbornene-based addition (co) polymers can also be preferably used, and are disclosed in JP-A No. 10-7732, JP-T 2002-504184, US Published Patent No. 200429129157A1 or WO 2004 / 070463A1. It can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds.
  • Tg glass transition temperatures
  • APL8008T Tg70 ° C
  • APL6013T Tg125 ° C
  • APL6015T Grades such as Tg145 ° C
  • Pellets such as TOPAS 8007, 6013, and 6015 are sold by Polyplastics Co., Ltd. Further, Appear 3000 is sold by Ferrania.
  • the glass transition temperature (Tg) of the cyclic polyolefin resin is preferably 110 ° C. to 200 ° C., more preferably 115 ° C. to 190 ° C., and further preferably 120 ° C. to 180 ° C. Further, the weight average molecular weight of the cyclic polyolefin resin is preferably in the range of 50,000 to 500,000.
  • the 1st and 2nd protective film may contain the well-known additive used for an organic acid and another polarizing plate protective film, unless it is contrary to the meaning of this invention.
  • the molecular weight of the additive is not particularly limited, but the additives described below can be preferably used. Additives show useful effects in terms of film modification such as improvement of thermal properties, optical properties, mechanical properties, imparting flexibility, imparting water absorption resistance, reducing moisture permeability, etc. .
  • control of mechanical properties includes the addition of a plasticizer to a film.
  • plasticizers that can be used as reference include various known esters such as phosphate esters, citrate esters, trimellitic acid esters, and sugar esters. Reference can be made to the description of ester plasticizers and polyester polymers in paragraph numbers 0042 to 0068 of International Publication No. 2011/102492.
  • the description of paragraph numbers 0069 to 0072 of International Publication No. 2011/102492 can be referred to, and adjustment of the retardation of the film
  • a known retardation adjusting agent can be used for controlling expression. This can help control the rate of change in humidity.
  • the molecular weight of the additive is not particularly limited, but the additives described below can be preferably used.
  • the first and second protective films may contain one or more arbitrary appropriate additives in addition to the above materials.
  • additives include ultraviolet absorbers, antioxidants, lubricants, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents.
  • the content of the thermoplastic resin in the second protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, still more preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. %. When the content of the thermoplastic resin in the second protective film is 50% by mass or more, high transparency and the like inherent in the thermoplastic resin can be sufficiently expressed, which is preferable.
  • first and second protective films contain a cellulose acylate resin
  • the film is preferably produced by a solvent cast method.
  • U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704, 2,739,069 and 2,739,070, British Patent Nos. 640731 and 736892 Reference can also be made to JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, 60-203430, and 62-1115035.
  • the cellulose acylate film may be subjected to a stretching treatment.
  • a stretching treatment refer to, for example, JP-A-62-115035, JP-A-4-152125, 4-284221, 4-298310, and 11-48271. can do.
  • a film material is pre-blended with a conventionally known mixer such as an omni mixer. After that, the obtained mixture is extrusion kneaded.
  • the mixer used for extrusion kneading is not particularly limited.
  • a conventionally known mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader can be used. .
  • the film forming method examples include conventionally known film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. Of these film forming methods, the melt extrusion method is particularly suitable.
  • melt extrusion method examples include a T-die method and an inflation method, and the molding temperature at that time may be appropriately adjusted according to the glass transition temperature of the film raw material, and is not particularly limited.
  • the temperature is preferably 150 ° C to 350 ° C, more preferably 200 ° C to 300 ° C.
  • a roll-shaped film can be obtained by attaching a T-die to the tip of a known single-screw extruder or twin-screw extruder and winding the film extruded into a film. it can. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the take-up roll and adding stretching in the extrusion direction. Further, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.
  • the film having a cyclic olefin-based resin as a main component it can be manufactured by the same manufacturing method as the above-described method for manufacturing a film having a (meth) acrylic polymer as a main component,
  • a film having a (meth) acrylic polymer as a main component For example, conventionally known film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendering method, and a compression molding method can be mentioned, and among them, the melt extrusion method is particularly suitable.
  • melt extrusion method examples include a T-die method and an inflation method, and the molding temperature at that time may be appropriately adjusted according to the glass transition temperature of the film raw material.
