[go: up one dir, main page]

WO2015076101A1 - Plaque polarisante et dispositif d'affichage à cristaux liquides l'utilisant - Google Patents

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

Info

Publication number
WO2015076101A1
WO2015076101A1 PCT/JP2014/079294 JP2014079294W WO2015076101A1 WO 2015076101 A1 WO2015076101 A1 WO 2015076101A1 JP 2014079294 W JP2014079294 W JP 2014079294W WO 2015076101 A1 WO2015076101 A1 WO 2015076101A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
protective film
group
polarizing plate
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/079294
Other languages
English (en)
Japanese (ja)
Inventor
真一郎 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2015549059A priority Critical patent/JPWO2015076101A1/ja
Priority to KR1020167012463A priority patent/KR20160070810A/ko
Priority to CN201480062796.1A priority patent/CN105745561B/zh
Publication of WO2015076101A1 publication Critical patent/WO2015076101A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays

Definitions

  • the present invention relates to a polarizing plate and a liquid crystal display device using the same.
  • a liquid crystal display device is generally composed of a liquid crystal cell in which a transparent electrode, a liquid crystal layer, a color filter and the like are sandwiched between glass plates, and two polarizing plates provided on both sides thereof. Each polarizing plate is usually configured to sandwich a polarizer between two transparent resin films.
  • a cellulose acylate film such as cellulose acetate having a function of protecting a polarizer is often used.
  • the cellulose acylate film has a high transmittance, and by immersing it in an alkaline aqueous solution to saponify its surface and make it hydrophilic, excellent adhesion to a polarizer is realized.
  • a resin film other than the cellulose acylate film as a protective film for the polarizing plate.
  • a resin film other than the cellulose acylate film as a protective film for the polarizing plate.
  • an outer resin film is formed into a transparent acrylic resin with a predetermined number average. It is said that a polarizing plate that is difficult to break even if it is thinned is provided by constituting it from a composition containing rubber elastic particles having a particle diameter.
  • JP 2012-256057 A when a polyester film made of polyethylene terephthalate or the like is used as a protective film for a polarizing plate, a film whose retardation is controlled to a predetermined value is used in combination with a specific light source. Thus, it is said that a polarizing plate excellent in durability and visibility is provided.
  • an acrylic resin as disclosed in the above-mentioned Japanese Patent Application Laid-Open Nos. 2012-181277 and 2012-256057 has a cellulose acylate film disposed on one surface of a polarizer as a protective film.
  • positioned on the other surface was produced, and the durability was examined. Specifically, a heat shock durability test and a high temperature and high humidity durability test were performed on the polarizing plate having such a configuration.
  • problems such as light leakage at the in-plane end of the polarizing plate and warping of the panel due to curling of the polarizing plate occur. There was found.
  • the present invention has been made in view of the above-mentioned problems, and the problem to be solved is that in a polarizing plate in which an acrylic resin or polyester-based film as a protective film is disposed on one surface of a polarizer. Even after the shock durability test and high temperature and high humidity durability test, there is a means that can minimize the occurrence of problems such as light leakage at the in-plane end of the polarizing plate and panel warping due to the curling of the polarizing plate. Is to provide.
  • the present inventor has a protective film A, a polarizer, and a protective film B in this order, and the protective film A and the protective film B use an ultraviolet curable adhesive.
  • a film mainly composed of acrylic resin or polyester is used as the protective film A, and the average degree of acetyl group substitution is 2.1 to 2.7 as the protective film B.
  • a cellulose acetate film containing a certain cellulose acetate as a main component is used, and the difference in vertical and horizontal directions of the photoelastic coefficient of the cellulose acetate film (absolute value obtained by subtracting the value in the TD direction from the MD direction) is 5.0 or less.
  • the protective film A is a film mainly composed of acrylic resin or polyester
  • the protective film B is a cellulose acetate film mainly composed of cellulose acetate having an average acetyl group substitution degree of 2.1 to 2.7,
  • the difference between the photoelastic coefficient (23 ° C. and 55% RH) in the vertical and horizontal directions of the cellulose acetate film is 5.0 or less. Board; 2.
  • FIG. 1 It is a schematic sectional drawing which shows an example of a structure of the polarizing plate of this invention. It is the figure which showed typically an example of the dope preparation process of the solution casting film forming method preferable for this invention, a casting process, and a drying process (solvent evaporation process).
  • the polarizing plate according to the present invention includes a protective film A, a polarizer, and a protective film B in this order, and the protective film A and the protective film B are bonded to the polarizer using an ultraviolet curable adhesive. It is a polarizing plate.
  • the protective film A is a film mainly composed of acrylic resin or polyester
  • the protective film B is a cellulose acetate mainly composed of cellulose acetate having an average acetyl group substitution degree of 2.1 to 2.7. It is a film.
  • the difference of the photoelastic coefficient of the said cellulose acetate film in the vertical and horizontal direction has the characteristics in the point which is 5.0 or less.
  • a polarizing plate in which a film mainly composed of acrylic resin or polyester is disposed as a protective film on one surface of a polarizer, after a heat shock durability test or a high temperature and high humidity durability test Even if it exists, generation
  • ⁇ is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the polarizing plate of the present invention has a protective film A, a polarizer, and a protective film B in this order.
  • the protective film A is a film mainly composed of acrylic resin or polyester (for example, polyethylene terephthalate), and the protective film B is It is a cellulose acetate film having a predetermined average degree of acetyl group substitution.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the polarizing plate of the present invention.
  • a polarizing plate 101 of the present invention has a protective film A (an acrylic resin film or a polyester film such as a PET film) 102 and a polarizer 104 from the surface side, and the protective film A102 and the polarizer.
  • 104 is bonded by an ultraviolet curable adhesive layer 103A.
  • the ultraviolet curable adhesive layer 103A is made of a material that is cured by irradiating ultraviolet rays or the like. The details of the ultraviolet curable adhesive will be described later.
  • the protective film B (cellulose acetate) is further disposed on the surface of the polarizer 104 opposite to the surface on which the protective film A102 is disposed via the ultraviolet curable adhesive layer 103B.
  • Film) 105 is laminated.
  • an antiglare layer for example, an antiglare layer, an antireflection layer, an antifouling layer, a hard coat layer and the like are provided as necessary. It may be provided.
  • the protective film A is a film mainly composed of acrylic resin or polyester.
  • the film “having a predetermined component as a main component” means that the ratio of the predetermined component to the total mass of resin components constituting the film is more than 50% by mass, preferably 55% by mass. It is above, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
  • the acrylic resin according to the present invention includes a methacrylic resin, and an acrylate / methacrylate derivative, particularly, an acrylate ester / methacrylate ester (co) polymer is preferable.
  • the acrylic resin is not particularly limited, but the acrylic resin is composed of 51 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of monomer units of other acrylic resins copolymerizable therewith. It is preferable for obtaining a high-quality optical film.
  • acrylic resin according to the present invention other acrylic resin monomers copolymerizable with the methyl methacrylate unit include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl group, and those having 1 to 18 carbon atoms in the alkyl number.
  • ⁇ , ⁇ -unsaturated acids such as alkyl acrylate, acrylic acid and methacrylic acid, divalent carboxylic acids containing unsaturated groups such as maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, Examples include ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, and glutaric anhydride. These may be used alone or in combination of two or more monomers. And can be used as a copolymerization component.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferably used.
  • Acrylic resins that can form highly transparent optical films with little performance change even in high-temperature and high-humidity environments contain alicyclic alkyl groups as copolymerization components, or are converted into molecular main chains by intramolecular cyclization.
  • An acrylic resin in which a ring structure is formed is preferable.
  • the acrylic resin having a cyclic structure formed in the molecular main chain include, for example, an acrylic resin containing a lactone ring-containing polymer described in Paragraph Nos. [0195] to [0202] described in JP 2012-1333078 A.
  • Examples of the resin composition and the synthesis method are described in, for example, Japanese Patent Application Laid-Open Nos. 2012-0666538 and 2006-171464.
  • Another preferred embodiment is a resin containing glutaric anhydride as a copolymerization component, and the copolymerization component and a specific synthesis method are described in, for example, JP-A-2004-070296.
  • the weight average molecular weight (Mw) of the acrylic resin applied to the present invention is preferably 80,000 or more from the viewpoint of excellent surface shape of the film to be formed. Also, from the viewpoint of further improving the film surface shape when laminated, the weight average molecular weight of the acrylic resin is preferably in the range of 100,000 to 4000000.
  • the upper limit of the weight average molecular weight of the acrylic resin can maintain the solution casting suitability without excessively increasing the viscosity, and can ensure compatibility with organic solvents and additives during dope preparation.
  • the upper limit is preferably 4000000.
  • the weight average molecular weight of the acrylic resin according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the method for producing the acrylic resin is not particularly limited, and a known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization can be used.
  • a commercially available product can be used as the acrylic resin according to the present invention.
  • a commercially available product can be used as the acrylic resin according to the present invention.
  • Delpet 60N, 80N above, manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Dialnal BR52, BR80, BR83, BR85, BR88 aboveve, manufactured by Mitsubishi Rayon Co., Ltd.
  • KT75 manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Two or more kinds of such commercially available acrylic resins can be used in combination.
  • thermoplastic resins that can be used in combination with acrylic resins
  • the protective film A is mainly composed of an acrylic resin
  • the content of the acrylic resin according to the present invention is not exceeded, that is, the “acrylic layer mainly composed of the acrylic resin” is maintained.
  • another thermoplastic resin can be further included.
  • thermoplastic resin a resin having a glass transition temperature of 100 ° C. or higher and a total light transmittance of 85% or higher is mixed with the acrylic resin according to the present invention to form a heat resistance and a machine. It is preferable in terms of improving the strength.
  • thermoplastic resins examples include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); polystyrene, styrene-methyl methacrylate copolymer, Styrene polymers such as styrene-acrylonitrile copolymer and acrylonitrile-butadiene-styrene block copolymer; ABS resin (acrylonitrile-butadiene-styrene resin) and ASA resin (acrylonitrile-styrene-) blended with polybutadiene rubber and acrylic rubber Rubber polymer such as acrylate resin).
  • olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); polystyrene, styrene-methyl methacrylate copolymer, Styrene polymers such as styrene-acrylonit
  • the rubbery polymer preferably has a graft portion having a composition compatible with the ring polymer on the surface, and the average particle diameter of the rubbery polymer is from the viewpoint of improving transparency when formed into a film. 100 nm or less, more preferably 70 nm or less.
  • thermoplastic resins resins that are thermodynamically compatible with acrylic resins are preferably used.
  • other thermoplastic resins for example, an acrylonitrile-styrene copolymer having a vinyl cyanide monomer unit and an aromatic vinyl monomer unit and a polyvinyl chloride resin are preferably exemplified.
  • an acrylonitrile-styrene copolymer can easily provide an optical film having a glass transition temperature of 120 ° C. or more, a retardation per 100 ⁇ m in the plane direction of less than 10 nm, and a total light transmittance of 85% or more. Therefore, it is preferable.
  • acrylonitrile-styrene copolymer those having a copolymerization ratio in a molar unit of 1:10 to 10: 1 are usefully used.
  • the composition of the acrylic resin that can be used for this purpose includes an aliphatic (meth) acrylic acid ester monomer, a (meth) acrylic acid ester monomer having an aromatic ring, or a (meth) acrylic acid ester monomer having a cyclohexyl group. preferable.
  • the constituent mass ratio of these components is 40 to 100% by mass, more preferably 60 to 100% by mass, and most preferably 70 to 100% by mass in the acrylic resin.
  • aliphatic (meth) acrylic acid ester monomers examples include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), Pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (N-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxy Propyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl) , Acrylic acid (2-eth
  • (meth) acrylic acid ester monomer having an aromatic ring for example, benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate and the like can be used.
  • Examples of the (meth) acrylic acid ester monomer having a cyclohexyl group may include cyclohexyl acrylate and cyclohexyl methacrylate.
  • further copolymerizable components include ⁇ , ⁇ -unsaturated acids such as acrylic acid and methacrylic acid, unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid and itaconic acid, and styrene.
  • Aromatic vinyl compounds such as ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like.
  • two or more monomers can be used in combination as a copolymerization component.
  • a method using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide a method using a polymerization initiator in a larger amount than normal polymerization
  • a polymerization A method using a chain transfer agent such as a mercapto compound or carbon tetrachloride in addition to the initiator a method using a polymerization terminator such as benzoquinone or dinitrobenzene in addition to the polymerization initiator, and JP-A No.
  • the protective film A according to the present invention contains an acrylic resin as a main component
  • the protective film A preferably contains rubber particles.
  • the rubber particles applicable to the present invention are not particularly limited, but acrylic rubber particles are preferable.
  • Acrylic rubber particles are particles having rubber elasticity obtained by polymerizing an acrylic monomer mainly composed of alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate in the presence of a polyfunctional monomer. It is.
  • the acrylic rubber particles may be one in which such rubber elastic particles are formed as a single layer, or may be a multilayer structure having at least one rubber elastic layer.
  • the acrylic rubber particles having a multilayer structure particles having rubber elasticity as described above are used as cores, and the periphery thereof is covered with a hard alkyl methacrylate ester polymer, or a hard alkyl methacrylate ester polymer.
  • the core is covered with an acrylic polymer having rubber elasticity as described above, or the hard core is covered with a rubber elastic acrylic polymer, and the periphery thereof is hard alkyl methacrylate. Examples thereof include those covered with a polymer.
  • the average diameter of the particles formed of the elastic layer is usually in the range of about 50 to 400 nm.
  • the content of the rubber particles in the protective film A according to the present invention is usually in the range of 5 to 50 parts by mass per 100 parts by mass of the acrylic resin. Since acrylic resin and acrylic rubber particles are commercially available in a state where they are mixed, commercially available products thereof can be used. Examples of commercially available (meth) acrylic resins containing acrylic rubber particles include Oroglass DR, previously sold by Sumika Hearth Co., Ltd., HT55X currently sold by Sumitomo Chemical Co., Ltd. For example, Technoloy S001.
  • polyester constituting the polyester film polyethylene terephthalate or polyethylene naphthalate can be used, but other copolymer components may be included. These resins are excellent in transparency and excellent in thermal and mechanical properties, and the retardation can be easily controlled by stretching.
  • polyethylene terephthalate is the most suitable material because it has a large intrinsic birefringence and relatively large retardation can be obtained even when the film is thin.
  • the retardation value of the protective film A can be obtained by measuring the refractive index and thickness in the biaxial direction, or a commercially available automatic birefringence measurement such as KOBRA-21ADH (Oji Scientific Instruments). It can also be determined using an apparatus.
  • the protective film A containing polyester as a main component can be manufactured according to a general polyester film manufacturing method.
  • the polyester resin is melted and the non-oriented polyester extruded and formed into a sheet shape is stretched in the longitudinal direction by utilizing the speed difference of the roll at a temperature equal to or higher than the glass transition temperature, and then stretched in the transverse direction by a tenter.
  • the method of performing heat processing is mentioned.
  • the polyester film of the present invention may be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as a polarizer protective film, it may be observed from directly above the film surface. Although rainbow-like color spots are not seen, caution is necessary because rainbow-like color spots may be observed when observed from an oblique direction. This phenomenon is because biaxially stretched films are composed of refractive index ellipsoids having different refractive indexes in the running direction, width direction, and thickness direction, and the retardation becomes zero depending on the direction of light transmission inside the film (refractive index). This is because there is a direction in which the ellipsoid looks like a perfect circle.
  • the light transmittance of the light which has a wavelength of 380 nm in the protective film A is 20% or less for the purpose of suppressing deterioration of optical functional pigments, such as an iodine pigment.
  • the light transmittance is more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. If the light transmittance is 20% or less, the optical functional dye can be prevented from being deteriorated by ultraviolet rays.
  • the transmittance in the present invention is measured by a method perpendicular to the plane of the film, and can be measured using a spectrophotometer (for example, Hitachi U-3500 type).
  • the ultraviolet absorber used in the present invention is a known substance.
  • the ultraviolet absorber include an organic ultraviolet absorber and an inorganic ultraviolet absorber, and an organic ultraviolet absorber is preferable from the viewpoint of transparency.
  • ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.
  • UV absorbers having a molecular weight of 400 or more are not sublimated or are not easily volatilized at a high boiling point. From the viewpoint of improving weather resistance, it is preferable.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- ( Benzotriazoles such as 1,1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Examples thereof include hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and two or more of them can be used in combination.
  • TINUVIN series such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, and TINUVIN 928 manufactured by BASF Japan are preferably used. sell.
  • the above ultraviolet absorbers can be used alone or in combination of two or more.
  • the protective film A can be subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the adhesion to the polarizer.
  • the film thickness of the protective film A is not particularly limited, but is preferably 40 to 100 ⁇ m, more preferably 55 to 80 ⁇ m. It is preferable that the film thickness of the protective film A is within such a range, particularly from the viewpoint of suppressing the warpage (curl) of the panel after the heat shock durability test and the high temperature and high humidity durability test.
  • the protective film A contains an acrylic resin as a main component, the above-mentioned film thickness is defined in that the occurrence of light leakage due to a slight amount of moisture passing through the protective film A can be more reliably suppressed. Is preferred.
  • the absolute value of the difference between the tensile elastic modulus in the MD direction of the protective film A (23 ° C. 55% RH) and the tensile elastic modulus in the TD direction (23 ° C. 55% RH) is preferably 500 MPa or less, more preferably It is 300 MPa or less, more preferably 200 MPa or less.
  • the tensile elastic modulus will take a close value by MD direction and TD direction of the protective film A, and there exists an advantage that it becomes difficult to produce curl.
  • cellulose acetate having a predetermined average acetyl group substitution degree is used as the main component of the protective film B.
  • the protective film A facing the protective film B having such a configuration is used as described above. It can be said that the form in which the tensile modulus of elasticity is close in the MD direction and the TD direction is preferable from the viewpoint of reliably suppressing the occurrence of curling.
  • the absolute value of the tensile elastic modulus of the protective film A is not particularly limited, but when the protective film A is mainly composed of an acrylic resin, the tensile elastic modulus in the MD direction is preferably 1500 to 4000 MPa, more preferably Is 2000 to 3000 MPa.
  • the tensile modulus in the TD direction is preferably 1500 to 5000 MPa, more preferably 2000 to 4000 MPa.
  • the tensile elastic modulus in the MD direction is preferably 3000 to 8000 MPa, and more preferably 5000 to 7500 MPa.
  • the tensile modulus in the TD direction is preferably 1500 to 8000 MPa, more preferably 2000 to 7000 MPa.
  • the value measured by the measuring method as described in the column of the Example mentioned later shall be employ
  • the change (increase) in the haze value when the protective film A is allowed to stand for 24 hours under high-temperature and high-humidity conditions is preferably 0.5 or less.
  • the change (increase) in the haze value under such conditions depends on minute foreign matters existing in the film. If the fine foreign matters are contained in the film in a large amount, When placed in a humidity condition, a craze is formed between the foreign material and the polymer, and the craze is manifested as a change in haze.
  • the balance of strength of the film is deteriorated due to generation of crazing, the balance of the polarizing plate is deteriorated, and the warp (curl) of the panel is caused.
  • the above definition evaluates durability against high-temperature and high-humidity conditions that cannot be observed with an absolute value of simple haze measurement.
  • a value of the haze (and its change (increase)) of the protective film A a value measured by the measurement method described in the column of Examples described later is adopted.
  • an acrylic resin which is a film forming raw material
  • the polyester is preferably filtered in a molten state.
  • the polymer component (dama) contained in the raw resin can be removed, and the molecular weight distribution of the raw resin can be made sharper.
  • filter media such as a conventionally well-known stainless steel sintered compact.
