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WO2017057255A1 - Film de protection de plaque polarisante, son procédé de fabrication, plaque polarisante, et dispositif d'affichage d'image - Google Patents

Film de protection de plaque polarisante, son procédé de fabrication, plaque polarisante, et dispositif d'affichage d'image Download PDF

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Publication number
WO2017057255A1
WO2017057255A1 PCT/JP2016/078232 JP2016078232W WO2017057255A1 WO 2017057255 A1 WO2017057255 A1 WO 2017057255A1 JP 2016078232 W JP2016078232 W JP 2016078232W WO 2017057255 A1 WO2017057255 A1 WO 2017057255A1
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Prior art keywords
polarizing plate
layer
polymer
group
protective film
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English (en)
Japanese (ja)
Inventor
伸隆 深川
一洋 雨宮
遊 内藤
靖和 桑山
寛 野副
真裕美 野尻
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2016107200A external-priority patent/JP6327289B2/ja
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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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

Definitions

  • the present invention relates to a polarizing plate protective film, a production method thereof, a polarizing plate and an image display device.
  • Image display devices represented by electroluminescence displays (ELDs) and liquid crystal display devices (LCDs) are increasingly required to be thin.
  • the usage environment of image display devices has been diversified, including outdoor applications, and image display devices can stably maintain good image quality even in harsh environments compared to conventional ones (high durability of performance) ) Is now required.
  • the decrease in image quality in the image display apparatus is partly caused by moisture entering the polarizing plate and degrading the polarizer.
  • the polarizer is protected by laminating a protective film (optical film) on the surface, but the protective film is also required to be thin. When the protective film is thinned, moisture is more likely to come into contact with the polarizer, and the image quality is likely to deteriorate. Such a decrease in image quality becomes more apparent when used in harsh environments such as outdoor applications.
  • optical film cellulose resins are widely used from the viewpoint of versatility or processability. Due to the necessity of further improving the durability, the optical film is being modified (for example, Patent Documents 1 to 6).
  • An object of the present invention is to provide a polarizing plate protective film having a cellulose ester layer, which is excellent in low moisture permeability and interlayer adhesion, and a method for producing the same.
  • the present invention also provides a polarizing plate capable of suppressing deterioration in image quality when used for a long time under high temperature and high humidity conditions when incorporated in an image display device, and an image display device using the polarizing plate. It is an issue to provide.
  • a polarizing plate protective film provided adjacent to the cellulose ester layer has improved interlayer adhesion between the polymer layer and the cellulose ester layer.
  • Polymer B1 contains the following repeating unit [a]:
  • the polymer B1 layer is formed by applying a composition containing the polymer B1 and a solvent in which fd defined by the following formula I satisfies the following relational expressions [1] and [2] on the surface of the cellulose ester layer. , 85 ° C., 85% relative humidity conditions, the polarizer protective film moisture permeability is 1600 g / m 2 or less 100 g / m 2 or more at 6 hours.
  • fd solvent represents the fd value of the solvent
  • fd cellulose represents the fd value of the cellulose ester
  • fd polymerB1 represents the fd value of the polymer B1.
  • the fd value is defined by the following formula I.
  • Formula I fd ⁇ d / ( ⁇ d + ⁇ p + ⁇ h)
  • ⁇ d, ⁇ p, and ⁇ h are a term corresponding to the London dispersion force, a term corresponding to the force between dipoles, and a term corresponding to the hydrogen bonding force, respectively, with respect to the solubility parameter ⁇ t calculated by the Hoy method.
  • Fd represents the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h.
  • repeating unit ⁇ 3> having a solubility parameter ⁇ t calculated by the Hoy method of 20.0 or more and 26.0 or less ⁇ 3> containing polymer B2 adjacent to the surface opposite to the cellulose ester layer of the polymer B1 layer Having a polymer B2 layer
  • Formula I fd ⁇ d / ( ⁇ d + ⁇ p + ⁇ h)
  • ⁇ d, ⁇ p, and ⁇ h are a term corresponding to the London dispersion force, a term corresponding to the force between dipoles, and a term corresponding to the hydrogen bonding force, respectively, with respect to the solubility parameter ⁇ t calculated by the Hoy method.
  • Fd represents the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h.
  • ⁇ 7> The polarizing plate according to ⁇ 6>, wherein the polymer B1 layer of the polarizing plate protective film is disposed on the surface side of the polarizer.
  • ⁇ 9> The polarizing plate according to ⁇ 8>, wherein the polymer B2 layer of the polarizing plate protective film is disposed on the surface side of the polarizer.
  • the polarizer When a polarizing plate protective film is provided on one surface of the polarizer, the polarizer has a cycloolefin film containing a cycloolefin polymer on the surface opposite to the polarizing plate protective film ⁇ 6>.
  • the polarizing plate according to any one of to ⁇ 9>.
  • An image display device having the polarizing plate according to any one of the above items ⁇ 6> to ⁇ 10>.
  • the present invention can provide a polarizing plate protective film having a cellulose ester layer, which is excellent in low moisture permeability and interlayer adhesion, and a method for producing the same.
  • the present invention also provides a polarizing plate capable of suppressing deterioration in image quality when used for a long time under high temperature and high humidity conditions when incorporated in an image display device, and an image display device using the polarizing plate. Can be provided.
  • FIG. 1 is a cross-sectional view showing a preferred embodiment of the polarizing plate protective film of the present invention.
  • FIG. 2 is a cross-sectional view showing a preferred embodiment of the polarizing plate protective film of the present invention.
  • FIG. 3 is a cross-sectional view showing a preferred embodiment of the polarizing plate protective film of the present invention.
  • FIG. 4 is a cross-sectional view showing a preferred embodiment of the polarizing plate protective film of the present invention.
  • FIG. 5 is a cross-sectional view showing a preferred embodiment of the polarizing plate of the present invention.
  • FIG. 6 is a cross-sectional view showing a preferred embodiment of the polarizing plate of the present invention.
  • FIG. 7 is a schematic diagram showing an outline of an embodiment of a liquid crystal display device including a polarizing plate incorporating the polarizing plate protective film of the present invention.
  • FIG. 8 is a partially enlarged schematic view showing an example of a method for producing a cellulose ester layer (co-casting).
  • the numerical range represented by “to” means that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • substituents, etc. when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are close (especially adjacent), they may be connected to each other or condensed to form a ring.
  • the display of a compound uses in the meaning containing its salt and its ion other than a compound itself.
  • the salt of the compound include an acid addition salt of the compound formed with the compound and an inorganic acid or an organic acid, or a base addition salt of the compound formed with the compound and an inorganic base or an organic base.
  • the ion of the compound include an ion generated by dissolving a salt of the above-described compound in water or a solvent.
  • a substituent that does not specify substitution or non-substitution means that the group may have an arbitrary substituent as long as a desired effect is achieved. . This is synonymous with a compound or repeating unit in which substitution or non-substitution is not specified.
  • substituent when simply referred to as “substituent”, a group selected from the following substituent group T may be mentioned unless otherwise specified.
  • substituent group T when only a substituent having a specific range is described (for example, when only described as “alkyl group”), a corresponding group of the following substituent group T (in the above case, an alkyl group) The preferred range in FIG.
  • this number of carbons means the total number of carbon atoms in the group. That is, when this group has a further substituent, it means the total number of carbon atoms including this substituent.
  • the certain group when a certain group can adopt a non-cyclic skeleton and a cyclic skeleton, unless otherwise specified, the certain group includes a non-cyclic skeleton group and a cyclic skeleton group.
  • the alkyl group includes a linear alkyl group, a branched alkyl group, and a cyclic (cyclo) alkyl group.
  • the lower limit of the number of carbon atoms in the group of the cyclic skeleton is 3 or more, preferably 5 or more, regardless of the lower limit of the number of carbon atoms specifically described in the certain group.
  • the term “(meth) acrylic acid” is used to include both methacrylic acid and acrylic acid. The same applies to “(meth) acrylamide”.
  • the term “acrylic acid” is used in a broader sense than usual.
  • acrylic acid is used to include all compounds having the structure of R A —C ( ⁇ CR B 2 ) COOH (R A and R B each independently represent a hydrogen atom or a substituent, provided that , When R A is methyl, means methacrylic acid).
  • R A is methyl, means methacrylic acid.
  • acrylamide is used to include all compounds having the structure of R A —C ( ⁇ CR B 2 ) COOH (R A and R B each independently represent a hydrogen atom or a substituent, provided that , When R A is methyl, means methacrylic acid).
  • R A is methyl, means methacrylic acid
  • Substituent group T An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n -Decyl group, n-hexadecyl, etc.
  • the number of carbon atoms is preferably 3 to 20, more preferably 3 to 12, particularly preferably 3 to 8.
  • cyclopropyl Group cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms such as vinyl group, allyl group, 2- Butenyl group, 3-pentenyl group, etc.
  • alkynyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 8 to 8 such as propargyl group and 3-pentynyl group
  • aryl group preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms such as phenyl group).
  • Biphenyl group, naphthyl group, etc. amino group (preferably having 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, such as amino group, methylamino group, dimethylamino group) Group, diethylamino group, dibenzylamino group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as methoxy group, ethoxy group, Butoxy groups), aryloxy groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 6 carbon atoms).
  • acyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as acetyl Group, benzoyl group, formyl group, pivaloyl group, etc.
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonyl group, An ethoxycarbonyl group, etc.
  • an aryloxycarbonyl group preferably having a carbon number of 7-20, more preferably 7-16, particularly preferably 7-10, such as a phenyloxycarbonyl group).
  • An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 1 carbon atoms). 0, and examples thereof include an acetoxy group and a benzoyloxy group. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more Preferably it is 7 to 16, particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group, etc.), a sulfonylamino group (preferably having 1
  • a sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably 0 to 16, particularly preferably 0 to 12, such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group,
  • a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenyl group).
  • Groups preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferred Or a sulfonyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 16, and particularly preferably 1 to 12, such as a mesyl group, tosyl, etc.).
  • Sulfinyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as methanesulfinyl group and benzenesulfinyl group).
  • Urethane group ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and particularly preferably 1 to 12 such as ureido group, methylureido group, phenylureido group, etc.), phosphoric acid Amido groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as diethyl phosphate Amides, phenylphosphoric acid amides and the like can be mentioned.
  • Hydroxy group mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the ring-constituting hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • halogen atom eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • cyano group eg fluorine atom, chlorine atom, bromine atom, iodine atom
  • sulfo group carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group
  • the heterocyclic ring includes an aromatic heterocyclic group and an aliphatic heterocyclic group, specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, A benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, etc.) and a silyl group (preferably having a carbon number) To 40, more preferably from 3 to 30, particularly preferably 3 to 24, e.g., a trimethylsilyl group, etc. triphenylsilyl group).
  • substituents may further have a substituent. Moreover, when there are two or more substituents, they may be the same or different. Further, adjacent substituents may be connected to each other to form a ring.
  • the polarizing plate protective film of the present invention has a cellulose ester layer containing a cellulose ester and a polymer B1 layer containing a polymer B1 containing a repeating unit of the following [a] adjacent to one surface of the cellulose ester layer. is doing.
  • the polymer B1 layer contains, on the surface of the cellulose ester layer, the polymer B1 and a solvent in which fd defined by the following formula I satisfies the following relational expressions [1] and “2”.
  • the composition is applied to form.
  • a polarizing plate protective film 85 ° C., the moisture permeability 6 hours under ambient conditions of relative humidity of 85%, indicating a 100 g / m 2 or more 1600 g / m 2 or less.
  • fd solvent represents the fd value of the solvent
  • fd cellulose represents the fd value of the cellulose ester contained in the cellulose ester layer
  • fd polymerB1 represents the fd value of the polymer B1.
  • the fd value is defined by the following formula I.
  • Formula I fd ⁇ d / ( ⁇ d + ⁇ p + ⁇ h)
  • ⁇ d, ⁇ p, and ⁇ h are a term corresponding to the London dispersion force, a term corresponding to the force between dipoles, and a term corresponding to the hydrogen bonding force, respectively, with respect to the solubility parameter ⁇ t calculated by the Hoy method.
  • Fd represents the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h.
  • the polarizing plate protective film of the present invention having the above configuration has low moisture permeability (low moisture permeability) and excellent interlayer adhesion (also simply referred to as adhesion). Even if this polarizing plate protective film is thinned, it can prevent deterioration of the polarizer under high temperature and high humidity conditions by being superimposed on the polarizer. The reason is not clear, but it is thought as follows. The above-described deterioration in image quality is considered to be due to the gradual decrease in the iodine content in the polarizer in the case of a polarizer formed of a polyvinyl alcohol resin dyed with iodine.
  • the polarizing plate protective film of the present invention includes a layer containing the polymer B1 containing the repeating unit [a], and can effectively suppress moisture permeability. Therefore, it is possible to prevent moisture from penetrating and prevent contact with the polarizer.
  • the polarizing plate protective film of the present invention has a cellulose ester layer and a polymer B1 layer adjacent to at least one surface of the cellulose ester layer.
  • a layer adjacent to the surface of a certain layer is one of the certain layers without an adhesive layer (adhesive layer) or the like that adheres or adheres both layers between the certain layer and the adjacent layer. It is a layer provided in a state of being in direct contact with the surface of (a laminated or superposed) layer.
  • the polarizing plate protective film of this invention has the said laminated structure
  • another structure will not be specifically limited.
  • each of the polymer B1 layer and the B2 layer may have a laminated structure of two or more layers.
  • the polymer B1 layer has a laminated structure of two or more layers, it is sufficient that at least the layer adjacent to the surface of the cellulose ester layer 11 is formed by the above composition, and each layer is formed by the above composition. It may be done. Moreover, the polymer B1 layer and B2 layer provided on both surfaces of the cellulose ester layer 11 may be the same or different.
  • the polymer B1 and the polymer B1 layer correspond to the polymer B2 and the polymer B2 layer, respectively. do not do.
  • the polymer B2 is used as a polymer not including the repeating unit [b] with respect to the polymer B1 including the repeating unit [b].
  • the polymer B2 layer is used as a layer containing the polymer B2 not containing the repeating unit [b] with respect to the layer containing the polymer B1 containing the repeating unit [b]. Therefore, when a plurality of layers containing a polymer containing the repeating unit [a] and not containing the repeating unit [b] are laminated, these layers are all polymer B1 layers.
  • the polymer B1 layer, the polymer B2 layer, or both layers may be referred to as an iodine diffusion preventing layer.
  • the term “iodine diffusion preventing layer” simply means a layer capable of preventing the diffusion of iodines, and is merely used to facilitate understanding of the present invention.
  • the “iodine diffusion preventing layer” includes all layers containing a polymer as defined in the present invention regardless of the degree to which the diffusion of iodines can be prevented. That is, in judging the gist and technical scope of the present invention, the term “iodine diffusion preventing layer” is not considered as an invention specific matter for limiting the present invention.
  • the polymer B1 layer is formed using a composition described later.
  • there is a mixed region (not shown in FIGS. 1 to 6) where the cellulose ester and the polymer B1 are mixed in the vicinity of the boundary between the cellulose ester layer and the polymer B1 layer (near the laminated surface of each layer).
  • This mixed region is included in either the cellulose ester layer or the polymer B1 layer when focusing on the content of the cellulose ester or polymer B1 contained in the region.
  • the mixed region a mixed region in which the content of the cellulose ester is 50% by mass or more is included in the cellulose ester layer with respect to 100% by mass in total of the cellulose ester and the polymer B1.
  • the mixed region is formed when the polymer B1 layer is formed. Therefore, even in the polymer B1 layer having a low affinity with the cellulose ester, the cellulose ester and the polymer B1 are mixed in the mixed region, and the interlayer adhesion with the cellulose ester layer is strengthened.
  • a mixed region where the polymer B1 and the polymer B2 are mixed may be provided in the vicinity of the boundary between the polymer B1 layer and the polymer layer B2. In this case, the interlayer adhesion between the polymer B1 layer and the polymer layer B2 layer is strengthened.
  • a method for forming the polymer B1 layer and the polymer B2 layer will be described later.
  • various functional layers specialized for specific functions may be directly provided on the surface of the cellulose ester layer or the iodine diffusion preventing layer.
  • a functional layer include a hard coat layer, an antireflection layer, a light scattering layer, an antifouling layer, and an antistatic layer.
  • the functional layer may serve as a plurality of functions.
  • the functional layer is preferably provided directly on the surface of the cellulose ester layer from the viewpoint of enhancing the effects of the present invention.
  • polymer B1 layer or “polymer B2 layer” means that the entire polymer layer (total mass) constituting the layer contains 50% by mass or more of polymer B1 or polymer B2 described later. It means the layer to do.
  • the content of each polymer in the entire polymer layer is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 85% by mass or more. The higher the content of the polymer B1 or the polymer B2, the better the adhesion with the cellulose ester layer or the like, which is preferable.
  • the content of each polymer B1 or B2 in the entire polymer layer may be 100% by mass, and is usually 99% by mass or less.
  • the remainder may include a resin other than the polymers B1 and B2, which will be described later, or an additive which will be described later.
  • Two or more kinds of polymers may be used as the polymer B1 or the polymer B2, respectively. That is, polymers having different composition ratios and / or molecular weights may be used in combination. In this case, the total amount of each polymer falls within the above range.
  • the film thickness of the iodine diffusion preventing layer is not particularly limited, preferably 1 to 25 ⁇ m, more preferably 1 to 20 ⁇ m, and particularly preferably 1 to 15 ⁇ m.