  • T-die method When forming a film by the T-die method, a roll-shaped film can be obtained by attaching a T-die to the tip of a known single-screw extruder or twin-screw extruder and winding the film extruded into a film. it can. At this time, it is possible to perform uniaxial stretching by appropriately adjusting the temperature of the take-up roll and adding stretching in the extrusion direction. Further, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.
  • a polarizer As a polarizer, what was manufactured by the conventionally well-known method can be used, and a polyvinyl alcohol-type polarizer is preferable.
  • a film made of a hydrophilic polymer such as polyvinyl alcohol or ethylene-modified polyvinyl alcohol having an ethylene unit content of 1 to 4 mol%, a polymerization degree of 2000 to 4000, and a saponification degree of 99.0 to 99.99 mol%
  • a film stretched by treatment with a dichroic dye such as the above, or a film oriented by treating a plastic film such as vinyl chloride is used.
  • Patent No. 5048120, Patent No. 5143918, Patent No. 5048120 No. 4, Patent No. 4691205, Patent No. 4751481 and Patent No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used for the polarizing plate of the present invention.
  • the thickness of the polarizer is not particularly limited, but is preferably 5 ⁇ m or more and 30 ⁇ m or less, and more preferably 10 ⁇ m or more and 20 ⁇ m or less from the viewpoint of the degree of polarization and warpage. If the film thickness of a polarizer is 30 micrometers or less, since the contraction force of a polarizer does not increase and the curvature of the liquid crystal panel which bonded this does not become large, it is preferable. On the other hand, if the thickness of the polarizer is 5 ⁇ m or more, it is preferable because the light of one polarized light passing through the polarizer can be sufficiently absorbed and the degree of polarization does not decrease.
  • the polarizing plate of the present invention has a structure in which a polarizer is sandwiched between a first protective film and a second protective film via an actinic radiation curable adhesive layer.
  • the actinic radiation curable adhesive constituting the actinic radiation curable adhesive layer will be described.
  • An embodiment in which the adhesive is changed to a cured product of an adhesive having a different structure by a curing reaction is also included in an embodiment in which the active ray curable adhesive layer includes an adhesive.
  • the present invention includes a case where the adhesive cured by the active radiation is completely cured in the actinic radiation curable adhesive layer and changed into a cured product of an adhesive having a different structure.
  • cationically polymerizable compounds such as epoxy compounds, more specifically, epoxy compounds that do not have an aromatic ring in the molecule as described in JP-A-2004-245925
  • an actinic radiation curable adhesive that contains selenium as one of the actinic radiation curable components.
  • an epoxy compound is, for example, a hydrogenated epoxy obtained by nuclear hydrogenation of an aromatic polyhydroxy compound, which is a raw material of an aromatic epoxy compound represented by diglycidyl ether of bisphenol A, and converting it to glycidyl ether.
  • the compound an alicyclic epoxy compound having at least one epoxy group bonded to the alicyclic ring in the molecule, an aliphatic epoxy compound typified by a glycidyl ether of an aliphatic polyhydroxy compound, and the like.
  • a cationic photopolymerization initiator for initiating polymerization of the compound is blended.
  • a thermal cationic polymerization initiator that initiates polymerization by heating, and other additives such as a photosensitizer may be blended.
  • the composition of the adhesive applied to each protective film may be the same or different, but from the viewpoint of productivity, moderate adhesive strength Therefore, it is preferable to use an adhesive having the same composition on both sides.
  • the polarizing plate of the present invention is a film at the time of manufacturing the absorption axis of the polarizer and the polarizing plate protective film (first protective film and second protective film) from the viewpoint of roll-to-roll production suitability. It is preferable that the layers are stacked so that a direction (TD (Transverse Direction) direction) orthogonal to the transport direction is substantially orthogonal.
  • TD Transverse Direction
  • substantially orthogonal means that the angle formed by the absorption axis of the polarizer and the TD direction of the polarizing plate protective film is 85 ° to 95 °, preferably 89 ° to 91 °. If the deviation from the right angle is within 5 ° (preferably within 1 °), the polarization degree performance under the polarizing plate crossed Nicol is unlikely to deteriorate, and light leakage is not likely to occur.
  • the actinic radiation curable adhesive layer may be formed by a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating and the like.
  • a coating method there is a description example in “Coating method” published by Yoji Harasaki in 1979.