  • the filter particle size (initial filtration efficiency 95%) of the filter medium is preferably 25 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the filtered raw material resin is mixed with an additive such as an ultraviolet absorber as necessary, put into an extruder, melted, extruded from a T-die, and adhered to a cooling roll.
  • an additive such as an ultraviolet absorber as necessary
  • the unstretched sheet is stretched in the MD direction as necessary by stretching between rolls having a speed difference (roll stretching), and further stretched by gripping and expanding by a clip (tenter stretching) as necessary.
  • the film is stretched also in the TD direction by stretching (inflation stretching) by expanding by air pressure, and finally biaxially oriented.
  • the draw ratio (longitudinal draw ratio) is preferably 1.00 to 1.20 times, more preferably 1.01 to 1 times when rubber particles are added when an acrylic resin is the main component. 10 times, particularly preferably 1.01 to 1.05 times.
  • rubber particles When rubber particles are not added, it is preferably 1.10 to 1.60 times, more preferably 1.15 to 1.40 times, and particularly preferably 1.2 to 1.35 times.
  • the main component is polyester, it is preferably 2 to 5 times, more preferably 3 to 5 times, and particularly preferably 3 to 4 times.
  • the most preferable stretching method includes a method using both roll heating and non-contact heating.
  • preheating the film to a relatively high temperature of 120 to 150 ° C. is important from the viewpoint of increasing the elastic modulus of the protective film A. Then, it can introduce
  • the stretching temperature in the longitudinal stretching step is preferably 90 to 180 ° C, more preferably 100 to 180 ° C.
  • the uniaxially stretched film thus obtained can be introduced into a tenter and stretched in the width direction as necessary.
  • the draw ratio (transverse draw ratio) is preferably 1.00 to 1.20 times, more preferably 1.01 to 1.10 times when the acrylic resin is the main component.
  • the ratio is preferably 1.01 to 1.05 times.
  • rubber particles When rubber particles are not added, it is preferably 1.00 to 1.50 times, more preferably 1.05 to 1.40 times, and particularly preferably 1.1 to 1.2 times.
  • the main component is polyester, it is preferably 1 to 5 times, more preferably 2 to 5 times, still more preferably 2 to 4 times, and particularly preferably 3 to 4 times.
  • the stretching temperature in the transverse stretching step is preferably 90 to 180 ° C, more preferably 100 to 150 ° C.
  • the biaxially stretched film thus obtained is subjected to heat treatment as necessary.
  • the heat treatment is preferably carried out in a tenter, preferably in the range of the melting point Tm-50 ° C. to Tm of the raw material resin.
  • a method of blending the ultraviolet absorber into the protective film A a known method can be used in combination.
  • a master batch is prepared by blending the dried ultraviolet absorber and the polymer raw material in advance using a kneading extruder.
  • it can be blended by a method of mixing a predetermined master batch and a polymer raw material at the time of film formation.
  • the concentration of the UV absorber in the master batch is preferably 5 to 30% by mass in order to uniformly disperse the UV absorber and mix it economically.
  • a condition for producing the master batch it is preferable to use a kneading extruder and to extrude at a temperature not lower than the melting point of the polyester raw material and not higher than 290 ° C. for 1 to 15 minutes. Above 290 ° C, the weight loss of the UV absorber is large, and the viscosity of the master batch is greatly reduced.
  • the extrusion temperature is -50 ° C. or lower, uniform mixing of the UV absorber becomes difficult.
  • a stabilizer, a color tone adjusting agent, and an antistatic agent may be added.
  • the protective film A may have a multilayer structure of at least three layers, and an ultraviolet absorber may be added to the intermediate layer of the film.
  • a film having a three-layer structure containing an ultraviolet absorber in the intermediate layer can be specifically produced as follows. The raw resin pellets alone for the outer layer, the masterbatch containing the UV absorber and the raw resin pellets for the intermediate layer are mixed at a predetermined ratio, dried, then supplied to a known melt laminating extruder, and slit A sheet-like die is extruded into a sheet shape and cooled and solidified on a casting roll to form an unstretched film.
  • a three-layer manifold or a merging block for example, a merging block having a square merging portion
  • a film layer constituting both outer layers and a film layer constituting an intermediate layer are laminated
  • An unstretched film can be produced by extruding a three-layer sheet from a die and cooling it with a casting roll.
  • the protective film B is a cellulose acetate film containing cellulose acetate as a main component.
  • cellulose acetate film conventionally known knowledge can be referred to as appropriate, except that the average degree of acetyl group substitution and the photoelastic coefficient have predetermined structures.
  • the cellulose acetate as the main component of the protective film B used in the polarizing plate according to the present invention is characterized in that the average degree of acetyl group substitution is 2.1 to 2.7, and more preferably The average degree of acetyl group substitution is 2.5 to 2.7. If the average degree of acetyl group substitution of cellulose acetate is less than 2.1, cellulose acetate is easily decomposed under the influence of moisture, so that the problem of the present application cannot be solved sufficiently. On the other hand, if the average degree of acetyl group substitution of cellulose acetate exceeds 2.7, haze and durability deteriorate, and the problem of the present application cannot be solved sufficiently.
  • the cellulose acetate film which comprises the protective film B used for the polarizing plate which concerns on this invention is the difference (the value which reduced the value of the TD direction from MD direction) of the photoelastic coefficient (23 degreeC55% RH) of the vertical and horizontal direction. Is an absolute value of 5.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.
  • the present inventor uses cellulose acetate having the above-mentioned predetermined average acetyl group substitution degree as the cellulose ester film, and controls the difference in the vertical and horizontal directions of the photoelastic coefficient of the cellulose acetate film in such a range.
  • a polarizing plate in which a protective film A is disposed on one surface of a polarizer, light leakage or polarization at the in-plane end of the polarizing plate even after a heat shock durability test or a high temperature and high humidity durability test It has been found that the occurrence of problems such as panel warpage due to curling of the plate can be minimized.
  • the value measured by the measuring method as described in the column of the Example mentioned later shall be employ
  • the cellulose acetate as the main component of the protective film B used in the polarizing plate according to the present invention is characterized in that the average degree of acetyl group substitution is 2.1 to 2.7.
  • the degree of substitution of the acetyl group can be measured by a method prescribed in ASTM-D817-96.
  • cellulose acetates having different degrees of substitution may be mixed and used in order to obtain desired optical properties.
  • the mixing ratio of different cellulose acetates is not particularly limited.
  • the number average molecular weight of cellulose acetate is preferably in the range of 4 ⁇ 10 4 to 3 ⁇ 10 5 in order to increase the mechanical strength of the resulting film, and is 4.5 ⁇ 10 4 to 2 ⁇ 10 5 .
  • the range is more preferable, and the range of 5 ⁇ 10 4 to 7 ⁇ 10 4 is particularly preferable.
  • “weight average molecular weight (Mw)” and “number average molecular weight (Mn)” are values measured using gel permeation chromatography (GPC). The measurement conditions are as follows.
  • the content of residual sulfuric acid in cellulose acetate is preferably in the range of 0.1 to 45 ppm by weight in terms of elemental sulfur, and more preferably in the range of 1 to 30 ppm by weight. Sulfuric acid is considered to remain in the film in a salt state. When the content of residual sulfuric acid exceeds 45 ppm by weight, the film tends to break when the film is stretched hot or when slitting is performed after the hot stretch.
  • the content of residual sulfuric acid can be measured by the method prescribed in ASTM D817-96.
  • the content of free acid in cellulose acetate is preferably in the range of 1 to 500 ppm by weight, more preferably 1 to 100 ppm by weight, and further preferably in the range of 1 to 70 ppm by weight. preferable.
  • the content of free acid can be measured by the method prescribed in ASTM D817-96.
  • the content of the iron (Fe) component in the cellulose acetate is preferably 3 ppm by weight or less, and more preferably 1 ppm by weight or less. Further, the content of the calcium (Ca) component in the cellulose derivative is preferably 60 ppm by weight or less, more preferably in the range of 0 to 30 ppm by weight. The content of the magnesium (Mg) component in the cellulose acetate is preferably in the range of 0 to 70 ppm by weight, and particularly preferably in the range of 0 to 20 ppm by weight.
  • the cellulose acetate having the above-mentioned predetermined average acetyl group substitution degree can be produced by a known method, and specifically can be synthesized with reference to the method described in JP-A-10-45804. In addition, you may use a commercial item as a cellulose acetate.
  • the cellulose acetate film as the protective film B preferably contains a retardation increasing agent.
  • the “retardation increasing agent” means an additive having a function of increasing the retardation of the cellulose acetate film by the addition thereof.
  • the retardation increasing agent for example, a compound represented by the following general formula (1) (hereinafter also referred to as “compound (I)”) may be mentioned.
  • compound (I) a compound represented by the following general formula (1)
  • the compound of the following general formula (1) can increase the retardation value in the thickness direction of the cellulose acetate film, and can also reduce the moisture permeability of the film.
  • the compound of the following general formula (1) has low volatility even under high temperature and high humidity. For this reason, the bleed resistance of the cellulose acetate film can be improved, and as a result, the sharpness of the image can be improved.
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom.
  • R 1 to R 4 may be the same or different from each other.
  • the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, and a chlorine atom are present.
  • a methyl group is preferable, and a methyl group is particularly preferable.
  • each X independently represents —O— or —O—C ( ⁇ O) —.
  • X represents —O—C ( ⁇ O) —
  • the ether oxygen (—O—) of —O—C ( ⁇ O) — is bonded to the phenyl skeleton in the general formula (1).
  • X is preferably —O—.
  • R 5 and R 6 each independently have the following definition.
  • R 5 and R 6 each independently represents a hydroxyl group, an ester group or an alkyl group which may be substituted with an optionally substituted aromatic group; or a glycidyl group .
  • R 5 and R 6 may each independently be substituted with a hydroxyl group, an ester group or an optionally substituted aromatic group. Represents an alkyl group; or an optionally substituted aromatic group.
