WO2022019121A1 - 偏光板、偏光板の製造方法及び表示装置 - Google Patents

偏光板、偏光板の製造方法及び表示装置 Download PDF

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Publication number
WO2022019121A1
WO2022019121A1 PCT/JP2021/025683 JP2021025683W WO2022019121A1 WO 2022019121 A1 WO2022019121 A1 WO 2022019121A1 JP 2021025683 W JP2021025683 W JP 2021025683W WO 2022019121 A1 WO2022019121 A1 WO 2022019121A1
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Prior art keywords
group
polarizing plate
liquid crystal
optical film
layer
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PCT/JP2021/025683
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English (en)
French (fr)
Japanese (ja)
Inventor
康 大久保
隆 建部
崇 南條
栞 佐藤
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コニカミノルタ株式会社
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Priority to CN202180059958.6A priority Critical patent/CN116490582A/zh
Priority to JP2022537916A priority patent/JPWO2022019121A1/ja
Priority to KR1020237001747A priority patent/KR20230021754A/ko
Publication of WO2022019121A1 publication Critical patent/WO2022019121A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8793—Arrangements for polarized light emission

Definitions

  • the present invention relates to a polarizing plate, a method for manufacturing a polarizing plate, and a display device. More specifically, the present invention relates to a polarizing plate using a dichroic organic dye, which is a thin film but has high durability and can be easily manufactured.
  • the display is being considered for installation not only in televisions but also in various mobile devices such as laptop computers, mobile phones, watches, and eyeglasses.
  • mobile devices there is a demand for further thinning, weight reduction and flexibility of displays, and liquid crystal display elements and organic EL elements are listed as candidates.
  • a polarizing plate is used in both elements, and there is a demand for further thinning of the polarizing plate.
  • the development of polarizing plates containing a dichroic organic dye in a polarizing element layer, which can be formed by a coating type that can be made thinner than the conventional stretching process, has been promoted. Improvement is required. Further, the polarizing plate made of a dichroic organic dye has higher heat resistance than iodine, which is a commonly used dichroic dye, and is expected to be applied to displays for new applications such as in-vehicle and outdoor.
  • Patent Document 1 discloses a technique of applying a composition for forming a protective layer on a polarizing element layer containing a dichroic organic dye and drying the solvent.
  • the dichroic organic dye in the polarizing layer is diffused into the protective layer during the drying step. There is a problem that the polarization performance is easily deteriorated and the polarization performance is deteriorated with time.
  • Patent Document 2 describes that the diffusion of a dichroic dye can be prevented by providing a diffusion prevention layer made of a water-soluble polymer.
  • the hydrophilic compound such as polyvinyl alcohol used as the diffusion prevention layer has insufficient acid resistance, and is also referred to as an adhesive (or "adhesive layer" used when the polarizing plate is attached to the display device. )
  • the anti-diffusion layer are adjacent to each other, the anti-diffusion layer and the dichroic dye are likely to be deteriorated by the acid contained in the adhesive layer. Further, when the function of the diffusion prevention layer is deteriorated, the dichroic dye is easily diffused, and the polarization performance is deteriorated with time. Further, there is a problem of durability in a high temperature environment.
  • Patent Document 3 presents a polarizing film capable of suppressing a decrease in polarization performance over time due to diffusion of a dichroic dye and having high acid resistance.
  • the process of forming as many as two coating layers is complicated and the yield is low, and when an ultraviolet curable resin is used for the protective layer, the influence of the decomposition products of the residual monomer and the initiator on the polarizing element layer and the curing are performed.
  • Our study found that the change over time in the degree of polarization due to shrinkage stress becomes a problem.
  • the present invention has been made in view of the above problems and situations, and the problem to be solved thereof is a polarizing plate using a dichroic organic dye, a method for producing the same, and the polarizing plate, which are highly durable and can be easily manufactured. Is to provide a display device provided with.
  • the present inventor came to the present invention by obtaining the following findings in the process of examining the cause of the above problem in order to solve the above problem.
  • an adhesive containing a water-based adhesive is adhered.
  • the pH value of the water-based adhesive is controlled to a specific range, and it is appropriate for such a water-based adhesive. It was found that the durability is improved and the product can be easily manufactured by setting the alkaline region that has a high permeability and traps the acid to be a region diffused at an appropriate concentration.
  • a polarizing plate having at least a polarizing element layer, an adhesive layer, and a protective layer in this order.
  • the polarizing layer contains a dichroic organic dye and is
  • the adhesive layer contains a water-based adhesive, and the pH value of the water-based adhesive is in the range of more than 7.0 and less than 9.0 at a measurement temperature of 25 ° C.
  • the retardation value (Ro) in the inner surface direction of the optical film measured in an environment of a measurement wavelength of 590 nm, 23 ° C. and 55% RH is in the range of 0 to 30 nm, and the retardation in the thickness direction.
  • the polarizing plate according to any one of items 1 to 5, wherein the support is an optical film having a thickness of 1 ⁇ m or more and less than 10 ⁇ m.
  • a display device comprising the polarizing plate according to any one of the items 1 to 9.
  • a polarizing element layer containing a dichroic organic dye and a protective layer provided with an optical film containing a thermoplastic resin as a main component are formed on the support, respectively, and then an adhesive containing a water-based adhesive is adhered.
  • PSA pressure-sensitive adhesive
  • the protective layer is directly formed on the polarizing layer, the influence of the formation of the protective layer on the polarizing layer has been a problem.
  • the polarizing layer and the protective layer are formed, they are bonded together. Therefore, it is presumed that the diffusion of the dichroic organic dye in the polarizing element layer into the protective layer and the influence of the decomposition products of the residual monomer and the initiator on the polarizing element layer can be suppressed. Furthermore, it is presumed that the process will be simplified and the yield will be improved by bonding with a water-based adhesive.
  • Basic layer structure of the polarizing plate of the present invention Another example of the basic layer structure of the polarizing plate of the present invention Schematic diagram of the manufacturing process of the polarizing plate having the basic layer structure of the present invention Schematic diagram of another example of the process of manufacturing a polarizing plate having a basic layer structure of the present invention.
  • Other configuration examples including the basic layer structure of the polarizing plate of the present invention Other configuration examples including the basic layer structure of the polarizing plate of the present invention
  • Other configuration examples including the basic layer structure of the polarizing plate of the present invention Schematic diagram showing an example of an optical film manufacturing apparatus Schematic diagram showing the manufacturing method and layer structure of the polarizing plate of the example
  • the polarizing plate of the present invention is a polarizing plate provided with at least a polarizing element layer, an adhesive layer and a protective layer in this order, wherein the polarizing element layer contains a dichroic organic dye and the adhesive layer is ,
  • the water-based adhesive is contained, and the pH value of the water-based adhesive is in the range of more than 7.0 and less than 9.0 at a measurement temperature of 25 ° C.
  • the protective layer contains a resin as a main component.
  • the optical film is provided, and the thickness of the optical film is 1 ⁇ m or more and less than 10 ⁇ m. This feature is a technical feature common to or corresponding to each of the following embodiments.
  • the moisture permeability of the optical film, the temperature 40 ° C., under a humidity of 90% RH is preferably 500 ⁇ 5000g / m 2 ⁇ 24h .
  • the polarizing element layer contains the polymerizable liquid crystal compound and the dichroic organic dye from the viewpoint of the use of a bendable ultra-thin polarizing plate.
  • the retardation value (Ro) in the inner surface direction of the optical film measured in an environment of a measurement wavelength of 590 nm, 23 ° C. and 55% RH is in the range of 0 to 30 nm, and the retardation in the thickness direction. It is preferable that the value (Rt) is in the range of ⁇ 30 to +30 nm from the viewpoint of image quality (color shift) at the time of bending.
  • the optical film is made of a thermoplastic resin having at least a carbonyl group in the side chain from the viewpoint of promoting the penetration of the water-based adhesive and improving the durability of the adhesiveness.
  • An optical film having a support under the polarizing layer and having a thickness of 1 ⁇ m or more and less than 10 ⁇ m controls the region where the water-based adhesive permeates, and has adhesive durability and acidity. It is preferable from the viewpoint of preventing deterioration after trapping and ensuring durability at the time of bending.
  • the adhesive layer contains polyvinyl alcohol because it has low compatibility with the dichroic organic dye, from the viewpoint of preventing bleeding out of the dichroic organic dye and improving durability.
  • the adhesive layer contains polyvinyl alcohol and an isocyanato-based additive or an oxazoline-based additive from the viewpoint of improving the water resistance of the adhesive layer. Further, it is more preferable that the embodiment contains polyvinyl alcohol and an oxazoline-based additive from the same viewpoint as described above.
  • a step of forming a polarizing element layer containing a dichroic organic dye on a first support and a step of forming a polarizing plate containing a dichroic organic dye on a peelable second support are used.
  • a step of applying an adhesive on the installed optical film as a protective layer and adhering it to the polarizing element layer formed in the above step, and a second support having a peelability after the adhesive layer has dried are provided. It is preferable that the manufacturing method has a step of peeling and a step of peeling.
  • the polarizing plate of the present invention can be suitably provided in a display device. As a result, a display device that can be easily manufactured and has high durability can be obtained.
  • the polarizing plate of the present invention is a polarizing plate having at least a polarizing element layer, an adhesive layer and a protective layer in this order, and the polarizing element layer is a dichroic organic dye.
  • the protective layer contains a water-based adhesive, and the pH value of the water-based adhesive is in the range of more than 7.0 and less than 9.0 at a measurement temperature of 25 ° C. It is characterized in that an optical film containing a resin as a main component is provided, and the thickness of the optical film is 1 ⁇ m or more and less than 10 ⁇ m.
  • FIGS. 1A and 1B show an example of the basic structure of the layer structure of the polarizing plate 1 of the present invention.
  • the polarizing plate 1 of the present invention shown in FIG. 1A includes a protective layer 2, an adhesive layer 3, and a polarizing element layer 4 in this order, and the polarizing element layer 4 contains a dichroic organic dye.
  • the configuration shown in FIG. 1A is the simplest configuration. Separately, the polarizing element layer 4 is bonded to a film, glass or the like via the adhesive layer 3 in a later process.
  • the polarizing element layer 4 is directly exposed to the outside air and the handleability is limited. That is, a support 5 (hereinafter, also referred to as a “first support”) for forming the liquid crystal alignment layer (not shown) and the polarizing layer 4 is provided below the polarizing layer 4. May be good. It is preferable that the support 5 is an optical film having a thickness of 1 ⁇ m or more and less than 10 ⁇ m from the viewpoint of ensuring durability at the time of bending. More preferably, the film thickness is in the range of 3 to 8 ⁇ m.
  • the present invention is characterized in that the thickness of the optical film as the protective layer 2 in FIGS. 1A and 1B is as thin as 1 ⁇ m or more and less than 10 ⁇ m. Therefore, in order to improve the handleability of such a thin protective layer 2, when the optical film as the protective layer 2 is formed on the surface of the protective layer 2 opposite to the adhesive layer 3, the support 6 ( In the following, it may also be provided as a “second support”).
  • the second support After the protective layer 2 is bonded and formed in the state of a laminated body in which the protective layer 2 is laminated on the second support 6, the second support can be peeled off to form a polarizing plate. As described above, it is preferable that the second support has a function of being peelable from the protective layer. Therefore, if necessary, a release layer may be provided between the second support and the protective layer. The process for obtaining such a configuration is shown in FIG. 2A.
  • the polarizing element layer using the dichroic organic dye there are two types of configurations of the polarizing element layer using the dichroic organic dye: one adsorbed on polyvinyl alcohol and one in which the dichroic organic dye is oriented and dispersed in the liquid crystal material. Of these, it is preferable to use a liquid crystal material as a matrix for dispersing the dichroic organic dye because a thin polarizing element layer can be obtained.
  • liquid crystal alignment layer 8 Under the polarizing element layer 4. (See FIG. 3A.).
  • the retardation layer 9a When the retardation layer 9a has an antireflection function (for example, a function as a quarter wave plate), it becomes easy to use an antireflection film used as an antireflection layer for, for example, an organic EL display (FIG. 3B). reference.).
  • an antireflection film used as an antireflection layer for, for example, an organic EL display (FIG. 3B). reference.
  • the retardation layer 9a is a liquid crystal retardation layer 9b, it may have a liquid crystal alignment layer 8b, a third support layer 10, and the like as shown in FIG. 3C.
  • the "peelable function" as used in the present invention means that the second support and the protective layer are in close contact with each other during normal production or general use and cannot be easily peeled off, but during polarizing plate processing or after polarizing plate processing.
  • the second (and third) support can be peeled off from the protective layer by external stress.
  • the stress when peeling the support from the protective layer is that in a film cut to a width of 25 mm and a length of 80 mm, the surface of the optical film opposite to the support side interface is supported by glass via an acrylic adhesive sheet.
  • a support at one end (one side with a width of 25 mm) in the length direction of the test piece is used with a tensile tester (RTF-1210 manufactured by A & D Co., Ltd.).
  • RTF-1210 tensile tester manufactured by A & D Co., Ltd.
  • 90 ° peeling test JIS K 6854-1: 1999 "Adhesive-peeling adhesive strength test method" at a crosshead speed (grasping movement speed) of 200 mm / min in an atmosphere of temperature 23 ° C and humidity 60% RH.
  • the support and the optical film can be peeled off with a stress of 0.05 to 2.00 N / 25 mm when the peeling stress is evaluated by performing "Part 1: 90 degree peeling". Can be mentioned as.
  • the stress is 0.05 N / 25 mm or more, peeling is less likely to occur during the polarizing plate processing process, and it is preferable.
  • the stress is 2.00 N / 25 mm or less, the polarizing plate is broken when the support is peeled. Is preferable because it does not occur.
  • the layer structure of the polarizing plate of the present invention is not limited to the basic structure shown in FIGS. 1 and 3, and various forms of layer structure can be adopted.
  • the polarizing plate of the present invention is formed by bonding a polarizing element layer and a protective layer via an adhesive layer, and has a functional layer or the like between the first support and the polarizing element layer. It may be present, and the first support may not be present.
  • the polarizing plate of the present invention includes an optical film containing a resin as a main component as a protective layer.
  • the optical film as the protective layer according to the present invention may have a function as a retardation film.
  • the present invention is characterized in that the thickness of the optical film is within the range of 1 ⁇ m or more and less than 10 ⁇ m. It is preferably in the range of 2 to 8 ⁇ m, and more preferably in the range of 3 to 7 ⁇ m.
  • the thickness is less than 1 ⁇ m, the waist becomes weak and the strength of the polarizing plate decreases. Further, when it is 10 ⁇ m or more, the strength of the polarizing plate against bending is lowered. Therefore, it is necessary to be within the above range.
  • moisture permeability of the optical film the temperature 40 ° C., under humidity of 90% RH, characterized in that it is in the range of 500 ⁇ 5000g / m 2 ⁇ 24h .
  • the moisture permeability of the optical film is a value measured by leaving the film to be measured under the conditions of 40 ° C. and 90% RH for 24 hours based on the calcium chloride-cup method described in JIS Z-0208: 1976. be.
  • the resin used for the optical film as the protective layer according to the present invention may be a thermoplastic resin or a three-dimensional resin (heat or photocurable resin). ) May be.
  • the three-dimensional resin include a resin obtained by applying a polyfunctional monomer and then irradiating it with light.
  • polyfunctional monomers examples include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene, ethylene glycol di (meth) acrylate, and diethylene glycol (diethylene glycol).
  • examples include meth) acrylate, triethylene glycol di (meth) acrylate, trimethyllol propanetri (meth) acrylate, tetromethylol methanetetra (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like.
  • a monomer in which a cyclic aliphatic hydrocarbon group is substituted with a plurality of polymerizable functional groups and in particular, it is possible to have a group derived from an alicyclic compound having 7 or more carbon atoms. It is preferable from the viewpoint of characteristics and the like.
  • thermoplastic resin examples include polystyrene-based resins, epoxy resins, methyl methacrylate resins (PMMA), and polymers of compounds having a group having an ethylenically unsaturated double bond, and examples thereof include internal stress. It is preferable that the thermoplastic resin is less likely to cause curl and film peeling due to shrinkage.
  • thermoplastic resin examples include cellulose ester resin, cycloolefin resin, fumaric acid diester resin, polypropylene resin, (meth) acrylic resin, polyester resin, polyarylate resin, polyimide resin, and styrene resin.
  • the composite resin thereof may be mentioned.
  • the preferred resin may be a fumaric acid diester resin, a (meth) acrylic resin, a styrene / (meth) acrylate copolymer, or the like.
  • the cellulosic resin is not particularly limited, but is preferably a lower fatty acid ester of cellulose.
  • the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
  • Examples of the cellulosic resin include cellulose acetate, cellulose propionate, cellulose acetate butyrate, and cellulose described in JP-A No. 10-45804, JP-A-08-231761, US Pat. No. 2319052, and the like.
  • Mixed fatty acid esters such as acetate propionate and cellulose acetate butyrate can be used. Of these, cellulose triacetate and cellulose acetate propionate are preferable.
  • These cellulosic resins may be used alone or in combination of two or more.
  • the cycloolefin-based resin used for the optical film is preferably a polymer of a cycloolefin monomer or a copolymer of a cycloolefin monomer and another copolymerizable monomer.
  • the cycloolefin monomer is preferably a cycloolefin monomer having a norbornene skeleton.