  • the first protective film and the second protective film may be subjected to surface treatment such as saponification treatment, corona treatment, and plasma treatment in advance.
  • the polarizing plate of this invention has an adhesive layer on the surface on the opposite side to the polarizer of a 2nd protective film.
  • the polarizing plate of this invention can be bonded together to a liquid crystal cell through an adhesive layer. That is, the second protective film of the polarizing plate of the present invention is an inner film disposed on the liquid crystal cell side.
  • the first protective film is an outer film.
  • an appropriate pressure-sensitive adhesive can be used, and the type thereof is not particularly limited.
  • Adhesives include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, Examples thereof include cellulose-based pressure-sensitive adhesives.
  • the attachment of the pressure-sensitive adhesive layer to the polarizing plate can be performed by an appropriate method.
  • a pressure-sensitive adhesive solution of about 10 to 40% by mass in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a suitable solvent alone or a mixture such as toluene and ethyl acetate is prepared.
  • An adhesive layer is formed on the separator in accordance with the above-described method of directly attaching it on the polarizing plate or optical member by an appropriate development method such as a casting method or a coating method, and transferring it onto the polarizing plate.
  • the method of wearing is mentioned.
  • the polarizing plate having the pressure-sensitive adhesive layer on the surface opposite to the surface on which the second protective film is bonded to the polarizer is preferably bonded to the liquid crystal cell described later via the pressure-sensitive adhesive layer. .
  • the polarizing plate of the present invention can be produced by laminating a polarizer and first and second protective films via an actinic radiation curable adhesive layer.
  • the bonding surfaces of the first and second protective films are preferably subjected to an alkali saponification treatment before the actinic radiation curable adhesive layer is provided.
  • the polarizing plate protective film (the first protective film and the second protective film) is subjected to alkali saponification treatment to provide adhesion with a polarizer material such as polyvinyl alcohol, and used as a polarizing plate protective film. Can do. Regarding the saponification method, the methods described in JP02-86748, [0211] and [0212] can be used.
  • the alkali saponification treatment for the polarizing plate protective film is preferably performed in a cycle of immersing the film surface in an alkaline solution, neutralizing with an acidic solution, washing with water and drying.
  • the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the concentration of hydroxide ions is preferably in the range of 0.1 to 5.0 mol / L, and preferably 0.5 to 4.0 mol / L. More preferably, it is in the range of L.
  • the alkaline solution temperature is preferably in the range of room temperature to 90 ° C, and more preferably in the range of 40 to 70 ° C.
  • the method for producing a polarizing plate of the present invention comprises a step of bonding a first protective film to one surface of a polarizer having polarizing performance via an active ray curable adhesive layer, and the other surface of the polarizer. It includes a step of bonding the second protective film via the actinic radiation curable adhesive layer.
  • a step of bonding a first protective film to one surface of the polarizer via an active ray curable adhesive layer, and a second protection to the other surface of the polarizer via an active ray curable adhesive layer may bond simultaneously, or may bond sequentially.
  • the step of bonding the first protective film to one surface of the polarizer via an active ray curable adhesive layer and the step of attaching the first protective film to the other surface of the polarizer via the active ray curable adhesive layer. It is preferable to simultaneously perform the step of bonding the second protective film, and it is more preferable to simultaneously perform the step of bonding both using a roll-to-roll method.
  • an apparatus and a method described in JP2012-203108A can be used, and a method described in JP2012-203108A can be used.
  • the contents are incorporated into the present invention.
  • the manufacturing apparatus described in Japanese Patent Application Laid-Open No. 2012-203108 while continuously transporting a polarizer, a first protective film is bonded to one surface, and a second protective film is formed to the other surface.
  • a polarizing plate which is wound around a winding roll.
  • a protective film is bonded to both sides of the polarizer.
  • a polarizing plate In the manufacturing method of a polarizing plate, it is preferable to produce by the method of corona-treating a polarizing plate protective film and bonding together on both surfaces of a polarizer using an adhesive agent.
  • the center portion refers to a region having a radius of 10 mm centered on the intersection and the center of a perpendicular that bisects the long side of the polarizing plate and a perpendicular that bisects the short side.
  • the edge part of a polarizing plate does not contact a flat plate.
  • the end refers to a region 5 mm from the long side end and the short side end of the polarizing plate.