  • the ester group capable of substituting the alkyl group is represented by the formula: —O—C ( ⁇ O) —R or —C ( ⁇ O) —O—R, wherein R is a straight chain having 1 to 8 carbon atoms.
  • R is a straight chain having 1 to 8 carbon atoms.
  • the alkyl group and aromatic group are as defined below.
  • the alkyl group as R 5 and R 6 is not particularly limited, but is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group.
  • the aromatic group may be an aryl group having 6 to 24 carbon atoms. More specifically, a phenyl group, p-tolyl group, naphthyl group, biphenyl group, fluorenyl group, anthryl group, pyrenyl group, azulenyl group, acenaphthylenyl group, terphenyl group, phenanthryl group and the like can be mentioned. Of these, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • the aromatic group may have a substituent.
  • the substituent capable of substituting the aromatic group is not particularly limited, and examples thereof include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, a methylphenyl group, and a phenylphenyl group. , Methylphenylphenyl group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group and the like.
  • the said substituent may be one, or may be two or more, and in the latter case, each substituent may be the same or different.
  • the aromatic group is a phenyl group, a methylphenyl group, or a methylphenylphenyl group. It is preferable that
  • R 5 and R 6 are preferably an alkyl group having a hydroxyl group and an ester group as a substituent, or a glycidyl group.
  • X is more preferably —O—.
  • the compounds described in JP 2011-140637 A and JP 2011-116912 A are included in the compound of the general formula (1).
  • some of the compounds described in JP-A-2006-45468 are also included in the compound of the general formula (1). More specifically, the following is mentioned as a more preferable example of the compound of General formula (1).
  • a compound is prescribed
  • the content of the compound of the general formula (1) is not particularly limited.
  • the content of the compound of the general formula (1) is, for example, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. .
  • the retardation function and tear strength of the protective film B can be improved.
  • the volatility under high temperature and high humidity is reduced, the bleed resistance of the protective film B, and hence the sharpness of the image can be improved.
  • the compound represented by the general formula (1) it may be added as a powder to the resin forming the protective film B. After dissolving in a solvent, the resin forming the protective film B is added. It may be added.
  • the protective film B according to the present invention preferably contains a compound (compound (II)) having a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle.
  • compound (II) is not particularly limited, and any compound having a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle may be used.
  • the compound in which the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocycle is connected to each other via a single bond or 2 or less atoms hereinafter also referred to as “additive N”. It is preferable that
  • the 5-membered or 6-membered aromatic ring is preferably a 6 ⁇ electron system. Since ⁇ / ⁇ interaction is strong in aromatic rings with a wide ⁇ conjugated system such as naphthalene ring (10 ⁇ ), benzoxazole ring (10 ⁇ ), anthracene ring (14 ⁇ ), etc., CH / ⁇ interaction between cellulose acetate and additive In addition, the ⁇ / ⁇ interaction between the additives becomes dominant, the compatibility with cellulose acetate deteriorates, the bleeding out easily occurs at the time of joining, and even when they are compatible, the cellulose Since the distance between the acetate and the additive is increased, the optical characteristics are likely to fluctuate.
  • aromatic rings examples include pyrrole ring, pyrazole ring, imidazole ring, triazole ring (1,2,3-triazole ring, 1,2,4-triazole ring), tetrazole ring, furan ring, oxazole ring, Examples include isoxazole ring, oxadiazole ring, isoxadiazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, isothiadiazole ring and the like.
  • an aromatic ring containing only a nitrogen atom as a hetero atom other than the carbon atom that forms the aromatic ring is preferable because of its excellent effect of suppressing fluctuations in optical properties.
  • the aromatic ring is preferably a pyrrole ring, a pyrazole ring, an imidazole ring, or a triazole ring (1,2,3-triazole ring, 1,2,4-triazole ring). More preferably, it is at least one selected from the group consisting of a ring and a triazole ring.
  • the dihedral angles of A and B and B and C are respectively preferably 0 ° to 45 °, more preferably 5 ° to 40 °, and more preferably 10 ° to 35 °. Is preferred.
  • the additive N is particularly preferably a compound having a structure represented by the following general formula (2).
  • a 1 , A 2 and B are each independently an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2- An ethenyl group), a cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocycle.
  • an aromatic hydrocarbon ring or an aromatic heterocycle is preferable.
  • the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A 1 , A 2 and B may have a substituent.
  • substituents include a halogen atom ( Fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl Groups (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl groups (vinyl group, allyl group, etc.), cycloalkenyl groups (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.) ), Alkynyl groups (ethynyl
  • a 1 , A 2 and B are benzene ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring (1,2,3-triazole ring, 1,2,4-triazole ring).
  • each of T 1 and T 2 independently represents a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring (1,2,3-triazole ring, 1,2,4-triazole ring). It is preferable to represent.
  • a pyrazole ring or a 1,2,4-triazole ring is preferable because a resin composition that is particularly excellent in the effect of suppressing fluctuations in optical properties and particularly excellent in durability can be obtained.
  • the pyrazole ring, imidazole ring or triazole ring (1,2,3-triazole ring, 1,2,4-triazole ring) represented by T 1 and T 2 may be a tautomer.
  • Specific structures of the pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring and 1,2,4-triazole ring are shown below.
  • R 8 represents a hydrogen atom or a non-aromatic substituent.
  • the non-aromatic substituent represented by R 8 include the same groups as the non-aromatic substituent among the substituents that A 1 in the general formula (2) may have.
  • R 8 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom.
  • T 1 and T 2 may have a substituent, and examples of the substituent include the substituent that A 1 and A 2 in the general formula (2) may have Similar groups can be mentioned.
  • L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent linking group, and are 5 or 6 via 2 or less atoms. Membered aromatic hydrocarbon rings or aromatic heterocycles are linked.
  • the term “via two or less atoms” refers to the minimum number of atoms existing between the connected substituents among the atoms constituting the linking group.
  • the divalent linking group having 2 or less linking atoms is not particularly limited, but includes an alkylene group, an alkenylene group, an alkynylene group, O, (C ⁇ O), NR, S, and (O ⁇ S ⁇ O). It is a divalent linking group selected from the group consisting of or a linking group in which two of them are combined.
  • R represents a hydrogen atom or a substituent.
  • substituent represented by R include an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group ( Cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), aromatic hydrocarbon ring group (phenyl group, p-tolyl group, naphthyl group, etc.), aromatic heterocyclic group (2-furyl group, 2-thienyl group, etc.) Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 2-pyridyl group, etc.), cyano group and the like.
  • the divalent linking group represented by L 1 , L 2 , L 3 and L 4 may have a substituent, and the substituent is not
  • L 1 , L 2 , L 3 and L 4 are CH / ⁇ mutual with the water-adsorbing resin by increasing the planarity of the compound represented by the general formula (2). Since the action becomes stronger and fluctuations in optical properties are suppressed, a single bond or O, (C ⁇ O) —O, O— (C ⁇ O), (C ⁇ O) —NR or NR— (C ⁇ O), and more preferably a single bond.
  • n represents an integer of 0 to 5.
  • the plurality of A 2 , T 2 , L 3 and L 4 in the general formula (2) may be the same or different.
  • n is larger, the CH / ⁇ interaction between the compound represented by the general formula (2) and cellulose acetate becomes stronger, so that the effect of suppressing fluctuations in optical properties is more excellent. Excellent compatibility.
  • n is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
  • the compound represented by the general formula (2) is preferably a compound represented by the following general formula (3).
  • a 1 , A 2 , T 1 , T 2 , L 1 , L 2 , L 3 and L 4 are respectively A 1 , A 2 , T 1 , T in the general formula (2).
  • a 3 and T 3 represent the same groups as A 1 and T 1 in the general formula (2), respectively.
  • L 5 and L 6 represent the same group as L 1 in the general formula (2).
  • m represents an integer of 0 to 4.
  • m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.
  • the compound having a structure represented by the general formula (2) is preferably a triazole compound having a structure represented by the following general formula (2.1).
  • a 1, B, L 1 and L 2 represents A 1, B, the same group as L 1 and L 2 in formula (2).
  • k represents an integer of 1 to 4.
  • T 1 represents a 1,2,4-triazole ring.
  • the triazole compound having a structure represented by the general formula (2.1) is preferably a triazole compound having a structure represented by the following general formula (2.2).
  • Z represents the structure of the following general formula (2.2a).
  • q represents an integer of 2 to 3. At least two Z are bonded to the ortho position or the meta position with respect to at least one Z substituted on the benzene ring.
  • R 10 represents a hydrogen atom, an alkyl group or an alkoxy group.
  • p represents an integer of 1 to 5. * Represents a bonding position with a benzene ring.
  • T 1 represents a 1,2,4-triazole ring.
  • the compound represented by the general formula (2), (3), (2.1) or (2.2) may form a hydrate, a solvate or a salt.
  • the hydrate may contain an organic solvent
  • the solvate may contain water. That is, “hydrate” and “solvate” include mixed solvates containing both water and organic solvents.
  • Salts include acid addition salts formed with inorganic or organic acids. Examples of inorganic acids include, but are not limited to, hydrohalic acids (hydrochloric acid, hydrobromic acid, etc.), sulfuric acid, phosphoric acid, and the like.
  • organic acids examples include acetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, citric acid, benzoic acid, alkylsulfonic acid (methanesulfonic acid, etc.), allylsulfonic acid (benzenesulfonic acid, 4-toluene) Sulfonic acid, 1,5-naphthalenedisulfonic acid, and the like), but are not limited thereto.
  • hydrochloride, acetate, propionate and butyrate are preferable.
  • salts are those in which the acidic moiety present in the parent compound is a metal ion (eg, an alkali metal salt, such as sodium or potassium salt, an alkaline earth metal salt, such as calcium or magnesium salt, an ammonium salt, an alkali metal ion, alkaline earth And salts formed when substituted with organic bases (ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.) It is not limited. Of these, sodium salts and potassium salts are preferred.