  • Examples of the copolymerizable monomer copolymerizable with the cycloolefin monomer include a copolymerizable monomer capable of ring-opening copolymerization with the cycloolefin monomer and an addition copolymerization with the cycloolefin monomer. Possible copolymerizable monomers and the like are included.
  • ring-opening copolymerizable copolymerizable monomers examples include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and dicyclopentadiene.
  • Examples of the copolymerizable monomer that can be additionally copolymerized include unsaturated double bond-containing compounds, vinyl-based cyclic hydrocarbon monomers, (meth) acrylates, and the like.
  • unsaturated double bond-containing compounds include olefin compounds having 2 to 12 (preferably 2 to 8) carbon atoms, and examples thereof include ethylene, propylene and butene.
  • vinyl-based cyclic hydrocarbon monomers include vinyl cyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene.
  • Examples of (meth) acrylates include alkyl (meth) acrylates having 1 to 20 carbon atoms such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate.
  • the content ratio of the cycloolefin monomer in the copolymer of the cycloolefin monomer and the copolymerizable monomer is, for example, 20 to 80 mol% with respect to the total of all the monomers constituting the copolymer. It can be preferably 30 to 70 mol%.
  • the polyimide-based resin is obtained, for example, by synthesizing a polyamic acid (polyimide precursor) from an acid anhydride and a diamine compound, and imidizing the polyamic acid by heat or a catalyst.
  • the acid anhydride used for the synthesis of polyimide is not particularly limited, and is, for example, biphenyltetracarboxylic acid dianhydride (BPDA), terphenyltetracarboxylic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, and pyroanhydride.
  • Aromatic tetracarboxylic acid dianhydrides such as merit acid (PMDA), oxydiphthalic acid dianhydrides, diphenylsulfone tetracarboxylic acid dianhydrides, hexafluoroisopropyridene diphthalic acid dianhydrides, cyclobutanetetracarboxylic acid dianhydrides, etc. Can be mentioned.
  • the diamine compound used for the synthesis of polyimide is not particularly limited, but for example, p-phenylenediamine (PDA), m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenyl ether (ODA), 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'- Diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5'-dioxide, 4,4'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide , 1,4-Bis (4-aminophenoxy) benzene
  • the fumaric acid diester resin used for the optical film is a fumaric acid diester resin containing a fumaric acid diisopropyl residue unit and a fumaric acid diester residue unit having an alkyl group having 1 or 2 carbon atoms.
  • the alkyl groups having 1 or 2 carbon atoms in the fumarate diester residue unit having an alkyl group having 1 or 2 carbon atoms are independent of each other, and examples thereof include a methyl group and an ethyl group. Further, these may be substituted with a halogen group such as fluorine or chlorine; an ether group; an ester group or an amino group.
  • a halogen group such as fluorine or chlorine
  • an ether group such as an ether group
  • an ester group or an amino group examples of the fumaric acid diester residue unit having an alkyl group having 1 or 2 carbon atoms include a dimethyl fumarate residue unit and a diethyl fumarate residue unit. Further, these may be contained alone or in combination of two or more.
  • fumaric acid diester resin examples include diisopropyl fumarate / dimethyl fumarate copolymer resin, diisopropyl fumarate / diethyl fumarate copolymer resin and the like.
  • the fumaric acid diester resin may contain another monomer residue unit, and examples of the other monomer residue unit include, for example, a styrene residue unit, an ⁇ -methylstyrene residue unit, and the like.
  • (Meta) Acrylic such as (meth) acrylate residue unit; (meth) methyl acrylate residue unit, (meth) ethyl acrylate residue unit, (meth) butyl acrylate residue unit, etc.
  • Acid ester residue unit Vinyl ester residue unit such as vinyl acetate residue unit, propionate vinyl residue unit; Acrylonitrile residue unit; Maleimideloryl residue unit; Methyl vinyl ether residue unit, Ethyl vinyl ether residue unit Units, vinyl ether residue units such as butyl vinyl ether residue units; N-substituted maleimide residue units such as N-methylmaleimide residue units, N-cyclohexylmaleimide residue units, N-phenylmaleimide residue units; ethylene Olefins residue units such as residue units and propylene residue units; or fumal other than the fumaric acid diester residue units such as din-butyl fumarate residue units and bis (2-ethylhexyl) fumarate residue units.
  • One or more selected from the acid diester residues and the lauric acid and lauric acid ester units can be mentioned.
  • the blending ratio of the fumaric acid diester resin used in the present invention is preferably 50 to 99 mol% of diisopropyl fumarate residue unit and 1 to 50 mol% of fumaric acid diester residue unit having an alkyl group having 1 or 2 carbon atoms.
  • a fumaric acid diester resin consisting of 40 mol% is particularly preferable.
  • the fumaric acid diester resin used in the present invention preferably has a standard polystyrene-equivalent number average molecular weight in the range of 50,000 to 250,000 obtained from the elution curve measured by the gel permeation chromatography.
  • the (meth) acrylic resin used in the optical film preferably contains at least a structural unit (U1) derived from methyl methacrylate and a structural unit (U2) derived from phenylmaleimide.
  • the (meth) acrylic resin containing the structural unit (U2) derived from phenylmaleimide has an advantage that the photoelastic coefficient of the optical film is reduced and unevenness is less likely to occur even if it absorbs and expands.
  • the (meth) acrylic resin may further contain structural units other than the above.
  • such other structural units include (meth) acrylic acid alkyl esters such as adamantyl acrylate; (meth) acrylic acid cycloalkyl esters such as 2-ethylhexyl acrylate.
  • the structural unit (U2) derived from phenylmaleimide it is preferable to further contain the structural unit (U3) derived from the acrylic acid alkyl ester.
  • the (meth) acrylic resin contains a structural unit (U1) derived from methyl methacrylate, a structural unit (U2) derived from phenylmaleimide, and a structural unit (U3) derived from an acrylic acid alkyl ester. Is more preferable.
  • the content of the structural unit (U1) derived from methyl methacrylate is preferably 50 to 95% by mass, preferably 70 to 90% by mass, based on all the structural units constituting the (meth) acrylic resin. Is more preferable.
  • the structural unit (U2) derived from phenylmaleimide has a relatively rigid structure, the mechanical strength of the optical film can be improved. Further, since the structural unit (U2) derived from phenylmaleimide has a relatively bulky structure, it has microscopic voids in the resin matrix that can move rubber particles, and the rubber particles are unevenly distributed on the surface layer of the optical film. It can be easy to make.
  • the content of the structural unit (U2) derived from phenylmaleimide is preferably 1 to 25% by mass with respect to all the structural units constituting the (meth) acrylic resin.
  • the content of the structural unit (U2) derived from phenylmaleimide is 1% by mass or more, the optical film is excellent in storage stability in a high humidity environment. When it is 25% by mass or less, the brittleness of the optical film is not easily impaired.
  • the content of the structural unit (U2) derived from phenylmaleimide is more preferably 7 to 15% by mass.
  • the structural unit (U3) derived from the acrylic acid alkyl ester can impart appropriate flexibility to the resin, for example, the brittleness due to containing the structural unit (U2) derived from phenylmaleimide can be improved.
  • the acrylic acid alkyl ester is preferably an acrylic acid alkyl ester having an alkyl moiety having 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms.
  • acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and the like.
  • the content of the structural unit (U3) derived from the acrylic acid alkyl ester is preferably 1 to 25% by mass with respect to all the structural units constituting the (meth) acrylic resin.
  • the (meth) acrylic resin can be imparted with appropriate flexibility, so that the optical film does not become too brittle and breaks. Hateful.
  • the content of the structural unit (U3) derived from the acrylic acid alkyl ester is 25% by mass or less, the glass transition temperature (Tg) of the optical film does not become too low, and the optical film can be stored in a high humidity environment. Excellent for.
  • the content of the structural unit (U3) derived from the acrylic acid alkyl ester is more preferably 5 to 15% by mass.
  • the ratio of the structural unit (U2) derived from phenylmaleimide to the total amount of the structural unit (U2) derived from phenylmaleimide and the structural unit (U3) derived from the acrylic acid alkyl ester shall be 20 to 70% by mass. Is preferable. When the ratio is 20% by mass or more, the tensile elastic modulus G2 of the optical film is likely to be increased, and when the ratio is 70% by mass or less, the optical film does not become too brittle.
  • the glass transition temperature (Tg) of the (meth) acrylic resin is preferably 100 ° C. or higher, more preferably 120 to 150 ° C.
  • the heat resistance of the optical film can be easily increased.
  • the glass transition temperature (Tg) of the (meth) acrylic resin for example, the content of the structural unit (U2) derived from phenylmaleimide or the structural unit (U3) derived from the acrylic acid alkyl ester is adjusted. Is preferable.
  • the weight average molecular weight (Mw) of the (meth) acrylic resin is not particularly limited and can be adjusted according to the purpose.
  • the weight average molecular weight of the (meth) acrylic resin is, for example, from the viewpoint of promoting entanglement between resin molecules to increase the toughness of the optical film and making it difficult to break, and to appropriately increase the CHE ratio and curl to a degree preferable for adhesion. From the viewpoint of facilitating adjustment to the amount, it is preferably 100,000 or more, and more preferably 1 million or more. When the weight average molecular weight of the (meth) acrylic resin is 1 million or more, the toughness of the obtained optical film can be enhanced.
  • the weight average molecular weight of the (meth) acrylic resin is more preferably 1.5 million to 3 million.
  • the weight average molecular weight can be measured by using a gel permeation chromatography method or the like.
  • styrene / (meth) acrylate copolymer The styrene / (meth) acrylate copolymer (hereinafter, also referred to as styrene / acrylic resin) has excellent transparency when used in an optical film. Further, since the coefficient of thermal expansion can be adjusted by the copolymerization ratio of the styrene portion, the curl as a laminated body can be controlled by changing these ratios.
  • the styrene / acrylic resin is formed by addition polymerization of at least a styrene monomer and a (meth) acrylic acid ester monomer.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 24 carbon atoms.
  • an acrylic acid ester derivative or a methacrylic acid ester derivative having a known side chain or functional group in the structure of these esters is included.
  • the above (meth) acrylic acid ester monomer may be one kind or more. For example, forming a copolymer using a styrene monomer and two or more kinds of acrylic acid ester monomers, or using a styrene monomer and two or more kinds of methacrylic acid ester monomers to coweight. It is possible to form a coalescence and to form a copolymer by using a styrene monomer, an acrylic acid ester monomer and a methacrylic acid ester monomer in combination.
  • the weight average molecular weight (Mw) of the styrene / acrylic resin is preferably in the range of 5,000 to 150,000, and more preferably in the range of 30,000 to 120,000, from the viewpoint of easy control of plasticity.
  • the styrene / acrylic resin used in the present invention may be a commercially available product, and the MS resin "TX320XL” manufactured by Denka Co., Ltd. can be mentioned as an example.
  • the optical film may further contain components other than the above, if necessary.
  • other components include antioxidants, rubber particles, and later-described matting agents (fine particles), plasticizers, ultraviolet absorbers, and the like.
  • the antioxidant contributes to the improvement of the storage stability of the optical film over time, and the rubber particles are preferably contained from the viewpoint of imparting toughness (suppleness) to the optical film.
  • ⁇ Antioxidant> it is preferable to contain an additive having a molecular weight of 1000 or less in the optical film in the range of 0.0001 to 0.01% by mass from the viewpoint of suppressing the diffusion of precipitates, and the additive is oxidized.
  • An inhibitor is a preferred embodiment.
  • antioxidant As the antioxidant according to the present invention, commonly known ones can be used.
  • lactone-based, sulfur-based, phenol-based, double-bonded, hindered amine-based, and phosphorus-based compounds can be preferably used.
  • lactone-based compound examples include "IrgafosXP40, IrgafosXP60 (trade name)" commercially available from BASF Japan Ltd.
  • sulfur-based compound examples include “Sumilizer (registered trademark) TPL-R” and “Sumilizer (registered trademark) TP-D” commercially available from Sumitomo Chemical Co., Ltd.
  • the phenolic compound preferably has a structure of 2,6-dialkylphenol.
  • "Irganox (registered trademark) 1076” and “Irganox (registered trademark) 1010” commercially available from BASF Japan Ltd.
  • Examples thereof include “Adecastab (registered trademark) AO-50” commercially available from ADEKA Co., Ltd.
  • the double bond compound is commercially available from Sumitomo Chemical Co., Ltd. under the trade names of "Sumilizer (registered trademark) GM” and “Sumilizer (registered trademark) GS”. Generally, it is added in the range of 0.05 to 20% by mass, preferably 0.1 to 1% by mass, based on the resin.
  • the above hindered amine compounds are, for example, "Tinuvin (registered trademark) 144" and “Tinuvin (registered trademark) 770” marketed by BASF Japan Ltd., and "ADK STAB (registered trademark)” marketed by ADEKA CORPORATION. LA-52 ”can be mentioned.
  • the phosphorus-based compounds include, for example, "Sumilizer (registered trademark) GP” marketed by Sumitomo Chemical Co., Ltd., "ADK STAB (registered trademark) PEP-24G” and “ADK STAB” marketed by ADEKA Co., Ltd. Registered trademark) PEP-36 “and” ADK STAB (registered trademark) 3010 ",” IRGAFOS P-EPQ “commercially available from BASF Japan Co., Ltd., and” GSY-P101 "commercially available from Sakai Chemical Industry Co., Ltd. Can be mentioned.
  • antioxidants and the like are preferably contained in the range of 0.0001 to 0.01% by mass, more preferably 0.002 to 0.01% by mass, based on the resin which is the main raw material of the optical film. It is added within the range of.
  • antioxidants and the like can be used alone or in combination with several different compounds.
  • the combined use of lactone-based, phosphorus-based, phenol-based and double-bonding compounds is preferable.
  • the rubber particles are particles containing a rubber-like polymer.
  • the rubber particles are added mainly for the purpose of improving the flexibility of the film.
  • the rubber-like polymer is a soft crosslinked polymer having a glass transition temperature of 20 ° C. or lower.
  • Examples of such cross-linked polymers include butadiene-based cross-linked polymers, (meth) acrylic-based cross-linked polymers, and organosiloxane-based cross-linked polymers.
  • the (meth) acrylic crosslinked polymer is preferable from the viewpoint that the difference in refractive index from the (meth) acrylic resin is small and the transparency of the optical film is not easily impaired, and the acrylic crosslinked polymer (acrylic rubber-like weight) is preferable. Combined) is more preferable.
  • the rubber particles are preferably particles containing the acrylic rubber-like polymer (a).
  • the acrylic rubber-like polymer (a) is a crosslinked polymer containing a structural unit derived from an acrylic acid ester as a main component. Including as a main component means that the content of the structural unit derived from the acrylic acid ester is in the range described later.
  • the acrylic rubber-like polymer (a) has a structural unit derived from an acrylic acid ester, a structural unit derived from another monomer copolymerizable with the structural unit, and two or more radically polymerizable groups in one molecule (. It is preferably a crosslinked polymer containing a structural unit derived from a polyfunctional monomer having a non-conjugated reactive double bond).
  • Acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic. It is preferably an acrylic acid alkyl ester having 1 to 12 carbon atoms of an alkyl group such as n-octyl acid. The acrylic acid ester may be one kind or two or more kinds.
  • the content of the structural unit derived from the acrylic acid ester is preferably 40 to 80% by mass, preferably 50 to 80% by mass, based on all the structural units constituting the acrylic rubber-like polymer (a1). Is more preferable.
  • the content of the acrylic acid ester is within the above range, it is easy to impart sufficient toughness to the optical film.
  • the other copolymerizable monomers are those other than the polyfunctional monomers among the monomers copolymerizable with the acrylic acid ester. That is, the copolymerizable monomer does not have two or more radically polymerizable groups.
  • Examples of copolymerizable monomers include methacrylic acid esters such as methyl methacrylate; styrenes such as styrene and methylstyrene; (meth) acrylonitriles; (meth) acrylamides; (meth) acrylic acid. ..
  • the other copolymerizable monomer preferably contains styrenes.
  • the other copolymerizable monomer may be one kind or two or more kinds.
  • the content of the structural unit derived from the other copolymerizable monomer is preferably 5 to 55% by mass with respect to the total structural unit constituting the acrylic rubber-like polymer (a), and is preferably 10 to 55% by mass. It is more preferably 45% by mass.
  • polyfunctional monomers examples include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene, ethylene glycol di (meth) acrylate, and diethylene glycol (diethylene glycol).
  • meth) acrylates triethylene glycol di (meth) acrylates, trimethyllol propanetri (meth) acrylates, tetromethylol methanetetra (meth) acrylates, dipropylene glycol di (meth) acrylates, polyethylene glycol di (meth) acrylates. ..
  • the content of the structural unit derived from the polyfunctional monomer is preferably 0.05 to 10% by mass, preferably 0.1 to 10% by mass, based on the total structural unit constituting the acrylic rubber-like polymer (a). More preferably, it is ⁇ 5% by mass.
  • the content of the polyfunctional monomer is 0.05% by mass or more, the degree of cross-linking of the obtained acrylic rubber-like polymer (a) is likely to be increased, so that the hardness and rigidity of the obtained optical film are impaired. If it is not too much and is 10% by mass or less, the toughness of the optical film is not easily impaired.
  • the monomer composition constituting the acrylic rubber-like polymer (a) can be measured by, for example, the peak area ratio detected by thermal decomposition GC-MS.
  • the glass transition temperature (Tg) of the rubber-like polymer is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower. When the glass transition temperature (Tg) of the rubber-like polymer is 0 ° C. or lower, appropriate toughness can be imparted to the film.