  • the polarizing plate of the present invention cut out to 940 mm in the MD direction and 530 mm in the TD direction is placed on the flat plate with the second protective film surface side placed on the flat plate side, the end of the polarizing plate is More preferably, it does not contact the flat plate. This indicates that the polarizing plate is positive curled.
  • the distance between the long side end of the polarizing plate and the flat plate and the distance between the short side end and the flat plate are preferably 0 mm or more and less than 10 mm.
  • the distance between the long side end of the polarizing plate and the flat plate, and the distance between the short side end and the flat plate represent the curl amount.
  • the distance between the long side end of the polarizing plate and the flat plate, and the distance between the short side end and the flat plate are more preferably 0 mm or more and less than 7 mm, and still more preferably 0 mm or more and less than 3 mm.
  • the liquid crystal display device of the present invention is a liquid crystal display device having a liquid crystal cell and two polarizing plates arranged on both sides of the liquid crystal cell, and at least one of the polarizing plates is a polarizing plate of the present invention. It is a board.
  • the polarizing plate of the present invention is preferably arranged so that the second protective film is closer to the liquid crystal cell than the first protective film. As for other configurations, any configuration of a known liquid crystal display device can be adopted.
  • the mode of the liquid crystal cell is not particularly limited, and a TN (Twisted Nematic) mode type liquid crystal cell, a lateral electric field switching IPS (In-Plane Switching) mode type liquid crystal cell, a FLC (Ferroelectric Liquid Crystal) mode type liquid crystal cell, AFLC (Anti-ferroelectric Liquid Crystal) mode type liquid crystal cell, OCB (Optically Compensatory Bend) mode type liquid crystal cell, STN (Super Twisted Nematic) mode type liquid crystal cell, VA (Vertical mode liquid crystal cell)
  • Various display modes such as (Hybrid Aligned Nematic) mode type liquid crystal cell
  • the liquid crystal display device can be configured.
  • the liquid crystal display device of the present invention is preferably a liquid crystal display device in which the liquid crystal cell is a transverse electric field switching IPS mode type liquid crystal cell.
  • a dope 1 for an intermediate layer (core layer) having the following composition was prepared.
  • ⁇ Composition of Dope 1 ⁇ Cellulose acetate (degree of acetylation 2.86 number average molecular weight 72000) 100 parts by mass Methylene chloride (first solvent) 289 parts by mass Methanol (second solvent) 75 parts by mass 1-butanol (third solvent) 7 parts by mass-Triphenyl phosphate 4.3 parts by mass-Biphenyl diphenyl phosphate 2.2 parts by mass-Compound 1 0.93 parts by mass-Compound 2 0.23 parts by mass
  • a support layer dope 2 having the following composition was prepared.
  • ⁇ Composition of Dope 2 ⁇ Cellulose acetate (degree of acetylation 2.86, number average molecular weight 72000) 100 parts by mass Methylene chloride (first solvent) 351 parts by mass Methanol (second solvent) 91 parts by mass 1-butanol (third solvent) 3 parts by mass-Triphenyl phosphate 4.3 parts by mass-Biphenyl diphenyl phosphate 2.2 parts by mass-Compound 1 0.93 parts by mass-Compound 2 0.23 parts by mass-Matting agent (silicon dioxide (particle size 20 nm) 0.033 parts by mass
  • a layer formed from the mainstream is referred to as a core layer
  • a support surface side layer is referred to as a support layer
  • an opposite surface is referred to as an air layer.
  • the dope liquid supply flow path three flow paths for the core layer, the support layer, and the air layer were used.
  • the cast dope film was dried by applying a dry air of 34 ° C. at 230 m 3 / min on the drum and peeled off from the drum. During peeling, the film was stretched at a stretching ratio of 118% in the MD direction (conveyance direction, longitudinal direction). Thereafter, the film was conveyed while being gripped by a pin tenter (a pin tenter described in FIG.
  • ⁇ Films 1-4 to 1-6> (Preparation of core layer cellulose acylate dope (dope 4)) The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution.