  • the film thickness of the polymer B1 layer and the polymer B2 layer is not particularly limited as long as the total film thickness is within the above range.
  • the film thickness of the polymer B1 layer is preferably 0.1 to 24 ⁇ m, more preferably 0.2 to 19 ⁇ m, and particularly preferably 0.5 to 14 ⁇ m.
  • the film thickness of the polymer B2 layer is preferably 0.1 to 24 ⁇ m, more preferably 0.2 to 19 ⁇ m, and particularly preferably 0.5 to 14 ⁇ m.
  • polymer B1 and polymer B2 which comprise the iodine diffusion prevention layer of this invention are each demonstrated.
  • ⁇ 2-1 Polymer B1>
  • the polymer B1 used in the present invention contains the following repeating unit [a].
  • the solubility parameter ⁇ t is determined for Amorphous Polymers literature "Properties of Polymers 3 rd, ELSEVIER , (1990)” in “2) Method of Hoy (1985, 1989) " column of 214-220 pages ⁇ t is assumed and is calculated according to the description in the above column of the above document.
  • the unit of ⁇ t is usually (J / cm 3) 1/2 or (cal / cm 3) uses a 1/2, in the present invention, use of (cal / cm 3) 1/2.
  • the polymer B1 is not particularly limited as long as it has a repeating unit satisfying the above [a], but a (meth) acrylic resin can be preferably used.
  • the (meth) acrylic resin includes a methacrylic resin in addition to the acrylic resin.
  • the (meth) acrylic resin includes a polymer of a (meth) acrylic acid compound, a copolymer of these compounds, a polymer of a (meth) acrylic acid ester, or a copolymer of these esters.
  • the (meth) acrylic resin may contain a ring structure formed by a cyclization reaction in the main chain after polymerizing the compound. Examples of the polymer having such a structure include a polymer having a lactone ring, a polymer having a glutaric anhydride ring, and a glutarimide ring-containing polymer.
  • the repeating unit of the (meth) acrylic resin is not particularly limited as long as it has a solubility parameter ⁇ t in the above range.
  • the (meth) acrylic resin preferably has a repeating unit derived from a (meth) acrylic acid ester as a repeating 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.
  • methacrylic acid esters such as acrylic acid ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. May be used alone or in combination of two or more.
  • the repeating unit derived from the (meth) acrylic acid ester is preferably 50 to 100% by mass, more preferably 70 to 100% by weight, in order to sufficiently exert the effects of the present invention with respect to the total mass of the repeating units of the acrylic resin. It is 100% by mass, more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass.
  • the glass transition temperature Tg of the (meth) acrylic resin is preferably in the range of 80 to 120 ° C.
  • This glass transition temperature Tg is measured using a differential scanning calorimeter (DSC), and in the present invention, the measuring method described below can be used.
  • DSC differential scanning calorimeter
  • As the measurement sample in addition to the (meth) acrylic resin powder itself, a powder obtained by scraping the polymer B1 layer from the polarizing plate protective film may be used. In addition, when using the powder which scraped off the polymer B1 layer, you may remove (purify) components other than polymer B1 as needed.
  • ⁇ Measuring method of glass transition temperature Tg> With a differential scanning calorimeter (X-DSC7000, manufactured by IT Measurement Control Co., Ltd.), 20 mg of a measurement sample is placed in a measurement pan, and this is heated from 30 ° C. to 120 ° C. at a rate of 10 ° C./min in a nitrogen stream. Hold for 15 minutes and cool to 30 ° C at -20 ° C / min. Thereafter, the temperature is raised again from 30 ° C. to 250 ° C., and the temperature at which the baseline starts to deviate from the low temperature side is defined as the glass transition temperature Tg.
  • X-DSC7000 manufactured by IT Measurement Control Co., Ltd.
  • the weight average molecular weight of the (meth) acrylic resin is not particularly limited.
  • the lower limit of the weight average molecular weight of the resin is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 30,000 or more from the viewpoint of the surface properties of the film.
  • the upper limit of the weight average molecular weight of the (meth) acrylic resin is preferably 2,000,000 or less, more preferably 1,800,000 or less, and further preferably 1,500,000 or less, from the viewpoint of film forming properties.
  • 1,000,000 or less is particularly preferable, and 500,000 or less is most preferable.
  • the molecular weight can be measured by the method described in Examples described later.
  • (Meth) acrylic resin may be appropriately synthesized or commercially available. Although it does not specifically limit as a commercially available (meth) acrylic resin, For example, Dianal BR83, BR80, BR85, and BR88 (all are brand names, the Mitsubishi Rayon company make), or 80N (brand name, the Asahi Kasei Delpet company make) ) Is preferred.
  • the polymer B1 preferably further has the following repeating unit [b].
  • the repeating unit [b] is not particularly limited as long as it has a solubility parameter ⁇ t in the above range, but is preferably a repeating unit represented by the following general formula (1). Since the ⁇ -ketoester structure in the repeating unit represented by the following general formula (1) has good affinity with the cellulose ester, the adhesion between the cellulose ester layer and the iodine diffusion preventing layer can be enhanced.
  • general formula (1) Since the ⁇ -ketoester structure in the repeating unit represented by the following general formula (1) has good affinity with the cellulose ester, the adhesion between the cellulose ester layer and the iodine diffusion preventing layer can be enhanced.
  • R 1 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and the aliphatic group, aromatic group and heterocyclic group may have a substituent.
  • L represents a single bond, a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group, —C ( ⁇ O) —, —O—, —N (R 2 ) — or The combination of is shown.
  • the divalent aliphatic group, divalent aromatic group and divalent heterocyclic group may have a substituent.
  • R 2 represents a hydrogen atom or an alkyl group.
  • Examples of the aliphatic group for R 1 include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and methyl is more preferable.
  • the heterocyclic group in R 1 is not particularly limited, and examples thereof include a pyridyl group, a pyrrolidyl group, a piperidyl group, a piperazol group, a pyrrolyl group, a morpholino group, a thiamorpholino group, an imidazolyl group, a pyrazolyl group, a pyrrolidonyl group, and a piperidonyl group. Among them, a morpholino group and a pyridyl group are preferable.
  • R 1 in the general formula (1) is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or methyl. It is more particularly preferable.
  • Examples of the substituent that the aliphatic group, aromatic group or heterocyclic group may have include, for example, an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl).
  • An alkenyl group having 2 to 6 carbon atoms for example, vinyl, allyl, 2-butenyl, 3-pentenyl
  • an alkynyl group having 2 to 6 carbon atoms for example, propargyl group, 3-pentynyl group
  • an amino group for example, Amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group
  • alkoxy group for example, methoxy group, ethoxy group, butoxy group
  • aryloxy group for example, phenyloxy group, 2-naphthyloxy group
  • Acyl group eg acetyl group, benzoyl group, formyl group, pivaloyl group
  • alkoxycarbo Group for example, methoxycarbonyl group, ethoxycarbonyl group
  • aryloxycarbonyl group for example, phenyloxycarbonyl group
  • acyloxy group for example,
  • L in the general formula (1) represents a single bond, a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group, —C ( ⁇ O) —, —O—, —N (R 2 )-or a combination thereof, and the divalent aliphatic group, divalent aromatic group and divalent heterocyclic group may have a substituent.
  • L is preferably a divalent aliphatic group, a divalent aromatic group, —C ( ⁇ O) —, or L 1 -L 2 — (wherein one of L 1 and L 2 is —C ( ⁇ O) —, —O—, —N (R 2 ) —, or a combination thereof, and the other represents a divalent aliphatic group, a divalent aromatic group, or a divalent heterocyclic group.
  • the divalent aliphatic group, divalent aromatic group and divalent heterocyclic group may have a substituent, and R 2 represents a hydrogen atom or an alkyl group.
  • L 1 is linked to the main chain.
  • the L is more preferably -L 1 -L 2- .
  • L 1 is —C ( ⁇ O) —, —O—, —N (R 2 ) —, or a combination thereof
  • L 2 is a divalent aliphatic group or divalent aromatic. A group or a divalent heterocyclic group is particularly preferable.
  • the divalent aliphatic group in L is preferably an alkylene group or an alkynyl group, more preferably an alkylene group which may have a substituent having 1 to 5 carbon atoms, and an ethylene group. More particularly preferred.
  • the divalent aromatic group in L is not particularly limited, but is preferably an aromatic group having 6 to 12 carbon atoms, preferably a phenylene group or a naphthylene group, and optionally substituted phenylene. It is more preferably a group, and an unsubstituted phenylene group is particularly preferable.
  • the divalent heterocyclic group in L is not particularly limited, but includes pyridylene group, pyrrolidylene group, piperidylene group, piperazylene group, pyrrolylene group, morpholinylene group, thiamorpholinenine group, imidazolylene group, pyrazolylene group, pyrrolidonylene group, A piperidonylene group can be mentioned, and among these, a morpholinylene group is preferable.
  • Examples of the substituent that the divalent aliphatic group, divalent aromatic group and divalent heterocyclic group may have include an alkyl group and a halogen group, and among them, an alkyl group Are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.
  • L 1 is preferably —C ( ⁇ O) —, —O—, —N (R 2 ) —, or a combination thereof.
  • —C ( ⁇ O) —, —O—, —N (R 2 ) —, or combinations thereof include —C ( ⁇ O) —, —O—, —C ( ⁇ O) —O—, — OC ( ⁇ O) —, —N (R 2 ) —C ( ⁇ O) —, —C ( ⁇ O) —N (R 2 ) —, or —N (R 2 ) —C ( ⁇ O ) —N (R 2 ) — is preferred.
  • L 1 is more preferably —C ( ⁇ O) —O— or —C ( ⁇ O) —N (R 2 ) —, and particularly preferably —C ( ⁇ O) —O—.
  • L 2 is preferably a divalent aliphatic group, a divalent aromatic group or a divalent heterocyclic group, an alkylene group optionally having a substituent having 1 to 5 carbon atoms, or A phenylene group which may have a substituent having 1 to 5 carbon atoms is more preferable, an alkylene group which may have a substituent having 1 to 5 carbon atoms is more preferable, and ethylene More preferably, it is a group.
  • the preferred ranges of the divalent aliphatic group, divalent aromatic group and divalent heterocyclic group in L 1 and L 2 are the divalent aliphatic group and divalent aromatic group in L. It is the same as the preferable range of the group and divalent heterocyclic group.
  • R 1 in the general formula (1) is a hydrogen atom or methyl
  • L is a divalent aliphatic group, a divalent aromatic group, In this embodiment, C ( ⁇ O) — or L 1 -L 2 —.
  • R 1 in the general formula (1) is a hydrogen atom or methyl
  • L is L 1 -L 2-
  • R 1 in the general formula (1) is a hydrogen atom or methyl
  • L 1 is —C ( ⁇ O) —O—
  • L 2 has a substituent having 1 to 5 carbon atoms. It is an embodiment that is an alkylene group that may be present.
  • R 1 in the general formula (1) is a hydrogen atom or methyl
  • L 1 is —C ( ⁇ O) —O—
  • L 2 is an ethylene group.
  • methyl is preferable for R 1 in the general formula (1).
  • R 2 represents a hydrogen atom or an alkyl group.
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or methyl, and particularly preferably a hydrogen atom.
  • the compound represented by the general formula (2) is more preferably ethyl acetoacetate or ethyl acetoacetate, and further preferably ethyl acetoacetate.
  • the polymer B1 containing the repeating unit [a] and containing the repeating unit [b] is represented by the general formula (2) as a compound capable of deriving the repeating unit [b].
  • One or two or more of the represented compounds can be used in combination. Among them, it is preferable to use ethyl acetoacetate methacrylate, ethyl acetoacetate acrylate or a mixture thereof.
  • the polymer containing the repeating unit [a] and the repeating unit [b] is a combination of the above compound capable of deriving the repeating unit [a] and the compound represented by the general formula (2). It becomes a polymer.
  • it may be a copolymer of the compound capable of deriving the repeating unit [a] and only one kind of the compound represented by the general formula (2). It is also possible to use a copolymer obtained by using two or more compounds represented by the above general formula (2) and the above compound capable of deriving. There is no particular limitation on the composition ratio of the repeating unit corresponding to each compound of the copolymer obtained by using two or more compounds represented by the general formula (2).
  • the compound represented by the general formula (2) used in the present invention can be obtained as a commercial product or synthesized with reference to known literature.
  • the polymer B1 may contain other repeating units in addition to the repeating unit [a] and the repeating unit [b]. That is, in the present invention, the compound capable of deriving the repeating unit [a], the compound represented by the general formula (2), if necessary, and at least one other repeating unit are copolymerized.
  • the polymer obtained can be used.
  • the compound that leads to the other repeating unit is not particularly limited as long as it can be copolymerized with the compound that can lead to the repeating unit of the above [a] and the compound represented by the general formula (2). Ethylenically unsaturated compounds are preferred.
  • ethylenically unsaturated compound other ethylenically unsaturated compounds other than the above compound capable of deriving the repeating unit [a] and the compound represented by the above general formula (2) are preferable. These may be used alone or in combination of two or more with the above compound capable of deriving the repeating unit [a] and, if necessary, with the compound represented by the above general formula (2). .
  • the content of the repeating unit is not particularly limited.
  • the molar amount of the repeating unit [a] in the total molar amount of the repeating units constituting the polymer B1 is preferably 100 mol% or less. .
  • the molar amount of the repeating unit of [a] in the total molar amount of the repeating unit constituting the polymer B1 is preferably 10 mol% or more, 20 mol% or more is more preferable, and 30 mol% or more is still more preferable. Moreover, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60 mol% or less is still more preferable.
  • the above [b] occupying in the total molar amount of the repeating units constituting the polymer B1.
  • the molar amount of the repeating unit [b] in the total molar amount of the repeating units constituting the polymer B1 is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less.
  • the molar amount of the repeating unit represented by the general formula (1) in the total molar amount of the repeating unit [b] is preferably 0.1 to 100 mol%. More preferably, it is ⁇ 100 mol%.
  • the content of the repeating unit of [a] and the content of the repeating unit of [b] are in the molar ratio [repeat of [[a]].
  • the total amount is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 50% by mass or more.
  • the molar amount of the repeating unit [a] and the repeating unit [b] is preferably 100 mol% or less in total, the repeating unit [a] and the repeating unit [b] It is also preferable that the unit consists of units.
  • the method for synthesizing the polymer B1 is not particularly limited, and a conventionally known method can be widely used. Examples thereof include a radical polymerization method, an anionic polymerization method, and a cation polymerization method using a compound that derives the repeating unit. It is done. Examples of the initiator used in the radical polymerization method include azo compounds or peroxides, and more specifically, azobisisobutyronitrile (AIBN), azoisobutyric acid diester derivatives, benzoyl peroxide, and the like. It is done.
  • the polymerization solvent is not particularly limited.
  • an aromatic hydrocarbon solvent such as toluene or chlorobenzene, a halogenated hydrocarbon solvent such as dichloroethane or chloroform, an ether solvent such as tetrahydrofuran or dioxane, an amide solvent such as dimethylformamide, methanol, etc.
  • solvent polymerization that polymerizes in a homogeneous system
  • precipitation polymerization that precipitates the produced polymer
  • emulsion polymerization that polymerizes in a micelle state
  • the weight average molecular weight of the polymer B1 is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,800,000, and 30,000 to 1,800,000. More preferred is 30,000 to 1,500,000.
  • the molecular weight can be measured by the method described in Examples described later.
  • the polarizing plate protective film of the present invention has, for example, the structure shown in FIG. 3 or FIG.
  • the polymer B1 layer contains the polymer B1 having the repeating unit [a] and the repeating unit [b].
  • the two types of repeating units in the polymer B1 function in a well-balanced manner.
  • the interlayer adhesion between the cellulose ester layer and the polymer B1 layer the interlayer adhesion between the iodine diffusion preventing layers, that is, the polymer B1 layer and the polymer B2 layer is also improved.
  • Polymer B2 contains the following repeating unit [a] and does not contain the following repeating unit [b].
  • the fact that the repeating unit of [b] is not included does not exclude the repeating unit of [b] which is inevitably present, for example, in the total molar amount of the repeating unit constituting the polymer B2. It means that the content of the repeating unit [b] is 1% by mass or less.
  • [b] Repeating unit with solubility parameter ⁇ t calculated by Hoy method of 20.0 or more and 26.0 or less
  • the repeating unit contained in the polymer B2 is synonymous with the repeating unit of [a] described in the polymer B1, and the preferred range is also the same.
  • the repeating unit not containing the polymer B2 is synonymous with the repeating unit [b] described above, and the preferred range is also the same.
  • the content of the repeating unit is not particularly limited.
  • the molar amount of the repeating unit [a] in the total molar amount of the repeating units constituting the polymer B2 is preferably 100 mol% or less.
  • the polymer B2 may have the other repeating unit.
  • the content of the repeating unit of [a] is preferably 5% by mass or more, more preferably 10% by mass or more, More preferably, it is at least 30% by mass, and particularly preferably at least 30% by mass.
  • the polymer B2 is also preferably in the form of the repeating unit [a].
  • the lower limit of the weight average molecular weight of the polymer B2 is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more from the viewpoint of the surface properties of the film.
  • the lower limit of the weight average molecular weight of the polymer B2 is preferably 2,000,000 or less, more preferably 1,800,000 or less, and further preferably 1,500,000 or less, from the viewpoint of the surface properties of the film.
  • the molecular weight can be measured by the method described in Examples described later.