  • a metal ion eg, an alkali metal salt, such as sodium or potassium salt, an alkaline earth metal salt, such as calcium or magnesium salt, an ammonium salt, an alkali metal ion, alkaline earth
  • organic bases ethanolamine, diethanolamine, triethanolamine, morpholine, piperidine, etc.
  • sodium salts and potassium salts are preferred.
  • Examples of the solvent contained in the solvate include any common organic solvent. Specifically, alcohol (eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol), ester (eg, ethyl acetate), hydrocarbon (eg, toluene, hexane) , Heptane), ether (eg, tetrahydrofuran), nitrile (eg, acetonitrile), ketone (acetone) and the like.
  • alcohol eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol
  • ester eg, ethyl acetate
  • hydrocarbon eg, toluene, hexane
  • Heptane Heptane
  • ether eg, tetrahydrofuran
  • nitrile
  • solvates of alcohols eg, methanol, ethanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, t-butanol.
  • solvents may be a reaction solvent used in the synthesis of the compound, a solvent used in crystallization purification after synthesis, or a mixture thereof.
  • two or more kinds of solvents may be included at the same time, or a form containing water and a solvent (for example, water and alcohol (for example, methanol, ethanol, t-butanol, etc.), etc.).
  • a solvent for example, water and alcohol (for example, methanol, ethanol, t-butanol, etc.), etc.).
  • the molecular weight of the compound represented by the general formula (2), (3), (2.1) or (2.2) is not particularly limited. However, the smaller the molecular weight, the better the compatibility with the resin, and the larger the environmental weight. In view of the high effect of suppressing the fluctuation of the optical value with respect to the change, the value is preferably 150 to 2000, more preferably 200 to 1500, and more preferably 300 to 1000.
  • the content of the compound (compound (II)) having a 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not particularly limited, and the amount is appropriately adjusted. It can be contained in the protective film B.
  • the content of the compound (II) is, for example, preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. With such an amount, the retardation function and tear strength of the protective film B can be improved. Further, since the volatility under high temperature and high humidity is reduced, the bleed resistance of the protective film B, and hence the sharpness of the image can be improved.
  • the compound (II) may be added in powder form to the resin forming the protective film B, or may be added to the resin forming the protective film B after being dissolved in a solvent.
  • the cellulose acetate film as the protective film B may contain a plasticizer in order to improve the fluidity of the composition during film production and the flexibility and workability of the film.
  • plasticizers include sugar ester plasticizers, polyester plasticizers, polyhydric alcohol ester plasticizers, acrylic compounds, polycarboxylic acid ester plasticizers (including phthalate ester plasticizers), glycosates.
  • rate plasticizers ester plasticizers (including citrate ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, trimellitic ester plasticizers, etc.), styrene compounds, and the like.
  • plasticizers it is effective for moisture permeability to include at least one plasticizer selected from the group consisting of the following sugar ester plasticizers (sugar ester compounds), polyester plasticizers, and acrylic compounds. This is preferable from the viewpoint of achieving both high control and compatibility with cellulose acetate. These may be used alone or in combination of two or more.
  • the molecular weight of the plasticizer is preferably 5000 or less, and more preferably 3000 or less from the viewpoint of achieving both improvement in wet heat resistance and compatibility with cellulose acetate.
  • the weight average molecular weight (Mw) is preferably 3000 or less.
  • a preferable molecular weight (Mw) is in the range of 100 to 2500, and more preferably in the range of 300 to 2000.
  • Sugar ester plasticizer is a compound having 1 to 12 furanose structures or pyranose structures, in which all or part of the hydroxy groups in the compound are esterified.
  • the sugar ester plasticizer can be added for the purpose of preventing hydrolysis.
  • sugar as a raw material for synthesizing the sugar ester compound according to the present invention examples include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, and the like.
  • the monocarboxylic acid used for esterifying all or part of the OH group in the pyranose structure or furanose structure is not particularly limited, and is a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic A monocarboxylic acid or the like can be used.
  • the carboxylic acid used may be one type or a mixture of two or more types.
  • Examples of preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid and the like.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include aromatic monocarboxylic acids having 1 to 5 alkyl groups or alkoxy groups introduced into the benzene ring of benzoic acid such as benzoic acid, phenylacetic acid, toluic acid, cinnamic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as benzylic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralincarboxylic acid, or derivatives thereof, and benzoic acid is particularly preferable.
  • sugar esters represented by the following general formula (FA).
  • R 1 to R 8 in formula (FA) each independently represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • R 1 to R 8 may be the same as or different from each other.
  • the substituted or unsubstituted alkylcarbonyl group is preferably a substituted or unsubstituted alkylcarbonyl group having 2 or more carbon atoms.
  • Examples of the substituted or unsubstituted alkylcarbonyl group include a methylcarbonyl group (acetyl group).
  • the substituted or unsubstituted arylcarbonyl group is preferably a substituted or unsubstituted arylcarbonyl group having 7 or more carbon atoms.
  • the arylcarbonyl group include a phenylcarbonyl group.
  • the substituent that the aromatic hydrocarbon ring group has include an alkyl group such as a methyl group, an alkoxyl group such as a methoxy group, and the like.
  • the compound represented by the general formula (FA) preferably has an average degree of substitution of 3.0 to 8.0, more preferably 4.0 to 7.5, and even more preferably 4.5 to 7.0. By taking this value, the moisture permeability control and the compatibility with cellulose acetate can be highly compatible.
  • the degree of substitution of the compound represented by the general formula (FA) represents the number substituted with a substituent other than hydrogen among the eight hydroxyl groups contained in the general formula (FA).
  • this represents a number containing a group other than hydrogen. Accordingly, when all of R 1 to R 8 are substituted with a substituent other than hydrogen, the degree of substitution is 8.0, which is the maximum value, and when R 1 to R 8 are all hydrogen atoms, 0.0 It becomes.
  • the compound having the structure represented by the general formula (FA) is difficult to synthesize a single kind of compound in which the number of hydroxyl groups and the number of OR groups are fixed. Since it is known that it becomes a compound in which several different components are mixed, it is appropriate to use the average substitution degree as the substitution degree of the general formula (FA) in the present invention.
  • the average substitution degree can be measured from the area ratio of the chart showing the substitution degree distribution.
  • R 1 to R 8 represent a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R 1 to R 8 may be the same or different.
  • R 1 to R 8 are also referred to as acyl groups).
  • Specific examples of R 1 to R 8 include acyl groups derived from monocarboxylic acids used during the synthesis of the sugar ester compounds exemplified above.
  • sugar ester compound according to the present invention any of R 1 to R 8 may be the same substituent R, and the present invention is not limited thereto.
  • polyester compounds are defined by the following symbols.
  • sugar ester compounds in which R 1 to R 8 are different groups can be used.
  • the sugar ester compound according to the present invention can be produced by reacting the sugar with an acylating agent (also referred to as an esterifying agent, for example, an acid halide such as acetyl chloride, an anhydride such as acetic anhydride).
  • an acylating agent also referred to as an esterifying agent, for example, an acid halide such as acetyl chloride, an anhydride such as acetic anhydride.
  • the distribution of the degree of substitution is made by adjusting the amount of acylating agent, the timing of addition, and the esterification reaction time, but it is a mixture of sugar ester compounds with different degrees of substitution or purely isolated compounds with different degrees of substitution. Can be used to adjust components having a target average substitution degree and a substitution degree of 4 or less.
  • sugar esters examples include compounds described in JP-A Nos. 62-42996 and 10-237084.
  • the polyester plasticizer is not particularly limited.
  • a polymer in which the terminal hydroxy group of the polyester polyol is sealed with a monocarboxylic acid (end-capped polyester) can be used.
  • the ester-forming derivative referred to here is an esterified product of dicarboxylic acid, dicarboxylic acid chloride, or dicarboxylic acid anhydride.
  • a polyester plasticizer represented by the following general formula (FB-1) from the viewpoint of highly compatible moisture permeability control and compatibility with cellulose acetate.
  • B represents a linear or branched alkylene group having 2 to 6 carbon atoms or a cycloalkylene group
  • A represents an aromatic ring group having 6 to 14 carbon atoms, or 4 to 12 carbon atoms.
  • N represents a natural number of 1 or more.
  • the compound represented by the above formula is obtained from a dicarboxylic acid having an aromatic ring (also referred to as an aromatic dicarboxylic acid) and a linear or branched alkylene or cycloalkylene diol having 2 to 6 carbon atoms, at both ends. Is not sealed with a monocarboxylic acid.
  • aromatic dicarboxylic acid having 6 to 16 carbon atoms examples include phthalic acid, isophthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and the like. Of these, phthalic acid and terephthalic acid are preferred.
  • aromatic dicarboxylic acid having 4 to 12 carbon atoms examples include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid), 1,4-butanedicarboxylic acid (adipic acid), Examples include 1,5-pentanedicarboxylic acid (pimelic acid) and 1,8-octanedicarboxylic acid (sebacic acid), and adipic acid and succinic acid are particularly preferable.
  • the dicarboxylic acid is mixed with an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid.
  • linear or branched alkylene or cycloalkylene diol having 2 to 6 carbon atoms examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butane.
  • diol and 1,4-cyclohexanedimethanol examples include diol and 1,4-cyclohexanedimethanol. Of these, ethanediol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol are preferable.
  • A is a naphthalene ring or a biphenyl ring which may have a substituent.
  • the substituent is an alkyl group, alkenyl group, or alkoxyl group having 1 to 6 carbon atoms.
  • the hydroxyl value (OH value) of the polyester compound is preferably 100 mgKOH / g or more and 500 mgKOH / g or less, more preferably 170 mgKOH / g to 400 mgKOH / g. When the hydroxyl value is within this range, the compatibility with cellulose acetate is suitable.
  • the hydroxyl value is 400 mgKOH / g or less, the hydrophobicity of the polyester compound does not increase too much, and when the hydroxyl value is 170 mgKOH / g or more, the intermolecular interaction (hydrogen bond, etc.) between the polyester compounds is excessively strong. It is thought that this is because precipitation in the film can be prevented.