  • ⁇ Composition of Dope 4 ⁇ ⁇ Acetyl substitution degree 2.88 Weight average molecular weight 260000 cellulose acetate 100 parts by mass ⁇ Phthalate ester oligomer A 10 parts by mass ⁇
  • Compound (A-1) 4 parts by mass ⁇
  • Ultraviolet absorber 1 compound of the following structural formula, BASF 2.7 parts by mass TINUVIN123 (HA-1, manufactured by BASF) 0.18 parts by mass Teclin DO (N-alkenylpropylenediaminetriacetic acid, manufactured by Nagase ChemteX Corporation) 0.02 parts by mass Methylene chloride (first solvent) 430 parts by mass Methanol (second solvent) 64 parts by mass ⁇ -
  • UV absorber 1 UV absorber 1
  • R 101 is a hydrogen atom
  • R 102 and R 103 are methyl groups.
  • ⁇ Composition of cellulose ester solution (dope 6) for air layer ⁇ -Cellulose ester (acetyl substitution degree 2.86) 100 parts by mass-Sugar ester compound of formula (eI) 3 parts by mass-Sugar ester compound of formula (eII) 1 part by mass-Ultraviolet absorber 2 2.4 parts by mass-Silica Particle dispersion (average particle size 20 nm) “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. 0.078 parts by mass • Methylene chloride 339 parts by mass • Methanol 74 parts by mass • Butanol 3 parts by mass ⁇ ⁇
  • UV absorber 2 UV absorber 2
  • ⁇ Composition of cellulose ester solution (dope 7) for drum layer ⁇ -Cellulose ester (acetyl substitution degree 2.86) 100 parts by mass-Sugar ester compound of formula (eI) 3 parts by mass-Sugar ester compound of formula (eII) 1 part by mass-Ultraviolet absorber 2 2.4 parts by mass-Silica Particle dispersion (average particle size 20 nm) “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. 0.091 parts by mass • Methylene chloride 339 parts by mass • Methanol 74 parts by mass • Butanol 3 parts by mass ⁇ ⁇
  • the cellulose ester web held by the pin tenter was conveyed to the drying zone.
  • a drying air of 45 ° C. was blown and then dried at 110 ° C. for 5 minutes.
  • the cellulose ester web was conveyed in the TD direction while stretching at a magnification of 109%.
  • the portion held by the pin tenter was continuously cut out and dried at 145 ° C. for 10 minutes while applying a 210 N tension in the conveying direction.
  • a film 1-9 having a film thickness of 60 ⁇ m is formed by continuously cutting the end portions in the width direction so that the web has a desired width, and providing unevenness with a width of 15 mm and a height of 10 ⁇ m at both ends in the width direction of the web.
  • the film 1 having a film thickness of 40 ⁇ m was formed in the same manner as the film 1-9 except that the MD direction stretching when peeling the film from the drum was 111% and the stretching in the TD direction when transporting the drying zone was 107%. 10 was produced.
  • composition of dope (dope 9) for air layer and casting support side layer ⁇ -Cellulose ester (acetyl substitution degree 2.86) 100 parts by mass-Triphenyl phosphate 9.9 parts by mass-Biphenyl diphenyl phosphate 5.5 parts by mass-Ultraviolet absorber 2 2.4 parts by mass-Silica particle dispersion ( Matting agent, average particle size 20 nm) “AEROSIL R972”, manufactured by Nippon Aerosil Co., Ltd. 0.078 parts by mass • Methylene chloride 339 parts by mass • Methanol 74 parts by mass • Butanol 3 parts by mass ⁇ ⁇
  • Co-casting film formation drum film formation method
  • a casting die an apparatus equipped with a feed block adjusted for co-casting so that a film having a three-layer structure can be formed was used.
  • the layer formed from the main stream is referred to as an intermediate layer
  • the layer on the casting support surface side is referred to as a casting support side layer
  • the opposite surface is referred to as an air layer.
  • the air layer dope 9, the intermediate layer dope 10, and the casting support side layer dope 9 were co-cast from a casting port onto a drum cooled to -7 ° C.
  • the dope was cast on a mirror surface stainless steel support which is a drum having a diameter of 3 m.
  • the cast film was subjected to 34 ° C. drying air at 270 m 3 / min on a drum.
  • the cellulose ester film cast and rotated 50 cm before the end point of the casting part was peeled off from the drum, and then both ends were held with a pin tenter. At the time of peeling, 104% stretching was performed in the longitudinal direction (MD direction / transport direction).