  • the glass transition temperature (Tg) of the rubber-like polymer is measured by the same method as described above.
  • the glass transition temperature (Tg) of the rubber-like polymer can be adjusted by the composition of the rubber-like polymer.
  • It is preferable to increase the mass ratio of other copolymerizable monomers for example, 3 or more, preferably 4 to 10).
  • the particles containing the acrylic rubber-like polymer (a) are a particle made of the acrylic rubber-like polymer (a) or a hard layer made of a hard crosslinked polymer (c) having a glass transition temperature of 20 ° C. or higher. , Particles having a soft layer made of the acrylic rubber-like polymer (a) arranged around the same (these are also referred to as “epolymer”); the acrylic rubber-like polymer (a).
  • the particles may be particles made of an acrylic graft copolymer obtained by polymerizing a mixture of monomers such as a methacrylic acid ester in at least one stage.
  • the particles made of the acrylic graft copolymer may be core-shell type particles having a core portion containing the acrylic rubber-like polymer (a) and a shell portion covering the core portion.
  • the core portion contains an acrylic rubber-like polymer (a), and may further contain a hard crosslinked polymer (c), if necessary. That is, the core portion may have a soft layer made of an acrylic rubber-like polymer and a hard layer made of a hard crosslinked polymer (c) arranged inside the soft layer.
  • the crosslinked polymer (c) can be a crosslinked polymer containing a methacrylic acid ester as a main component. That is, the crosslinked polymer (c) includes a structural unit derived from a methacrylic acid alkyl ester, a structural unit derived from another monomer copolymerizable therewith, and a structural unit derived from a polyfunctional monomer. It is preferably a crosslinked polymer containing.
  • the alkyl methacrylate ester may be the above-mentioned alkyl methacrylate ester; the other copolymerizable monomer may be the above-mentioned styrenes, acrylic acid ester, etc .; the polyfunctional monomer may be. The same as those mentioned above as the polyfunctional monomer can be mentioned.
  • the content of the structural unit derived from the methacrylic acid alkyl ester can be 40 to 100% by mass with respect to the total structural unit constituting the crosslinked polymer (c).
  • the content of the structural unit derived from the other copolymerizable monomer can be 0 to 60% by mass with respect to the total structural unit constituting the other crosslinked polymer (c).
  • the content of the structural unit derived from the polyfunctional monomer can be 0.01 to 10% by mass with respect to the total structural unit constituting the other crosslinked polymer.
  • the shell portion contains a methacrylic polymer (b) (another polymer) graft-bonded to the acrylic rubber-like polymer (a) and containing a structural unit derived from a methacrylic acid ester as a main component.
  • a methacrylic polymer (another polymer) graft-bonded to the acrylic rubber-like polymer (a) and containing a structural unit derived from a methacrylic acid ester as a main component.
  • “Included as a main component” means that the content of structural units derived from methacrylic acid ester is in the range described later.
  • the methacrylic acid ester constituting the methacrylic acid polymer (b) is preferably an alkyl methacrylic acid ester having 1 to 12 carbon atoms of an alkyl group such as methyl methacrylate.
  • the methacrylic acid ester may be one kind or two or more kinds.
  • the content of the methacrylic acid ester is preferably 50% by mass or more with respect to all the structural units constituting the methacrylic acid polymer (b).
  • the content of methacrylic acid ester is 50% by mass or more, compatibility with a methacrylic resin containing a structural unit derived from methyl methacrylate as a main component can be easily obtained.
  • the content of the methacrylic acid ester is more preferably 70% by mass or more with respect to all the structural units constituting the methacrylic acid polymer (b).
  • the methacrylic polymer (b) may further contain a structural unit derived from another monomer copolymerizable with the methacrylic acid ester.
  • examples of other copolymerizable monomers are acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate; benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, A (meth) acrylic monomer having an alicyclic, heterocyclic or aromatic ring such as phenoxyethyl (meth) acrylate (ring-containing (meth) acrylic monomer) is included.
  • the content of the structural unit derived from the copolymerizable monomer is preferably 50% by mass or less, preferably 30% by mass or less, based on the total structural unit constituting the methacrylic polymer (b). Is more preferable.
  • the shape of the rubber particles can be a shape close to a true sphere. That is, the aspect ratio of the rubber particles when observing the cross section or the surface of the optical film may be about 1 to 2.
  • the average particle size of the rubber particles is preferably 100 to 400 nm.
  • the average particle diameter of the rubber particles is 100 nm or more, it is easy to impart sufficient toughness and stress relaxation property to the optical film, and when it is 400 nm or less, the transparency of the optical film is not easily impaired.
  • the average particle size of the rubber particles is more preferably 150 to 300 nm.
  • the average particle size of the rubber particles can be calculated by the following method.
  • the average particle size of the rubber particles can be measured as the average value of the equivalent circle diameters of 100 particles obtained by SEM photography or TEM photography of the surface or section of the laminated film.
  • the equivalent circle diameter can be obtained by converting the projected area of the particles obtained by photography into the diameter of a circle having the same area.
  • the rubber particles observed by SEM observation and / or TEM observation at a magnification of 5000 times are used for calculating the average particle diameter.
  • the content of the rubber particles is not particularly limited, but is preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the optical film.
  • the optical film as a protective layer according to the present invention can function as a retardation film.
  • the optical film has a retardation value (Ro) in the inner surface direction of the optical film measured in an environment of a measurement wavelength of 590 nm, 23 ° C. and 55% RH, in the range of 0 to 30 nm, and has a thickness. It is preferable that the retardation value (Rt) in the radial direction is in the range of -30 to +30 nm from the viewpoint of using it as a retardation film for, for example, the IPS mode.
  • the optical film has a retardation value (Ro) in the in-plane direction, more preferably (Ro) in the range of 0 to 10 nm, and a retardation value (Rt) in the thickness direction.
  • ) Is in the range of -20 to +20 nm.
  • (Ro) is in the range of 0 to 5 nm
  • the retardation value (Rt) in the thickness direction is in the range of ⁇ 5 to +15 nm.
  • n x represents the refractive index in the in-plane slow phase axial direction (the direction in which the refractive index becomes maximum) of the optical film.
  • n y represents a refractive index in a direction perpendicular to the in-plane slow axis of the optical film.
  • n z represents the refractive index in the thickness direction of the optical film.
  • d represents the film thickness (nm) of the optical film.
  • the in-plane slow phase axis of the optical film can be confirmed by, for example, an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Polarimeter: manufactured by Axometrics).
  • Ro and Rt can be measured by the following methods.
  • the retardation values Ro and Rt of the optical film can be adjusted, for example, by the type of resin, stretching conditions, and drying conditions. For example, Rt can be lowered by raising the drying temperature.
  • optical film as the protective layer according to the present invention is not particularly limited, but may be, for example, a band shape. That is, the optical film according to the present invention is preferably wound into a roll in a direction orthogonal to the width direction thereof to form a roll.
  • the method for producing an optical film as a protective layer according to the present invention includes 1) a step of obtaining a solution for an optical film, 2) a step of applying the obtained optical film solution to the surface of a support, and 3) a step of applying the obtained optical film solution. It has a step of removing a solvent from a solution for an optical film to form an optical film.
  • Step of obtaining a solution for an optical film An optical film solution (also referred to as "dope") containing the above-mentioned resin and a solvent is prepared.
  • the solvent used for the optical film solution is not particularly limited as long as it can satisfactorily disperse or dissolve the resin.
  • the organic solvent used in the present invention alcohols (methanol, ethanol, diol, triol, tetrafluoropropanol, etc.), glycols, cellosolves, ketones (acetone, methylethylketone, etc.), carboxylic acids (girate, acetic acid, etc.) Etc.), carbonates (ethylene carbonate, propylene carbonate, etc.), esters (ethyl acetate, propyl acetate, etc.), ethers (isopropyl ether, THF, etc.), amides (dimethylsulfoxide, etc.), hydrocarbons (heptane, etc.) , Nitriles (acetoyl, etc.), aromatics (cyclohexylbenzene, toluene, xylene, chlorobenzene, etc.), alkyl halides
  • the solvent of the optical film has a boiling point of 100 ° C. or lower under atmospheric pressure, is a chlorine-based solvent as a type, and more specifically, dichloromethane (also referred to as "methylene chloride"). It is preferable from the viewpoint of ease of handling when preparing and forming a dope for a film. This is preferable from the viewpoint of high solubility and high drying rate when preparing and forming a dope for an optical film, whereby the film quality of the coating film can be adjusted.
  • hydrophilic solvent examples include ketones and alcohols, but alcohols are preferable. Isopropanol, ethanol, methanol and the like are more preferable, and methanol is most preferable.
  • the addition amount is preferably in the range of 1 to 20% by mass, more preferably in the range of 3 to 10% by mass.
  • the resin concentration of the optical film solution is preferably, for example, 1.0 to 20% by mass from the viewpoint of facilitating the adjustment of the viscosity to the range described later. Further, from the viewpoint of reducing the amount of shrinkage of the coating film during drying, the resin concentration of the optical film solution is preferably moderately high, more preferably more than 5% by mass and 20% by mass or less, and more preferably more than 5% by mass. It is more preferably 15% by mass or less. Further, by adjusting the solution concentration, the time until the film is formed is shortened, and the drying time thereof can also be a means for controlling the surface state of the optical film. A mixed solvent may be appropriately used for increasing the concentration.
  • the viscosity of the optical film solution is not particularly limited as long as it can form an optical film having a desired film thickness, but is preferably 5 to 5000 mPa ⁇ s, for example.
  • the viscosity of the optical film solution is 5 mPa ⁇ s or more, it is easy to form an optical film having an appropriate film thickness, and when it is 5000 mPa ⁇ s or less, it is possible to suppress the occurrence of film thickness unevenness due to the increase in the viscosity of the solution. sell.
  • the viscosity of the optical film solution is more preferably 100 to 1000 mPa ⁇ s.
  • the viscosity of the optical film solution can be measured with an E-type viscometer at 25 ° C.
  • Step of applying the optical film solution the obtained optical film solution is applied to the surface of the support (corresponding to the second support). Specifically, the obtained optical film solution is applied to the surface of the support.
  • the support (corresponding to the second support) supports at the time of forming the optical film, and usually includes a resin film.
  • the film thickness of the support is preferably 50 ⁇ m or less.
  • the film thickness of the support is preferably in the range of 15 to 45 ⁇ m, more preferably in the range of 20 to 40 ⁇ m, because it is a thin film but requires some strength (waist and rigidity) as the support.
  • the resin used examples include cellulose ester-based resin, cycloolefin-based resin, polypropylene-based resin, acrylic-based resin, polyester-based resin, polyarylate-based resin, and styrene-based resin or a composite resin thereof. It is preferable to use a polyester resin as a resin having excellent storage stability in a humidity environment.
  • polyester resins examples include polyester resins (eg, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.). Etc. are included. Among them, a polyester resin film containing polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is preferable from the viewpoint of ease of handling.
  • PET polyethylene terephthalate
  • PBT polytrimethylene terephthalate
  • PEN polybutylene terephthalate
  • PBN polybutylene naphthalate
  • Etc. are included.
  • a polyester resin film containing polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is preferable from the viewpoint of ease of handling.
  • the resin film may be heat-treated (heat-relaxed) or stretch-treated.
  • the heat treatment is for reducing the residual stress of the resin film (for example, the residual stress due to stretching) and is not particularly limited.
  • the glass transition temperature of the resin constituting the resin film is Tg, (Tg + 60) to (Tg + 60) to ( It can be carried out at Tg + 180) ° C.
  • the stretching treatment is for increasing the residual stress of the resin film, and the stretching treatment is preferably performed in the biaxial direction of the resin film, for example.
  • the stretching treatment can be performed under any conditions, for example, with a stretching ratio of about 120 to 900%. Whether or not the resin film is stretched can be confirmed by, for example, whether or not there is an in-plane slow layer axis (an axis extending in the direction of maximizing the refractive index).
  • the stretching treatment may be performed before laminating the functional layers or after laminating, but it is preferable that the functional layers are stretched before laminating.
  • polyester resin film for example, polyethylene terephthalate film TN100 (manufactured by Toyobo Co., Ltd.), MELINEX (registered trademark) ST504 (manufactured by Teijin DuPont Film Co., Ltd.), and the like. It can be suitably used.
  • the support may further have a release layer provided on the surface of the resin film.
  • the release layer may facilitate peeling of the support from the optical film when making the polarizing plate.
  • the release layer may contain a known release agent and is not particularly limited.
  • Examples of the release agent contained in the release layer include a silicone-based release agent and a non-silicone-based release agent.
  • silicone-based release agents include known silicone-based resins.
  • the non-silicone-based release agent include a long-chain alkyl pendant type polymer obtained by reacting a polyvinyl alcohol or an ethylene-vinyl alcohol copolymer with a long-chain alkyl isocyanate, and an olefin resin (for example, a copolymerized polyethylene, a cyclic polyolefin, etc.).
  • fluororesins eg, polytetrafluoroethylene (PTFE), polyfluorovinylidene (PVDF), polyfluorovinyl). (PVF), PFA (copolymer of ethylene tetrafluoride and perfluoroalkoxyethylene), FEP (copolymer of tetrafluor
  • the thickness of the release layer may be as long as it can exhibit the desired peelability, and is not particularly limited, but is preferably 0.1 to 1.0 ⁇ m, for example.
  • the support may contain a plasticizer as an additive.
  • the plasticizer is not particularly limited, but is preferably a polyhydric alcohol ester-based plasticizer, a phthalic acid ester-based plasticizer, a citric acid-based plasticizer, a fatty acid ester-based plasticizer, a phosphoric acid ester-based plasticizer, and a polyvalent carboxylic acid. It is preferably selected from an ester-based plasticizer, a polyester-based plasticizer, and the like.
  • the support can also contain an ultraviolet absorber.
  • the ultraviolet absorber used include benzotriazole-based, 2-hydroxybenzophenone-based, and phenyl salicylate-based agents.
  • the support used in the present invention preferably contains fine particles in order to improve the transportability.
  • fine particles examples include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, and aluminum silicate. Calcium silicate and calcium phosphate can be mentioned. Further, fine particles of an organic compound can also be preferably used. Examples of organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethylmethacrylate, polyppill methacrylate, polymethylacrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, and melamine resin. , Polyethylene powder, polyester resin, polyamide resin, polyimide resin, polyfluoroethylene resin, crushed class of organic polymer compound such as starch, or polymer compound synthesized by suspension polymerization method can be used. can.
  • Fine particles containing silicon are preferable in that the turbidity is low, and silicon dioxide is particularly preferable.
  • Aerosil registered trademark
  • R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 It is commercially available under the trade name of Nippon Aerosil Co., Ltd. and can be used.
  • a normal inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, a hot press method, or the like can be used, but coloring is suppressed.
  • the solution casting method and the melt casting method are preferable as the film forming method.
  • the temperature in the processing step is low, and therefore, it is possible to impart high functionality by using various additives.
  • the support is manufactured by dissolving and dispersing an additive such as a thermoplastic resin and the above-mentioned fine particles in a solvent to prepare a dope (dissolution step; dope preparation step).
  • a step of casting the dope onto an endless metal support (casting step), a step of drying the cast dope as a web (solvent evaporation step), and a step of peeling the dope from the metal support (peeling step). It is preferable to include a step of drying, stretching, and holding the width (stretching, width holding, and drying step), and a step of winding the finished film into a roll (winding step).
  • optical film according to the present invention it is preferable to form the optical film according to the present invention by the following method using the support manufactured as described above.
  • the method for applying the solution for an optical film is not particularly limited, and may be, for example, a known method such as a back roll coating method, a gravure coating method, a spin coating method, a wire bar coating method, or a roll coating method. Above all, the back coat method is preferable from the viewpoint of being able to form a thin and uniform film thickness.
  • Step 3 Step of forming an optical film
  • the solvent is removed from the solution for the optical film applied to the support to form (manufacture) the optical film.
  • the optical film solution applied to the support is dried. Drying can be performed, for example, by blowing air or heating. Above all, from the viewpoint of facilitating curling of the optical film and the like, it is preferable to dry by blowing air, and further, it is preferable to make a difference in wind speed between the initial stage of drying and the latter half of drying in terms of controlling the film thickness deviation described below. Specifically, the higher the initial wind speed, the larger the film thickness deviation, and the lower the initial wind speed, the smaller the film thickness deviation.
  • the optical film according to the present embodiment may be strip-shaped as described above. Therefore, it is preferable that the method for producing a laminated film according to the present embodiment further includes 4) a step of winding a strip-shaped laminated film into a roll to form a roll.
  • Step of winding the optical film to obtain a roll body The obtained strip-shaped optical film is wound into a roll shape in a direction orthogonal to the width direction thereof to form a roll body.
  • the length of the strip-shaped optical film is not particularly limited, but may be, for example, about 100 to 10,000 m.
  • the width of the strip-shaped laminated film is preferably 1 m or more, more preferably 1.1 to 4 m. From the viewpoint of improving the uniformity of the film, it is more preferably 1.3 to 2.5 m.
  • optical film manufacturing equipment The method for producing an optical film used in the present invention can be performed by, for example, the manufacturing apparatus shown in FIG.
  • FIG. 4 is a schematic diagram of a manufacturing apparatus B200 for carrying out the method for manufacturing an optical film according to the present embodiment.