  • the method for synthesizing the polymer B2 is not particularly limited, and conventionally known methods can be widely employed. Examples thereof include various synthesis methods described in the method for synthesizing the polymer B1.
  • the polymer B1 layer and the B2 layer may each contain an additive as long as the effects of the present invention are not impaired.
  • an additive the additive used for the cellulose-ester layer mentioned later is mentioned.
  • the additive examples include a fluoroaliphatic group-containing polymer (sometimes abbreviated as “fluorine polymer”).
  • fluorine polymer When this polymer is contained, the surface smoothness of the iodine diffusion preventing layer can be improved.
  • the fluoroaliphatic group-containing polymer is preferably a polymer having a perfluoroalkyl group having 4 or more carbon atoms or a fluoroalkyl group having 4 or more carbon atoms and —CF 2 H in the side chain.
  • the amount of the monomer unit derived from the fluoroaliphatic group-containing monomer represented by the general formula [2] described in paragraph [0193] of JP2012-214004A in the fluoropolymer is determined based on the total amount of monomers of the fluoropolymer. It is preferable that it is 10 mass% or more with respect to unit amount, More preferably, it is 40 mass% or more. In the fluoropolymer, the amount of monomer units derived from the monomer represented by the general formula [3] described in paragraph [0193] of JP2012-214004A is 90% with respect to the total monomer unit amount of the fluoropolymer. It is preferable to use less than mass%, more preferably less than 60 mass%.
  • the preferred weight average molecular weight of the fluoropolymer is preferably from 3,000 to 100,000, more preferably from 6,000 to 80,000, and even more preferably from 8,000 to 60,000.
  • the weight average molecular weight was measured using a TPCgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL columns (both manufactured by Tosoh Corporation, trade name) with a solvent THF (tetrohydrofuran) and polystyrene by differential refractometer detection.
  • the molecular weight expressed in terms of conversion.
  • the molecular weight is calculated from the peak area of 300 or more components.
  • the total solid content in the composition (coating liquid) for forming each polymer layer is preferably 0.001% to 5% by mass, and more preferably 0.005 to 2.0% by mass.
  • additives other than the above include fine particles.
  • the fine particles are not particularly limited, but fine oxide particles such as silicon, titanium, zirconium or aluminum, or crosslinked particles such as polyethylene, polystyrene, poly (meth) acrylate or polydimethylsiloxane, or SBR (Styrene-).
  • examples thereof include organic fine particles such as crosslinked rubber fine particles such as butadiene rubber (styrene-butadiene rubber) or NBR (acrylonitrile-butadiene rubber).
  • the average particle size of the fine particles is preferably 1 nm to 20000 nm.
  • the shape of the fine particles can be used without any particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape.
  • the amount of fine particles added is preferably 60% by volume or less, and more preferably 40% by volume or less in each polymer layer.
  • the cellulose ester layer (also referred to as cellulose ester film) constituting the polarizing plate protective film of the present invention is a layer containing 50% by mass or more of cellulose ester in the layer. 60 mass% or more is preferable, as for content of the cellulose ester in a cellulose-ester layer, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 85 mass% or more is especially preferable. The higher the content of the cellulose ester in the cellulose ester layer, the more preferable is that the adhesiveness with the iodine diffusion preventing layer can be maintained.
  • the upper limit of the content of the cellulose ester is not particularly limited, but is preferably 99% by mass or less, more preferably 96% by mass or less, still more preferably 95% by mass or less, and particularly preferably 92% by mass or less.
  • the remainder excluding the cellulose ester includes, for example, an additive described later.
  • the cellulose ester layer may contain other resins in the layer, and examples of the polymer B1 or B2 are preferable. When the cellulose ester layer contains the polymer B1 or B2, interlayer adhesion with the polymer layer can be further improved.
  • the cellulose ester used for the cellulose ester film of the present invention will be described.
  • the cellulose ester can be used without particular limitation as long as it is a cellulose ester used for the production of a cellulose ester film.
  • the ⁇ -1,4-bonded glucose unit constituting cellulose has free hydroxy groups at the 2nd, 3rd and 6th positions.
  • the cellulose ester is a polymer (polymer) obtained by esterifying a part of these hydroxy groups with an esterifying agent or the like. Examples of cellulose include cotton linter and wood pulp (hardwood pulp, softwood pulp), and the like. Any cellulose obtained from any raw material cellulose can be used, and in some cases, a mixture may be used.
  • the acyl substitution degree indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and is 2 for all glucose units.
  • substitution degree indicates the degree of acylation of the hydroxy group of cellulose located at the 2-position, 3-position and 6-position, and is 2 for all glucose units.
  • the total acyl substitution degree is 1 when all of any one of the 6-position and 2-position is acylated in each glucose unit in all hydroxy groups of all glucose. That is, the degree of substitution indicates the degree of acylation, where 3 is the case where all the hydroxy groups in the glucose molecule are all acylated.
  • the degree of substitution of cellulose acylate is described in Tezuka et al., Carbohydrate. Res. , 273, 83-91 (1995), or according to the method prescribed in ASTM-D817-96.
  • the total acyl substitution degree of the cellulose acylate used in the present invention is preferably 1.50 or more and 3.00 or less, more preferably 2.00 to 2.97, from the viewpoint of moisture permeability. It is more preferably 30 or more and less than 2.97, and particularly preferably 2.30 to 2.95.
  • the form which has 1 type of acyl groups may be sufficient, and the form which has 2 or more types of acyl groups may be sufficient.
  • the cellulose acylate that can be used in the present invention preferably has an acyl group having 2 or more carbon atoms as a substituent.
  • the acyl group having 2 or more carbon atoms is not particularly limited, and may be an aliphatic acyl group or an aromatic acyl group.
  • the cellulose acylate substituted with these acyl groups is, for example, an alkyl carbonyl ester, alkenyl carbonyl ester, aromatic carbonyl ester, or aromatic alkyl carbonyl ester of cellulose, and each further has a substituted group. Also good.
  • acyl group having 2 or more carbon atoms include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, isobutanoyl, tert-butanoyl, cyclohexanecarbonyl Oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.
  • acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, tert-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl are preferable, acetyl, propionyl, and butanoyl are more preferable, and acetyl is particularly preferable.
  • the cellulose acylate preferably has an acyl group having 2 to 4 carbon atoms as a substituent. When two or more kinds of acyl groups are used, it is preferable that one of them is an acetyl group. These cellulose acylates can produce a solution having a preferable solubility, and in particular, a non-chlorine organic solvent can be used to produce a good solution. Furthermore, it becomes possible to produce a solution having a low viscosity and good filterability.
  • Cellulose acetate using only an acetyl group as the acyl group of cellulose acylate can be suitably used in the present invention.
  • the total acyl substitution degree of this cellulose acetate is 2.00 to from the viewpoint of moisture permeability and optical properties. It is preferably 3.00, more preferably 2.20 to 3.00, still more preferably 2.30 to 3.00, and particularly preferably 2.30 to 2.97. Most preferably, it is 2.30-2.95.
  • a mixed fatty acid ester having two or more kinds of acyl groups can also be preferably used as the cellulose acylate in the present invention.
  • the acyl group of the mixed fatty acid ester preferably includes an acetyl group and an acyl group having 3 to 4 carbon atoms.
  • the degree of acetyl substitution is preferably less than 2.5 and more preferably less than 1.9.
  • the degree of substitution of the acyl group having 3 to 4 carbon atoms is preferably 0.1 to 1.5, and preferably 0.2 to 1.2.
  • two types of cellulose esters or cellulose acylates having one or both of an ester group and a degree of substitution can be used in combination.
  • the degree of polymerization of the cellulose ester or cellulose acylate used in the present invention is preferably 250 to 800, more preferably 300 to 600.
  • the number average molecular weight of the cellulose ester or cellulose acylate used in the present invention is preferably 40000 to 230,000, more preferably 60000 to 230,000, and most preferably 75,000 to 200000.
  • the degree of polymerization can be determined by dividing the number average molecular weight measured in terms of polystyrene by Gel Permeation Chromatography (GPC) by the molecular weight of the glucopyranose unit of cellulose ester or cellulose acylate.
  • GPC Gel Permeation Chromatography
  • the cellulose ester used in the present invention can be synthesized by a conventional method.
  • 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 acylate In general industrial production of cellulose acylate, an organic acid (acetic acid, propionic acid, butyric acid, etc.) or an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride, etc.) corresponding to the desired acyl group in cellulose is used. Is used to esterify the hydroxy group. For example, a cellulose derived from cotton linter or wood pulp is used as a raw material, and this is activated with an organic acid such as acetic acid and then esterified with an organic acid having a desired structure in the presence of a sulfuric acid catalyst. Acylate can be obtained.
  • cellulose is generally esterified using an excess amount of the organic acid anhydride relative to the amount of hydroxy groups present in the cellulose.
  • Cellulose acylate can also be synthesized, for example, by the method described in JP-A-10-45804.
  • the cellulose ester film preferably contains 5 to 99% by mass of a cellulose ester as a resin from the viewpoint of moisture permeability, more preferably 20 to 99% by mass, and particularly preferably 50 to 95% by mass.
  • the cellulose ester layer may contain an additive as long as the effects of the present invention are not impaired.
  • the additive include known plasticizers, organic acids, dyes, polymers, retardation adjusting agents, ultraviolet absorbers, antioxidants, and matting agents. Regarding these, the description of paragraph numbers [0062] to [0097] of JP2012-155287A can be referred to, and the contents thereof are incorporated in the present specification.
  • the additive include a peeling accelerator, an organic acid, and a polyvalent carboxylic acid derivative. With respect to these, the description of WO2015 / 005398, paragraphs [0212] to [0219] can be referred to, and the contents thereof are incorporated in the present specification.
  • examples of the additive include a radical scavenger, a deterioration inhibitor, and a barbituric acid compound, which will be described later.
  • the content of additives is preferably 50 parts by mass or less with respect to 100 parts by mass of the cellulose ester, 30 The amount is more preferably at most 5 parts by mass, and still more preferably 5-30 parts by mass.
  • Plasticizer One preferred additive is a plasticizer.
  • a plasticizer By adding a plasticizer to the cellulose ester film, the hydrophobicity of the cellulose ester film can be increased. This point is preferable from the viewpoint of reducing the moisture permeability of the cellulose ester film.
  • a plasticizer when used, when the cellulose ester film is used as a protective film for a polarizer (referred to as a polarizing plate protective film), display unevenness of an image display device due to humidity may be less likely to occur. This is preferable because it is possible.
  • polyhydric alcohol ester plasticizer The polyvalent ester compound (henceforth "polyhydric alcohol ester plasticizer") of a polyhydric alcohol, and a polycondensation ester compound (henceforth "polycondensation ester plasticizer”) Or a carbohydrate compound (hereinafter also referred to as “carbohydrate derivative plasticizer”).
  • carbohydrate derivative plasticizers For polyhydric alcohol ester plasticizers, paragraphs [0081] to [0098] of WO2015 / 005398, and for polycondensed ester plasticizers, paragraphs [0099] to [0122] of the same publication, carbohydrate derivative plasticizers.
  • the molecular weight of the plasticizer is preferably 3000 or less, more preferably 1500 or less, and still more preferably 1000 or less, from the viewpoint of obtaining the above-described effect by adding it satisfactorily.
  • the molecular weight of the plasticizer is, for example, 300 or more, preferably 350 or more, from the viewpoint of low volatility. In the case of multimeric plasticizers, the molecular weight is the number average molecular weight.
  • the content of the plasticizer is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the cellulose ester from the viewpoint of achieving both the effect of adding the plasticizer and suppressing the precipitation of the plasticizer. More preferred is 5 to 15 parts by mass.
  • Two or more plasticizers may be used in combination. Also when using 2 or more types together, the specific example and preferable range of content are the same as the above.
  • One preferable additive may include an antioxidant.
  • an antioxidant reference can be made to the description of paragraphs [0143] to [0165] of International Publication No. 2015/005398, the contents of which are incorporated herein.
  • radical scavenger One preferred additive may include a radical scavenger.
  • the description in paragraphs [0166] to [0199] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.
  • a deterioration preventing agent As one of preferable additives, a deterioration preventing agent can be mentioned. Regarding the deterioration preventing agent, the description in paragraphs [0205] to [0206] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated in the present specification.
  • the cellulose ester film can also contain a compound having a barbituric acid structure (barbituric acid compound).
  • a barbituric acid compound is a compound which can express various functions to a cellulose-ester film by adding this compound.
  • a barbituric acid compound is effective for improving the hardness of a cellulose ester film.
  • the barbituric acid compound is also effective in improving the durability of a polarizing plate provided with a cellulose ester film containing this compound against light, heat or humidity.
  • the barbituric acid compound that can be used in the cellulose ester film for example, the descriptions in paragraphs [0029] to [0060] of International Publication No. 2015/005398 can be referred to, and the contents thereof are incorporated herein.
  • the cellulose ester film of the present invention preferably has the following physical properties or characteristics.
  • the average film thickness of the cellulose ester film can be appropriately determined according to the use, but is preferably, for example, 10 to 100 ⁇ m, more preferably 15 to 80 ⁇ m, and further preferably 25 to 60 ⁇ m. .
  • the handling property when producing a web-like film is improved, which is preferable.
  • it by setting it as 100 micrometers or less, it is easy to respond to a humidity change and it is easy to maintain an optical characteristic.
  • the thickness of the core layer is preferably 3 to 70 ⁇ m, and more preferably 5 to 60 ⁇ m.
  • the film thicknesses of the first skin layer (also referred to as air surface layer or air side surface layer) and the second skin layer (also referred to as support layer or support side surface layer) in the case of the three-layer structure are both 0.5. Is preferably 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and even more preferably 0.5 to 3 ⁇ m.
  • the core layer is a layer located inside in the laminated structure, and in the case of a three-layer structure, the core layer is an intermediate layer, and both skin layers are layers located outside in the laminated structure or the three-layer structure.
  • the cellulose ester film can be appropriately determined depending on the application.
  • the film width is preferably 700 to 3000 mm, more preferably 1000 to 2800 mm, and particularly preferably 1470 to 2500 mm.
  • Moisture permeability of polarizing plate protective film The moisture permeability of the polarizing plate protective film is 100 to 1600 g / m 2 per 6 hours. When the moisture permeability per 6 hours is less than 100 g / m 2 , drying in the polarizing plate production process is slow and productivity is lowered. On the other hand, if it exceeds 1600 g / m 2 , deterioration of the polarizer may not be effectively suppressed when used as a protective film for the polarizer.
  • the moisture permeability per 6 hours preferably from 150 ⁇ 1200g / m 2, more preferably 200 ⁇ 1000g / m 2, and particularly preferably 300 ⁇ 800g / m 2.
  • the moisture permeability in the polarizing plate protective film of the present invention is a value calculated by the following method based on “moisture-proof packaging material moisture permeability test method (cup method)” of JIS Z 0208 (1976).
  • the polarizing plate protective film was cut into 60 mm ⁇ 60 mm, subjected to a temperature of 85 ° C. and 85% relative humidity, the mass of water vapor passing through the cut films to 6 hours was measured, the mass per surface area 1 m 2 of cut films It can be obtained as a converted value.
  • the mass of water vapor is measured by the mass change of the moisture absorbent (anhydrous calcium chloride).
  • the polarizing plate protective film includes, for example, a step of applying a composition (formation liquid) for forming a polymer B1 layer on at least one surface of the cellulose ester layer after preparing the cellulose ester layer by a method described later. It is manufactured by the method of including.
  • the composition for forming the polymer B1 layer contains polymer B1 and a solvent in which fd defined by the following formula I satisfies the following relational expressions [1] and [2]. Thereby, the interlayer adhesiveness of a cellulose-ester layer and polymer B1 layer can be made stronger.
  • the above-mentioned mixed region can be formed in the vicinity of the boundary between the cellulose ester layer and the polymer B1 layer, and the effect of improving the interlayer adhesion is increased.
  • region is not specifically limited, It can set suitably according to the ease of melt
  • the thickness of the mixed region in the cellulose ester layer or the polymer B1 layer is derived from the cellulose ester and the polymer B1 by performing time-of-flight secondary ion mass spectrometry of the film cross section near the boundary between the cellulose ester layer and the polymer B1 layer. It can be measured by the distribution of fragment ions.
  • ⁇ 5-1 Method for Producing Cellulose Ester Layer> The manufacturing method of the cellulose-ester layer used for the manufacturing method of the polarizing plate protective film of this invention is demonstrated.
  • the cellulose ester film is not particularly limited, and is preferably produced by, for example, a melt casting method or a solution casting method (solvent casting method). In consideration of volatilization and decomposition of the additive, More preferably it is manufactured.
  • a melt film forming method a production method such as a T-die method is preferably used, and a simultaneous coextrusion method is particularly preferable.
  • the solution casting method it is preferable to use a lamination casting method such as a co-casting method, a sequential casting method, or a coating method, which will be described later. It is particularly preferable to use it from the viewpoint of stable production and production cost reduction.
  • 2,336,310, 2,367,603, 2,492,078, and 2,492,977 describe examples of film production utilizing the solution casting method.
  • Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035 can be referred to. .
  • the solution casting method includes a method of uniformly extruding the prepared dope from a pressure die onto a metal support, and a doctor that adjusts the film thickness with a blade of the dope once cast on a metal support.
  • a method using a blade and a method using a reverse roll coater which adjusts with a reverse rotating roll and a method using a pressure die is preferred.