  • the cellulose ester film held by the pin tenter was conveyed to the drying zone. In the initial drying, a drying air of 45 ° C. was blown and then dried at 110 ° C. for 5 minutes. At this time, the cellulose ester film was conveyed while being widened to 120% in the width direction. After the cellulose ester film was detached from the pin tenter, the portion held by the pin tenter was continuously cut out. The width of the cellulose ester film at this time was 1610 mm. The film was dried at 145 ° C. for 10 minutes while applying a tension of 130 N in the conveying direction.
  • the end portion in the width direction is continuously cut so that the cellulose ester film has a desired width, and a knurling having a width of 15 mm and a height of 10 ⁇ m is attached to both ends in the width direction to produce a film 1-11 having a thickness of 56 ⁇ m. did.
  • Preparation of cellulose acylate film ⁇ Preparation of in-line additive solution> 10 parts by weight of Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 16 nm, apparent specific gravity of 90 g / liter) and 90 parts by weight of methanol were stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. A fine particle dispersion was obtained.
  • Aerosil 972V manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 16 nm, apparent specific gravity of 90 g / liter
  • composition of main dope Dope 11
  • 100 parts by mass of the main dope 11 and 2.5 parts by mass of the in-line additive solution were sufficiently mixed with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ) to obtain a dope.
  • an in-line mixer Toray static type in-pipe mixer Hi-Mixer, SWJ
  • the obtained dope was uniformly cast on a stainless steel band support using a belt casting apparatus under the conditions of a dope temperature of 35 ° C. and a width of 1.6 m.
  • the solvent in the obtained dope film was evaporated until the residual solvent amount reached 100% to obtain a web, and then the web was peeled from the stainless steel band support.
  • the obtained web was further dried at 35 ° C. and then slit so as to have a width of 1.4 m.
  • the film was stretched in the MD direction at 190 ° C. and a stretch ratio of 200% by the first stretching apparatus. At that time, the residual solvent amount of the web at the start of stretching was 20%.
  • the film was stretched in the TD direction at 170 ° C. at a stretch ratio of 150% by the second stretching apparatus. At that time, the residual solvent amount of the web at the start of stretching was 5%.
  • the obtained film was dried at 125 ° C. for 15 minutes while being transported by a number of rollers in the drying apparatus, then slit to 2.0 m width, and the height of the convex portion was 10 ⁇ m at both ends in the width direction.
  • a long cellulose acylate film (film 1-12) having a width of 2.0 m, a length of 4000 m and a film thickness of 30 ⁇ m was produced.
  • ⁇ Film 2-2> ⁇ Preparation of cellulose acylate> (Preparation of cellulose acetate 1) After 26.8 parts by mass of acetic acid was sprayed on 100 parts by mass of pulverized pulp and stirred well, the mixture was allowed to stand for 60 hours as a pretreatment. The pretreated pulp was added to a mixture consisting of 323 parts by mass of acetic acid, 245 parts by mass of acetic anhydride, and 13.1 parts by mass of sulfuric acid, adjusted to 40 ° C., and acetylated for 90 minutes. A neutralizing agent (24% magnesium acetate aqueous solution) was added so that the amount of sulfuric acid was adjusted to 2.5 parts by mass.
  • a neutralizing agent (24% magnesium acetate aqueous solution) was added so that the amount of sulfuric acid was adjusted to 2.5 parts by mass.
  • Preparation of cellulose acetate 2 100 parts by mass of crushed pulp was sprayed with 50 parts by mass of acetic acid and pretreated. A mixture consisting of 445 parts by mass of acetic acid, 265 parts by mass of acetic anhydride and 8.3 parts by mass of sulfuric acid was added to the pretreated pulp for acetylation. After adding a neutralizing agent (24% magnesium acetate aqueous solution) so that the sulfuric acid amount is adjusted to 4.0 parts by mass, aging is carried out at a temperature of 85 ° C., and the mixture is discharged into dilute acetic acid. The precipitate obtained was dehydrated, washed with pure water, solid-liquid separated, and dried to obtain flakes.
  • a neutralizing agent (24% magnesium acetate aqueous solution
  • the cellulose triacetate flakes were immersed in an aqueous calcium hydroxide solution having a concentration of 2 ⁇ 10 ⁇ 5 g / g for 0.5 hours at 20 ° C., then filtered and dried to obtain cellulose acetate 2.