  • the manufacturing apparatus B200 includes a supply unit B210, a coating unit B220, a drying unit B230, a cooling unit B240, and a winding unit B250.
  • Ba to Bd indicate transport rolls for transporting the support B110.
  • the supply unit B210 has a feeding device (not shown) for feeding out the roll body B201 of the strip-shaped support B110 wound around the winding core.
  • the coating unit B220 is a coating device, and is a coating device B221 that coats the backup roll B221 that holds the support B110, the coating head B222 that coats the optical film solution on the support B110 held by the backup roll B221, and the coating head B222. It has a decompression chamber B223 provided on the upstream side.
  • the flow rate of the optical film solution discharged from the coating head B222 can be adjusted by a pump (not shown).
  • the flow rate of the optical film solution discharged from the coating head B222 is set to an amount capable of stably forming a coating layer having a predetermined film thickness when continuously coated under the conditions of the coating head B222 adjusted in advance.
  • the decompression chamber B223 is a mechanism for stabilizing the bead (pool of coating liquid) formed between the optical film solution from the coating head B222 and the support B110 at the time of coating, and the degree of decompression can be adjusted. It has become.
  • the decompression chamber B223 is connected to a decompression blower (not shown) so that the inside is decompressed.
  • the pressure reducing chamber B223 is in a state where there is no air leakage, and the gap between the pressure reducing chamber B223 and the backup roll is narrowly adjusted so that a stable bead of the coating liquid can be formed.
  • the drying unit B230 is a drying device that dries the coating film applied to the surface of the support B110, and has a drying chamber B231, a drying gas introduction port B232, and a discharge port B233.
  • the temperature and air volume of the dry air are appropriately determined depending on the type of the coating film and the type of the support B110.
  • the amount of residual solvent in the coating film after drying can be adjusted.
  • the amount of residual solvent in the coating film after drying can be measured by comparing the unit mass of the coating film after drying with the mass after the coating film is sufficiently dried.
  • the amount of residual solvent can be controlled by the concentration of the solvent used / coating liquid, the wind speed applied to dry the optical film, the drying temperature / time, the conditions of the drying chamber (outside air or inside air circulation), the heating temperature of the back roll at the time of coating, etc. ..
  • the residual solvent amount of the optical film satisfies the following formula 1 when the residual solvent amount of the optical film is S 1 from the viewpoint of curl balance of the optical film.
  • the residual solvent amount of the optical film is more preferably less than 800 ppm, and more preferably less than 500 to 700 ppm in consideration of the curl balance of the optical film. Further, by selecting a solvent / coating process in which the solvent remains on the support, the adhesion between the support and the optical film is improved.
  • the amount of residual solvent in the support is preferably in the range of 10 to 100 ppm.
  • the amount of residual solvent in the support and the optical film can be measured by headspace gas chromatography.
  • a sample is enclosed in a container, heated, and the gas in the container is promptly injected into a gas chromatograph with the container filled with volatile components, and mass analysis is performed to identify the compound.
  • the volatile components are quantified while doing this.
  • the cooling unit B240 cools the temperature of the support B110 having the coating film (optical film B120) obtained by drying in the drying unit B230, and adjusts the temperature to an appropriate temperature.
  • the cooling unit B240 has a cooling chamber B241, a cooling air inlet B242, and a cooling air outlet B243.
  • the temperature and air volume of the cooling air can be appropriately determined depending on the type of the coating film and the type of the support B110. Further, even if the cooling unit B240 is not provided, the cooling unit B240 may not be provided if the cooling temperature is appropriate.
  • the winding unit B250 is a winding device (not shown) for winding the support B110 on which the optical film B120 is formed to obtain the roll body B251.
  • the adhesive layer according to the present invention contains a water-based adhesive, and the pH value of the water-based adhesive is within the range of more than 7.0 and less than 9.0 at a measurement temperature of 25 ° C. It is characterized by being.
  • an adhesive layer in which the pH value is controlled in a specific range between the polarizing layer and the protective layer deterioration of the polarizing layer due to acid can be prevented. It is preferably in the range of pH 7.2 to 8.6, and further in the range of 7.4 to 8.4. Most preferably, it is in the range of 7.8 to 8.3.
  • the pH value of the water-based adhesive When the pH value of the water-based adhesive is 7.0 or less, the acid contained in the adhesive deteriorates the adjacent polarizing element layer. Further, when the pH value of the water-based adhesive is 9.0 or more, the adhesiveness with the adhesive layer used when installing the water-based adhesive in the display device is lowered. Therefore, in order to provide a polarizing plate having high durability and capable of being adhered by an adhesive layer, it is necessary to be within the above range.
  • an alkaline compound to the water-based adhesive.
  • an acid may be added for adjustment, but it is preferable to adjust with only an alkaline compound.
  • the alkaline compound include an inorganic compound, an organic compound, and an organic metal complex, but it is preferable to use an organic compound that does not easily cause coloring or peeling during a durability test.
  • water-based adhesive a known water-based adhesive is used.
  • the resin contained in the water-based adhesive include polyvinyl alcohol-based resin and urethane resin. Above all, a polyvinyl alcohol-based resin is preferable. Further, a polyvinyl alcohol-based resin or a urethane resin may be used in combination, or conventionally known additives can be appropriately used.
  • the adhesive layer according to the present invention is preferably composed of a material having low compatibility with the dichroic organic dye from the viewpoint of preventing the bleed-out of the dichroic organic dye and improving the durability.
  • a material having low compatibility with the dichroic organic dye examples include water-soluble polymers (also referred to as "resins”), which have significantly different polarities from dichroic organic dyes.
  • polyacrylamide-based polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers, (meth) acrylic acid or its anhydride-vinyl alcohol copolymers; carboxyvinyl-based polymers; polyvinylpyrrolidone. It is preferable to contain a water-soluble polymer such as starches; sodium alginate; or a polyethylene oxide-based polymer, and an oxazoline-based polymer.
  • the content of the small molecule having a molecular weight of 1000 or less is preferably 1% by mass or less, more preferably 0.1% by mass or less. Above all, it is preferable to contain polyvinyl alcohol.
  • cross-linking agents may be added in order to improve the water resistance of the adhesive layer. It is preferable to contain an isocyanate-based additive, an oxazoline-based additive, and a nitrogen-containing heterocyclic additive such as an aziridine-based additive. In particular, it is more preferable to contain polyvinyl alcohol and an oxazoline-based additive.
  • the water-based adhesive according to the present invention is one in which an adhesive component is dissolved or dispersed in water, and polyvinyl as a main component in forming a highly durable adhesive layer. It preferably contains alcohol.
  • the average degree of polymerization of polyvinyl alcohol is preferably in the range of 100 to 3000, and more preferably in the range of 500 to 3000.
  • the degree of saponification is preferably in the range of 85 to 100 mol%, more preferably 90 mol% or more (for example, 95 mol% or more).
  • the average degree of polymerization of the polyvinyl alcohol-based polymer (C) can be measured according to JIS K 6726: 1994, and the saponification degree can be measured according to JIS K 6726: 1994.
  • the polyvinyl alcohol-based polymer (C) is limited to vinyl alcohol homopolymers (fully saponified polyvinyl alcohol or partially saponified polyvinyl alcohol) obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate. Instead, it may be a polyvinyl alcohol-based copolymer obtained by saponifying a copolymer of vinyl acetate and another monomer copolymerizable therewith. Further, it may be a modified version of polyvinyl alcohol.
  • modified polyvinyl alcohol-based polymer examples include carboxy group-modified polyvinyl alcohol, acetacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol, and carbonyl-modified polyvinyl alcohol.
  • the water-based adhesive according to the present invention is one in which an adhesive component is dissolved or dispersed in water, and may contain urethane resin as a main component.
  • the urethane resin is not particularly limited, but is, for example, a urethane polymer obtained by reacting (i) a component containing an average of two or more active hydrogens in one molecule with (ii) a polyhydric isocyanate component. Or, the above-mentioned components (i) and (ii) are subjected to a urethanization reaction in an organic solvent which is inert to the reaction and has a high affinity with water under the condition of excess isocyanate group to obtain an isocyanate group-containing prepolymer, and then the isocyanate group-containing prepolymer. , The prepolymer is neutralized, the chain is extended using a chain extender, and water is added to form an aqueous dispersion. An acid component (acid residue) may be contained in these urethane-based polymers.
  • the chain extension method of the isocyanate group-containing prepolymer may be a known method.
  • water, a water-soluble polyamine, glycols and the like are used as the chain extender, and the isocyanate group-containing prepolymer and the chain extender component are used. And, if necessary, may be reacted in the presence of a catalyst.
  • the component containing an average of two or more active hydrogens in one molecule of the component (i) is not particularly limited, but a component having hydroxyl group active hydrogen is preferable. Specific examples of such compounds include the following.
  • Diol compound ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5- Pentandiol, neopentyl glycol, 1,6-hexaneglycol, 2,5-hexanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclodecanedimethanol, 1,4- Cyclohexanedimethanol, etc.
  • Polyether diol An alkylene oxide adduct of the above diol compound, a ring-opening (co) polymer of alkylene oxide or cyclic ether (such as tetrahydrofuran), for example, polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol (block). Or random) copolymer, glycol, polytetramethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, etc.
  • a ring-opening (co) polymer of alkylene oxide or cyclic ether such as tetrahydrofuran
  • Polyesterdiol Dicarboxylic acids (anhydrous) such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, and phthalic acid, and ethylene glycol and propylene glycol as mentioned in (1) above.
  • 1,4-Butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentyl glycol and other diol compounds are polycondensed under the condition of excess hydroxyl group.
  • the lactone is opened by using ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-adipic acid condensate, ethylene glycol-propylene glycol-adipic acid condensate, or glycol as an initiator.
  • examples thereof include polymerized polylactone diols.
  • Polyether ester diol An ether group-containing diol (polyether diol, diethylene glycol, etc. of (2) above) or a mixture of this and other glycol is a (anhydrous) dicarboxylic acid as exemplified in (3) above.
  • an alkylene oxide for example, a polytetramethylene glycol-adipic acid condensate and the like.
  • Polycarbonate diol General formula HO-R- (OC (O) -OR) x-OH (in the formula, R is a saturated fatty acid diol residue having 1 to 12 carbon atoms, and x is a molecular molecule. A compound or the like indicating the number of repeating units, usually an integer of 5 to 50.).
  • These are transesterification methods in which saturated aliphatic diols and substituted carbonates (diethyl carbonate, diphenyl carbonate, etc.) are reacted under conditions where the hydroxyl group is excessive, and the saturated aliphatic diols are reacted with phosgen, or if necessary. After that, it can be further obtained by a method of reacting with a saturated aliphatic diol or the like.
  • the compounds exemplified in the above (1) to (5) can be used alone or in combination of two or more.
  • an aliphatic, alicyclic or aromatic compound containing an average of two or more isocyanate groups in one molecule can be used.
  • an aliphatic diisocyanate having 1 to 12 carbon atoms is preferable, and examples thereof include hexamethylene diisocyanate and 2,2,4-trimethylhexane diisocyanate.
  • an alicyclic diisocyanate having 4 to 18 carbon atoms is preferable, and examples thereof include 1,4-cyclohexanediisocyanate and methylcyclohexylene diisocyanate.
  • the aromatic isocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.
  • a urethane-based polymer containing an acid residue can be dispersed in water without using a surfactant or even if the amount thereof is small, so that the water resistance of the coating film is improved.
  • the acid value of the urethane-based polymer is preferably in the range of 25 to 150 (mgKOH / g), preferably 30 to 100 (mgKOH / g). If the acid value is less than 25, the water dispersibility tends to be insufficient, and it is often necessary to use a surfactant in combination. On the other hand, if the acid value is larger than 150, the water resistance of the coating film tends to be inferior.
  • dimethylol alkanoic acid is one of the glycol components described in (2) to (4) above.
  • a method of introducing an acid group by introducing a carboxyl group into a polyether diol, a polyester diol, a polyether ester diol, or the like in advance by replacing the part or the whole is preferable.
  • the dimethylol alkanoic acid used here include trimethylol acetic acid, trimethylol propionic acid, and trimethylol butyric acid.
  • the dispersion of the urethane resin can be improved by neutralizing the acid component remaining in the urethane-based polymer, it is preferable that the urethane resin is neutralized.
  • the neutralizing agent for neutralizing the acid component include organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine and triethanolamine, and inorganic substances such as sodium hydroxide, potassium hydroxide and ammonia. Examples include bases.
  • the number average molecular weight of the urethane resin of the present invention is preferably 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, and more preferably 200,000 or less.
  • the particle size of the urethane resin particles in the aqueous dispersion of the present invention is preferably 0.01 ⁇ m to 0.5 ⁇ m. Further, the resin solid content is preferably 15 to 70% by weight.
  • the liquid viscosity is preferably 1 to 10,000 mPa ⁇ s.
  • the water-based adhesive may further contain components other than polyvinyl alcohol, if necessary, and it is preferable to add a cross-linking agent in order to improve the adhesiveness. Further, various acids / bases may be contained in order to adjust the pH of the adhesive layer within the predetermined range.
  • the cross-linking agent used in the present invention is not particularly limited as long as it can form an adhesive layer having excellent reworkability, but isocyanato-based additives, oxazoline-based additives, nitrogen-containing heterocyclic compounds, and water-based epoxies.
  • a compound selected from any of a compound, an aqueous amino compound, an aqueous carbodiimide compound, and an aqueous aldehyde compound is preferable.
  • it is preferable to use an isocyanate-based additive or an oxazoline-based additive and it is more preferable to use an oxazoline-based additive.
  • the oxazoline-based additive and the nitrogen-containing heterocyclic compound can also be used for adjusting the pH of the water-based adhesive and are suitable.
  • the nitrogen-containing heterocyclic compound is preferable because it has a strong alkalinity and is useful for adjusting the pH of the water-based adhesive to an appropriate range, and also has the effect of increasing the durability of the water-based adhesive layer by a cross-linking reaction.
  • These cross-linking agents may be used alone or in combination.
  • the isocyanate-based additive according to the present invention has two or more non-blocking isocyanate groups or blocked isocyanates that are soluble in water or emulsified. It is preferably a compound having a group.
  • non-blocking isocyanate compound examples include compounds obtained by reacting a polyfunctional isocyanate compound with a monovalent or polyvalent nonionic polyalkylene ether alcohol.
  • block type isocyanate compound examples include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), and xylylene diisocyanate.
  • Isocyanate (XDI), Isophoron diisocyanate (IPDI), Methylcyclohexyldiisocyanate (H6TDI), 4,4'-dicyclohexylmethanediisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), Tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate (NBDI), 2,4,6-triisopropylphenyldiisocyanate (TIDI), 1,12-diisocyanate Dodecane (DDI), 2,4, -bis- (8-isocyanate octyl) -1,3-dioctylcyclobutane (OCDI), n-pentane
  • the oxazoline-based additive according to the present invention is preferably an oxazoline group-containing polymer.
  • the oxazoline group-containing polymer is a polymer having an oxazoline group in the molecule, and is preferably a polymer having an oxazoline group in the side chain.
  • the main chain of the polymer is not particularly limited, and is composed of, for example, one or more skeletons selected from a (meth) acrylic skeleton, a styrene skeleton, and the like.
  • Preferred examples of the oxazoline group-containing polymer include an oxazoline group-containing (meth) acrylic polymer having a main chain composed of a (meth) acrylic skeleton and having an oxazoline group in the side chain of the main chain.
  • a linking group may be interposed between the main chain and the oxazoline group, but it is preferable that the main chain and the oxazoline group are directly bonded.
  • oxazoline group examples include 2-oxazoline group, 3-oxazoline group, 4-oxazoline group and the like, but 2-oxazoline group and the like are preferable.
  • the number average molecular weight of the oxazoline group-containing polymer is preferably 5000 or more, and more preferably 10,000 or more. When the number average molecular weight is within the above range, good adhesion is exhibited.
  • the number average molecular weight of the oxazoline group-containing polymer is usually 100,000 or less.
  • the number average molecular weight of the oxazoline group-containing polymer can be measured as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).
  • the amount of oxazoline group (the number of moles of oxazoline group per 1 g of the oxazoline group-containing polymer (A) solid content) of the oxazoline group-containing polymer is preferably 0.4 mmol / g ⁇ solid or more and 10 mmol / g ⁇ solid or less. If the amount of oxazoline groups is excessively high, it is difficult to obtain good adhesion, and if the amount of oxazoline groups is smaller than the above range, the water resistance of the adhesive layer may decrease. From this point of view, the amount of the oxazoline group of the oxazoline group-containing polymer (A) is more preferably 3 mmol / g ⁇ solid or more and 9 mmol / g ⁇ solid or less.
  • the oxazoline group-containing polymer is water-based, that is, a water-soluble heavy weight, when the adhesive composition is a water-based adhesive composition (an adhesive in which the adhesive component is dissolved in water or dispersed in water). It is preferably a coalesced or water-dispersible polymer. From the viewpoint of the optical properties of the adhesive layer, the oxazoline group-containing polymer is preferably a water-soluble polymer.
  • oxazoline group-containing polymer As the oxazoline group-containing polymer, a commercially available product may be used. Specifically, oxazoline group-containing acrylic polymers such as Epocross (registered trademark) WS-300, Epocross (registered trademark) WS-500, and Epocross (registered trademark) WS-700 (all trade names) manufactured by Nippon Catalyst Co., Ltd .; Examples thereof include oxazoline group-containing acrylic / styrene polymers such as Epocross (registered trademark) K-1000 series, Epocross (registered trademark) K-2000 series, and Epocross (registered trademark) RPS series (trademarks) manufactured by Nippon Catalyst Co., Ltd. ..