  • the pressure die includes a coat hanger type and a T die type, and any of them can be preferably used.
  • it can be carried out by various known methods for casting a cellulose ester solution, and each condition is set in consideration of differences in the boiling point of the solvent used. can do.
  • the metal support one that runs endlessly is preferable, and a drum whose surface is mirror-finished by chrome plating or a stainless steel belt (which may be called a band) whose surface is mirror-finished is used.
  • a product made from SUS for example, SUS316.
  • One or two or more pressure dies may be installed above the metal support. Preferably one or two are installed. When two or more are installed, the dope amount to be cast may be divided into various ratios for each die, or the dope may be fed to the dies from each of a plurality of precision quantitative gear pumps at each ratio.
  • the temperature of the dope (resin solution) used for casting is preferably ⁇ 10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all solution temperatures in the process may be the same or different at different points in the process. If they are different, the temperature may be a desired temperature just before casting.
  • the cellulose ester film is a multilayer
  • a lamination casting method such as a co-casting method, a sequential casting method or a coating method, and particularly a simultaneous co-casting method (also referred to as a simultaneous multi-layer co-casting method). It is particularly preferable from the viewpoint of stable production and production cost reduction.
  • a cellulose ester solution also referred to as a dope
  • this solution is cast on a support.
  • a casting dope for each layer (which may be three layers or more) is provided on a casting support (band or drum) from a separate slit or the like.
  • the dope is extruded using a casting die that can be extruded at the same time, and the layers are cast simultaneously.
  • It is a casting method in which after casting, the film is peeled off from the support after an appropriate time and dried to form a film.
  • a co-casting die for example, a total of three layers: a surface layer two layers formed from a surface layer dope on a casting support, and a core layer composed of a core layer dope sandwiched between these surface layers.
  • FIG. 8 is a schematic diagram (partially enlarged view) showing an example of co-casting.
  • the co-casting according to the example shown in FIG. 8 will be further described in an example described later.
  • a casting dope for the first layer is first extruded from a casting die on a casting support, cast, and dried or dried without being dried.
  • the dope for casting for two layers is extruded from a casting die, and if necessary, the dope is successively casted to the third layer or more, laminated, and peeled off from the support after an appropriate time. And dried to form a cellulose ester film.
  • the coating method generally, a core layer is formed into a film by a solution casting method, and a coating solution that is a target cellulose ester solution is applied to the surface layer, followed by drying to form a cellulose ester having a laminated structure. A film can be produced.
  • the cellulose ester film is also preferably stretched after casting and drying.
  • the cellulose ester film preferably has a degree of orientation in the thickness direction within a certain range, but the orientation degree in the thickness direction can be increased by stretching treatment.
  • the stretching direction of the cellulose ester film may be either a film transport direction (MD (Machine Direction) direction) or a direction (TD (Transverse Direction) direction) orthogonal to the transport direction. Considering the subsequent polarizing plate processing process, the TD direction is preferable.
  • the stretching process may be performed a plurality of times in two or more stages.
  • the film can be stretched by conveying the film while holding the film with a tenter and gradually widening the width of the tenter. Further, after the polymer film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine). In the case of stretching in the MD direction, for example, it can be performed by adjusting the speed of the film conveyance roller to make the winding speed faster than the film peeling speed.
  • the stretching ratio of the cellulose ester film (meaning the ratio of the stretching amount to the dimension before stretching) is preferably 1% or more and 100% or less, more preferably 5% or more and 60% or less, and more preferably 10% or more and 40% or less. Particularly preferred.
  • the draw ratio is preferably 5% or more and 30% or less, and more preferably 8% or more and 20% or less.
  • the film may be stretched in both the transport direction and the width direction. In that case, the stretch ratio in the transport direction is 1% or more and 20% or less, and the stretch ratio in the width direction is 5% or more and 30% or less. It is preferable that the draw ratio in the conveyance direction is 1% or more and 8% or less, and the draw ratio in the width direction is 10% or more and 20% or less.
  • the stretching process may be performed in the middle of the film forming process, or the raw film that has been formed and wound may be stretched, but in the production method of the present invention, the support is used in a state containing a residual solvent. It is preferable to exfoliate and stretch, that is, stretch in the middle of the film forming process.
  • the amount of residual solvent at the time of peeling from the support is preferably 10 to 100% by mass, and more preferably 15 to 60% by mass.
  • M represents the mass of the cellulose ester film before drying
  • N represents the mass when the cellulose ester film before drying is dried at 110 ° C. for 3 hours.
  • the method for producing the cellulose ester film includes a step of drying the cellulose ester film and a step of stretching the dried cellulose ester film at a temperature of Tg ⁇ 10 ° C. or higher. preferable.
  • the dope is dried on the metal support for producing the cellulose ester film by applying hot air from the surface side of the metal support (drum or belt), that is, from the surface of the web on the metal support.
  • Method, method of applying hot air from the back of the drum or belt contact the temperature-controlled liquid from the back of the belt or drum opposite the dope casting surface, and heat the drum or belt by heat transfer to control the surface temperature
  • There is a back surface liquid heat transfer method and the back surface liquid heat transfer method is preferable.
  • the surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. However, in order to accelerate drying and to lose fluidity on the metal support, the temperature should be set to 1 to 10 ° C. lower than the boiling point of the lowest boiling solvent used. Is preferred. Note that this is not the case when the casting dope is cooled and peeled off without drying.
  • the method for producing the cellulose ester film preferably includes a step of peeling the dope film from the metal support.
  • peeling method in the manufacturing method of the said cellulose-ester film, When a well-known method is used, peelability can be improved. It can also peel in the above-mentioned extending
  • the film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness.
  • the length of the cellulose ester film obtained as described above is preferably wound at 100 to 10000 m per roll, more preferably 500 to 7000 m, still more preferably 1000 to 6000 m.
  • knurling is preferably applied to at least one end, the knurling width is preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 ⁇ m, more preferably 1 to 200 ⁇ m. is there. This may be a single push or a double push.
  • the cellulose ester film is particularly suitable for use in a large-screen liquid crystal display device.
  • the film width is preferably set to 1470 mm or more.
  • the polarizing plate protective film of the present invention is produced not only in the form of a film piece cut into a size that can be incorporated into a liquid crystal display device as it is, but also in a long shape by continuous production. The film of the aspect wound up in the shape is also included.
  • the polarizing plate protective film of the latter mode is stored and transported in that state, and is cut into a desired size and used when it is actually incorporated into a liquid crystal display device or bonded to a polarizer or the like. Similarly, it is cut into a desired size when it is actually incorporated into a liquid crystal display device after being bonded to a polarizer or the like made of a polyvinyl alcohol film or the like that has been made into a long shape. Used.
  • a mode in which the roll length is rolled up to 2500 m or more can be mentioned.
  • the polymer B1 layer can be formed by applying the following composition on the cellulose ester layer. Thereby, a cellulose-ester layer and polymer B1 layer can be laminated
  • the composition is preferably dried after application.
  • composition for forming polymer B1 layer is formed using the following composition.
  • a composition (also referred to as an iodine diffusion preventing layer forming composition) B1 for forming a polymer B1 layer used in this method is composed of a polymer B1 and fd defined by the following formula I: And a solvent satisfying the relational expression [2] and, if necessary, an additive described later.
  • the solubility or swelling property with respect to the cellulose ester is too low, the formation of the mixed region may be insufficient and sufficient interlayer adhesion may not be exhibited.
  • the solubility or swellability is too high, after the solvent is removed by drying, the cellulose ester and the polymer B1 may be phase-separated and the mixed region may become brittle, and sufficient interlayer adhesion will not be exhibited.
  • the solvent contained in the composition B1 a solvent in which fd defined by the following formula I satisfies the following relational expressions [1] and [2] is used.
  • Formula I fd ⁇ d / ( ⁇ d + ⁇ p + ⁇ h)
  • ⁇ d, ⁇ p, and ⁇ h are a term corresponding to the London dispersion force, a term corresponding to the force between dipoles, and a term corresponding to the hydrogen bonding force, respectively, in the solubility parameter ⁇ t calculated by the Hoy method.
  • Fd represents the ratio of ⁇ d to the sum of ⁇ d, ⁇ p, and ⁇ h.
  • fd solvent represents the fd value of the solvent
  • fd cellulose represents the fd value of the cellulose ester contained in the cellulose ester layer
  • fd polymerB1 represents the fd value of the polymer B1.
  • calculated by the relational expression [1] exceeds 0.050, swelling or dissolution of the cellulose ester by the solvent becomes insufficient, and adhesion is deteriorated.
  • the solvent contained in this composition will not be specifically limited if the said relational expressions [1] and [2] are satisfy
  • This solvent preferably satisfies the relational expressions [1-1] and [2-1] in terms of interlayer adhesion.
  • d solvent , fd cellulose, and fd polymerB1 are synonymous with the relational expressions [1] and [2], respectively.
  • the solvent satisfies the relational expression [1] or [1-1] and the relational expression [2] or [2-1], and further includes the following relational expression [1-2] and relational expression [ Those satisfying at least one of 2-2] are more preferable.
  • d solvent , fd cellulose, and fd polymerB1 are respectively synonymous with the above relational expressions [1] and [2].
  • the fd value when two or more solvents are used in combination is calculated by the following equation.
  • (Fd value of mixed solvent) ⁇ (wi ⁇ fdi)
  • wi represents the mass fraction of the i-th solvent
  • fdi represents the fd value of the i-th solvent.
  • the fd value when two or more kinds of polymers B1 are used in combination is calculated by the following equation.
  • (Fd value of mixed polymer B1) ⁇ (wi ⁇ fdi)
  • wi represents the mass fraction of the i-th polymer B1
  • fdi represents the fd value of the i-th polymer B1.
  • the fd value of the polymer B1 in the relational expression [2] is calculated by ⁇ d, ⁇ p, and ⁇ h obtained by the following formula.
  • ( ⁇ d value of polymer B1) ⁇ (mi ⁇ ⁇ di)
  • mi represents the mole fraction of the i-th repeating unit
  • ⁇ di represents the ⁇ d value of the i-th repeating unit.
  • ( ⁇ p value of polymer B1) ⁇ (mi ⁇ ⁇ pi)
  • mi represents the mole fraction of the i-th repeating unit
  • ⁇ pi represents the ⁇ p value of the i-th repeating unit.
  • ( ⁇ h value of polymer B1) ⁇ (mi ⁇ ⁇ hi)
  • mi represents the mole fraction of the i-th repeating unit
  • ⁇ hi represents the ⁇ h value of the i-th repeating unit.
  • the fd value of the cellulose ester is calculated as follows.
  • (Fd value of cellulose ester) ⁇ (wi ⁇ fdi)
  • wi represents the mass fraction of the i-th cellulose ester
  • fdi represents the fd value of the i-th cellulose ester.
  • fd represented by the above formula I is calculated for each of the cellulose ester or polymer B1 to be used and the solvent.
  • ⁇ Term ⁇ d corresponding to London dispersion force ⁇ Term corresponds to the London dispersion force ⁇ d is calculated for Amorphous Polymers literature "Properties of Polymers 3 rd, ELSEVIER , (1990)" in “2) Method of Hoy (1985,1989)” column of 214-220 pages Is calculated according to the description in the above column of the above document.
  • the fd of the solvent, the polymer B1, and the cellulose ester are calculated by Formula I using ⁇ d, ⁇ p, and ⁇ h calculated as described above. Thereby, it can be judged whether the solvent to be used satisfies the relational expressions [1] and [2].
  • the solubility parameter ⁇ t is a physical property index having the following relationship with respect to the term ⁇ d corresponding to the London dispersion force, the term ⁇ p corresponding to the dipole force, and the term ⁇ h corresponding to the hydrogen bond force.
  • ⁇ t 2 ⁇ d 2 + ⁇ p 2 + ⁇ h 2
  • the cellulose ester has a glucopyranose ring portion having a small polarity and an ester portion having a high polarity and capable of forming a hydrogen bond.
  • the present inventors found that the swelling or solubility of cellulose ester in the solvent corresponds to the term ⁇ d corresponding to the London dispersion force, the affinity to the glucopyranose ring part, the term ⁇ p corresponding to the force between dipoles, and the hydrogen bonding force.
  • the sum of the terms ⁇ h corresponds to the affinity for the ester moiety, and we thought it important to balance the two.
  • the solubility in a solvent can be adjusted by balancing the affinity for the hydrocarbon group part and the affinity for the polar group and the hydrogen bonding group part.
  • the inventors focus on the contribution rate fd of the London dispersion force to the sum of the term ⁇ d corresponding to the London dispersion force, the term ⁇ p corresponding to the dipole force, and the term ⁇ h corresponding to the hydrogen bond force.
  • a correlation was found between the adhesion of the polarizing plate protective film of the present invention or the effect of improving the durability of the polarizing plate. The present inventors consider this as follows.
  • the polymer B1 and the cellulose ester present on the surface of the laminated interface and in the vicinity thereof are used by using a solvent having an fd value similar to that of the polymer B1 and the cellulose ester. Each dissolves in a solvent. As a result, the interaction between the polymer B1 and the cellulose ester is increased through the solvent at the laminated interface, and in addition, a mixed region of the polymer B1 and the cellulose ester is formed in the vicinity of the interface between the two layers. ing.
  • fill said relational expression [1] and relational expression [2] An organic solvent is mentioned, 1 type can be used individually or multiple types can be used together. Among these, it is preferable to select and use a ketone solvent, an acetate solvent, and a hydrocarbon solvent that satisfy the above relational expression [1] and relational expression [2]. Although it does not specifically limit as a ketone solvent, For example, acetone, MEK (methyl ethyl ketone), MiBK (methyl isobutyl ketone), etc. are mentioned.
  • acetate solvent For example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, or butyl acetate is mentioned.
  • hydrocarbon solvent For example, toluene or a cyclohexane is mentioned.
  • the mass ratio of the polymer B1 and the solvent is not particularly limited, but 3 to 3 of the polymer B1 with respect to the total amount of the solvent exhibiting the fd value satisfying the relational expression [1] and the relational expression “2”. It is preferable to contain 50 mass%. By setting it as such mass ratio, the composition excellent in manufacture aptitude can be obtained.
  • the polymer B1 contained in the composition liquid is as described above.
  • the composition liquid may contain the above-described polymer B1, other resins, and various additives.
  • This composition preferably further includes a material (binder) for forming the active energy ray-cured layer from the viewpoint of promoting drying of the solvent after application.
  • a material for forming the active energy ray-cured layer from the viewpoint of promoting drying of the solvent after application.
  • a binder is not particularly limited, and ordinary binders can be used.
  • the method for applying the iodine diffusion preventing layer forming composition B1 is not particularly limited, and a normal method can be adopted.
  • a coating method and the like can be mentioned. From the viewpoint of productivity, the coating method is preferable, and the spray coating method is more preferable among the coating methods.
  • the coating method of the iodine diffusion preventing layer forming composition B1 is not particularly limited, and a normal method can be adopted.
  • the polymer layer B1 can also be formed by various coating methods. Examples of various coating methods include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating (die coating) (see US Pat. No. 2,681,294). ) Or a known method such as a micro gravure coating method is used. Among these, the micro gravure coating method is preferable.
  • the transport speed at the time of application is not particularly limited, but it is preferable to apply under the condition of a transport speed of 1 to 100 m / min.
  • the drying conditions after application are not particularly limited, when drying is fast (evaporation of the solvent is fast), the time during which the cellulose ester and the polymer B1 can be mixed becomes short, and the thickness of the mixing region becomes thin. Therefore, the drying conditions take into consideration the thickness of the mixed region to be formed, for example, the temperature of the drying air, the solvent content in the drying air, the thickness of the composition after application, the molecular weight of the solvent, the boiling point of the solvent, etc. It is preferable to set appropriately.
  • the drying temperature is preferably selected from the range of 25 to 140 ° C. and the drying time of 30 to 1000 seconds. In this way, the polymer B1 layer is formed on the cellulose ester layer.
  • a polymer B2 layer is formed on the surface of the polymer B1 layer formed as described above on the side opposite to the cellulose ester layer.
  • the polymer B2 layer can be formed by applying a composition (also referred to as an iodine diffusion preventing layer forming composition) B2 for forming the polymer B2 layer on the surface.
  • the application method of this composition B2 is not specifically limited, The same method as the application method of composition B1 for iodine diffusion prevention layer formation is mentioned, A coating method is preferable.
  • Composition B2 is preferably dried after application.
  • the iodine diffusion preventing layer forming composition B2 contains the polymer B2, the solvent, and, if necessary, the additives described above.
  • the solvent contained in the iodine diffusion preventing layer forming composition B2 is not particularly limited, and there is no limitation regarding fd defined by Formula I such as the above relational expression.
  • a solvent various organic solvents can be used.
  • an organic solvent a ketone solvent, an acetate solvent, or a hydrocarbon solvent is mentioned preferably, for example, The same kind as the solvent contained in the composition B1 for iodine diffusion prevention layer formation is mentioned.
  • chain aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, liquid paraffin or mineral spirit, or cyclopentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethyl
  • An alicyclic hydrocarbon solvent such as cyclohexane, diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene or cyclooctane can also be used.
  • the interaction between the polymer B1 and the polymer B2 is increased during the formation of the polymer B2 layer.
  • a mixed region of the polymer B1 and the polymer B2 is formed in the vicinity.