  • ⁇ Preparation of dope> (Preparation of core layer dope (dope 12) solution) The following composition was put into a mixing tank and stirred to dissolve each component to prepare a core layer dope solution.
  • Dope 12 composition ⁇ Cellulose acetate 1 100 parts by weight Additive 1 (oligomer 1) 4 parts by weight Additive 2 (Compound P15) 2.3 parts by weight Methylene chloride 398.5 parts by weight Methanol 59.7 parts by weight ⁇ ⁇
  • composition of matting agent dispersion M1 ⁇ 2.0 parts by mass of silica particles having an average particle size of 20 nm (AEROSIL (registered trademark) R972, manufactured by Nippon Aerosil Co., Ltd.) Methylene chloride 76.1 parts by weight Methanol 11.4 parts by weight Skin layer dope (dope 13) solution 12.6 parts by weight ⁇ ⁇
  • the dope solution prepared above was used for casting with a band casting machine.
  • the dope was co-cast from the casting die on the traveling band.
  • a cast film was formed by simultaneous multi-layer co-casting.
  • the cast film was peeled off from the cast band to form a wet film, and then dried by a crossover and a tenter to obtain a film.
  • the amount of residual solvent immediately after stripping the dope was about 25% by mass.
  • the film was sent to a drying chamber, and drying was sufficiently promoted while being conveyed while being wound around a number of rollers.
  • the film obtained by casting was gripped with a clip and stretched in the TD direction under the condition of a uniaxial fixed end.
  • the stretching temperature was 182 ° C. and the stretching rate was 129%.
  • the film subjected to the stretching treatment was sequentially subjected to a condensation prevention treatment, a wet heat treatment (water vapor contact treatment) and a heat treatment.
  • the film temperature Tf0 was adjusted to 120 ° C. by applying dry air to the film.
  • the wet heat treatment absolute humidity is 250 g / m 3
  • the dew point of the wet gas is 10 than the film temperature Tf0.
  • the film was transported while maintaining a state where the temperature of the film (wet heat treatment temperature) was 100 ° C. for only the treatment time (60 seconds).
  • the absolute humidity of the gas in the heat treatment chamber was set to 0 g / m 3
  • the film temperature was set to the same temperature as the wet heat treatment temperature
  • the treatment time was maintained.
  • the film surface temperature was determined from the average value obtained by attaching a tape-type thermocouple surface temperature sensor (ST series manufactured by Anri Keiki Co., Ltd.) to the film at three points.
  • ⁇ Film 2-4> In film formation of film 2-2, the film thickness was changed from 53 ⁇ m to 58 ⁇ m after drying, and the film was formed under the same conditions as film 2-2 except that the film was stretched 10% in the transport direction when peeled off from the band. Thus, a film 2-4 having a thickness of 47 ⁇ m was obtained.
  • Example 1 1) Production of Polarizer A polyvinyl alcohol (PVA) film having a thickness of 80 ⁇ m was dyed by immersing it in an aqueous iodine solution having an iodine concentration of 0.05% by mass at 30 ° C. for 60 seconds, and then having a boric acid concentration of 4% by mass. While immersed in an aqueous boric acid solution for 60 seconds, it was longitudinally stretched to 5 times the original length. Thereafter, the film was dried at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 ⁇ m.
  • PVA polyvinyl alcohol
  • UV curable adhesive 100 parts by mass of 2-hydroxyethyl acrylate, 10 parts by mass of tolylene diisocyanate and 3 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by BASF) were added to prepare an ultraviolet curable adhesive. Prepared.
  • the line speed was 20 m / min, and the cumulative amount of ultraviolet light was 300 mJ / cm 2 .
  • an adhesive layer was provided on the surface of the film 2-1 opposite to the polarizer. That is, the film 2-1 is an inner film (second protective film), and the film 1-1 is an outer film (first protective film). When bonding a polarizing plate to a liquid crystal cell at the time of liquid crystal display device manufacture, it bonds through the said adhesive.
  • Examples 2 to 7 and Comparative Examples 1 to 9 In the production of the polarizing plate of Example 1, the polarizations of Examples 2 to 7 and Comparative Examples 1 to 9 were the same as Example 1 except that the type of protective film used was changed as described in Table 3 below. A plate was made. In each example and comparative example, the absorption axis direction of the polarizer was the MD direction when the polarizing plate was produced, and the transmission axis direction of the polarizer was the TD direction when the polarizing plate was produced.