  • oxazoline group-containing polymers Two or more kinds can be used in combination. From the viewpoint of adhesion, optical properties, and water resistance, oxazoline group-containing acrylic polymers such as Epocross (registered trademark) WS-300 and Epocross (registered trademark) WS-700 are preferable.
  • Nitrogen-containing heterocyclic compound has a cyclic structure (nitrogen-containing heterocyclic structure) in which at least one of the carbon atoms constituting the ring of the cyclic hydrocarbon structure is replaced with a nitrogen atom. It is a compound.
  • the nitrogen-containing heterocyclic structure may be a monocyclic ring or a polycyclic ring such as a condensed ring. While the nitrogen-containing heterocyclic compound functions as a cross-linking agent, it can also be used for the purpose of adjusting the pH value.
  • the nitrogen-containing heterocyclic compound may have only one nitrogen-containing heterocyclic structure in the molecule, or may have two or three or more nitrogen-containing heterocyclic structures.
  • the nitrogen-containing heterocyclic compounds may have the same structure or different structures.
  • the water-based adhesive layer is strengthened by the crosslinking reaction, and the durability can be improved.
  • the nitrogen-containing heterocyclic structure is preferably the same structure.
  • nitrogen-containing heterocyclic structure examples include an aziridine structure, an azylin structure, an azetidine structure, a 1,2-oxazetidine structure, a 1,3-oxazetidine structure, a 1,2-thiazetidine structure, a 1,3-thiazetidine structure, and 1,2.
  • -Dihydroazet structure 1,3-diazate structure, pyrrolidine structure, pyrrolin structure, imidazoline structure, imidazoline structure, pyrazolidine structure, pyrazoline structure, oxazoline structure, thiazolin structure, pyrrole structure, pyrazole structure, imidazole structure, oxazole structure, isooxazole Structure, thiazole structure, thiazylazole structure, isothiazole structure, 1,2,3-triazole structure, 1,2,4-triazole structure, tetrazole structure, 1,3,4-oxazazole structure, frazane structure, pyridine structure, Single ring structure such as pyridazine structure, pyrimidine structure, pyrazine structure, piperazin structure, piperidin structure, morpholin structure, thiazine structure, piperidone structure, triazole structure, oxazole structure, tetrazine structure; Polycyclic structures such as
  • the nitrogen-containing heterocyclic structure can have one or more substituents bonded to the ring structure.
  • substituents include a hydrocarbon group having 1 or more and 12 or less carbon atoms (for example, an alkyl group).
  • the nitrogen-containing heterocyclic compound is preferably a compound having a structure capable of forming a crosslinked structure with an oxazoline group-containing polymer or an optical film as a protective layer.
  • the nitrogen-containing heterocyclic compound can form a crosslinked structure with an oxazoline group-containing polymer or an optical film, it exhibits good adhesion.
  • crosslinkable structure (1) The structure capable of forming a crosslinked structure with the oxazoline group-containing polymer or the optical film (hereinafter, may be referred to as “crosslinkable structure (1)”) is not particularly limited.
  • the crosslinkable structure (1) may be any structure that can form a crosslinked structure with a functional group such as a hydroxy group or a carboxy group, and may be a nitrogen-containing heterocyclic structure itself.
  • nitrogen-containing heterocyclic structure examples include an oxazoline ring, an aziridine ring, and the like, and an aziridine ring is preferable from the viewpoint of adhesion.
  • the nitrogen-containing heterocyclic compound preferably has two or more crosslinkable structures (1), more preferably contains two or more nitrogen-containing heterocyclic structures as the crosslinkable structure (1), and contains 2 aziridine rings. It is more preferable to have more than one.
  • the nitrogen-containing heterocyclic compound is usually a non-polymer.
  • the molecular weight of the nitrogen-containing heterocyclic compound is usually in the range of 41 to 2000.
  • the molecular weight of the nitrogen-containing heterocyclic compound may be 1500 or less, or may be 1000 or less.
  • the content of the nitrogen-containing heterocyclic compound in the adhesive composition is usually in the range of 0.1 to 50 parts by mass, preferably 0.2 to 50 parts by mass with respect to 100 parts by mass of the oxazoline group-containing polymer (A). It is 30 parts by mass, more preferably 0.5 to 20 or less. When the content of the nitrogen-containing heterocyclic compound is in this range, good adhesion tends to be easily exhibited.
  • the nitrogen-containing heterocyclic compound preferably has a crosslinkable structure (1) at the end, and more preferably has an aziridine ring at the end.
  • examples of the nitrogen-containing heterocyclic compound include diphenylmethane-4,4'-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, and isophthaloylbis-1- (2).
  • Tris-1-aziridinylphosphinoxide Hexamethylene-1,6-bis (1-aziridincarboxamide), Trimethylolpropane Tris- ⁇ -aziridinylpropionate, Tetramethylolmethane Tris- ⁇ -Aziridine propionate, piperidine, 4-picolin, 3,5-diethylpyridine, 1,4-bis (3-aminopropyl) piperazine, and the formula (B1) described in JP-A-2018-199756. Examples thereof include a compound represented by -1) to a compound represented by the formula (B1-4).
  • the nitrogen-containing heterocyclic compound may be a commercially available product.
  • Chemitite (registered trademark) PZ-33 and Chemitite (registered trademark) DZ-22E both trade names
  • Examples thereof include aziridine compounds such as CROSSLINKER CL-422, CROSSLINKER CL-427, and CROSSLINKER CL-467 (all trade names).
  • CROSSLINKER CL-427 and CROSSLINKER CL-467 are preferable.
  • the aqueous epoxy compound may be a compound having two or more epoxy groups that is soluble in water or emulsified.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexaneglycol, neopentyl glycol and 2 mol of epichlorohydrin.
  • Diepoxy compounds obtained by etherification Polyepoxy compounds obtained by etherification of 1 mol of polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitol and 2 mol or more of epichlorohydrin; phthalic acid, terephthalic acid. , Diepoxy compounds obtained by esterification of 1 mol of dicarboxylic acid such as oxalic acid and adipic acid with 2 mol of epichlorohydrin; and the like.
  • polyhydric alcohols such as glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitol and 2 mol or more of epichlorohydrin
  • phthalic acid terephthalic acid.
  • Diepoxy compounds obtained by esterification of 1 mol of dicarboxylic acid such as oxalic acid and adipic acid with 2 mol
  • ethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, and diglycidyl amine. ..
  • the aqueous amino compound may be any compound that is soluble in water or has two or more amino groups that have been emulsified.
  • amines such as ethylene dihydric acid, triethylene dihydric acid, and hexamethylene dihydric acid, carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succi acid dihydrazide, adipic acid dihydrazide, sebatic acid dihydrazide, dodecanodiic acid dihydrazide, isoftal acid dihydrazide, and terephthalic acid dihydrazide.
  • Glyhydric acid dihydrazide such as polyacrylic acid dihydrazide, methylol urea, methylol melamine, alkylated methylol urea, alkylated methylolized melamine, acetoguanamine, amino-formaldehyde resin such as a condensate of benzoguanamine and formaldehyde, melamine. Examples thereof include resin, urea resin, and guanamine resin.
  • the polyisocyanate and the carbodiimidization catalyst used in synthesizing the compound having two or more carbodiimide bonds are not particularly limited, and conventionally known ones can be used.
  • Examples of the compound having an aldehyde group include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, benzaldehyde and formaldehyde, dialdehydes such as glioxal, malondialdehyde, glutaaldehyde and terephthalaldehyde, dialdehyde starch and achlorine. Examples thereof include a copolymerized acrylic resin.
  • Polarizer layer is a layer having a function of a polarizing element, and the polarizing element layer according to the present invention is characterized by containing a dichroic organic dye.
  • the "polarizer” refers to an element that allows only light on a plane of polarization in a certain direction to pass through.
  • the polarizing element layer according to the present invention contains a polymerizable liquid crystal compound in addition to the dichroic organic dye.
  • the polarizing element layer according to the present invention can be formed by curing a polymerizable liquid crystal composition containing at least a dichroic organic dye and further containing a polymerizable liquid crystal compound.
  • the dichroic organic dye and the polymerizable liquid crystal compound will be described in detail.
  • Dichroic organic dye refers to a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different.
  • the dichroic dye that can be used in the present invention is preferably a dichroic organic dye composed of an organic compound, and more preferably one having a maximum absorption wavelength ( ⁇ max) in the range of 300 to 700 nm.
  • Examples of such a dichroic organic dye include an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye and the like.
  • the azo dye examples include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye and the like, and a bisazo dye and a trisazo dye are preferable, and for example, a compound represented by the general formula (I) (hereinafter, "" Compound (I) ”).
  • K 1 and K 3 have a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent independently of each other. Represents a good monovalent heterocyclic group.
  • K 2 is a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent complex which may have a substituent.
  • p represents an integer of 1 to 4.
  • the plurality of K 2s may be the same or different from each other.
  • Examples of the monovalent heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole.
  • Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from the heterocyclic compound.
  • Phenyl group in K 1 and K 3, a naphthyl group and a monovalent heterocyclic group, and p- phenylene group in K 2, the substituent naphthalene-1,4-diyl group and divalent heterocyclic group has optionally Is an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; an alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; Nitro group; Halogen atom; Substituent or unsubstituted amino group such as amino group, diethylamino group, pyrrolidino group (Substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or two. It means an amino group in which substituted alkyl groups are bonded to each other to form an alcandiyl group
  • B 1 ⁇ B 30 are independently of one another, a hydrogen atom, an alkyl group, an alkoxy group having 1 to 4 carbon atoms having 1 to 6 carbon atoms, a cyano group , Nitro group, substituted or unsubstituted amino group (the definition of substituted amino group and unsubstituted amino group is as described above), chlorine atom or trifluoromethyl group.
  • n1 to n4 represent integers of 0 to 3 independently of each other. If n1 is 2 or more, a plurality of B 2 may be the same or different from each other, If n2 is 2 or more, plural B 6 may be the same or different from each other, If n3 is 2 or more, plural B 9 may be the same or different from each other, When n4 is 2 or more, the plurality of B 14s may be the same or different from each other.
  • the anthraquinone dye a compound represented by the formula (I-9) is preferable.
  • R 1 to R 8 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • a compound represented by the formula (I-10) is preferable.
  • R 9 to R 15 represent hydrogen atoms, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or halogen atoms independently of each other.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • a compound represented by the formula (I-11) is preferable.
  • R 16 to R 23 independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms of Rx includes a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.
  • a hexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.
  • cyanine dye a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.
  • D 1 and D 2 represent a group represented by any of the formulas (I-12a) to (I-12d) independently of each other.
  • n5 represents an integer of 1 to 3.
  • D 3 and D 4 represent a group represented by any of the formulas (I-13a) to (1-13h) independently of each other.
  • n6 represents an integer of 1 to 3.
  • the azo dye has high linearity and is suitable for forming a polarizing element layer having excellent polarization performance.
  • the weight average molecular weight of the dichroic organic dye is usually in the range of 300 to 2000, preferably in the range of 400 to 1000.
  • polymerizable liquid crystal compound (A) is a liquid crystal compound having a polymerizable group.
  • the "polymerizable group” refers to a group that can participate in the polymerization reaction by an active radical, an acid, or the like generated from the polymerization initiator.
  • Examples of the polymerizable group of the polymerizable liquid crystal compound (A) include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxylanyl group. Examples thereof include an oxetanyl group. Of these, a radically polymerizable group is preferable, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and a vinyloxy group are more preferable, and an acryloyloxy group and a methacryloyloxy group are preferable.
  • the polymerizable liquid crystal compound (A) is preferably a compound exhibiting smectic liquid crystal properties.
  • a polymerizable liquid crystal compound exhibiting smectic liquid crystal properties it is possible to form a polarizing element having a high degree of orientation order.
  • the liquid crystal state indicated by the polymerizable liquid crystal compound (A) is a smectic phase (smetic liquid crystal state), and from the viewpoint of achieving a higher degree of orientation order, it is more likely to be a higher-order smectic phase (higher-order smectic liquid crystal state). preferable.
  • the "higher-order smectic phase” means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase and a smectic L. It means a phase, and among these, the smectic B phase, the smectic F phase, and the smectic I phase are more preferable.
  • the liquid crystal may be a thermotropic liquid crystal or a riotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible.
  • the polymerizable liquid crystal compound (A) may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.
  • the polymerizable liquid crystal compound (A) is not particularly limited as long as it is a liquid crystal compound having at least one polymerizable group, and known polymerizable liquid crystal compounds can be used, but compounds exhibiting smectic liquid crystal properties are preferable.
  • Examples of such a polymerizable liquid crystal compound include a compound represented by the following formula (A1) (hereinafter, also referred to as “polymerizable liquid crystal compound (A1)”).
  • X 1 and X 2 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.
  • the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. It may be substituted with an alkoxy group, a cyano group or a nitro group of the number 1 to 4.
  • the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.
  • at least one of X 1 and X 2 is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
  • Y 1 is a single bond or divalent linking group.
  • n is 1-3, when n is 2 or more, to a plurality of X 1 may be the same as each other or may be different.
  • X 2 may be the same as or different from any or all of the plurality of X 1.
  • n is preferably 2 or more.
  • U 1 represents a hydrogen atom or a polymerizable group.
  • U 2 represents a polymerizable group.
  • W 1 and W 2 are single-bonded or divalent linking groups independently of each other.
  • V 1 and V 2 represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent independently of each other, and -CH 2- constituting the alkanediyl group is -O-, It may be replaced with -CO-, -S- or NH-.
  • X 1 and X 2 are independent of each other and preferably have a 1,4-phenylene group or a substituent which may have a substituent. It is a good cyclohexane-1,4-diyl group, and at least one of X 1 and X 2 has a 1,4-phenylene group which may have a substituent, or a substituent. It is also a good cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group.
  • the substituents arbitrarily possessed by the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include a methyl group and an ethyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group and a butyl group, a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. It is preferably unsubstituted.
  • the polymerizable liquid crystal compound (A1) tends to exhibit smectic liquid crystal properties when the following portion (hereinafter referred to as “partial structure (A1-1)”) in the formula (A1) has an asymmetric structure. It is preferable in terms of points. : "-(X 1- Y 1- ) n- X 2- ": (Partial structure (A1-1) [In the formula, X 1 , Y 1 , X 2 and n have the same meanings as described above. ]
  • the polymerizable liquid crystal compound (A1) having an asymmetric structure in the partial structure (A1-1) for example, the polymerizable liquid crystal compound (A1) in which n is 1 and one X 1 and X 2 have different structures from each other. ).
  • n 2
  • a two Y 1 are compounds of the same structure each other, have the same structure two X 1 from each other, one of X 2 is a structure different from the two X 1 the polymerizable liquid crystal compound (A1), X 1 to bind to W 1 of the two X 1 is a structure that is different from the other of X 1 and X 2, the other of X 1 and X 2 and are mutually the same structure Also mentioned is a polymerizable liquid crystal compound (A1).
  • n is 3, a compound of the same structure each other three Y 1, is any one differs from the all the other three structures of the three X 1 and one X 2 Polymerization The sex liquid crystal compound (A1) can be mentioned.
  • Ra and Rb independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Y 1 is, -CH 2 CH 2 -, - COO- or more preferably a single bond, when a plurality of Y 1 are present, Y 1 which binds to X 2 is, -CH 2 CH 2 - or CH It is more preferably 2 O-.
  • X 1 and X 2 are all identical structure, it is preferred that there are two or more Y 1 are different coupling method together.
  • there are a plurality of Y 1 are different coupling method together since the asymmetric structure, there is a tendency that the smectic liquid crystal is likely to result.
  • U 2 is a polymerizable group.
  • U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group. Both U 1 and U 2 are preferably polymerizable groups, and both are preferably radically polymerizable groups. Examples of the polymerizable group include the same groups as those exemplified above as the polymerizable group of the polymerizable liquid crystal compound (A).
  • the polymerizable group represented by U 1 and the polymerizable group represented by U 2 may be different from each other, but are preferably the same type of group. Further, the polymerizable group may be in a polymerized state or a non-polymerized state, but is preferably in a non-polymerized state.
  • the alkanediyl group represented by V 1 and V 2 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-. 1,5-Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Examples include groups and icosan-1,20-diyl groups.
  • V 1 and V 2 are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.
  • alkanediyl group examples include a cyano group and a halogen atom, and the alkanediyl group is preferably unsubstituted and is an unsubstituted linear alkanediyl group. Is more preferable.
  • W 1 and W 2 are independent of each other, preferably single bond, —O—, —S—, —COO— or OCOO—, and more preferably single bond or O—.
  • the polymerizable liquid crystal compound (A) is not particularly limited as long as it is a polymerizable liquid crystal compound having at least one polymerizable group, and a known polymerizable liquid crystal compound can be used, but it may exhibit smectic liquid crystal properties.
  • a structure that easily exhibits smectic liquid crystallinity it is preferable to have an asymmetric molecular structure in the molecular structure, and specifically, the polymerizable property having the following partial structures (Aa) to (Ai). It is more preferable that the liquid crystal compound is a polymerizable liquid crystal compound exhibiting smectic liquid crystal properties.
  • polymerizable liquid crystal compound (A) examples include compounds represented by the following (A-1) to (A-25).
  • the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group
  • the cyclohexane-1,4-diyl group is preferably a trans form.