  • the above-described method of applying the iodine diffusion preventing layer forming composition B2 is the same as the above method of applying the iodine diffusion preventing layer forming composition B1. Also in a preferable coating method, the coating method (conditions) and drying method (conditions) of the iodine diffusion preventing layer forming composition B2 are the same as the coating method and drying method of the iodine diffusion preventing layer forming composition B1. .
  • the polymer B2 layer can be formed on the polymer B1 layer.
  • the polarizer when an iodine diffusion preventing layer is provided on both sides of the polarizer, the polarizer is prepared in the same manner as in “5-2: Formation of polymer B1 layer” and “5-3: Formation of polymer B2 layer”. An iodine diffusion preventing layer can be formed on each side.
  • Polarizing plate of the present invention comprises at least one polarizer and the polarizing plate protective film of the present invention.
  • the polarizing plate of the present invention having the polarizing plate protective film of the present invention has strong adhesion between the polarizer and the polarizing plate protective film, effectively prevents deterioration of the polarizer, and exhibits high polarizer durability. Below, the structure and performance of a polarizing plate, a polarizer, etc. are demonstrated.
  • Polarizer is not particularly limited as long as it comprises at least a dichroic dye and a resin, and those usually used for polarizing plates can be used.
  • a film obtained by immersing and stretching a polyvinyl alcohol film in an iodine solution can be used.
  • the saponification surface of the cellulose ester layer in the laminate is bonded to at least one surface of the polarizer using an adhesive. Can do.
  • Shape and structure of polarizing plate The shape of the polarizing plate of the present invention is not only a polarizing plate in the form of a film piece cut into a size that can be incorporated into a display device as it is, but also produced in a long shape by continuous production.
  • a polarizing plate of an aspect wound in a roll shape (for example, an aspect having a roll length of 2500 m or more or 3900 m or more) is also included.
  • the width of the polarizing plate is preferably 1470 mm or more.
  • a polarizing plate in which both sides are protected by sandwiching a polarizer with a polarizing plate protective film is widely used as the polarizing plate, but the polarizing plate of the present invention protects the polarizing plate on at least one surface of the polarizer.
  • Other configurations are not particularly limited as long as the film is included.
  • FIG. 5 there are a polarizer 16 and a polarizing plate 15 ⁇ / b> A having at least one polarizing plate protective film 10 ⁇ / b> A of the present invention only on one surface of the polarizer 16.
  • the polarizing plate which has the polarizing plate protective film of this invention on both surfaces of a polarizer is also mentioned.
  • the polarizing plate of the present invention may have a film on the surface on which the polarizing plate protective film of the present invention is not provided in that the surface of the polarizer is protected and optically compensated.
  • the cycloolefin film containing a cycloolefin polymer is mentioned preferably at the point which shows high moisture resistance.
  • An example of a polarizing plate having a cycloolefin film is a polarizing plate 15B shown in FIG. This polarizing plate 15B has the polarizing plate protective film 10A of the present invention on one surface of the polarizer 16, and the cycloolefin film 17 on the other surface.
  • Examples of the cycloolefin polymer include (1) a polymer containing a structural unit derived from a norbornene compound, (2) a polymer containing a structural unit derived from a monocyclic olefin compound other than the norbornene compound, (3) A polymer containing a structural unit derived from a cyclic conjugated diene compound, (4) a polymer containing a structural unit derived from a vinyl alicyclic hydrocarbon compound, and a structure derived from each compound of (1) to (4) Examples include hydrides of polymers containing units.
  • the polymer containing a structural unit derived from a norbornene compound and the polymer containing a structural unit derived from a monocyclic olefin compound include a ring-opening polymer of each compound.
  • the cycloolefin polymer is not particularly limited, but a polymer having a structural unit derived from a norbornene compound represented by the following general formula (A-II) or (A-III) is preferable.
  • a polymer having a structural unit represented by the following general formula (A-II) is an addition polymer of a norbornene compound
  • a polymer having a structural unit represented by the following general formula (A-III) is a norbornene compound. It is a ring-opening polymer.
  • R 3 to R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrocarbon group is not particularly limited as long as it is a group composed of a carbon atom and a hydrogen atom, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group (aromatic hydrocarbon group). Among these, an alkyl group or an aryl group is preferable.
  • X 2 and X 3 , Y 2 and Y 3 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,- (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 the X 2 and Y 2 or X 3 and Y 3 bonded to form together, (- CO) 2 O or ( —CO) 2 NR 15 is represented.
  • R 11 to R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen
  • W represents Si ( R 16 ) p D (3-p)
  • R 16 represents a hydrocarbon group having 1 to 10 carbon atoms
  • D is a halogen atom
  • —OCOR 17 or —OR 17 R 17 is a hydrocarbon having 1 to 10 carbon atoms) Group
  • p is an integer of 0 to 3.
  • n is an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6.
  • R 3 to R 6 are each preferably a hydrogen atom or —CH 3, and more preferably a hydrogen atom in terms of moisture permeability.
  • X 2 and Y 2 are each preferably a hydrogen atom, —CH 3 , or —C 2 H 5, and more preferably a hydrogen atom in terms of moisture permeability.
  • X 3 and Y 3 are each preferably a hydrogen atom, a halogen atom (particularly a chlorine atom) or — (CH 2 ) nCOOR 11 (particularly —COOCH 3 ), and more preferably a hydrogen atom in terms of moisture permeability.
  • Other groups are appropriately selected.
  • m is 0 or 1
  • R 3 to R 6 , X 2 to X 3 and Y 2 to Y 3 are all hydrogen atoms. Particularly preferred.
  • the polymer having a structural unit represented by the general formula (A-II) or (A-III) may further contain at least one structural unit represented by the following general formula (AI).
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • X 1 and Y 1 each independently represent a hydrogen atom, or a carbon group having 1 to 10 carbon atoms.
  • R 11 to R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen
  • W represents Si ( R 16 ) p D (3-p) (R 16 represents a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, —OCOR 17 or —OR 17 (R 17 is a hydrocarbon having 1 to 10 carbon atoms) Group)
  • p is an integer of 0 to 3.
  • n represents an integer of 0 to 10.
  • R 1 , R 2 , X 1 and Y 1 are each more preferably a hydrogen atom.
  • Addition (co) polymers of norbornene compounds are described in JP-A-10-7732, JP-T 2002-504184, U.S. Patent Publication No. 200429129157A1, or International Publication No. 2004/070463.
  • the norbornene compound polymer is obtained by addition polymerization of norbornene compounds (for example, norbornene polycyclic unsaturated compounds).
  • a polymer of norbornene compound a norbornene compound and an olefin such as ethylene, propylene and butene, a conjugated diene such as butadiene and isoprene, a non-conjugated diene such as ethylidene norbornene, acrylonitrile, acrylic acid
  • a copolymer with ethylene is preferable.
  • Such norbornene compound addition (co) polymers are sold under the trade name of Apel by Mitsui Chemicals, and have different glass transition temperatures (Tg), such as APL8008T (Tg70 ° C.), APL6013T (Tg125). ° C) or APL6015T (Tg145 ° C).
  • Tg glass transition temperatures
  • pellets such as TOPAS 8007, 6013, and 6015 are commercially available from Polyplastics.
  • Appear 3000 is commercially available from Ferrania.
  • a hydride of a polymer of a norbornene compound can be synthesized by subjecting a norbornene compound or the like to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.
  • Examples of the synthesis method include JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-1159767, or JP-A-2004-309799. It is described in each gazette.
  • the mass average molecular weight of the cycloolefin polymer is not particularly limited, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, still more preferably 30,000 to 500,000, and 50,000 to 300,000. Is particularly preferred, with 50,000 to 200,000 being most preferred.
  • the molecular weight of the cycloolefin polymer can be measured under the following conditions. As the mass average molecular weight, a mass average molecular weight measured in terms of polystyrene by Gel Permeation Chromatography (GPC) was adopted. Specific measurement conditions are shown below.
  • Method for Laminating Polarizer and Polarizing Plate Protective Film In the method for producing a polarizing plate of the present invention, at least one polarizing plate protective film of the present invention is laminated on at least one surface of the polarizer. In the method for producing a polarizing plate of the present invention, the polarizing plate protective film surface is treated with an alkali, and a PVA (polyvinyl alcohol) film is immersed and stretched in an iodine solution. It is preferable to prepare by a method of bonding using a completely saponified polyvinyl alcohol aqueous solution.
  • PVA polyvinyl alcohol
  • an adhesive agent used for bonding the process surface of a polarizing plate protective film and a polarizer
  • a polarizer for example, the aqueous solution of polyvinyl alcohol or polyvinyl acetal (for example, polyvinyl butyral), vinyl polymer (for example, , Polybutyl acrylate) latex, ultraviolet curable adhesive, and the like.
  • Particularly preferred adhesives are aqueous solutions of fully saponified polyvinyl alcohol or UV curable adhesives.
  • the bonding method described in JP-A-2015-11094 can be preferably used as a method by bonding the polarizing plate protective film of the present invention and a polarizer.
  • the active energy ray-curable adhesive composition is applied, bonded to a polarizer, irradiated with ultraviolet rays, and cured after drying the resin. .
  • the polarizing plate protective film of the present invention is preferably bonded to the cellulose ester film so that the iodine diffusion preventing layer is closer to the polarizer (see FIGS. 5 and 6).
  • the above configuration is preferable because diffusion of iodine to the polarizing plate protective film can be effectively suppressed, and polarization performance deterioration is less likely to occur when stored in a high temperature and high humidity environment for a long period of time.
  • the cellulose ester film of the present invention is preferably bonded to the polarizer so that the transmission axis of the polarizer and the slow axis of the cellulose ester film of the present invention are parallel, orthogonal or 45 °.
  • the slow axis can be measured by various known methods, for example, using a birefringence meter (KOBRADH, manufactured by Oji Scientific Instruments).
  • parallel, orthogonal, or 45 ° includes a range of errors allowed in the technical field to which the present invention belongs.
  • the parallel of the transmission axis of the polarizer and the slow axis of the cellulose ester film of the present invention is an angle of ⁇ 10 ° between the direction of the main refractive index nx of the cellulose ester film of the present invention and the direction of the transmission axis of the polarizer. It means that we are in a circle.
  • This angle is preferably within a range of ⁇ 5 °, more preferably within a range of ⁇ 3 °, further preferably within a range of ⁇ 1 °, and most preferably within a range of ⁇ 0.5 °.
  • the orthogonality of the transmission axis of the polarizer and the slow axis of the cellulose ester film of the present invention means that the direction of the main refractive index nx of the cellulose ester film of the present invention and the direction of the transmission axis of the polarizer are 90 ° ⁇ It means that they intersect at an angle in the range of 10 °.
  • This angle is preferably in the range of 90 ° ⁇ 5 °, more preferably in the range of 90 ° ⁇ 3 °, even more preferably in the range of 90 ° ⁇ 1 °, most preferably 90 ° ⁇ 0.1 °. Within range. If it is the above ranges, the fall of the polarization degree performance under polarizing plate cross Nicol will be suppressed, and light omission will be reduced and it is preferable.
  • a method for bonding the polarizing plate protective film and the polarizer a method of providing an easy-adhesion layer on the surface of the polarizing plate protective film on the side to be bonded to the polarizer is also one preferred embodiment.
  • the easy-adhesion layer provided on the surface of the polarizing plate protective film of the present invention that is bonded to the polarizer is referred to as “polarizer-side easy-adhesion layer”.
  • the polarizer-side easy-adhesion layer is a layer for improving the adhesion between various polarizers and the polarizing plate protective film of the present invention, and is used for bonding the polarizer and the polarizing plate protective film of the present invention. It can be used to improve adhesion with various adhesives. From the viewpoint of improving the polarizer durability, the polarizer-side easy-adhesion layer is preferably provided on the iodine diffusion preventing layer side, and most preferably provided adjacent to the iodine diffusion preventing layer.
  • the polarizer-side easy-adhesion layer preferably contains an organic conductive material, as disclosed in JP-A-2015-102636. Reference can be made to the description of paragraphs [0058] to [0068], the contents of which are incorporated herein.
  • the organic conductive material may be contained only in the polarizer-side easy adhesion layer.
  • the polarizer-side easy-adhesion layer preferably contains at least one selected from a cellulose acylate resin, a polyester resin, a polyvinyl alcohol resin, an acrylic resin, and a urethane resin, and particularly contains a cellulose acylate resin and / or a urethane resin. Is preferred.
  • the polarizer side easily bonding layer may contain the crosslinking agent.
  • the crosslinking agent is preferably an isocyanate compound, and those described in paragraphs [0070] to [0071] of JP-A-2015-102636 can be used.
  • the polarizer-side easy-adhesion layer becomes strong, and therefore, in addition to interlayer adhesion, moisture and heat resistance or scratch resistance may be further improved.
  • Two or more polarizer-side easy-adhesion layers may be provided on the polarizing plate protective film of the present invention.
  • two or more kinds of the above-described resins may be used in combination in the same layer, or two or more layers having different compositions may be provided as the polarizer-side easy adhesion layer.
  • Examples of the cellulose acylate resin used in the polarizer easy-adhesion layer include the cellulose acylate described in the cellulose ester layer, and these can be preferably used.
  • the polyester resin the description in paragraphs [0077] to [0079] of JP-A-2015-102636 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polyvinyl alcohol resin the description in paragraphs [0080] to [0081] of JP-A-2015-102636 can be referred to, and the contents thereof are incorporated in the present specification.
  • As the acrylic resin the description in paragraphs [0083] to [0084] of JP-A-2015-102636 can be referred to, and the contents thereof are incorporated in the present specification.
  • the urethane resin the description in paragraphs [0085] to [0093] of JP-A-2015-102636 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polarizer-side easy-adhesion layer may be used in combination with a binder polymer other than the above-described resin in order to improve the coated surface state or transparency of the polarizer-side easy-adhesion layer.
  • a binder polymer other than the above-described resin
  • the binder polymer reference can be made to the descriptions in paragraphs [0095] to [0096] of JP-A No. 2015-102636, the contents of which are incorporated herein.
  • the polarizer-side easy-adhesion layer may contain an ultraviolet absorber or particles for adjusting the refractive index.
  • an ultraviolet absorber or particles for adjusting the refractive index As other materials that the polarizer-side easy-adhesion layer may contain, reference can be made to the descriptions in paragraphs [0073] to [0074] of JP-A-2015-102636, the contents of which are incorporated herein. .
  • the method for providing the polarizer-side easy-adhesion layer on the polarizing plate protective film of the present invention is not particularly limited.
  • the description in paragraphs [0106] to [0110] of JP-A No. 2015-102636 can be referred to. The contents are incorporated herein.
  • the polarizing plate of the present invention is an antireflection film, a hard coat layer, a brightness enhancement film, a forward scattering layer, or a forward scattering layer for improving the visibility of a liquid crystal display device within the scope of the present invention. It is also preferably used as a functionalized polarizing plate combined with a polarizing plate protective film having a functional layer such as an antiglare (antiglare) layer.
  • a functionalized polarizing plate combined with a polarizing plate protective film having a functional layer such as an antiglare (antiglare) layer.
  • the antireflection film, the brightness enhancement film, the other functional optical film, the forward scattering layer, and the antiglare layer for functionalization are described in paragraph numbers [0257] to [0276] of JP-A-2007-86748, A functionalized polarizing plate can be produced based on these descriptions.
  • the hard coat layer as the functional layer will be described below.
  • the cellulose ester film may be provided with a hard coat layer as desired on the surface where the iodine diffusion preventing layer is not provided.
  • a hard-coat layer can be formed on a cellulose-ester film by apply
  • fillers and additives By adding fillers and additives to the hard coat layer, it is possible to impart mechanical, electrical, optical physical performance, or chemical performance such as water repellency or oil repellency to the hard coat layer.
  • the thickness of the hard coat layer is preferably in the range of 0.1 to 6 ⁇ m, and more preferably in the range of 3 to 6 ⁇ m. By having a thin hard coat layer in such a range, it is possible to obtain a polarizing plate including a hard coat layer that has improved physical properties such as brittleness or curl suppression, reduced weight, and reduced manufacturing costs.
  • An example of a coating composition for forming a hard coat layer contains a monomer or oligomer for a matrix forming binder, polymers, and an organic solvent.
  • a hard coat layer can be formed by curing the coating composition after coating. For curing, a crosslinking reaction or a polymerization reaction can be used. Details of these can be referred to the descriptions in paragraphs [0088] to [0101] of JP2012-215812A, the contents of which are incorporated herein.
  • the coating composition can be prepared by, for example, dissolving and / or dispersing the above-described components in an organic solvent.
  • a coating composition suitable for forming the hard coat layer is a curable composition containing a (meth) acrylate compound.
  • the (meth) acrylate compound includes an acrylic compound and a methacrylic compound.
  • Polarization degree> In the polarizing plate of the present invention, the degree of polarization is preferably 95.0% or more, more preferably 98% or more, and most preferably 99.5% or more.
  • the polarization degree of the polarizing plate can be determined by the following formula (I) from the orthogonal transmittance and the parallel transmittance measured at a wavelength of 380 to 780 nm using an automatic polarizing film measuring apparatus: VAP-7070 (manufactured by JASCO Corporation). ), And the weighted average of the light source (auxiliary illuminant C) and CIE visibility (Y) is calculated according to the following formula (II).
  • Polarization degree spectrum (%) ⁇ (Parallel transmittance ⁇ orthogonal transmittance) / (parallel transmittance + orthogonal transmittance) ⁇ 1/2 ⁇ 100
  • T ⁇ ( ⁇ ) indicates the polarization degree spectrum
  • L ( ⁇ ) indicates the emission spectrum of the light source
  • y ( ⁇ ) indicates the visibility.