  • the number average molecular weight (Mn) of the polyester compound can be calculated from the following formula.
  • a preferred number average molecular weight of the polyester compound is 300 to 2,000.
  • the polyester compound can be obtained by a conventional method such as a hot melt condensation method using a polyesterification reaction or a transesterification reaction between the dicarboxylic acid and a diol, or an interfacial condensation method between an acid chloride of these acids and a glycol. Easy to synthesize.
  • a polyester plasticizer represented by the following general formula (FB-2) from the viewpoint of highly compatible moisture permeability control and compatibility with cellulose acetate.
  • B represents a hydroxy group or a carboxylic acid residue
  • G represents an alkylene glycol residue having 2 to 18 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or 4 carbon atoms.
  • A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms
  • n represents an integer of 1 or more.
  • a hydroxy group or carboxylic acid residue represented by B an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue represented by G, and an alkylene dicarboxylic acid residue represented by A It is composed of a group or an aryl dicarboxylic acid residue, and can be obtained by a reaction similar to that of a normal ester compound.
  • Examples of the carboxylic acid component of the polyester compound represented by the general formula (FB-2) include acetic acid, propionic acid, butyric acid, benzoic acid, p-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, and dimethyl.
  • acetic acid propionic acid
  • butyric acid butyric acid
  • benzoic acid p-tert-butylbenzoic acid
  • orthotoluic acid metatoluic acid
  • p-toluic acid and dimethyl.
  • benzoic acid ethyl benzoic acid
  • normal propyl benzoic acid aminobenzoic acid
  • acetoxybenzoic acid aliphatic acid and the like
  • Examples of the alkylene glycol component having 2 to 18 carbon atoms of the polyester compound represented by the general formula (FB-2) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,2-butanediol.
  • alkylene glycols having 2 to 12 carbon atoms are particularly preferred because of their excellent compatibility with cellulose acetate. More preferred are alkylene glycols having 2 to 6 carbon atoms, and still more preferred are alkylene glycols having 2 to 4 carbon atoms.
  • Examples of the aryl glycol having 6 to 12 carbon atoms of the polyester plasticizer represented by the general formula (FB-2) include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, cyclohexanediethanol, 1,4 -There are cyclic glycols such as benzenedimethanol, and these glycols can be used as one kind or a mixture of two or more kinds.
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the polyester compound represented by the general formula (FB-2) include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. These glycols can be used as one kind or a mixture of two or more kinds.
  • Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the polyester compound represented by the general formula (FB-2) include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. , Dodecanedicarboxylic acid and the like, and these are used as one kind or a mixture of two or more kinds, respectively.
  • Examples of the aryl dicarboxylic acid component having 6 to 12 carbon atoms of the polyester compound represented by the general formula (FB-2) include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, and 1,4-naphthalene. There are dicarboxylic acids and the like.
  • the polyester compound represented by the general formula (FB-2) has a weight average molecular weight of preferably 300 to 3000, more preferably 350 to 1500.
  • the acid value is 0.5 mgKOH / g or less
  • the hydroxy group (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less
  • the hydroxy group (hydroxyl group) value is 15 mgKOH / g or less. Is.
  • the weight average molecular weight of the polyester plasticizer is calculated by measurement using gel permeation chromatography (GPC) under the following measurement conditions.
  • polyester compounds are defined by the following symbols.
  • the viscosity of the polyester plasticizer depends on the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, it has a high compatibility with cellulose acetate and has a high effect of imparting plasticity. It is preferably in the range of s (25 ° C.).
  • One type of polyester plasticizer may be used, or two or more types may be used in combination.
  • the polyhydric alcohol ester plasticizer is an ester compound (alcohol ester) of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, preferably a divalent to 20-valent aliphatic polyhydric alcohol ester.
  • the polyhydric alcohol ester compound preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • polyhydric alcohol ester plasticizer examples include trimethylolpropane triacetate, trimethylolpropane benzoate, pentaerythritol tetraacetate, and an ester represented by the general formula (I) described in JP-A-2008-88292. Compound (A) and the like are included.
  • the polyvalent carboxylic acid ester plasticizer is an ester compound of a divalent or higher, preferably 2 to 20 valent polycarboxylic acid and an alcohol compound.
  • the polyvalent carboxylic acid is preferably a 2-20 valent aliphatic polyvalent carboxylic acid, a 3-20 valent aromatic polyvalent carboxylic acid, or a 3-20 valent alicyclic polyvalent carboxylic acid.
  • polyvalent carboxylic acids include trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof; succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid Contains aliphatic polycarboxylic acids such as fumaric acid, maleic acid and tetrahydrophthalic acid; oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid and citric acid, etc., and suppresses volatilization from the film. For this, oxypolycarboxylic acids are preferred.
  • the alcohol compound examples include an aliphatic saturated alcohol compound having a straight chain or a side chain, an aliphatic unsaturated alcohol compound having a straight chain or a side chain, an alicyclic alcohol compound, or an aromatic alcohol compound.
  • the carbon number of the aliphatic saturated alcohol compound or the aliphatic unsaturated alcohol compound is preferably 1 to 32, more preferably 1 to 20, and still more preferably 1 to 10.
  • Examples of the alicyclic alcohol compound include cyclopentanol, cyclohexanol and the like.
  • the aromatic alcohol compound include phenol, paracresol, dimethylphenol, benzyl alcohol, cinnamyl alcohol and the like.
  • the alcohol compound may be one kind or a mixture of two or more kinds.
  • the molecular weight of the polyvalent carboxylic acid ester plasticizer is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. A larger molecular weight of the polyvalent carboxylic acid ester plasticizer is preferable from the viewpoint of suppressing bleeding out. From the viewpoint of moisture permeability and compatibility with cellulose acetate, a smaller one is preferable.
  • Examples of the polyvalent carboxylic acid ester plasticizer include an ester compound (B) represented by the general formula (II) described in JP-A-2008-88292.
  • the polycarboxylic acid ester plasticizer may be a phthalate ester plasticizer.
  • the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate and the like.
  • glycolate plasticizers include alkylphthalyl alkyl glycolates.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate and the like. .
  • the ester plasticizer includes a fatty acid ester plasticizer, a citrate ester plasticizer, a phosphate ester plasticizer, a trimellitic acid plasticizer, and the like.
  • Examples of the fatty acid ester plasticizer include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate and the like.
  • Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate and the like.
  • Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate (BDP), trioctyl phosphate, tributyl phosphate and the like.
  • trimellitic acid plasticizers include octyl trimellitic acid, n-octyl trimellitic acid, isodecyl trimellitic acid, and isononyl trimellitic acid.
  • the content of the plasticizer is not particularly limited, but is preferably in the range of 0.1 to 30% by mass with respect to 100% by mass of cellulose acetate contained in the protective film B (cellulose acetate film). More preferably, it is in the range of ⁇ 20% by mass. With such an amount, the cellulose acetate film is less likely to bleed out.
  • the protective film B according to the present invention may further contain other additives, if necessary, instead of the plasticizer or in addition to the plasticizer.
  • additives include, but are not limited to, hydrogen bonding compounds, activators, antioxidants, colorants, ultraviolet absorbers, matting agents, acrylic particles, hydrogen bonding solvents, ionic interfaces. An active agent etc. are mentioned.
  • the hydrogen bonding compound can reduce the fluctuation of the retardation value Rt with respect to the change in humidity.
  • the hydrogen bonding compound preferably has at least a plurality of functional groups selected from a hydroxy group, an amino group, a thiol group, and a carboxylic acid group in one molecule, and a plurality of different functional groups in one molecule. It is more preferable to have a hydroxy group and a carboxylic acid group in one molecule.
  • the hydrogen bonding compound preferably contains 1 to 2 aromatic rings as a mother nucleus, and the value obtained by dividing the number of functional groups contained in one molecule by the molecular weight of the compound is 0.00. It is preferably 01 or more.
  • the above effect is such that the hydrogen-bonding compound is bonded (hydrogen bond) to a site where the cellulose acetate and water molecules interact (hydrogen bonds), thereby suppressing the change in charge distribution due to desorption of water molecules. For the reason.
  • the hydrogen bonding compound can be added in the range of 1 to 30 parts by mass with respect to 100 parts by mass of cellulose acetate.
  • the protective film B according to the present invention preferably also contains an ultraviolet absorber for the purpose of imparting an ultraviolet absorbing function. It does not specifically limit as an ultraviolet absorber, What was mentioned above as what can be contained in the protective film A can be used similarly.
  • the amount of the UV absorber used in the cellulose acetate film as the protective film B is not uniform depending on the type of UV absorber, usage conditions, etc., but generally it is preferably 0.05 with respect to 100% by mass of cellulose acetate. It is added in a range of ⁇ 10% by mass, more preferably 0.1 to 5% by mass.
  • the matting agent is fine particles imparting slipperiness of the film, and may be either an inorganic compound or an organic compound as long as it does not impair the transparency of the resulting film and has heat resistance during melting. These matting agents can be used alone or in combination of two or more. By using particles having different particle sizes and shapes (for example, acicular and spherical), both transparency and slipperiness can be made highly compatible. Among these, silicon dioxide, which is excellent in transparency (haze), is particularly preferably used because it has a refractive index close to that of the acrylic copolymer or cellulose acetate used as a compatible resin.
  • silicon dioxide examples include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP- 30, Seahoster KEP-50 (above, manufactured by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (manufactured by Fuji Silysia), Nip Seal E220A (manufactured by Nippon Silica Industry), Admafine SO (manufactured by Admatechs) Goods etc. can be preferably used.
  • the shape of the particles can be used without particular limitation, such as indefinite shape, needle shape, flat shape, spherical shape, etc. However, the use of spherical particles is preferable because the transparency of the resulting film can be improved.