  • the polymerizable liquid crystal compound (A) one type may be used alone, or two or more types may be used in combination.
  • the polymerizable liquid crystal compound (A) may be described in, for example, Lub or the like, Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), Japanese Patent No. 4719156, and the like.
  • the polarizing element layer according to the present invention is formed by curing a polymerizable liquid crystal composition (referred to as a polymerizable liquid crystal composition (A)) containing at least a dichroic organic dye and further containing a polymerizable liquid crystal compound.
  • a polymerizable liquid crystal composition containing a dichroic organic dye and a polymerizable liquid crystal compound will be described.
  • the content of the dichroic organic dye in the polymerizable liquid crystal composition (A) can be appropriately determined depending on the type of the dichroic organic dye used and the like, but is preferably obtained with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is 0.1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and further preferably 0.1 to 12 parts by mass.
  • the content of the dichroic organic dye is within the above range, the orientation of the polymerizable liquid crystal compound is not easily disturbed, and a polarizing element layer having a high degree of orientation order can be obtained.
  • the polymerizable liquid crystal composition (A) may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound (A), but is polymerized from the viewpoint of obtaining a polarizing film having a high degree of orientation order.
  • the ratio of the polymerizable liquid crystal compound (A) to the total mass of the total polymerizable liquid crystal compound contained in the property liquid crystal composition (A) is preferably 51% by mass or more, more preferably 70% by mass or more, and further. It is preferably 90% by mass or more.
  • the polymerizable liquid crystal composition (A) contains two or more kinds of polymerizable liquid crystal compounds (A), at least one of them may be the polymerizable liquid crystal compound (A1), and all of them are polymerizable. It may be a liquid crystal compound (A1).
  • the liquid crystal property may be temporarily maintained even at a temperature equal to or lower than the liquid crystal-crystal phase transition temperature.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition (A) is preferably 40 to 99.9% by mass, more preferably 60 to 9% by mass, based on the solid content of the polymerizable liquid crystal composition (A). It is 99% by mass, more preferably 70 to 99% by mass. When the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to be high.
  • the solid content of the polymerizable liquid crystal composition (A) means the total amount of the components of the polymerizable liquid crystal composition (A) excluding the solvent.
  • the polymerizable liquid crystal composition (A) for forming a polarizing element may contain a polymerization initiator.
  • the polymerization initiator is a compound that can initiate the polymerization reaction of the polymerizable liquid crystal compound, and the photopolymerization initiator is preferable in that the polymerization reaction can be initiated under lower temperature conditions.
  • Specific examples thereof include photopolymerization initiators capable of generating active radicals or acids by the action of light, and among them, photopolymerization initiators that generate radicals by the action of light are preferable.
  • the polymerization initiator can be used alone or in combination of two or more.
  • a known photopolymerization initiator can be used as the photopolymerization initiator.
  • a self-cleaving type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator can be used as the photopolymerization initiator. There is.
  • Self-cleaving benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, ⁇ -aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. are used as self-cleaving photopolymerization initiators. Can be used. Further, as a hydrogen abstraction type photopolymerization initiator, a hydrogen abstraction type benzophenone compound, a benzoin ether compound, a benzyl ketal compound, a dibenzosverone compound, an anthraquinone compound, a xanthone compound, a thioxanthone compound, and a halogenoacetophenone compound. Compounds, dialkoxyacetophenone-based compounds, halogenobis imidazole-based compounds, halogenotriazine-based compounds, triazine-based compounds and the like can be used.
  • an iodonium salt, a sulfonium salt, or the like can be used as the photopolymerization initiator that generates an acid.
  • the reaction at a low temperature is preferable from the viewpoint of preventing the dissolution of the dye, and the self-cleaving photopolymerization initiator is preferable from the viewpoint of the reaction efficiency at a low temperature, and in particular, an acetophenone-based compound, a hydroxyacetophenone-based compound, and ⁇ -aminoacetophenone.
  • System compounds and oxime ester compounds are preferable.
  • photopolymerization initiator examples include the following.
  • Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [4- (2- (2-) Hydroxyacetophenone such as hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one oligomers Phenyl compound; ⁇ -Aminoacetophenone such as 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one, etc. System compounds;
  • 1,2-octanedione 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il]-, 1- (O-acetyloxime) and other oxime ester compounds;
  • Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide;
  • Benzophenone o-Methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4 Benzophenone compounds such as 6-trimethylbenzophenone;
  • Dialkoxyacetophenone compounds such as diethoxyacetophenone; 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5) -Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl]
  • photopolymerization initiator a commercially available photopolymerization initiator may be used.
  • Commercially available photopolymerization initiators include Irgacure® 907, 184, 651, 819, 250, and 369, 379, 127, 754, OXE01, OXE02, OXE03 (above, manufactured by BASF); Omnirad.
  • BCIM Esasure 1001M, Esasure KIP160 (above, IDM Resins BV); Sakeol (registered trademark) BZ, Z, and BEE (above, Seiko Kagaku Co., Ltd.); Kayacure (registered trademark) BP100 , And UVI-6992 (all manufactured by Dow Chemical Co., Ltd.); , ADEKA Co., Ltd.); TAZ-A and TAZ-PP (all manufactured by Nippon Sibel Hegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); and the like.
  • the content of the polymerization initiator in the polymerizable liquid crystal composition (A) for forming a polarizing element is preferably 1 to 10 parts by mass, and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is by mass, more preferably 2 to 8 parts by mass, and particularly preferably 4 to 8 parts by mass.
  • the content of the polymerization initiator is within the upper and lower limits, the polymerization reaction of the polymerizable liquid crystal compound can be carried out without significantly disturbing the orientation of the polymerizable liquid crystal compound.
  • the polymerization rate of the polymerizable liquid crystal compound in the present invention is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, from the viewpoint of line contamination during production and handling.
  • the polymerizable liquid crystal composition (A) may further contain a photosensitizer.
  • a photosensitizer By using a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further promoted.
  • the photosensitizer include xanthone compounds such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene, alkoxy group-containing anthracene (eg, dibutoxyanthracene, etc.); Examples thereof include phenothiazine and rubrene.
  • the photosensitizer can be used alone or in combination of two or more.
  • the content thereof may be appropriately determined according to the type and amount of the polymerization initiator and the polymerizable liquid crystal compound, but the polymerizable liquid crystal compound 100 With respect to the parts by mass, 0.1 to 30 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 0.5 to 8 parts by mass is further preferable.
  • the polymerizable liquid crystal composition (A) may contain a leveling agent.
  • the leveling agent has a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the coating film obtained by applying the polymerizable liquid crystal composition. Can be mentioned.
  • the leveling agent in the polymerizable liquid crystal composition (A) at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component is preferable.
  • the leveling agent can be used alone or in combination of two or more.
  • leveling agent containing a polyacrylate compound as a main component examples include “BYK (registered trademark) -350”, “352”, “353”, “354", “355", and “358N”. Examples thereof include the same “361N”, the same “380”, the same “381” and the same “392” (above, BYK Chemie).
  • leveling agent containing a fluorine atom-containing compound as a main component examples include “Megafuck (registered trademark) R-08", “R-30”, “R-90”, “F-410”, and the same.
  • F-411, “F-443”, “F-445”, “F-470”, “F-471”, “F-477”, “F-479”, “F-479” F-482 “and” F-483 "(DIC Co., Ltd.);” Surflon (registered trademark) S-381 “,” S-382 “,” S-383 “,” S-393 “, “SC-101", “SC-105", “KH-40” and “SA-100” (above, AGC Seimi Chemical Co., Ltd.); “E1830”, “E5844” (Daikin Fine Chemical Research Co., Ltd.) Place); "Ftop (registered trademark) EF301", “EF303”, “EF351” and “EF352” (hereinafter referred to as Mitsubishi Material Denshikasei Co.,
  • the content thereof is preferably 0.05 to 5 parts by mass and 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. More preferred.
  • the content of the leveling agent is within the above range, the polymerizable liquid crystal compound tends to be easily horizontally oriented, unevenness is less likely to occur, and a smoother polarizing element tends to be obtained.
  • the polymerizable liquid crystal composition (A) may contain additives other than the photosensitizer and the leveling agent.
  • additives include antioxidants, mold release agents, stabilizers, colorants such as bluing agents, flame retardants and lubricants.
  • the content of the other additives is more than 0% and 20% by mass with respect to the solid content of the polymerizable liquid crystal composition (A). It is preferably less than or equal to, and more preferably more than 0% and 10% by mass or less.
  • the polymerizable liquid crystal composition (A) can be produced by a conventionally known method for preparing the polymerizable liquid crystal composition (A), and is usually a polymerizable liquid crystal compound and a dichroic organic dye, and if necessary. It can be prepared by mixing and stirring the polymerization initiator and the above-mentioned additives.
  • the polarizing element is preferably a polarizing element having a high degree of orientation order.
  • a polarizing element having a high degree of orientation order can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
  • the Bragg peak means a peak derived from the plane periodic structure of molecular orientation. Therefore, it is preferable that the polarizing element constituting the polarizing plate of the present invention shows a Bragg peak in the X-ray diffraction measurement.
  • the polymerizable liquid crystal compound or a polymer thereof is oriented so that the polarizing element shows a Bragg peak in the X-ray diffraction measurement, and the light is emitted.
  • the "horizontal orientation" is such that the molecules of the polymerizable liquid crystal compound are oriented in the absorption direction.
  • a splitter having a plane period interval of molecular orientation of 3.0 to 6.0 ⁇ is preferable.
  • a high degree of orientation order indicating the Bragg peak can be realized by controlling the type of the polymerizable liquid crystal compound used, the type and amount of the dichroic organic dye, the type and amount of the polymerization initiator, and the like.
  • the thickness of the polarizing element can be appropriately selected depending on the display device to which it is applied, and is preferably a film in the range of 0.1 to 5 ⁇ m, more preferably in the range of 0.3 to 4 ⁇ m, and further. It is preferably in the range of 0.5 to 3 ⁇ m.
  • the polarizing plate of the present invention forms a coating film of the polymerizable liquid crystal composition (A) containing a polymerizable liquid crystal compound having a polymerizable group and a bicolor organic dye, removes a solvent from the coating film, and then removes the solvent.
  • the temperature is raised to a temperature higher than the temperature at which the polymerizable liquid crystal compound undergoes a phase transition to the liquid phase, and then the temperature is lowered to cause the polymerizable liquid crystal compound to undergo a phase transition to the smectic phase, and the polymerizable liquid crystal compound is polymerized while maintaining the smectic phase. It can be manufactured by obtaining a polarizing element (hereinafter, also referred to as “polarizer forming step”).
  • the coating film of the polymerizable liquid crystal composition (A) is formed by applying the polymerizable liquid crystal composition (A) directly on the optical film according to the present invention or via a liquid crystal alignment layer described later. It can be done by.
  • a compound exhibiting smectic liquid crystal property has a high viscosity, and therefore, from the viewpoint of improving the coatability of the polymerizable liquid crystal composition (A) and facilitating the formation of a polarizing element, a solvent is added to the polymerizable liquid crystal composition (A).
  • the viscosity may be adjusted by adding the solvent (hereinafter, the composition obtained by adding a solvent to the polymerizable liquid crystal composition is also referred to as a "polarizer forming composition").
  • the solvent used in the polarizing element forming composition can be appropriately selected depending on the solubility of the polymerizable liquid crystal compound and the dichroic organic dye used.
  • alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone.
  • Ester solvents such as propylene glycol methyl ether acetate and ethyl lactate, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylamylketone and methylisobutylketone, aliphatic hydrocarbon solvents such as pentane, hexane and heptane, toluene.
  • Aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran and dimethoxyethane, and chlorinated hydrocarbon solvents such as chloroform and chlorobenzene.
  • the content of the solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 900 parts by mass, and further preferably 100 parts by mass with respect to 100 parts by mass of the solid component constituting the polymerizable liquid crystal composition (A). It is 180 to 600 parts by mass.
  • a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexographic method is used.
  • a known method such as a printing method such as is mentioned.
  • a dry coating film is formed by removing the solvent by drying or the like under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polarizing element forming composition does not polymerize.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • the temperature is raised to a temperature higher than the temperature at which the polymerizable liquid crystal compound undergoes a phase transition to the liquid phase, and then the temperature is lowered to bring the polymerizable liquid crystal compound into a smectic phase (smectic liquid crystal state).
  • a phase transition may be carried out after the solvent is removed from the coating film, or may be carried out at the same time as the solvent is removed.
  • the light irradiating the dry coating film includes the type of the polymerizable liquid crystal compound contained in the dry coating film (particularly, the type of the polymerizable group of the polymerizable liquid crystal compound), the type of the polymerization initiator, and the type of the polymerization initiator. It is appropriately selected according to the amount thereof and the like. Specific examples thereof include one or more types of active energy rays and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, ⁇ rays, ⁇ rays and ⁇ rays.
  • ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerizable liquid crystal compound is polymerized at a lower temperature, a stator can be appropriately formed even if a support (substrate) having a relatively low heat resistance is used. A patterned polarizing element can also be obtained by masking or developing during photopolymerization.
  • Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range.
  • Examples thereof include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.
  • the ultraviolet irradiation intensity is usually 10 to 3000 mW / cm 2 .
  • the ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the polymerization initiator.
  • the time for irradiating with light is usually 0.1 seconds to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and even more preferably 10 seconds to 1 minute.
  • the integrated light amount is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , and more preferably 100 to 1,000 mJ / cm. It is 2.
  • the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase, and a stator is formed.
  • the polarizing element obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is a conventional host-guest type polarizing plate, that is, the liquid crystal state of the nematic phase due to the action of the dichroic organic dye.
  • the polarizing plate of the present invention may be provided with a liquid crystal alignment layer in addition to the polarizing element layer. It is preferable that the polarizing element layer is laminated on the support (substrate) via the liquid crystal alignment layer from the viewpoint of increasing the degree of liquid crystal alignment.
  • the liquid crystal alignment layer an optical liquid crystal alignment layer is preferable from the viewpoints of accuracy and quality of the alignment angle, water resistance and flexibility of the polarizing plate including the liquid crystal alignment layer.
  • the thickness of the liquid crystal alignment layer is preferably 10 to 5000 nm, more preferably 10 to 1000 nm.
  • the polarizing element layer is preferably formed via a liquid crystal alignment layer.
  • the liquid crystal alignment layer has an orientation regulating force that orients the polymerizable liquid crystal compound in a desired direction.
  • the liquid crystal alignment layer has solvent resistance that does not dissolve when a composition containing a polymerizable liquid crystal compound is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound. Is preferable.
  • the liquid crystal alignment layer is preferably an optical liquid crystal alignment layer from the viewpoints of accuracy and quality of the alignment angle, water resistance and flexibility of the polarizing plate including the liquid crystal alignment layer.
  • the optical liquid crystal alignment layer is also advantageous in that the direction of the orientation restricting force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • the photo-liquid crystal alignment layer is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photo-liquid crystal alignment layer”) to a support (substrate). It is obtained by irradiating with polarized light (preferably "polarized UV").
  • a photoreactive group is a group that produces a liquid crystal alignment ability when irradiated with light.
  • groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or the photocrosslinking reaction are preferable because they have excellent orientation.
  • a photoreactive group involved in the photodimerization reaction is preferable, and a light liquid crystal alignment layer having a relatively small amount of polarized light irradiation required for photoalignment and having excellent thermal stability and stability over time can be easily obtained.
  • Synnamoyl group and chalcone group are preferable.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group having a cinnamon acid structure at the end of the side chain of the polymer is particularly preferable.
  • the optical orientation-inducing layer can be formed on the support (substrate).
  • the solvent contained in the composition include the same solvents as those exemplified above as the solvent that can be used when forming the polarizing element, and are appropriately used depending on the solubility of the polymer or monomer having a photoreactive group. You can choose.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming the optical liquid crystal alignment layer can be appropriately adjusted depending on the type of the polymer or the monomer and the thickness of the target optical liquid crystal alignment layer, but the optical liquid crystal alignment layer It is preferably at least 0.2% by mass, more preferably 0.3 to 10% by mass, based on the mass of the forming composition.
  • the composition for forming the optical liquid crystal alignment layer may contain a resin material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the optical liquid crystal alignment layer are not significantly impaired.
  • the composition for forming a polarizing element As a method of applying the composition for forming the optical liquid crystal alignment layer on the support (substrate) and a method of removing the solvent from the applied composition for forming the optical liquid crystal alignment layer, the composition for forming a polarizing element is supported. Examples thereof include a method of applying to the body (substrate) and a method of removing the solvent.
  • Polarized UV irradiation is performed by irradiating polarized UV from the support (substrate) side and polarized UV even in the form of directly irradiating polarized UV obtained by removing the solvent from the composition for forming an optical liquid crystal alignment layer applied on the substrate. It may be a form in which UV is transmitted and irradiated. Further, it is particularly preferable that the polarized UV is substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the polarized UV irradiation include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. More preferred.
  • a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizing element.
  • a polarizing element a polarizing filter, a polarizing prism such as Gran Thomson or Gran Tailor, or a wire grid type polarizing element can be used.
  • the polarizing plate of the present invention is a polarizing plate (for example, an elliptical polarizing plate) provided with a retardation film as a film (opposing film) different from the optical film constituting the protective layer. You may.
  • the retardation film preferably satisfies the following retardation value (phase difference value).