  • the polarizing plate of the present invention is excellent in durability under wet heat aging conditions. For this reason, the amount of change in the degree of polarization before and after the polarizing plate durability test described later is small.
  • the polarizing plate of the present invention uses an automatic polarizing film measuring apparatus: VAP-7070 (manufactured by JASCO Corporation) to measure orthogonal transmittance and parallel transmittance, and calculate the degree of polarization by the above formula. It is preferable that the amount of change in polarization degree is less than 5% when stored for 500 hours in an environment with a relative humidity of 85%.
  • the orthogonal transmittance and the parallel transmittance are respectively measured as follows in the form in which the polarizing plate of the present invention is attached to glass via an adhesive.
  • Two samples (about 5 cm ⁇ 5 cm) in which the polarizing plate of the present invention is pasted on a glass plate so that the polarizing plate protective film side of the present invention is on the air interface side (opposite side of the glass plate) are prepared. .
  • a glass plate side is set toward a light source, and orthogonal transmittance and parallel transmittance are measured.
  • Each of the two samples is measured, and the arithmetic average value is taken as the orthogonal transmittance and the parallel transmittance.
  • the polarizing plate of the present invention preferably has excellent punching characteristics as processing characteristics, such that even after cutting such as punching, the cut polarizing plate is less likely to peel or crack at the end.
  • the polarizing plate is usually cut by punching or the like according to the panel size of the image display device. At this time, if the punching characteristic of the polarizing plate protective film is poor, the yield is reduced and the manufacturing cost is increased.
  • the polarizing plate of the present invention includes the above-described polarizing plate protective film, and is excellent in punching workability, thereby avoiding the above-described problems.
  • the polarizing plate protective film of the present invention preferably has high surface smoothness before being bonded to the polarizer. That is, the height difference between adjacent portions in the 500 ⁇ m ⁇ 500 ⁇ m region on the surface to be bonded to the polarizer is less than 0.1 ⁇ m.
  • the surface smoothness can be evaluated by the method described in the examples. In the polarizing plate of the present invention, when the surface smoothness is high, defects due to foreign matters and the like can be easily detected after manufacturing the polarizing plate protective film, and the quality of the polarizing plate and thus the liquid crystal display device can be improved.
  • the polarizer of the present invention is preferably used as an image display device application using a polarizer.
  • Examples of such an image display device include a liquid crystal display device and an organic electroluminescence display device.
  • a liquid crystal display device as an image display device includes a liquid crystal cell having a liquid crystal supported between two electrode substrates, and two polarizing plates disposed on both sides thereof. And at least one optical compensation film between the liquid crystal cell and the polarizing plate as necessary. A preferred embodiment of the liquid crystal display device will be described.
  • FIG. 7 is a schematic view showing an embodiment of the liquid crystal display device.
  • the liquid crystal display device 20 includes a liquid crystal layer 24 and a first (upper liquid crystal cell) electrode substrate 23 and a second (lower liquid crystal cell) electrode substrate 25 disposed on both surface sides (referred to as upper and lower sides in FIG. 7).
  • a first (upper) polarizing plate 21 and a second (lower) polarizing plate 26 disposed on both sides of the liquid crystal cell.
  • a color filter may be disposed between the liquid crystal cell and each polarizing plate.
  • a cold cathode or hot cathode fluorescent tube, or a backlight using a light emitting diode, a field emission element, or an electroluminescent element as a light source is provided on the back surface (lower side in FIG. 7).
  • the substrate of the liquid crystal cell generally has a thickness of 50 ⁇ m to 2 mm.
  • the first polarizing plate 21 and the second polarizing plate 26 are not shown in FIG. 7, the first polarizing plate 21 and the second polarizing plate 26 usually have a configuration in which a polarizer is sandwiched between two polarizing plate protective films.
  • the polarizing plate of the present invention it is preferable that at least one polarizing plate is the polarizing plate of the present invention. Moreover, after arrange
  • the liquid crystal display device 20 of the present invention may be laminated in the order of the polarizing plate protective film of the present invention as a polarizing plate protective film, a polarizer, and a general transparent protective film from the outside of the device (the side far from the liquid crystal cell). preferable.
  • the liquid crystal layer 24 of the liquid crystal cell is usually formed by sealing liquid crystal in a space formed by sandwiching a spacer between two substrates.
  • the transparent electrode layer is formed on the substrate as a transparent film containing a conductive substance. Thereby, it becomes an electrode substrate provided with the substrate and the transparent electrode layer.
  • the liquid crystal cell may further be provided with a gas barrier layer, a hard coat layer, or an undercoat layer (undercoat layer) (used for adhesion of the transparent electrode layer). These layers are usually provided on the substrate.
  • the polarizing plate protective film of the present invention can also be preferably used as an optical compensation film for liquid crystal display devices.
  • the liquid crystal display device has a liquid crystal cell in which liquid crystal is supported between two electrode substrates, two polarizers disposed on both sides thereof, and at least between the liquid crystal cell and the polarizer described above. More preferably, the polarizing plate protective film of the present invention is arranged as an optical compensation film.
  • the polarizing plate protective film of the present invention can be used for liquid crystal cells (liquid crystal display devices) of various display modes.
  • TN Transmission Nematic
  • IPS In-Plane Switching
  • FLC Fluoroelectric Liquid Crystal
  • AFLC Anti-Ferroelectric Liquid Crystal
  • OCB Optically LilyCryBTS
  • Various display modes such as (Electrically Controlled Birefringence) or HAN (Hybrid Aligned Nematic) have been proposed.
  • a display mode in which the above display mode is oriented and divided has been proposed.
  • the polarizing plate protective film or polarizing plate of the present invention can be suitably used in any display mode liquid crystal display device. Further, it can be suitably used in any of a transmissive type, a reflective type, and a transflective liquid crystal display device.
  • dope 101 for air side surface layer 1.3 parts by mass of the following matting agent solution 2 and 98.7 parts by mass of the following cellulose acylate solution 1 are mixed using an in-line mixer, and the dope 101 solution for air side surface layer is prepared. Prepared.
  • ⁇ 2-1 Preparation of Cellulose Acylate Solution 1> Each component was put into a mixing tank with the composition shown below and dissolved by stirring to prepare a cellulose acylate solution 1.
  • ⁇ Composition of Cellulose Acylate Solution 1 ⁇ 100.0 parts by mass of cellulose acetate having an acetyl substitution degree of 2.87 and a polymerization degree of 370 Sucrose benzoate (benzoyl substitution degree of 5.5) 6.0 parts by mass Sucrose acetate isobutyrate manufactured by Sigma-Aldrich 4.0 parts by mass Methylene chloride (first solvent) 353.9 parts by mass Methanol (second solvent) 89.6 parts by mass n-butanol (third solvent) ) 4.5 parts by mass ⁇
  • ⁇ 2-2 Preparation of matting agent solution 2> Each component was put into a disperser with the composition shown below and dissolved by stirring to prepare a matting agent solution 2.
  • ⁇ Composition of Matte Solution 2 Silica particles having an average particle size of 20 nm (AEROSIL R972, 2.0 parts by mass Methylene chloride (first solvent) 69.3 parts by mass Methanol (second solvent) 17.5 parts by mass n-butanol (third solvent) 0.9 parts by mass
  • the cellulose acylate Solution 1 0.9 parts by mass ⁇
  • Base Layer Dope 102 Cellulose Acylate Solution 3
  • Each component was charged into a mixing tank with the composition shown below, and dissolved by stirring to prepare a base layer dope 102.
  • composition of base layer dope 102 100.0 parts by mass of cellulose acetate having an acetyl substitution degree of 2.87 and a polymerization degree of 370 Sucrose benzoate (benzoyl substitution degree of 5.5) 6.0 parts by mass Sucrose acetate isobutyrate manufactured by Sigma-Aldrich 4.0 parts by mass
  • the following UV absorber C 2.0 parts by mass Methylene chloride (first solvent) 297.7 parts by mass Methanol (second solvent) 75. 4 parts by mass n-butanol (third solvent) 3.8 parts by mass ⁇
  • FIG. 8 is a diagram for explaining a method for producing a cellulose acylate film having a three-layer structure using a drum casting apparatus.
  • 89 indicates a casting die
  • 70 indicates a casting film in which a dope is cast.
  • 122 in FIG. 8 is a support-side surface dope 103
  • 120 is a base layer dope 102
  • 121 is an air-side surface dope 101
  • three layers are made of stainless steel simultaneously.
  • the film was uniformly cast from a casting port provided in a casting die 89 to a cast casting support 85 (support temperature ⁇ 9 ° C.).
  • Examples 101 to 107 and Comparative Examples 201 to 208 In Examples 101 to 107 and Comparative Examples 203 to 208, a polarizing plate protective film (FIG. 1) in which an iodine diffusion preventing layer is directly provided on one surface of a polarizer, and a polarizing plate provided therewith (FIG. 6). ) And the characteristics thereof were evaluated. For Comparative Examples 201 and 202, only the cellulose acylate film was used as the polarizing plate protective film.
  • Example 101 ⁇ 1-1 Production of polarizing plate protective film>
  • a polarizing plate protective film 10A provided with the iodine diffusion prevention layer (polymer B1 layer) 12 having a single layer structure shown in FIG. 1 was produced as follows. (Preparation of Composition Ba-1 for Formation of Iodine Diffusion Prevention Layer) Each component was mixed in the following composition, and filtered through a polypropylene filter having a pore size of 30 ⁇ m to prepare an iodine diffusion preventing layer forming composition Ba-1. In preparing the composition Ba-1, the cellulose acylate film No. used as a solvent was used.
  • polarizing plate protective film No.
  • group film was produced.
  • active energy ray-curable adhesive composition Each component was mixed by the composition shown below, and it stirred at 50 degreeC for 1 hour, and obtained the active energy ray hardening-type adhesive composition.
  • Composition of active energy ray-curable adhesive composition ⁇ Radical polysynthetic compound: Aronix M-220 manufactured by Toa Gosei Co., Ltd.
  • the produced polarizing plate protective film No. The surface of 101 on the iodine diffusion preventing layer side was subjected to corona treatment.
  • the active energy ray-curable adhesive composition prepared above is applied to the surface of the iodine diffusion preventing layer subjected to corona treatment (MCD coater (manufactured by Fuji Machine)) (cell shape: honeycomb, number of gravure roll wires: 1000 / (INCH, rotational speed 140% / vs line speed) was applied to a thickness of 0.5 ⁇ m.
  • cycloolefin film (Arton G7810 manufactured by JSR) was subjected to corona treatment, and the surface was similarly coated with the active energy ray-curable adhesive composition having a thickness of 0. It was applied so as to be 5 ⁇ m.
  • polarizing plate protective film No. which apply
  • the active energy rays shown below were irradiated from both surfaces of the bonded film (polarizing plate protective film No. 101 or cycloolefin film) to cure the active energy ray-curable adhesive composition. . Thereafter, it was dried with hot air at 70 ° C. for 3 minutes. 101 was obtained.
  • UV rays ultraviolet rays (gallium filled metal halide lamp), irradiation apparatus: Fusion UV Systems, Inc.
  • the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
  • Example 102 ⁇ 2-1: Polarizing plate protective film No. 102 and polarizing plate No. Production of 102>
  • the polymer B1 polymethyl methacrylate
  • the polymer A having the following structure
  • propyl acetate was used.
  • MEK methyl ethyl ketone
  • the fd value of the cellulose acylate, the fd value of the polymer A, and the fd value of the solvent were selected so as to satisfy the relational expression [1] and the relational expression [2]. .
  • the obtained white precipitate was filtered off, then redispersed and washed with 2 L of methanol three times, and dried at 60 ° C. overnight to obtain 139.6 g of the target polymer A.
  • ⁇ 2-3 Evaluation of polymer>
  • the structure and composition ratio of the repeating unit were identified by 1 H-NMR measurement using a nuclear magnetic resonance spectrum measuring apparatus (NMR300 MHz) manufactured by BRUKER.
  • NMR300 MHz nuclear magnetic resonance spectrum measuring apparatus
  • GPC gel permeation chromatography
  • Example 103 ⁇ 3-1 Production of cellulose acylate film>
  • Reference Example 101 Reference Example 103 was performed in the same manner as Reference Example 101, except that the cellulose acylate solution 1 used for the air side surface dope and the support side surface layer dope was changed to the cellulose acylate solution 5 having the following composition.
  • Cellulose acylate film no. 103 was produced.
  • the fd cellulose of the cellulose acetate used is shown in Table 1.
  • cellulose acylate solution 5 Each component was put into a mixing tank with the composition shown below and dissolved by stirring to prepare a cellulose acylate solution 5.
  • ⁇ Composition of Cellulose Acylate Solution 5 ⁇ 100.0 parts by mass of cellulose acetate having an acetyl substitution degree of 2.87 and a polymerization degree of 370 Sucrose benzoate (benzoyl substitution degree of 5.5) 6.0 parts by weight Sucrose acetate isobutyrate manufactured by Sigma-Aldrich 4.0 parts by weight Polymer A 15.0 parts by weight Methylene chloride (first solvent) 353.9 parts by weight Methanol (second solvent) 89.6 parts by weight Part n-Butanol (3rd solvent) 4.5 parts by mass ⁇
  • Example 101 instead of propyl acetate, methyl ethyl ketone (MEK) was used as a solvent satisfying each of the above relational expressions, and cellulose acylate film no. In place of 101, the cellulose acylate film no.
  • the polarizing plate protective film No. 10 of Example 103 was the same as Example 101 except that 103 was used. 103 and polarizing plate No. 103 was produced.
  • the fd value of cellulose acylate, the fd value of polymer B1 (polymethyl methacrylate: PMMA), and the fd value of the solvent satisfy the relational expressions [1] and [2]. So selected.
  • Example 104 and 105 In the preparation of the iodine diffusion preventing layer forming composition Ba-1 of Example 101, Example 101 was used except that instead of propyl acetate, the solvent described in Table 1 was used as the solvent satisfying the above relational expressions. In the same manner as in Examples 104 and 105, the polarizing plate protective film No. 104 and 105 and polarizing plate No. 104 and 105 were produced.
  • Example 106 In the production of the polarizing plate of Example 101, the surface of the cellulose acylate film was subjected to corona treatment, and then the active energy ray-curable adhesive composition was applied to the surface opposite to the iodine diffusion preventing layer 12 to diffuse the iodines.
  • the polarizing plate No. 10 of Example 106 was the same as Example 101 except that the prevention layer 12 was bonded to the cellulose acylate layer so as to be opposite to the polarizer. 106 was produced.
  • Example 107 The iodine diffusion preventing layer forming composition Ba-1 prepared in Example 101 was applied to the iodine diffusion preventing layer (polymer B1 layer) 12 containing polymer A prepared in Example 102 in the same manner as in Example 101.
  • the polarizing plate protective film No. 1 of Example 107 provided with an iodine diffusion preventing layer having a two-layer structure shown in FIG. 107 was produced.
  • polarizing plate protective film No. The polarizing plate No. 107 in Example 107 was prepared in the same manner as in the production of the polarizing plate in Example 101 except that 107 was used. 107 was produced.
  • Polarizing plate No. In 107, the iodine diffusion preventing layer 13 and a polarizer were bonded together.
  • Comparative Example 201 ⁇ 7-1 Production of cellulose acylate film>
  • Reference Example 101 is the same as Reference Example 101 except that cellulose acylate solution 1 is changed to cellulose acylate solution 6 having the following composition, and cellulose acylate solution 3 is changed to cellulose acylate solution 7 having the following composition.
  • the cellulose acylate film No. 201 was produced.
  • the fd cellulose of the cellulose acetate used is shown in Table 1.
  • polarizing plate protective film No. 201 was immersed in a 2.3 mol / L sodium hydroxide aqueous solution at 55 ° C. for 3 minutes. Then, it wash
  • the polarizing plate protective film No. 1 of Comparative Example 201 subjected to saponification treatment was used.
  • a drum (support) side surface surface 122a of 201 was attached to one side surface of a polarizer manufactured in the same procedure as in Example 101, using a polyvinyl alcohol-based adhesive.
  • a cycloolefin-based film (Arton G7810 manufactured by JSR Co.) subjected to corona treatment and application of an active energy ray-curable adhesive composition in the same manner as in Example 101 was bonded to the opposite surface of the polarizer.
  • Comparative Example 202 Cellulose acylate film no. 101 is polarizing plate protective film No. 101. 202. In the production of the polarizing plate of Comparative Example 201, cellulose acylate film No. In place of 201, the cellulose acylate film no. The polarizing plate No. of Comparative Example 202 was the same as Comparative Example 201 except that 101 was used. 202 was produced.
  • Comparative Example 203 In Example 101, a comparative example was prepared in the same manner as in Example 101 except that the composition Ba-1 for forming an iodine diffusion preventing layer was changed to a composition Ba-5 for forming an iodine diffusion preventing layer having the following composition. No. 203 polarizing plate protective film No. 203 and polarizing plate No. 203 was produced. Table 1 shows the calculated values of fd solvent and fd polymerB1 , and relational expressions [1] and [2] in Comparative Example 203.