  • the elastic modulus (GPa) of each protective film was measured by preparing a sample with a length of 200 mm in the MD direction and a width of 10 mm and immediately leaving the sample in an environment of 25 ° C. and 60% relative humidity for 2 hours. Using the graph V10-C, the sample shape was measured with a width of 10 mm and a length between chucks of 100 mm.
  • A 1.5 mm or more and less than 6.6 mm in a state where the central part is in contact and the end part is not in contact
  • B 0.1 mm or more and less than 1.5 mm in a state where the central part is in contact and the end part is not in contact 6.6 mm or more and less than 8.6 mm
  • C 8.6 mm or more and less than 10.0 mm in a state where the central portion is in contact and the end portion is not in contact
  • D In a state in which the central portion is in contact and the end portion is not in contact. 0 mm or more
  • E The end is in contact
  • A There are 0 bright spots on the screen.
  • B There are no bright spots visible when observed 3 meters away on the screen, and 1 or 2 bright spots visible when observed 0.2 meters away.
  • C Screen There are no bright spots visible when observed at a distance of 3 m, and there are 3 to 10 bright spots visible when observed at a distance of 0.2 m.
  • D Bright spots that are visible even when observed at a distance of 3 m on the screen Is 1 or more, but there is no light leakage
  • E There is one or more bright spots that can be seen even if observed 3m away from the screen, and there is also light leakage
  • the polarizing plate of the present invention having a specific creep moment ratio has a small value of positive curl (curl with the outer film inside), and the polarizing plate and the liquid crystal display device At the time of production, the polarizing plate had good manufacturability. Further, in the liquid crystal display device using the polarizing plate of the present invention, good display performance such as less air bubbles and excellent optical compensation is obtained, and a creep moment A2 of the inner film (second protective film) is obtained. When 40 or less polarizing plates were used, more preferable evaluation results were obtained.
  • Comparative Examples 1, 3, 4, 5, 7, 8, and 9 are negative curls (curls that have the inner film on the inner side) that are not in contact with the center portion but are in contact with the end portions.
  • the display performance has deteriorated.
  • Comparative Examples 2 and 6 because of the large plus curl, the end portion of the polarizing plate was bent during the conveyance, and a bright spot was generated at the bent portion, so that the display performance was deteriorated.
  • a polarizing plate in which an actinic radiation curable adhesive is used, which is excellent from the viewpoint of curling and has excellent display quality when used in a liquid crystal display device, and the polarizing plate.
  • a liquid crystal display device can be provided.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention fournit une plaque polarisante, et un dispositif d'affichage à cristaux liquides possédant cette plaque polarisante. La plaque polarisante de l'invention est telle qu'un polariseur est enserré entre un premier et un second film protecteur avec pour intermédiaire une couche adhésive durcissable par rayon actinique, et un rapport (A1/A2) d'une valeur (A1) d'un moment de fluage dans une direction parallèle à un axe d'absorption dudit polariseur du premier film protecteur par rapport à une valeur (A2) d'un moment de fluage dans une direction parallèle à un axe d'absorption dudit polariseur du second film protecteur, est supérieur ou égal à 1,1 et inférieur ou égal à 3,5.
PCT/JP2016/069925 2015-07-06 2016-07-05 Plaque polarisante, et dispositif d'affichage à cristaux liquides WO2017006938A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011095560A (ja) * 2009-10-30 2011-05-12 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2011154257A (ja) * 2010-01-28 2011-08-11 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2012215821A (ja) * 2010-10-29 2012-11-08 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2013186180A (ja) * 2012-03-06 2013-09-19 Konica Minolta Inc 偏光板の製造方法および液晶表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011095560A (ja) * 2009-10-30 2011-05-12 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2011154257A (ja) * 2010-01-28 2011-08-11 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2012215821A (ja) * 2010-10-29 2012-11-08 Sumitomo Chemical Co Ltd 偏光板の製造方法
JP2013186180A (ja) * 2012-03-06 2013-09-19 Konica Minolta Inc 偏光板の製造方法および液晶表示装置

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