  • Formula X 100 ⁇ Ro (550) ⁇ 180 [In the formula, Ro (550) represents an in-plane retardation value at a wavelength of 550 nm. ]
  • the retardation film When the retardation film has an in-plane retardation value represented by the above formula X, it functions as a so-called ⁇ / 4 plate. From the viewpoint of optical performance, the formula X is preferably 100 nm ⁇ Ro (550) ⁇ 180 nm, and more preferably 120 nm ⁇ Ro (550) ⁇ 160 nm.
  • the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing plate is preferably substantially 45 °.
  • substantially 45 ° means 45 ° ⁇ 5 °.
  • Equation Y Ro (450) / Ro (550) ⁇ 1
  • Ro (450) and Ro (550) represent in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively.
  • the retardation film satisfying the above formula Y has so-called reverse wavelength dispersibility and exhibits excellent polarization performance.
  • the value of Ro (450) / Ro (550) is preferably 0.93 or less, more preferably 0.88 or less, still more preferably 0.86 or less, preferably 0.80 or more, and more preferably 0. It is 82 or more.
  • the retardation film may be a stretched film that imparts a retardation by stretching a polymer, but from the viewpoint of reducing the thickness of the polarizing plate, a polymerizable liquid crystal composition containing a polymer of a polymerizable liquid crystal compound (hereinafter referred to as a polymerizable liquid crystal composition). , Also referred to as "polymerizable liquid crystal composition (B)").
  • the polymerizable liquid crystal compound In the retardation film, the polymerizable liquid crystal compound is usually polymerized in an oriented state.
  • the polymerizable liquid crystal compound (hereinafter, also referred to as “polymerizable liquid crystal compound (B)”) that forms a retardation film means a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group.
  • the photopolymerizable functional group refers to a group that can participate in the polymerization reaction by an active radical, an acid, or the like generated from the photopolymerization initiator.
  • Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxylanyl group, an oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • the liquid crystal may be a thermotropic liquid crystal or a lyotropic liquid crystal, and the phase-ordered structure may be a nematic liquid crystal or a smectic liquid crystal.
  • the polymerizable liquid crystal compound only one kind may be used, or two or more kinds may be used in combination.
  • the polymerizable liquid crystal compound (B) is a compound having the following characteristics (a) to (d) from the viewpoint of facilitating film formation and imparting retardation represented by the above formula (Y). Is preferable.
  • a compound having a thermotropic liquid crystal property (A) The polymerizable liquid crystal compound has ⁇ electrons in the long axis direction (a). (C) It has ⁇ electrons in the direction [intersection direction (b)] that intersects the major axis direction (a). (D) A polymerizable liquid crystal compound defined by the following formula (i), where the total number of ⁇ electrons existing in the major axis direction (a) is N ( ⁇ a) and the total molecular weight existing in the major axis direction is N (Aa).
  • the polymerizable liquid crystal compound (B) satisfying the above (a) to (d) is, for example, applied onto the liquid crystal alignment layer formed by the rubbing treatment and heated to a temperature equal to or higher than the phase transition temperature to form a nematic phase. It is possible to do.
  • the polymerizable liquid crystal compound is usually oriented so that the major axis directions are parallel to each other, and this major axis direction is the orientation direction of the nematic phase. It becomes.
  • the polymerizable liquid crystal compound (B) having the above characteristics generally exhibits reverse wavelength dispersibility.
  • Specific examples of the compound satisfying the above-mentioned characteristics (a) to (d) include a compound represented by the following general formula (II).
  • the compound represented by the above formula (II) can be used alone or in combination of two or more.
  • Ar represents a divalent aromatic group that may have a substituent.
  • the aromatic group referred to here is a group having a planar structure having a planar structure, and the number of ⁇ electrons of the cyclic structure is [4n + 2] according to Hückel's law.
  • n represents an integer.
  • the divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
  • G 1 and G 2 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, respectively.
  • the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon.
  • the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an alkoxy group, a cyano group or a nitro group of the number 1 to 4, and is an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.
  • L 1 , L 2 , B 1 and B 2 are independently single-bonded or divalent linking groups, respectively.
  • k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ⁇ k + l.
  • B 1 and B 2 when 2 ⁇ k + l, B 1 and B 2 , G 1 and G 2 may be the same or different from each other.
  • E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, where the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom.
  • -CH 2- contained in the alkanediyl group may be substituted with -O-, -S-, -Si-.
  • P 1 and P 2 independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • G 1 and G 2 may be independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, respectively 1.
  • a 1,4-cyclohexanediyl group which may be substituted with at least one substituent selected from the group consisting of a 4-phenylenediyl group, a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably methyl.
  • R a1 to R a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms
  • R c and R d represent an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
  • L 1 and L 2 are each independently, more preferably a single bond, -OR a2-1 -, - CH 2 -, - CH 2 CH 2 -, - COOR a4-1 -, or OCOR a6-1 - a .
  • R a2-1 , R a4-1 , and R a6-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2-.
  • L 1 and L 2 are independent, more preferably single bond, —O—, —CH 2 CH 2 ⁇ , ⁇ COO ⁇ , —COOCH 2 CH 2 ⁇ , or OCO ⁇ , respectively.
  • At least one of G 1 and G 2 in formula (II) is a divalent alicyclic hydrocarbon group, wherein the divalent alicyclic hydrocarbon group is used.
  • a polymerizable liquid crystal compound bonded by a divalent aromatic group Ar which may have a substituent and L 1 and / or L 2 which is -COO- is used.
  • R a9 to R a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms.
  • B 1 and B 2 are independent, more preferably single bonds, -OR a10-1- , -CH 2- , -CH 2 CH 2- , -COOR a12-1- , or OCOR a14-1-. ..
  • R a10-1 , R a12-1 , and R a14-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2-.
  • B 1 and B 2 are independent, more preferably single bond, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- , -OCO-, or OCOCH 2 CH 2-. ..
  • E 1 and E 2 are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.
  • examples of the polymerizable group represented by P 1 or P 2 include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group and an acryloyloxy group. , Methacloyloxy group, oxylanyl group, oxetanyl group and the like. Among these, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxylanyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
  • Ar has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Is preferable.
  • the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable.
  • aromatic heterocycle examples include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring.
  • a thiazole ring a benzothiazole ring, or a benzofuran ring
  • Ar contains a nitrogen atom
  • the nitrogen atom preferably has ⁇ electrons.
  • 2-valent of [pi Total N [pi electrons contained in the aromatic group is preferably 8 or more represented by Ar, more preferably 10 or more, more preferably 14 or more, particularly It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.
  • Examples of the aromatic group represented by Ar include groups of the following formulas (Ar-1) to (Ar-23).
  • Z 0 , Z 1 and Z 2 are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms.
  • (Ar-1) ⁇ formula (Ar-23), Q 1 and Q 2 independently, -CR 2'R 3'-, - S -, - NH -, - NR 2 '-, - represents CO- or O- a, R 2'and fine R 3'are each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • J 1 and J 2 independently represent a carbon atom or a nitrogen atom, respectively.
  • Y 1 , Y 2 and Y 3 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
  • W 1 and W 2 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
  • Examples of the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group.
  • a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic group has 4 to 20 carbon atoms including at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, an oxygen atom and a sulfur atom.
  • a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group
  • an aromatic heterocyclic group and a frill group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group are preferable.
  • Y 1 and Y 2 may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively.
  • the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
  • the polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are independently hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, cyano group and nitro group, respectively. It is preferably an alkoxy group having 1 to 12 carbon atoms, Z 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z 1 and Z 2 are a hydrogen atom, a fluorine atom and chlorine. Atomic, methyl and cyano groups are more preferred.
  • (Ar-1) ⁇ formula (Ar-23), Q 1 and Q 2, -NH -, - S -, - NR 2 '-, - O- are preferable, R 2' is preferably a hydrogen atom .. Of these, -S-, -O-, and -NH- are particularly preferable.
  • the formulas (Ar-1) to (Ar-23) are preferable from the viewpoint of molecular stability.
  • Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0.
  • the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have.
  • a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indole examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, a pyrroline ring, and the like.
  • This aromatic heterocyclic group may have a substituent.
  • Y 1 may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y 1 is bonded and Z 0.
  • a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.
  • the compound represented by the formula (II) can be produced, for example, according to the method described in JP-A-2010-31223.
  • the content of the polymerizable liquid crystal compound (B) in the polymerizable liquid crystal composition (B) constituting the retardation film is, for example, 70 to 99 with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B). It is .5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass. When the content is within the above range, the orientation of the retardation film tends to be high.
  • the solid content means the total amount of the components excluding the volatile components such as the solvent from the polymerizable liquid crystal composition (B).
  • the polymerizable liquid crystal composition (B) may contain a polymerization initiator for initiating the polymerization reaction of the polymerizable liquid crystal compound (B).
  • the polymerization initiator may be appropriately selected from those conventionally used in the art and may be a thermal polymerization initiator or a photopolymerization initiator, but under lower temperature conditions.
  • a photopolymerization initiator is preferable because it can initiate a polymerization reaction.
  • Preferred examples of the photopolymerization initiator that can be used in the polymerizable liquid crystal composition (A) include those similar to those exemplified above.
  • the polymerizable liquid crystal composition (B) contains, if necessary, a photosensitizer, a leveling agent, an additive exemplified as an additive contained in the polymerizable liquid crystal composition (A), and the like. May be good.
  • a photosensitizer exemplified as an additive contained in the polymerizable liquid crystal composition (A)
  • the leveling agent include those similar to those exemplified above as those that can be used in the polymerizable liquid crystal composition (A).
  • the retardation film is prepared, for example, by adding a solvent to the polymerizable liquid crystal composition (B) containing the polymerizable liquid crystal compound (B) and, if necessary, a polymerization initiator, an additive, etc., and mixing and stirring the mixture.
  • a composition (hereinafter, also referred to as “composition for forming a retardation film”) is applied onto a support (substrate) or a liquid crystal alignment layer, the solvent is removed by drying, and the polymerizable liquid crystal in the obtained coating film is obtained.
  • Compound (B) can be obtained by heating and / or curing with active energy rays.
  • Examples of the support (substrate) and / or the liquid crystal alignment layer used for producing the retardation film include those similar to those exemplified above as those that can be used for producing the polarizing plate of the present invention.
  • the solvent used in the composition for forming a retardation film, the method for applying the composition for forming a retardation film, the curing conditions using active energy rays, and the like can all be adopted in the method for forming a polarizing element layer according to the present invention. Similar things can be mentioned.
  • the film thickness of the retardation film can be appropriately selected depending on the display device to be applied, but from the viewpoint of thinning and flexibility, it is preferably 0.1 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m. It is preferably 1 to 3 ⁇ m, and more preferably 1 to 3 ⁇ m.
  • the polarizing plate of the present invention may further include other layers (adhesive layer, etc.) in addition to the polarizing plate of the present invention and the retardation film.
  • the polarizing element of the polarizing plate of the present invention and the retardation film may be bonded to each other via an adhesive layer.
  • the thickness of the polarizing plate of the present invention is preferably 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m, and even more preferably 25 to 50 ⁇ m from the viewpoint of flexibility and visibility of the display device.
  • the polarizing plate according to the embodiment of the present invention may be band-shaped. Therefore, a polarizing element is formed on the strip-shaped optical film, and another strip-shaped protective film (also referred to as “opposite film”) is unwound from the roll body and bonded by roll-to-roll to obtain polarized light. It is preferable to perform plate processing.
  • the length and width of the strip-shaped polarizing plate are the same as the length and width of the optical film.
  • a step of forming the optical film on a support a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and a dichroic organic dye is applied onto the support (substrate). It is preferable to include a step of curing to form a polarizing element layer and a step of winding the polarizing element layer, the support (substrate), and the support in this order from the inside of the roll.
  • the support according to the present invention since the support according to the present invention is arranged on the outside of the polarizing plate roll, it exerts a function as a protective film and prevents the support (substrate) from being scratched during the polarizing plate processing. Or, curling can be suppressed to facilitate handling.
  • an opposed film is wound on the surface of the polarizing element layer opposite to the support (substrate) while being bonded to the polarizing element layer via an adhesive layer or an adhesive layer to polarize the polarized light.
  • a plate roll may be formed.
  • the adhesive layer may be a cured product layer of an active energy ray-curable adhesive, or may be a layer obtained from a water-soluble polymer.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 5 ⁇ m, respectively.
  • the pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive composition containing a base polymer, a prepolymer and / or a cross-linking monomer, a cross-linking agent and a solvent, dried and partially cross-linked. That is, at least a part of the pressure-sensitive adhesive composition may be crosslinked.
  • the pressure-sensitive adhesive composition examples include an acrylic pressure-sensitive adhesive composition using a (meth) acrylic polymer as a base polymer, a silicone-based pressure-sensitive adhesive composition using a silicone-based polymer as a base polymer, and a rubber-based pressure-sensitive adhesive composition using a rubber as a base polymer.
  • a pressure-sensitive adhesive composition is included.
  • an acrylic pressure-sensitive adhesive composition is preferable from the viewpoint of transparency, weather resistance, heat resistance, and processability.
  • the thickness of the pressure-sensitive adhesive layer is usually about 3 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
  • a polarizing element layer containing a dichroic organic dye is formed on the first support.
  • the manufacturing method has a step of peeling off the second support which is peelable after the layer has dried (see FIGS. 2A and 2B). Details of the method for manufacturing the polarizing plate will be described with reference to Examples described later.
  • the display device of the present invention is characterized by comprising the polarizing plate of the present invention.
  • the display device of the present invention can be obtained, for example, by adhering the polarizing plate or the polarizing plate of the present invention to the surface of the display device via the adhesive layer.
  • the display device is a device having a display mechanism, and includes a light emitting element or a light emitting device as a light emitting source.
  • Display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (electric field emission display devices (FED, etc.), surface electric field emission display devices). (SED)), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection type display device (grating light valve (GLV) display device, display device having a digital micromirror device (DMD)). Etc.) and piezoelectric ceramic displays and the like.
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images, or may be stereoscopic display devices that display three-dimensional images.
  • an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable.
  • Example 1 The production of the polarizing plate of the present invention was carried out according to the following flow as an overall process. ⁇ Coating and film formation of the liquid crystal alignment layer on the first support (TAC film, etc.) (step of [1] below) ⁇ Coating and film formation of a polarizing element layer on the liquid crystal alignment layer (step [2] below) -Formation of a polarizing plate by bonding an optical film as a protective layer on a liquid crystal polarizing element layer (step [5] below).
  • the water-based adhesive prepared in the following [3] and the optical film laminate prepared in the following [4], that is, the release layer on the second support are optically used. A laminated body formed by applying a film was used.
  • Photo-oriented polymer The following polymer (number average molecular weight 28000) 2 parts by mass Solvent: o-xylene 98 parts by mass
  • a triacetyl cellulose film (KC2UA: manufactured by Konica Minolta Co., Ltd.) was used as the first support in the present invention, and the surface of the film was subjected to corona treatment, and then the composition for forming a photoalignment film was applied. It was dried at 120 ° C. to obtain a dry film (thickness of about 0.1 ⁇ m). The dried film was irradiated with polarized UV to form a photo-alignment film, and a film with a photo-alignment film was obtained.
  • the polarized UV treatment was carried out using a UV irradiation device (SPOT CURE SP-7 manufactured by Ushio, Inc.) under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ.
  • Polymerizable liquid crystal compound 90 parts by mass of the following polymerizable liquid crystal compound (A-6) 10 parts by mass of the following polymerizable liquid crystal compound (A-7)
  • [Dichroic organic dye] Azo dye 2.5 parts by mass of the following dichroic organic dye A 2.5 parts by mass of the following dichroic organic dye B 2.5 parts by mass of the following dichroic organic dye C
  • composition P for Forming Polarizer Layer ⁇ Preparation of Composition P for Forming Polarizer Layer>
  • the composition for forming a polarizing element was applied onto the optical liquid crystal alignment layer of the first support with the optical liquid crystal alignment layer to form a polarizing layer having a thickness of about 2.3 ⁇ m.
  • Water-based adhesive A1 (for the present invention 1)> Polyvinyl alcohol containing 5% by mass of an acetoacetyl group (average polymerization degree 2000, saponification degree 94%) was dissolved in pure water to prepare a 3.8% by mass aqueous solution. Next, a zirconium amine compound (AC-7: manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) was dissolved in pure water to prepare a 3.8% by mass aqueous solution. The water-based adhesive A1 was prepared by mixing in the following ratios. PVA solution 100 parts by mass Zirconium amine compound solution 20 parts by mass
  • Adhesives A2 and A3 were prepared in the same manner as the adhesive A1 except that the pH values were adjusted to 6.0 and 9.2, respectively.
  • ⁇ Water-based adhesive B> The following components were mixed to prepare a water-based adhesive B.
  • Urethane resin (Hydran AP-20: manufactured by Dainippon Ink and Chemicals Co., Ltd .: solid content concentration 30%, viscosity 30 mPa ⁇ s) 100 parts by mass oxetane compound (OXT-101: manufactured by Toa Synthetic Co., Ltd .: chemical name 3- Ethyl-3-hydroxymethyloxetane) 5 parts by mass
  • Epoxy compound KBM-303: Shin-Etsu Chemical Industry Co., Ltd .: Chemical name 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) 5 parts by mass
  • a water-based adhesive C was prepared with reference to the method described in JP-A-2009-237388. (Preparation of urethane resin) The following components were placed in a reactor in a 2000 ml four-necked flask equipped with a thermometer, agitator, nitrogen introduction tube, and cooling tube, and water generated at 200 ° C was retained outside the reaction system while passing nitrogen gas under normal pressure. The esterification reaction was carried out while leaving. When the acid value of the polyester reached 1.0 mgKOH / g, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. The obtained polyester polyol had a hydroxyl value of 56.1 mgKOH / g, an acid value of 0.2 mgKOH / g, and a number average molecular weight (calculated from the hydroxyl value) of 2000.