  • Cycloolefin polymer APL6013T manufactured by Mitsui Chemicals, Inc. 18.0 parts by mass Cyclohexane (solvent) 82.0 parts by mass ⁇
  • Comparative Examples 204-208 In the preparation of the composition for forming an iodine diffusion preventing layer Ba-1 in Example 101, except that propyl acetate was used, the solvent shown in Table 1 was used as a solvent that did not satisfy at least one of the above relational expressions. In the same manner as in Example 101, the polarizing plate protective film No. 204 to 208 and polarizing plate No. 204-208 were produced.
  • Moisture permeability The moisture permeability in the polarizing plate protective film of the present invention was calculated by the following method based on “moisture-proof packaging material moisture permeability test method (cup method)” of JIS Z 0208 (1976). Specifically, the polarizing plate protective film is cut to 60 mm ⁇ 60 mm, and the mass of water passing through the cut polarizing plate protective film in an atmosphere of 85 ° C. and 85% relative humidity in 6 hours (g / 6hours) was measured and converted into a mass per 1 m 2 of the cut polarizing plate protective film (g / m 2 / 6ours). The mass of moisture that passed through the polarizing plate protective film was calculated from the mass change of the moisture absorbent (anhydrous calcium chloride).
  • a polarizing plate protective film provided with an iodine diffusion preventing layer was conditioned to a polarizing plate protective film at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours.
  • 11 vertical and 11 horizontal cuts were made at a 1 mm interval with a cutter knife, and a total of 100 square squares were carved.
  • a polyester pressure-sensitive adhesive tape (No. 31B) manufactured by Nitto Denko Co., Ltd. was attached to the surface (grid). After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria.
  • Polarization degree change (%)
  • the polarizing plate protective film No. 1 of the present invention was obtained.
  • 101 to 107 are all polarizing plate protective films of Comparative Examples No. 101 to 107.
  • 201 and 202 it was shown that a decrease in the degree of polarization can be suppressed even when stored in a high temperature and high humidity environment.
  • the polarizing plate protective film No. 1 of the present invention Nos. 101 to 107 are polarizing plate Nos.
  • Comparative Example No. 203 polarizing plate No.
  • the interlayer adhesion between the iodine diffusion preventing layer and the cellulose acylate layer was excellent.
  • No. 101 is a polarizing plate No. 101 in which the iodine diffusion preventing layer is disposed on the far side from the polarizer with respect to the cellulose acylate film. Compared to 106, it was found that polarization performance is hardly deteriorated when stored in a high-temperature and high-humidity environment, which is particularly preferable. Furthermore, polarizing plate protective film No.
  • No. 102 is a polarizing plate protective film
  • No. 102 provided with an iodine diffusion preventing layer containing a polymer that does not contain the repeating unit [b] when used in a polarizing plate.
  • the interlaminar adhesion between the cellulose acylate film and the iodine diffusion preventing layer was further improved.
  • Examples 301 to 302 and Comparative Example 401 [4. Examples 301 to 302 and Comparative Example 401]
  • a polarizing plate protective film (FIG. 1) in which an iodine diffusion preventing layer was directly provided on one surface of a polarizer, and a polarizing plate provided with the protective film were prepared, and the characteristics were evaluated. did.
  • a polarizing plate protective film in which only the cellulose acylate film was directly provided on both surfaces of the polarizer, and a polarizing plate provided therewith were prepared.
  • Example 301 In Example 301, a polarizing plate protective film No. 1 in which an iodine diffusion preventing layer was directly provided on both surfaces of the polarizer as follows. 301A and 301B (FIG. 1) and the polarizing plate provided with this were produced, respectively.
  • ⁇ 1-1 Preparation of Cellulose Acylate Film 301A> (Preparation of core layer dope solution 301A) Each component was put into a mixing tank with the composition shown below and dissolved by stirring to prepare a core layer dope solution 301A.
  • oligomer 1 After reacting the following molar ratios of terephthalic acid and succinic dicarboxylic acid with the following molar ratios of ethylene glycol and propylene glycol diol, the end-capping was performed to obtain oligomer 1.
  • Table 2 shows the types and molar ratios (feed ratios) of the dicarboxylic acid and diol as raw materials, and the end-capping structure and molecular weight of the obtained oligomer 1.
  • matting agent dispersion M1 Each component was charged into a disperser with the composition shown below, and dissolved by stirring to prepare a matting agent dispersion M1.
  • ⁇ Preparation 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 mass Methanol 11.4 parts by mass
  • the skin layer dope solution prepared above 12.6 parts by mass ⁇ ⁇
  • the dope solution prepared above was used for casting with a band casting machine.
  • the core layer dope solutions 301A, 122, and 121 are co-cast so that the skin layer dope solution containing the matting agent is used.
  • the core layer is made the thickest.
  • a cast film was cast.
  • the cast film was peeled off from the band 85 to form a wet film, and then dried with a transfer part and a tenter.
  • the residual solvent amount of the wet film immediately after peeling off the dope was about 25% by mass.
  • the wet film was sent to a drying chamber, and while being wound around a large number of rollers, drying was sufficiently promoted to obtain a film obtained by casting.
  • the film obtained by casting was gripped with a clip and stretched in the transverse direction under the condition of uniaxial fixed end.
  • the stretching temperature was 185 ° C. and the stretching rate was 31%.
  • each film was conveyed, maintaining only the processing time (60 second) that the temperature (wet heat treatment temperature) of each film was 100 ° C.
  • the absolute humidity of the gas in the heat treatment chamber (heat treatment absolute humidity) is set to 0 g / m 3
  • the temperature of each film (heat treatment temperature) is set to the same temperature as the wet heat treatment temperature, and the treatment time (2 minutes) is maintained. did.
  • the film surface temperature was determined from the average value of three tape-type thermocouple surface temperature sensors (ST series manufactured by Anri Keiki Co., Ltd.) attached to the film.
  • the thickness of each layer in the cellulose acylate film 301A thus produced was 40 ⁇ m for the core layer and 2 ⁇ m for the skin layer.
  • ⁇ 1-2 Preparation of Composition Ba-2 for Formation of Iodine Diffusion Prevention Layer> (Preparation of matting agent solution M3) Each component was charged into a disperser with the composition shown below, and dissolved by stirring to prepare a matting agent solution M3.
  • Preparation of matting agent solution M3 ⁇ 2.0 parts by mass of silica particles having an average particle size of 20 nm (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil NX90S) Polymethylmethacrylate: Mitsubishi Rayon Dianal BR80 4.0 parts by mass Propyl acetate 94.0 parts by mass ⁇
  • composition Ba-2 for Formation of Iodine Diffusion Prevention Layer
  • fd value is related to the fd value of the cellulose acylate contained in the skin layer 122a and the fd value of the following polymer B1 (polymethyl methacrylate) as a solvent.
  • polymer B1 polymethyl methacrylate
  • Table 3 shows the calculated values of fd polymerB1 and relational expressions [1] and [2] at this time.
  • composition of composition Ba-2 for formation of iodine diffusion barrier layer ⁇
  • Polymethylmethacrylate Mitsubishi Rayon Dianal BR80 10.0 parts by mass
  • the following fluorine-based polymer F weight average molecular weight 14900
  • Matting agent solution M3 25.0 parts by mass
  • the weight average molecular weight of the fluoropolymer F was measured in terms of polystyrene by gel permeation chromatography.
  • the number given to the above repeating unit represents the molar ratio of each repeating unit.
  • Polarizing plate protective film No. Production of 301A> (Formation of iodine diffusion preventing layer (polymer B1 layer))
  • the coating solution Ba-2 for the iodine diffusion preventing layer prepared above. was applied by a micro gravure coating method under conditions of a conveyance speed of 30 m / min. This was dried at 100 ° C. for 120 seconds to form an iodine diffusion preventing layer 12 having a thickness of 5 ⁇ m.
  • the polarizing plate protective film o.e. having the single-layered iodine diffusion preventing layer 12 shown in FIG. 301A was obtained.
  • ⁇ 1-4 Preparation of Cellulose Acylate Film 301B> (Preparation of dope 301B for air side surface layer) 1.3 parts by mass of the following matting agent solution 302B and 98.7 parts by mass of the following cellulose acylate solution 301B were added and mixed using an in-line mixer to prepare an air-side surface dope 301B.
  • a cellulose acylate solution 301B Each component was put into a mixing tank with the composition shown below and dissolved by stirring to prepare a cellulose acylate solution 301B.
  • Composition of Cellulose Acylate Solution 301B ⁇ Cellulose acetate with an acetyl substitution degree of 2.87 and a polymerization degree of 370 100.0 parts by mass Sucrose benzoate (benzoyl substitution degree 5.5) 3.0 parts by mass Sucrose acetate isobutyrate 1.0 part by mass Sigma-Aldrich Barbituric acid derivative (E) 6.0 parts by mass The following ultraviolet absorber (D) 2.3 parts by mass Methylene chloride (first solvent) 353.9 parts by mass Methanol (second solvent) 89.6 parts by mass n- Butanol (3rd solvent) 4.5 parts by mass ⁇
  • matting agent solution 302B Each component was charged into a disperser with the composition shown below, and dissolved by stirring to prepare a matting agent solution 302B.
  • Composition of matting agent solution 302B Silica particles having an average particle size of 20 nm (AEROSIL R972, 2.0 parts by mass Methylene chloride (first solvent) 69.3 parts by mass Methanol (second solvent) 17.5 parts by mass n-butanol (third solvent) 0.9 parts by mass
  • the cellulose acylate Solution 301B 0.9 parts by mass ⁇
  • base layer dope 303B (cellulose acylate solution 303B)
  • Each component was put into a mixing tank with the composition shown below and dissolved by stirring to prepare a base layer dope 303B.
  • ⁇ Composition of dope 303B for the base layer ⁇ Cellulose acetate having an acetyl substitution degree of 2.87 and a polymerization degree of 370 10 parts by mass Sucrose benzoate (benzoyl substitution degree 5.5) 3.0 parts by mass Sucrose acetate isobutyrate manufactured by Sigma-Aldrich 1.0 part by mass Barbituric acid derivative (E) 6.0 parts by mass
  • the above UV absorber (D) 2.3 parts by mass Methylene chloride (first solvent) 297.7 parts by mass Methanol (second solvent) 75.4 parts by mass n- Butanol (third solvent) 3.8 parts by mass ⁇
  • the base layer dope 303B (120 in FIG. 8) prepared above, the surface layer dope (air side surface layer dope 301B (121 in FIG. 8) and the support side) on both sides thereof
  • Three layers of the surface layer dope 304B (122 in FIG. 8) were cast uniformly onto a casting support 85 (support temperature ⁇ 9 ° C.) 85 made of stainless steel simultaneously from the casting port. Stripped in a state where the residual solvent amount in the dope of each layer is about 70% by mass, fixed both ends in the width direction of the film with a pin tenter, and 1.28 in the lateral direction in a state where the residual solvent amount was 3-5% by mass. The film was dried while being stretched twice.
  • cellulose acylate film No. 301B was obtained.
  • the obtained cellulose acylate film No. The thickness of 301B was 55 ⁇ m (air side surface layer (121a in FIG. 8) 3 ⁇ m, base layer (120a in FIG. 8) 49 ⁇ m, support side surface layer (122a in FIG. 8) 3 ⁇ m), and the width was 1480 mm.
  • ⁇ 1-5 Polarizing plate protective film No. Production of 301B> (Formation of iodine diffusion preventing layer (polymer B1 layer))
  • the above-mentioned cellulose acylate film No. On the band surface of 301B (the surface of the support side surface layer 122a of the cellulose acylate film No. 301B that was in contact with the stainless steel casting support at the time of film formation), the above-mentioned coating solution Ba-2 for the iodine diffusion preventing layer was applied by a micro gravure coating method under conditions of a conveyance speed of 30 m / min. This was dried at 100 ° C. for 120 seconds to form an iodine diffusion preventing layer having a thickness of 5 ⁇ m.
  • the fd value of the cellulose acylate contained in the skin layer 122a as the solvent and the fd value of the following polymer B1 (polymethyl methacrylate) were respectively Selected propyl acetate satisfying the above relational expression [1] and the above relational expression [2].
  • the cellulose acylate is the same as that used in Example 101, and the polymer B1 is the same type as that used in Example 101.
  • Table 3 shows the calculated values of fd polymerB1 and relational expressions [1] and [2] at this time.
  • polarizing plate protective film No. 1 provided with the iodine diffusion preventing layer 12 having a single layer structure shown in FIG. 301B was obtained.
  • ⁇ 1-6 Production of polarizing plate> (Preparation of active energy ray-curable adhesive composition 2) Each component was mixed with the composition shown below, and the active energy ray hardening-type adhesive composition 2 was obtained.
  • ⁇ Composition of active energy ray curable adhesive composition 2 ⁇ Cationic polymerizable compound A having the following structure 75.0 parts by mass Cationic polymerizable compound B having the following structure 20.0 parts by mass Cationic polymerizable compound C having the following structure 5.0 parts by mass Photocationic polymerization initiator: 2.25 parts by mass of triarylsulfonium hexafluorophosphate ⁇
  • the surface of the polarizing plate protective film 301B provided with the iodine diffusion preventing layer was subjected to corona treatment on the surface of the iodine diffusion preventing layer side.
  • the active energy ray-curable adhesive composition 2 prepared above was applied to the surface of the iodine diffusion preventing layer subjected to the corona treatment using a bar coater. Further, for the polarizing plate protective film 301A provided with an iodine diffusion preventing layer, after the corona treatment was performed on the surface on the iodine diffusion preventing layer side, the surface of the iodine diffusion preventing layer was similarly prepared as described above. The active energy ray-curable adhesive composition 2 was applied.
  • coated the active energy ray hardening-type adhesive composition of each film was bonded together on the one side surface of the polarizer, respectively.
  • the slow axis of 301A was parallel, and the transmission axis of the polarizer and the slow axis of 301B were perpendicular.
  • the belt conveyor with ultraviolet irradiation device (UV lamp, "D bulb” Using Fujon UV System, Inc.) using a polarizing plate protective film as integrated light quantity becomes 250 mJ / cm 2 No.
  • the active energy ray-curable adhesive composition was cured by irradiating ultraviolet rays from the 301A side. Thereafter, it was dried with hot air at 70 ° C. for 3 minutes. 301 was obtained.
  • Example 302 In Example 302, a polarizing plate protective film No. 1 in which an iodine diffusion preventing layer was directly provided on one surface of the polarizer as follows. A polarizing plate provided with 301A was produced.
  • the air surface of 301B (the surface on the side opposite to the support-side surface layer 122a that was in contact with the stainless steel casting support during film formation) was subjected to corona treatment and then subjected to iodine on the surface subjected to corona treatment.
  • Polarizing plate protective film No. provided with a diffusion preventing layer.
  • the active energy ray-curable adhesive composition 2 prepared above was applied.
  • polarizing plate protective film No. 1 provided with an iodine diffusion preventing layer coated with the active energy ray-curable adhesive composition, respectively.
  • 301A and cellulose acetate film no. 301B was produced.
  • coated the active energy ray hardening-type adhesive composition of each film was bonded together on the one side surface of the polarizer, respectively.
  • the belt conveyor with ultraviolet irradiation device UV lamp, "D bulb” Using Fujon UV System, Inc.
  • the active energy ray-curable adhesive composition was cured by irradiating ultraviolet rays from the 301A side. Thereafter, it was dried with hot air at 70 ° C. for 3 minutes. 302 was obtained.
  • Comparative Example 401 a polarizing plate in which cellulose acetate films were directly provided on both surfaces of a polarizer was produced as follows. ⁇ 3-1: Production of polarizing plate> (Saponification treatment of polarizing plate protective film) Cellulose acylate film no. 301A and cellulose acylate film no. 301B was immersed in an aqueous 2.3 mol / L sodium hydroxide solution at 55 ° C. for 3 minutes. This was washed in a room temperature water bath and neutralized at 30 ° C. with 0.05 mol / L sulfuric acid. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. Thus, the cellulose acylate film No. 301A and cellulose acylate film no. The surface of 301B was saponified.
  • the air surface 301A (the surface opposite to the support-side surface layer 122a that was in contact with the stainless steel casting support at the time of film formation) was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive. Furthermore, saponified cellulose acylate film no.
  • the air surface of 301B (the surface on the side opposite to the support side surface layer 122a that was in contact with the stainless steel casting support at the time of film formation) was attached to the surface on the opposite side of the polarizer using a polyvinyl alcohol-based adhesive. It was. In this way, the polarizing plate No. 401 was produced.
  • the polarizing plate protective film No. 1 of the present invention 301 and 302 were excellent in interlayer adhesion between the iodine diffusion preventing layer and the cellulose acylate layer. Further, the polarizing plate protective film No. 1 of the present invention. When 301A and 301B were used for polarizing plates, the decrease in the degree of polarization could be suppressed. Specifically, it is assumed that the polarizing plate protective film 301A of the present invention is used on the liquid crystal cell side, polarizing plate No. 302 is a polarizing plate No. 302. The polarizer durability was superior to 401. Furthermore, the polarizing plate protective film of the present invention is also applied to the polarizing plate protective film on the air side. Assuming that 301B is used, polarizing plate No. No. 301 was more excellent in polarizer durability.
  • Examples 501 to 505 a polarizing plate protective film 10A (FIG. 1) provided with a two-layered iodine diffusion preventing layer 12 on one surface of a polarizer, and a polarizing plate provided with this polarizing plate protective film Each plate was prepared and its characteristics were evaluated. First, a polarizing plate protective film 10A was produced.