  • the particle size is preferably smaller than the wavelength of visible light, and more preferably 1 ⁇ 2 or less of the wavelength of visible light. . If the size of the particles is too small, the slipperiness may not be improved, so the range of 80 nm to 180 nm is particularly preferable.
  • the particle size means the size of the aggregate when the particle is an aggregate of primary particles. Moreover, when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.
  • the matting agent is added in an amount of 0.05 to 10% by mass, preferably 0.1 to 5% by mass with respect to the resin (cellulose acetate).
  • Protective film B according to the present invention may contain, for example, acrylic particles described in International Publication No. 2010/001668 in an amount within a range where transparency can be maintained.
  • the acrylic particles have an action of improving the brittleness of the film.
  • the thickness of the protective film B is not particularly limited, but is preferably 12 to 60 ⁇ m, more preferably 15 to 40 ⁇ m, and most preferably 15 to 30 ⁇ m.
  • the thickness of the protective film B is 12 ⁇ m or more, it is preferable from the viewpoint that there is no variation in the retardation value and unevenness of the display device and light leakage is less likely to occur, while the thickness of the protective film B is 60 ⁇ m or less. It is preferable from the viewpoint that the panel is hardly warped.
  • a haze value (turbidity) is used as an index for judging the transparency of the cellulose acetate film.
  • the haze value is preferably 0.6% or less, and is 0.4% or less. Is more preferably 0.3 or less, and most preferably 0.2 or less.
  • the haze value may exceed the above range.
  • the internal haze of the film is preferably 0.01 to 0.1, more preferably 0.02 to 0.06.
  • the cellulose acetate film as the protective film B according to the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%.
  • the haze value and transmittance can be measured using a haze meter.
  • a film satisfying the above physical properties can be preferably used as a polarizing plate protective film for a large-sized liquid crystal display device or a liquid crystal display device for outdoor use.
  • the retardation value in the cellulose acetate film as the protective film B is not particularly limited, but the in-plane retardation value Ro defined by the following formulas (i) and (ii) is in the range of 30 to 70 nm,
  • the retardation value Rt in the thickness direction is preferably in the range of 95 to 140 nm from the viewpoint of improving contrast and viewing angle when mounted on a VA display device.
  • the retardation value Ro in the in-plane direction is in the range of 45 to 60 nm and the retardation value Rt in the thickness direction is in the range of 110 to 135 nm
  • the contrast and field of view when mounted on the VA display device The corner is particularly improved and preferable.
  • n x a refractive index in the direction x in which the refractive index in the plane direction is maximized in the film.
  • n y in-plane direction of the film, the refractive index in the direction y perpendicular to the direction x.
  • nz represents the refractive index in the thickness direction z of the film.
  • d represents the thickness (nm) of the film. The measurement is performed at a measurement wavelength of 590 nm in an environment of 23 ° C. and 55% RH.
  • the film forming method is preferably a solution casting film forming method and a melt casting film forming method. More preferred for obtaining.
  • the cellulose acetate film is produced by dissolving cellulose acetate and a desired additive in a solvent to prepare a dope (dissolution process; dope preparation process), and moving the dope indefinitely.
  • FIG. 2 is a diagram schematically showing an example of a dope preparation step, a casting step, and a drying step (solvent evaporation step) of a solution casting film forming method preferable for the present invention.
  • the main dope is filtered by the main filter 3, and the additive solution is added in-line from 16 to this.
  • the main dope may contain about 10 to 50% by mass of the recycled material.
  • the return material is a product obtained by finely pulverizing a film, and is produced by forming a film by cutting off both sides of the film, or by using a film raw material that has been speculated out by scratches or the like.
  • a pellet obtained by pelletizing cellulose acetate and a desired additive in advance can be preferably used as a raw material for the resin used for preparing the dope.
  • Dissolution process This step is a step of forming a dope by dissolving the cellulose acetate and a desired additive in a dissolution vessel while stirring them in a solvent mainly composed of a good solvent for cellulose acetate.
  • the concentration of cellulose acetate in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose acetate is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration for achieving both of these is preferably 10 to 35% by mass, more preferably 15 to 22% by mass.
  • the solvent used in the dope may be used alone or in combination of two or more. However, it is preferable to use a mixture of a good solvent and a poor solvent of cellulose acetate in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of solubility of cellulose acetate.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • a good solvent and a poor solvent what dissolve
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2% by mass of water.
  • the solvent used for dissolving cellulose acetate the solvent removed from the film by drying in the film forming process is recovered and reused.
  • the recovery solvent may contain trace amounts of additives added to cellulose acetate, such as plasticizers, UV absorbers, polymers, monomer components, etc., but these are preferably reused even if they are included. Can be purified and reused if necessary.
  • a general method can be used as a method for dissolving cellulose acetate in preparing the dope described above. Specifically, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557, Various dissolution methods such as a method using a cooling dissolution method as described in Kaihei 9-95538 and a method using a high pressure as described in Japanese Patent Application Laid-Open No. 11-21379 can be used. Among them, a method of performing pressurization at a temperature equal to or higher than the boiling point of the main solvent is preferable.
  • a method in which cellulose acetate is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
  • the pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside.
  • a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of cellulose acetate, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C.
  • the pressure is adjusted so that the solvent does not boil at the set temperature.
  • a cooling dissolution method is also preferably used, whereby cellulose acetate can be dissolved in a solvent such as methyl acetate.
  • this cellulose acetate solution (dope during or after dissolution) is preferably filtered using a suitable filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.007 mm is more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
  • a bright spot foreign object is placed when two polarizing plates are placed in a crossed Nicol state, a film or the like is placed between them, light is applied from one polarizing plate, and the opposite is observed when observed from the other polarizing plate. It is a point (foreign matter) where light from the side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less. More preferably, it is 100 pieces / cm 2 or less, further preferably 50 pieces / m 2 or less, and further preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small and preferable.
  • a preferable temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and further preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the dope is cast on a metal support. That is, in this step, the dope is fed to the pressurizing die 30 through a liquid feed pump (for example, a pressurized metering gear pump) and transferred indefinitely, for example, an endless metal belt 31 such as a stainless steel belt or a rotating metal drum. The dope is cast from the pressure die slit to the casting position on the metal support.
  • a liquid feed pump for example, a pressurized metering gear pump
  • ⁇ Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred.
  • the pressure die include a coat hanger die and a T die, and any of them is preferably used.
  • the surface of the metal support is preferably a mirror surface.
  • two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.
  • the cast width is preferably 1.4 m or more from the viewpoint of productivity. More preferably, it is 1.4 to 4 m. When it exceeds 4 m, there is a risk of streaking in the manufacturing process or lowering of stability in the subsequent transport process. More preferably, it is 1.6 to 2.5 m in terms of transportability and productivity.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying rate can be increased. May deteriorate.
  • the preferred support temperature is 0 to 55 ° C, more preferably 25 to 50 ° C.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.
  • Solvent evaporation step This step is a step of evaporating the solvent by heating the web (the dope is cast on the casting support and the formed dope film is called the web) on the casting support. It is.
  • the drying efficiency is good and preferable.
  • a method of combining them is also preferably used.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.
  • peeling step Next, the web is peeled from the metal support. That is, this step is a step of peeling the web where the solvent is evaporated on the metal support at the peeling position. The peeled web is sent to the next process.
  • the temperature at the peeling position on the metal support is preferably within the range of ⁇ 50 to 40 ° C., more preferably within the range of 10 to 40 ° C., and within the range of 15 to 30 ° C. when the stainless steel belt is formed. Most preferably, it is ⁇ 30 to 10 ° C. when forming a drum.
  • the residual solvent amount of the web on the metal support at the time of peeling is appropriately adjusted depending on the strength of drying conditions, the length of the metal support, and the like.
  • the amount of residual solvent when peeling the web from the metal support is preferably controlled to 15 to 40% by mass, more preferably 20 to 35% by mass.
  • the amount of residual solvent is defined by the following formula.
  • M is the weight of a sample collected at any time during or after the production of the web or film
  • N is the weight after heating M at 115 ° C. for 1 hour.
  • the peeling tension when peeling the metal support and the film is preferably 300 N / m or less. More preferably, it is within the range of 196 to 245 N / m. However, when wrinkles easily occur during peeling, peeling with a tension of 190 N / m or less, preferably 100 to 190 N / m is preferred.
  • the web is peeled off from the metal support, and further dried, so that the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, particularly preferably. Is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
  • a drying device 35 that alternately conveys the web through rollers arranged in the drying device and / or a tenter stretching device 34 that clips and conveys both ends of the web with a clip, dry.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air in terms of simplicity. Too rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent. Throughout, the drying is generally carried out in the range of 40-250 ° C. It is particularly preferable to dry within the range of 40 to 200 ° C. The drying temperature is increased stepwise and is preferably heated to about 100 to 150 ° C., preferably 5 to 30 minutes, more preferably 6 to 12 minutes.
  • tenter stretching apparatus When using a tenter stretching apparatus, it is preferable to use an apparatus that can independently control the film gripping length (distance from the start of gripping to the end of gripping) left and right by the left and right gripping means of the tenter. In the tenter process, it is also preferable to intentionally create sections having different temperatures in order to improve planarity.
  • the web is preferably stretched in at least one direction from the metal support.
  • the orientation of molecules in the film can be controlled by the stretching treatment.
  • the control of the conveying tension is further performed. It is preferable to control the refractive index by a stretching operation. For example, the retardation value can be changed by lowering or increasing the tension in the longitudinal direction.
  • two axes are sequentially or simultaneously applied to the longitudinal direction (film forming direction; casting direction; MD direction) of the film and the direction orthogonal to the film plane, that is, the width direction (TD direction).
  • Stretching or uniaxial stretching can be performed.
  • it is a biaxially stretched film that is biaxially stretched in the casting direction (MD direction) and the width direction (TD direction), but the cellulose acetate film according to the present invention may be a uniaxially stretched film. And an unstretched film may be sufficient.
  • the stretching operation may be performed in multiple stages. When biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.
  • stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages.