  • the following components were placed in a 2000 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, and the mixture was reacted at 75 ° C. for 1 hour while introducing nitrogen. After completion of the reaction, the mixture was cooled to 60 ° C.
  • the following components were added and reacted at 75 ° C. to obtain a prepolymer solution.
  • the prepolymer was cooled to 40 ° C., 1500 parts by mass of water was added, and the mixture was emulsified by stirring at high speed with a homomixer. Methyl ethyl ketone was distilled off from this emulsion under heating and reduced pressure to obtain an aqueous polyurethane resin solution having a solid content of 40%.
  • ⁇ Water-based adhesive D> A PVA solution prepared by dissolving 100 g of a polyvinyl alcohol resin (Gosefimer Z210: manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: PVA containing an acetoacetyl group) in 900 g of pure water was prepared, and the following components were mixed to prepare an aqueous adhesive D.
  • ⁇ Water-based adhesive E> After mixing the following components, defoaming was performed to prepare a water-soluble adhesive liquid, and a water-based adhesive E was prepared.
  • Oxazoline group-containing polymer (Epocross (registered trademark) WS-300: Nippon Shokubai: 10% aqueous solution) 100 parts by mass Specially modified polyvinyl alcohol (Gosenex (registered trademark) Z-200: manufactured by Mitsubishi Chemical Corporation) 8.0 parts by mass Nitrogen-containing heterocyclic compound (having an aziridine ring at the end) (CROSSLINKER CL-427: manufactured by MENADIONA) 0.2 parts by mass Pure water 91.8 parts by mass
  • Non-water adhesive F for Comparative Example 4
  • defoaming was performed to prepare an adhesive liquid, and an adhesive F was prepared.
  • Polyfunctional acrylate (Aronix (registered trademark) M-403: manufactured by Toagosei Co., Ltd.) 50 parts by mass Evecryl (registered trademark) 4858 (manufactured by Daicel UCB) 50 parts by mass Irgacure 907 (manufactured by BASF Japan, Ltd.) 3 parts by mass Isopropanol 250 parts by mass
  • optical film laminates 1 to 8 were prepared as optical films for protecting the polarizing element layer of [2] above via the adhesive layer.
  • the retardation value of the optical film was measured by the following method after the support was peeled off.
  • the retardation Ro and Rt of the film after humidity control at a measurement wavelength of 590 nm were measured in an environment of 23 ° C. and 55% RH using an automatic birefringence meter Axoscan (Axo Scan Mueller Matrix Matrix Polarimeter), respectively. Measured below.
  • the film thickness of the optical film was measured by the following method. After peeling the support from the produced optical film laminate, it was calculated from the average value of the film thicknesses of three randomly selected points in the width direction. The film thickness was measured using F20-UV (manufactured by Filmometry) as a film thickness measuring system.
  • the film to be measured was measured at 40 ° C. and 90% RH based on the calcium chloride-cup method described in JIS-Z-0208: 1976. It was left for 24 hours under the conditions for measurement.
  • PET film polyethylene terephthalate film
  • TN100 manufactured by Toyobo Co., Ltd., with a release layer containing a non-silicone release agent, and a film thickness of 38 ⁇ m
  • PET film polyethylene terephthalate film
  • TN100 manufactured by Toyobo Co., Ltd., with a release layer containing a non-silicone release agent, and a film thickness of 38 ⁇ m
  • Tricyclodecanedimethanol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 100.0 parts by mass Irgacure 127 (manufactured by BASF Japan) 2.0 parts by mass Megafuck (registered trademark) F-784-F (manufactured by DIC) 0.08 parts by mass Ethyl acetate 100.0 parts by mass
  • An optical film laminate 3 was prepared with reference to Example 3 of JP-A-2018-45220. It was applied onto the base film by a die coat method at a transport speed of 30 m / min, and dried at 60 ° C. for 150 seconds. After that, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% and an output of 160 W / cm under nitrogen purging, ultraviolet rays with an illuminance of 400 mW / cm 2 and an irradiation dose of 120 mJ / cm 2 were emitted. The coating layer was cured by irradiation, and a translucent film was formed on the base film and wound up. The coating amount was adjusted so that the film thickness of the optical film layer was 5 ⁇ m, and the optical film laminate 3 was obtained.
  • PET film polyethylene terephthalate film
  • TN100 manufactured by Toyobo Co., Ltd., with a release layer containing a non-silicone release agent, and a film thickness of 38 ⁇ m
  • optical film laminates 5 to 8 were produced in the same manner except that the film thickness at the time of drying was changed to 1, 3, 9, and 15 ⁇ m.
  • PET film polyethylene terephthalate film
  • TN100 manufactured by Toyobo Co., Ltd., with a release layer containing a non-silicone release agent, and a film thickness of 38 ⁇ m
  • Deionized water 180 parts by mass Polyoxyethylene lauryl ether phosphoric acid 0.002 parts by mass Borate 0.473 parts by mass Sodium carbonate 0.047 parts by mass Sodium hydroxide 0.008 parts by mass
  • the internal temperature was set to 80 ° C., and 0.021 parts by mass of potassium persulfate was added as a 2% by mass aqueous solution.
  • a monomer consisting of 84.6% by mass of methyl methacrylate, 5.9% by mass of butyl acrylate, 7.9% by mass of styrene, 0.5% by mass of allyl methacrylate, and 1.1% by mass of n-octyl mercaptan.
  • a mixed solution prepared by adding 0.07 parts by mass of polyoxyethylene lauryl ether phosphate to 21 parts by mass of the mixture (c') was continuously added to the above solution over 63 minutes. Further, the innermost hard polymer (c) was obtained by continuing the polymerization reaction for 60 minutes.
  • a soft layer (a layer made of an acrylic rubber-like polymer (a)).
  • the glass transition temperature (Tg) of the soft layer was ⁇ 30 ° C.
  • the glass transition temperature of the soft layer was calculated by averaging the glass transition temperature of the homopolymer of each monomer constituting the acrylic rubber-like polymer (a) according to the composition ratio.
  • the obtained polymer was put into a 3 mass% sodium sulfate warm aqueous solution and salted out and coagulated. Then, after repeating dehydration and washing, the particles were dried to obtain acrylic graft copolymer particles (rubber particles R1) having a three-layer structure.
  • the average particle diameter of the obtained rubber particles R1 was 200 nm.
  • the average particle size of the rubber particles was measured by the following method.
  • the dispersed particle size of the rubber particles in the obtained dispersion was measured by a zeta potential / particle size measuring system (ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd.).
  • both the surface of the polarizing element prepared in the step [2] and the surface on the optical film 1 side as the protective layer prepared in the step [4] have a corona output strength of 2.0 kW and a line speed of 18 m / min.
  • the treated surface is coated with the water-soluble adhesive solution 1 prepared above with a bar coater so that the thickness after drying is about 0.5 ⁇ m, and then 50 ° C., 60 ° C., 70 ° C. After drying at ° C. in this order for 60 seconds each, and then laminating, the support (second support) of the optical film 1 was peeled off to obtain a polarizing plate 1 (see FIG. 5 for the layer structure of the polarizing plate). .).
  • the axes in the longitudinal direction of the polarizing element layer and the axes in the longitudinal direction of the optical film were aligned and bonded.
  • the polarizing plates 2 to 18 were formed in the same manner as the polarizing plate 1 except that the combination of the adhesive and the optical film (optical film laminate) as the protective layer was the combination shown in Table 1. Made.
  • ⁇ Preparation of Polarizing Plate 19 (Comparative Example 4)> A polarizing layer was produced in the same manner up to the step [2], and the surface of the polarizing layer was subjected to corona discharge treatment at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the above-mentioned curing composition F was applied, heated and dried at 50 ° C. for 1 minute, and then exposed to ultraviolet rays at an exposure amount of 400 mJ / cm2 (SPOT CURE SP-7; manufactured by Ushio, Inc.) using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio, Inc.). By irradiating with (based on 365 nm), a protective layer of 2.8 ⁇ m was formed on the polarizing layer, and a polarizing plate 19 was produced.
  • ⁇ Preparation of Polarizing Plate 20 (Comparative Example 5)> A polarizing layer was produced in the same manner up to the step [2], and the surface of the polarizing layer was subjected to corona discharge treatment at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the above composition G was applied so that the film thickness after drying was 0.5 ⁇ m, and dried at 100 ° C. for 1.5 minutes to prepare a first layer. The surface of the composition G was subjected to the same corona treatment again, and then the following hard coat liquid H was applied so that the film thickness after drying was 1.5 ⁇ m. After coating, the polarizing plate 20 of the comparative example was prepared by irradiating with ultraviolet rays having an exposure amount of 500 mJ / cm 2 (365 nm standard) after heating and drying at 50 ° C. for 1 minute.
  • the polarizing plate 21 was produced in the same manner as the polarizing plate 1 except that the optical film laminate 4 produced above was used as the first support instead of KC2UA, and the optical film laminate was produced. 4 By peeling off the second support at the time of production, a polarizing plate 21 made of an optical film having both sides of the polarizing plate of 5 ⁇ m was produced.
  • the polarizing plate 22 was produced in the same manner as the polarizing plate 1 except that the optical film laminate 9 produced above was used as the first support instead of the KC2UA, and the optical film laminate was produced. 9 By peeling off the second support at the time of production, a polarizing plate 22 made of an optical film having both sides of the polarizing plate of 5 ⁇ m was produced.
  • the moisture permeability of the optical film as a protective layer is based on the calcium chloride-cup method described in JIS Z-0208: 1976, and the optical film to be measured is left for 24 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH. And measured.
  • the peeling strength (adhesion) when peeled at the interface between the adhesive layer laminated on the optical film as the protective layer of the obtained polarizing plate and the polarizing element layer is measured in an environment of a temperature of 23 ° C. and a humidity of 55% RH.
  • the 90 ° peel test (based on JIS Z0237: 2009) was measured and evaluated with a 90 ° peeling test jig (P90-200N) manufactured by Imada Co., Ltd.
  • the evaluation criteria are as follows.
  • Peeling strength is 3.0 (N / 25mm) or more ⁇ : Peeling strength is 2.0 (N / 25mm) or more and less than 3.0 (N / 25mm) ⁇ : Peeling strength is 1.0 (N / 25mm) More than 2.0 (N / 25 mm) ⁇ : If the peel strength is less than 1.0 (N / 25 mm) ⁇ or more, it is judged to be good.
  • test piece was stored for 48 hours in an environment with a temperature of 85 ° C. and a relative humidity of 85%, and then stored overnight in an environment with a temperature of 23 ° C. and a relative humidity of 55%, and the peel strength was measured and evaluated in the same manner.
  • the transmittance (Ta) in the transmission axis direction and the transmittance (Tb) in the absorption axis direction in the wavelength range of 380 to 780 nm in the obtained polarizing plate are polarized by a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation).
  • the measurement was performed by the double beam method using a device in which a folder with a child layer was set. In the folder, a mesh that cuts the amount of light by 50% was installed on the reference side.
  • Equation 2 the single transmittance and the degree of polarization at each wavelength are calculated, and the luminosity factor is corrected by the 2 degree field (C light source) of JIS Z8701.
  • the degree of polarization Py and the single transmittance Ty were measured again, and the amount of change ( ⁇ Py and ⁇ Ty) before and after the moisture resistance heat test was calculated. However, it was evaluated according to the following criteria.
  • ⁇ The amount of change in both Ty and Py is ⁇ 1% ⁇ : The larger change amount of Ty and Py is 1 to 3%. ⁇ : The amount of change in both Ty and Py is 1 to 3%. ⁇ : The larger change amount of Ty and Py is ⁇ 3%
  • the obtained polarizing plate was cut into a width of 15 mm and a length of 150 mm (the length direction is the MD direction) to obtain a test piece.
  • This test piece was allowed to stand at a temperature of 25 ° C. and a humidity of 65% RH for 1 hour or more.
  • a folding resistance tester manufactured by Tester Sangyo Co., Ltd., MIT, BE-201 type, bending radius of curvature 0.38 mm
  • the support on the TAC film side, the optical film 4 or 9 adjacent to the liquid crystal alignment layer on the polarizing plate 21 and 22
  • bend so that the crease direction is the TD direction until the test piece breaks.
  • the number of times of bending was measured.
  • the MIT bending resistance (resistance to bending) of the polarizing plate was evaluated according to the following criteria. ⁇ : 5000 times or more ⁇ : 3000 to 4999 times ⁇ : 2999 times or less
  • the adhesive layer in the polarizing plate of the present invention exhibits excellent adhesion even in a high temperature and high humidity environment. Further, the polarizing plate of the present invention is excellent in moisture and heat resistance, water resistance, acid resistance and bending resistance, and by applying the optical film of the present invention to the first support, the bending resistance can be further improved. confirmed.
  • Example 2 With reference to Example 1 described in International Application 2012/165224, a polarizing plate in which the polarizing layer contains the following dichroic organic dye and polyvinyl alcohol was prepared.
  • a polyvinyl alcohol-based resin film (VF series manufactured by Kuraray) having a saponification degree of 99% or more and a film thickness of 75 ⁇ m was immersed in warm water at 40 ° C. for 2 minutes for swelling treatment.
  • the swollen film was immersed in an aqueous solution at 45 ° C. containing 0.05% by mass of the above dichroic organic dye and 0.1% by mass of sodium tripolyphosphate to adsorb the dye.
  • the film on which the dye was adsorbed was washed with water, and after washing, boric acid treatment was carried out for 1 minute with an aqueous solution at 40 ° C. containing 2% by mass of boric acid.
  • the film obtained by boric acid treatment was treated in an aqueous solution at 55 ° C. containing 3.0% by mass of boric acid for 5 minutes while stretching 5.0 times.
  • the film obtained by the boric acid treatment was washed with water at 30 ° C. for 15 seconds while maintaining the tension.
  • the film obtained by the treatment was immediately dried at 70 ° C. for 9 minutes to obtain a polarizing element layer having a thickness of 28 ⁇ m.
  • the simple substance transmittance of ⁇ max of the obtained polarizing element layer was 43.95%, and ⁇ max was 580 nm.
  • a polarizing plate was produced using the above-mentioned polarizing element layer, the above-mentioned optical film laminate, and the water-based adhesive.
  • the present invention can be used for a polarizing plate using a dichroic organic dye, a method for producing the same, and a display device provided with the polarizing plate, which have high durability and can be easily manufactured.
  • Polarizing plate 1 Polarizing plate 2 Protective layer (optical film) 3 Adhesive layer 4 Polarizer layer 5 Support (first support) 6 Support (second support) 7 Release layer 8 Liquid crystal alignment layer 8a Liquid crystal alignment layer 8b Liquid crystal alignment layer 9a Phase difference layer 9b Liquid crystal phase difference layer 10 Support (third support) B110 Support B120 Support (board) Film B200 Manufacturing equipment B210 Supply part B220 Coating part B230 Drying part B240 Cooling part B250 Winding part

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JP2016522454A (ja) * 2013-06-18 2016-07-28 エルジー・ケム・リミテッド 延伸積層体、薄型偏光子の製造方法、これを用いて製造される薄型偏光子及びこれを含む偏光板
JP2018200465A (ja) * 2017-05-25 2018-12-20 住友化学株式会社 偏光板
JP6706399B1 (ja) * 2018-11-12 2020-06-03 日東電工株式会社 画像表示装置

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JP6171276B2 (ja) 2011-07-12 2017-08-02 住友化学株式会社 偏光子及びその製造方法
TWI713619B (zh) 2015-10-30 2020-12-21 日商住友化學股份有限公司 偏光板、具備該偏光板的顯示裝置，及其製造方法
JP7185460B2 (ja) 2018-09-21 2022-12-07 住友化学株式会社 偏光フィルム並びにそれを含む偏光板および表示装置

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JP2009237388A (ja) * 2008-03-28 2009-10-15 Nippon Zeon Co Ltd 偏光板
JP2012041533A (ja) * 2010-08-13 2012-03-01 Dongwoo Fine-Chem Co Ltd 偏光板用接着剤組成物及びこれを利用した偏光板｛ａｄｈｅｓｉｖｅｃｏｍｐｏｓｉｔｉｏｎｆｏｒｐｏｌａｒｉｚｅｒａｎｄｐｏｌａｒｉｚｅｒｕｓｉｎｇｔｈｅｓａｍｅ｝
WO2012165224A1 (ja) * 2011-05-31 2012-12-06 日本化薬株式会社 染料系偏光素子及び偏光板
JP2015536485A (ja) * 2013-06-18 2015-12-21 エルジー・ケム・リミテッド 延伸積層体、薄型偏光子の製造方法、これを用いて製造される薄型偏光子及びこれを含む偏光板
JP2016522454A (ja) * 2013-06-18 2016-07-28 エルジー・ケム・リミテッド 延伸積層体、薄型偏光子の製造方法、これを用いて製造される薄型偏光子及びこれを含む偏光板
JP2018200465A (ja) * 2017-05-25 2018-12-20 住友化学株式会社 偏光板
JP6706399B1 (ja) * 2018-11-12 2020-06-03 日東電工株式会社 画像表示装置

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