  • Example 501 ⁇ 1-1 Film formation of an iodine diffusion preventing layer> (Preparation of Composition Ba-5 for Formation of Iodine Diffusion Prevention Layer) Each component was mixed with the composition shown below, and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare an iodine diffusion preventing layer forming composition Ba-5.
  • the fd value of the cellulose acylate and the fd value of the following polymer B1 (polymethyl methacrylate) are respectively expressed by the above relational expression [1] and the above relation. Propyl acetate satisfying formula [2] was selected.
  • Cellulose acylate is the same as that used in Example 101, and polymer B1 is the same type (PMMA) used in Example 101. Therefore, in preparing the composition Ba-5, the calculated values of fd cellulose, fd solvent, and fd polymer B1 , and the relational expressions [1] and [2] are the same as those in Example 101, and will be omitted.
  • Composition of Composition Ba-5 for Iodine Diffusion Prevention Layer Formation ⁇ Polymethylmethacrylate: Mitsubishi Rayon Dianal BR83 16.0 parts by mass Propyl acetate (solvent) 84.0 parts by mass ⁇
  • composition Ba-6 for Formation of Iodine Diffusion Prevention Layer
  • a component was mixed in the following composition, and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare an iodine diffusion preventing layer forming composition Ba-6.
  • the fd value of the cellulose acylate and the fd value of the following polymer B1 are respectively expressed by the above relational expression [1] and the above relation.
  • Propyl acetate satisfying formula [2] was selected.
  • Cellulose acylate is the same as that used in Example 101
  • polymer B1 is the same type (PMMA) used in Example 101. Therefore, in the preparation of the composition Ba-6, the calculated values of fd cellulose, fd solvent and fd polymer B1 , and relational expressions [1] and [2] are the same as those in Example 101, and will be omitted.
  • Composition of Composition Ba-6 for Iodine Diffusion Prevention Layer Formation ⁇ Polymethylmethacrylate: Mitsubishi Rayon Dianal BR83 14.5 parts by mass The following matting agent solution 7 3.6 parts by mass Propyl acetate (solvent) 81.9 parts by mass ⁇ ⁇
  • the matting agent solution 7 used in the iodine diffusion preventing layer forming composition Ba-6 was prepared by charging each component with a composition shown below into a disperser and stirring to dissolve.
  • ⁇ Composition of Matte Solution 7 Silica particles having an average particle size of 20 nm (AEROSIL R972, 2.0 parts by mass of propyl acetate (solvent) 97.8 parts by mass of polymethyl methacrylate: Dianal BR83 manufactured by Mitsubishi Rayon Co., Ltd. 0.2 parts by mass ⁇
  • Example 502 In the preparation of the composition Ba-6 for forming the iodine diffusion preventing layer of Example 501, the same procedure as in Example 501 was conducted except that Mitsubishi Rayon's Dianal BR83 was changed to Mitsubishi Rayon's Dianal BR80. The polarizing plate protective film No. 502 was produced.
  • Example 503 In the preparation of the composition for forming an iodine diffusion preventing layer Ba-6 of Example 501, Example Example except that Mitsubishi Rayon Dianal BR83 was changed to Mitsubishi Rayon Dianal BR80 and the solvent was changed to methyl acetate. In the same manner as in Example 501, polarizing plate protective film No. 503 was produced. When the solvent is changed, the fd value satisfies the relational expression [1] and the relational expression [2] with respect to the fd value of cellulose acylate and the fd value of the following polymer B2 (polymethyl methacrylate). No methyl acetate was selected (see Comparative Example 207 for specific values).
  • Example 504 In the preparation of the composition Ba-6 for forming an iodine diffusion preventing layer of Example 501, the dialal BR83 manufactured by Mitsubishi Rayon Co. was changed to the dialal BR80 manufactured by Mitsubishi Rayon Co., and the solvent was changed to methyl acetate, and iodines Except for changing the thickness of the diffusion preventing layer (the thickness of the first layer to 4 ⁇ m and the thickness of the second layer to 1 ⁇ m), in the same manner as in Example 501, the polarizing plate protective film No. 504 was produced.
  • Example 505 In preparation of the composition Ba-6 for forming an iodine diffusion preventing layer of Example 501, the dialal BR83 manufactured by Mitsubishi Rayon Co. was changed to the dialal BR80 manufactured by Mitsubishi Rayon Co., and the solvent was changed to methyl acetate.
  • a polarizing plate was produced using each obtained polarizing plate protective film.
  • the polarizing plate protective film No. Polarizing plate Nos. 501 to 505 of Examples 501 to 505 were the same as Example 101 except that 501 to 505 were used. 501 to 505 were produced.
  • ⁇ 7-1 Film surface: Surface smoothness> An area of 620 ⁇ m ⁇ 465 ⁇ m is used for the central portion of the surface of the polarizing plate protective film provided with the iodine diffusion preventing layer on the iodine diffusion preventing layer side, using Bart Scan 2.0 (model number: R5300H) manufactured by Ryoka System. Were observed at three arbitrary locations with a resolution of 640 ⁇ 480 pixels, and the smoothness of the surface was evaluated by the presence or absence of irregularities with an elevation difference of 0.1 ⁇ m or more. Here, the height difference of the unevenness was obtained as the difference between the adjacent bottom and height in the 620 ⁇ m ⁇ 465 ⁇ m region of the surface.
  • the evaluation criteria are “no unevenness” when no unevenness with an elevation difference of 0.1 ⁇ m or more exists in all of the above regions, and one unevenness with an elevation difference of 0.1 ⁇ m or more in one of the above regions. However, when it was present, it was defined as “with unevenness”.
  • ⁇ 7-2 Applicability for punching polarizing plate> Polarizing plate No.
  • Each of 501 to 505 was stored for 24 hours in an environment of 80 ° C. and a relative humidity of 10% or less, and then conditioned for 24 hours in an environment of 25 ° C. and a relative humidity of 10%.
  • One sample of 40 mm ⁇ 40 mm square was punched from the humidity-controlled polarizing plate using a Thomson blade with a blade angle of 43 ° from the cellulose acylate layer side toward the iodine diffusion preventing layer.
  • the following standards evaluated the grade of peeling between each layer which comprises a polarizing plate.
  • the maximum value of the depth of the peeled portion of the sample (the shortest straight line distance from the edge of each side to the tip of the peeled portion in the direction toward the inside of the sample) A: Less than 1.0 mm B: 1.0 mm or more and less than 1.5 mm C: 1.5 mm or more and 5.0 mm or less
  • the polarizing plate protective film No. 1 of the present invention 501 to 505 were excellent in interlayer adhesion between the iodine diffusion preventing layer and the cellulose acylate layer. Further, the polarizing plate protective film No. 1 of the present invention. It has been found that 501 to 505 are excellent in polarizer durability when used for polarizing plates. Further, Examples 502 to 505 in which polymethyl methacrylate having a weight average molecular weight of 95,000 is used for the second layer are more suitable for punching a polarizing plate than Example 501 in which polymethyl methacrylate having a weight average molecular weight of 40000 is used for the second layer. It was excellent. In particular, Example 505 containing a fluorosurfactant in the polymer layer B1 was preferable because of high smoothness of the film surface compared to Example 504 not containing a fluorosurfactant.
  • Examples 701 to 704 In Examples 701 to 704, a polarizing plate protective film (FIG. 1) in which an iodine diffusion preventing layer was directly provided on one surface of a polarizer, and a polarizing plate provided with this polarizing plate protective film were prepared. The characteristics were evaluated.
  • Example 701 ⁇ 1-1 Preparation of Composition Ba-8 for Formation of Iodine Diffusion Prevention Layer> Each component was mixed in the following composition and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare an iodine diffusion preventing layer forming composition Ba-8.
  • the fd value of the cellulose acylate and the fd value of the following polymer B1 were respectively expressed by the above relational expression [1] and the above relation.
  • Propyl acetate satisfying formula [2] was selected.
  • Cellulose acylate is the same as that used in Example 101, and polymer B1 is the same type (PMMA) used in Example 101. Therefore, in preparing the composition Ba-8, the calculated values of fd cellulose, fd solvent, and fd polymer B1 , and relational expressions [1] and [2] are the same as those in Example 101, and will be omitted.
  • Composition of Composition Ba-8 for Iodine Diffusion Prevention Layer Formation Polymethylmethacrylate: Mitsubishi Rayon Dianal BR80 8.0 parts by mass Fluoropolymer F having the above structure 0.004 parts by mass Propyl acetate (solvent) 92.0 parts by mass ⁇ ⁇
  • ⁇ 1-2 Preparation of matting agent solution 9> Each component was put into a disperser with the composition shown below and dissolved by stirring to prepare a matting agent solution 9.
  • ⁇ Composition of Matting Agent Solution 9 Silica particles having an average particle size of 20 nm (AEROSIL NX90S, 2.0 parts by weight Cellulose Acetate Propinate: CAP-482-20 4.0 parts by weight Propyl acetate (solvent) 96.0 parts by weight ⁇ ⁇
  • composition Ba-10 for Forming Polarizer Side Easy Adhesion Layer Each component was mixed with the composition shown below, and filtered through a polypropylene filter having a pore diameter of 10 ⁇ m to prepare a composition Ba-10 for easily bonding layer formation.
  • Composition of composition for easy adhesion layer formation Ba-10 ⁇ Cellulose acetate propionate: CAP-482-20, 7.8 parts by mass, manufactured by Eastman Chemical Co. 93.6 parts by mass of the above matting agent solution, 88.6 parts by mass of propyl acetate (solvent) ⁇ CAP-482-20 manufactured by Eastman Chemical Co. is a cellulose acetate propionate having an acetyl substitution degree of 0.18 and a propionyl substitution degree of 2.47.
  • ⁇ 1-4 Formation of Iodine Diffusion Prevention Layer and Polarizer Side Adhesive Layer> Cellulose acetate film No. 1 prepared in Reference Example 101 On the band surface of 101 (the surface of the support surface layer 122a of the cellulose acylate film that was in contact with the casting support 85 made of stainless steel at the time of film formation) By the method, it apply
  • the easy-adhesion layer coating solution Ba-10 was applied on the polymer B1 layer 12 by a slot die method. This was dried at 100 ° C. for 60 seconds to form a polarizer-side easy-adhesion layer having a thickness of 0.5 ⁇ m.
  • the obtained polarizing plate protective film with a polarizer-side easy-adhesion layer was bonded to the polarizing plate protective film No. 701 of Example 701. 701.
  • polarizing plate protective film No. 701 In preparation of the polarizing plate of Comparative Example 401, polarizing plate protective film No. Instead of 301B (air interface side polarizing plate protective film), polarizing plate protective film No. 701, the polarizer easy-adhesion layer was in contact with the polarizer, and the slow axis of the cellulose acylate film was changed to be perpendicular to the transmission axis of the polarizer. Polarizing plate No. of the invention. 701 was produced.
  • Example 702 The same procedure as in Example 701 was performed except that CAP-482-20 added to composition Ba-10 for easily bonding layer formation in Example 701 was changed to CAB-171-15 manufactured by Eastman Chemical Co., Ltd. Polarizing plate protective film No. 702 of Example 702 702 and polarizing plate No. 702. 702 were produced respectively.
  • CAB-171-15 manufactured by Eastman Chemical Co. is cellulose acetate butyrate having an acetyl substitution degree of 2.0 and a butyryl substitution degree of 0.7.
  • Example 703 In Example 702, it was the same as Example 702, except that the fluorine-based surfactant having the above structure (the above-mentioned fluorine-based polymer F) was added to composition Ba-10 for easy adhesion layer formation in the amount shown in Table 5.
  • the polarizing plate protective film No. of Example 703 was obtained.
  • 703, and polarizing plate No. 703 were produced.
  • Example 704 In Example 701, the polarizing plate protective film No. 704 of Example 704 was the same as Example 701 except that the composition Ba-10 for easily bonding layer formation was not applied. 704 and polarizing plate No. 704. 704 were produced.
  • Each of 701 to 704 is a polarizing plate protective film No. On the side of 701 to 704, it was attached on a glass substrate through an adhesive to prepare a test specimen. For this test specimen, using a Tensilon universal material testing machine (model number: RTC-1210A, manufactured by Orientec Co., Ltd.), the polarization in the attached polarizing plate at a peeling angle of 90 ° and a peeling speed of 300 m / min. The peel strength (N / 25 mm) when the child was peeled from the polarizing plate protective film was measured.
  • polarizing plate protective film No. of this invention From the result of Table 5, polarizing plate protective film No. of this invention. It has been found that the polarizing plate of the present invention having 701 to 704 is excellent in durability. Further, Examples 701 to 703 in which the polarizer-side easy-adhesion layer is provided on the polymer layer 12 have higher adhesion between the layers constituting the polarizing plate than Example 704 in which the polarizer-side easy-adhesion layer is not provided. It was shown to be preferable. Polarizing plate protective film No. 701 to 704 all had high interlayer adhesion between the iodine diffusion preventing layer and the cellulose acylate layer, and had a moisture permeability in the above range.

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Abstract

La présente invention concerne : un film de protection de plaque polarisante ayant une couche de polymère B1 contenant un polymère B1 comprenant des unités de répétition (a) ayant un paramètre de solubilité δt de 13,5 à moins de 20,0 de manière adjacente à au moins une surface d'une couche d'ester de cellulose, la couche de polymère B1 étant obtenue en appliquant, sur une surface de la couche d'ester de cellulose, une composition contenant le polymère B1 et un solvant satisfaisant des expressions relationnelles spécifiques [1] et [2], et la perméabilité à la vapeur d'eau du film de protection de plaque polarisante dans des conditions d'une température de 85 °C et d'une humidité relative de 85 % est de 100 g/m2 à 1600 g/m2 ; son procédé de fabrication ; et une plaque polarisante et un dispositif d'affichage à cristaux liquides.
PCT/JP2016/078232 2015-09-30 2016-09-26 Film de protection de plaque polarisante, son procédé de fabrication, plaque polarisante, et dispositif d'affichage d'image Ceased WO2017057255A1 (fr)

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JP2016-107200 2016-05-30
JP2016107200A JP6327289B2 (ja) 2015-09-30 2016-05-30 偏光板保護フィルム、その製造方法、偏光板及び画像表示装置

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018190211A1 (fr) * 2017-04-12 2018-10-18 富士フイルム株式会社 Filtre, unité de rétroéclairage et dispositif d'affichage à cristaux liquides
WO2020138358A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque de polarisation et rouleau de plaque de polarisation
WO2020138329A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque polarisante et rouleau de plaque polarisante
WO2020138368A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque de polarisation pourvue de couche à difféerence de phase
WO2020209222A1 (fr) * 2019-04-09 2020-10-15 日東電工株式会社 Stratifié pour protection de polariseur et plaque de polarisation utilisant ledit stratifié
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JP2021173982A (ja) * 2020-04-30 2021-11-01 日東電工株式会社 偏光板および光学機能層付偏光板
CN113661421A (zh) * 2019-04-09 2021-11-16 日东电工株式会社 偏光板

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WO2018190211A1 (fr) * 2017-04-12 2018-10-18 富士フイルム株式会社 Filtre, unité de rétroéclairage et dispositif d'affichage à cristaux liquides
US20210198602A1 (en) * 2018-05-25 2021-07-01 Basf Se Use of compositions comprising a solvent mixture for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below
US12146125B2 (en) * 2018-05-25 2024-11-19 Basf Se Use of compositions comprising a solvent mixture for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below
TWI839433B (zh) * 2018-12-27 2024-04-21 日商日東電工股份有限公司 附相位差層之偏光板
TWI835966B (zh) * 2018-12-27 2024-03-21 日商日東電工股份有限公司 偏光板及偏光板捲材
WO2020138368A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque de polarisation pourvue de couche à difféerence de phase
CN113272688A (zh) * 2018-12-27 2021-08-17 日东电工株式会社 偏光板及偏光板卷材
JPWO2020138368A1 (ja) * 2018-12-27 2021-10-14 日東電工株式会社 位相差層付偏光板
JPWO2020138358A1 (ja) * 2018-12-27 2021-10-14 日東電工株式会社 偏光板および偏光板ロール
JPWO2020138329A1 (ja) * 2018-12-27 2021-10-14 日東電工株式会社 偏光板および偏光板ロール
CN119224890A (zh) * 2018-12-27 2024-12-31 日东电工株式会社 偏光板及偏光板卷材
WO2020138358A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque de polarisation et rouleau de plaque de polarisation
WO2020138329A1 (fr) * 2018-12-27 2020-07-02 日東電工株式会社 Plaque polarisante et rouleau de plaque polarisante
JPWO2020209222A1 (ja) * 2019-04-09 2021-11-18 日東電工株式会社 偏光子保護用積層体および該積層体を用いた偏光板
CN113711093A (zh) * 2019-04-09 2021-11-26 日东电工株式会社 偏振片保护用层叠体及使用该层叠体的偏光板
WO2020209222A1 (fr) * 2019-04-09 2020-10-15 日東電工株式会社 Stratifié pour protection de polariseur et plaque de polarisation utilisant ledit stratifié
CN113711093B (zh) * 2019-04-09 2024-11-05 日东电工株式会社 偏振片保护用层叠体及使用该层叠体的偏光板
CN113661421A (zh) * 2019-04-09 2021-11-16 日东电工株式会社 偏光板
JP7596079B2 (ja) 2020-04-30 2024-12-09 日東電工株式会社 偏光板および光学機能層付偏光板
JP2021173982A (ja) * 2020-04-30 2021-11-01 日東電工株式会社 偏光板および光学機能層付偏光板

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