  • stretching steps are possible: -Stretch in the casting direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction-Stretch in the width direction-> Stretch in the width direction-> Stretch in the casting direction-> Stretch in the casting direction.
  • Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
  • the draw ratios in the biaxial directions perpendicular to each other should ultimately be in the range of 0.01 to 2.0% in the casting direction (MD direction) and 10 to 50% in the width direction (TD direction), respectively.
  • the range is preferably 0.1 to 1.0% in the casting direction and 20 to 40% in the width direction.
  • the residual solvent amount at this time is preferably in the range of 15 to 40% so that the cellulose acetate film exhibits a predetermined toughness value.
  • the stretching temperature is usually preferably performed in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the stretching temperature is preferably from 120 ° C. to 200 ° C., more preferably from 130 ° C. to 200 ° C., and more preferably from 140 ° C. to 190 ° C. or less.
  • the amount of residual solvent in the film at the time of stretching is not particularly limited, but the amount of residual solvent at the time of stretching in the width direction is preferably 2 to 5% by mass.
  • the method of stretching the web For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction, the both ends of the web are fixed with clips and pins, and the interval between the clips and pins is increased in the traveling direction And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination. Among them, it is particularly preferable to perform stretching in the width direction (lateral direction) by a tenter method in which both ends of the web are gripped by clips or the like.
  • a tenter it may be a pin tenter or a clip tenter.
  • the slow axis or the fast axis of the cellulose acetate film according to the present invention exists in the film plane, and ⁇ 1 is ⁇ 1 ° or more and + 1 ° or less when the angle formed with the film forming direction in the entire film width and length is ⁇ 1. It is preferably ⁇ 0.5 ° or more and + 0.5 ° or less, more preferably ⁇ 0.2 ° or more and + 0.2 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • KOBRA-21ADH Oji Scientific Instruments
  • a cellulose acetate film is obtained by winding the obtained web (finished film). More specifically, it is a step of winding the film as a film by a winder 37 after the residual solvent amount in the web becomes 2% by mass or less, and the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less. A film having good properties can be obtained. In particular, it is preferable to wind in the range of 0.00 to 0.10% by mass.
  • a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.
  • the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking and scratching during winding.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. Note that the clip holding portions at both ends of the film are usually cut off because the film is deformed and cannot be used as a product. If the material has not deteriorated due to heat, it is reused after recovery.
  • the cellulose acetate film is preferably a long film.
  • the cellulose acetate film has a thickness of about 100 m to 10000 m, and is usually in the form of a roll.
  • the width of the film is preferably 1.4 to 4 m, more preferably 1.4 to 4 m, and more preferably 1.6 to 4 m in order to meet demands for an increase in the size of liquid crystal display devices and production efficiency. More preferably, it is ⁇ 3 m.
  • the cellulose acetate film laminate produced by the above method is preferably subjected to aging treatment for 3 days or more under conditions of 50 ° C. or higher after the outer peripheral portion is packaged.
  • aging treatment for 3 days or more under conditions of 50 ° C. or higher after the outer peripheral portion is packaged.
  • the polarizer which is the main component of the polarizing plate of the present invention, is an element that passes only light having a plane of polarization in a certain direction
  • a typical known polarizer is a polyvinyl alcohol polarizing film.
  • the polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
  • a polarizer obtained by forming a polyvinyl alcohol aqueous solution into a film and dyeing it by uniaxial stretching or dyeing and then uniaxially stretching and then preferably performing a durability treatment with a boron compound may be used.
  • the thickness of the polarizer is preferably 2 to 30 ⁇ m, more preferably 2 to 15 ⁇ m from the viewpoint of thin film suitability, and further preferably 3 to 10 ⁇ m from the viewpoint of further thin film suitability and handleability.
  • the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%
  • the degree of polymerization is 2000 to 4000
  • the degree of saponification is 99.0 to 99.99 mol%.
  • the ethylene-modified polyvinyl alcohol is also preferably used.
  • an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used.
  • a polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability, and has few color spots, and is particularly preferably used for a large-sized liquid crystal display device.
  • a coating-type polarizer is produced by the method described in JP2011-1000016, JP46991205, JP4751481, and JP4804589 and is bonded to the protective film according to the present invention. It is also preferable to produce a plate.
  • each of the protective film A and the protective film B demonstrated above and the polarizer are bonded by the ultraviolet curable adhesive.
  • the productivity is high and the durability of the polarizer is increased. Excellent properties can be obtained.
  • a photo radical polymerization composition using photo radical polymerization As the UV curable adhesive composition for polarizing plates, a photo radical polymerization composition using photo radical polymerization, a photo cation polymerization composition using photo cation polymerization, and photo radical polymerization and photo cation polymerization are used in combination. Hybrid type compositions are known.
  • the radical photopolymerizable composition includes a radically polymerizable compound containing a polar group such as a hydroxy group and a carboxy group described in JP-A-2008-009329 and a radically polymerizable compound not containing a polar group at a specific ratio.
  • Composition) and the like are known.
  • the radical polymerizable compound is preferably a compound having a radical polymerizable ethylenically unsaturated bond.
  • the compound having an ethylenically unsaturated bond capable of radical polymerization include a compound having a (meth) acryloyl group.
  • Examples of the compound having a (meth) acryloyl group include an N-substituted (meth) acrylamide compound and a (meth) acrylate compound.
  • (Meth) acrylamide means acrylamide or methacrylamide.
  • cationic photopolymerization type composition as disclosed in JP2011-08234A, ( ⁇ ) a cationic polymerizable compound, ( ⁇ ) a cationic photopolymerization initiator, and ( ⁇ ) a wavelength longer than 380 nm.
  • an ultraviolet curable adhesive composition containing each component of a photosensitizer exhibiting maximum absorption in the light of ( ⁇ ) and a naphthalene-based photosensitization aid.
  • other ultraviolet curable adhesives may be used.
  • a pre-processing process is a process of performing an easily bonding process to the adhesive surface of a cellulose-ester film with a polarizer.
  • an easy adhesion treatment is performed on the surface of each protective film that is bonded to the polarizer. Examples of the easy adhesion treatment include corona treatment and plasma treatment.
  • the ultraviolet curable adhesive is applied to at least one of the adhesive surfaces of the polarizer and the protective film.
  • the application method is not particularly limited. For example, various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
  • various wet coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
  • the method of pressurizing with a roll etc. and spreading it uniformly can also be utilized.
  • Bonding process After apply
  • this bonding step for example, when an ultraviolet curable adhesive is applied to the surface of the polarizer in the previous application step, a protective film is superimposed thereon.
  • a polarizer is superimposed thereon.
  • the ultraviolet curable adhesive is cast between the polarizer and the protective film, the polarizer and the protective film A are superposed in that state.
  • the protective film A and the protective film B are bonded to both surfaces of the polarizer, respectively, and both surfaces use an ultraviolet curable adhesive
  • the protective film is provided on both surfaces of the polarizer via an ultraviolet curable adhesive.
  • a and protective film B are overlaid.
  • both sides when the protective film A is superposed on one side of the polarizer, the protective film A and the protective film B are superposed on the polarizer side and the protective film A side, and on both sides of the polarizer.
  • the pressure is sandwiched between a pressure roller or the like from the protective film A and the protective film B side).
  • Metal, rubber, or the like can be used as the material of the pressure roller.
  • the pressure rollers arranged on both sides may be made of the same material or different materials.
  • an uncured ultraviolet curable adhesive is irradiated with ultraviolet rays, and a cationic polymerizable compound (for example, epoxy compound or oxetane compound) or a radical polymerizable compound (for example, acrylate compound, acrylamide compound, etc.)
  • a cationic polymerizable compound for example, epoxy compound or oxetane compound
  • a radical polymerizable compound for example, acrylate compound, acrylamide compound, etc.
  • ultraviolet rays are applied in a state where the protective film A and the protective film B are superimposed on the both surfaces of the polarizer via an ultraviolet curable adhesive, respectively. It is advantageous to irradiate and simultaneously cure the UV curable adhesive on both sides.
  • the ultraviolet irradiation conditions can be adopted as the ultraviolet irradiation conditions as long as the ultraviolet curable adhesive applied to the present invention can be cured.
  • the dose of ultraviolet is 50 ⁇ 1500mJ / cm 2 in accumulated light quantity, and even more preferably 100 ⁇ 500mJ / cm 2.
  • the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and further preferably 10 to 100 m / min. is there. If the line speed is 1 m / min or more, productivity can be ensured, or damage to the protective film A can be suppressed, and a polarizing plate having excellent durability can be produced. If the line speed is 500 m / min or less, the ultraviolet curable adhesive is sufficiently cured, and an ultraviolet curable adhesive layer having a desired hardness and excellent adhesiveness can be formed.
  • the polarizing plate according to the present invention can be used for various display devices, but is particularly preferably applied to a liquid crystal display device.
  • a TN (Twisted Nematic) method As a liquid crystal display device having the polarizing plate of the present invention, a TN (Twisted Nematic) method, a STN (Super Twisted Nematic) method, an IPS (In-Plane Switched) method, an OCB (Optically Compensated Birefringence Vrefringence Virgent Affinity A nt Virgentence V irencement V irencement V irencement V irencement V irencement V refrenceence method. It can be preferably used for MVA (including Multi-domain / Vertical / Alignment and PVA; Patterned / Vertical / Alignment), HAN (Hybrid Aligned / Nematic), and the like. In order to increase the contrast, the VA (MVA, PVA) method is preferable.
  • MVA Multi-domain / Vertical / Alignment and PVA; Patterned / Vertical / Alignment
  • HAN Hybri
  • ⁇ Resin composition Acrylic resin (filtered above) 80 parts by mass Acrylic rubber particles (average particle size: 200 ⁇ m) 20 parts by mass
  • the above resin composition was melt-kneaded at 200 ° C. with a twin screw extruder, Extruded into a strand.
  • the resin composition extruded in a strand form was cooled with water and then cut to obtain pellets.
  • the obtained pellets were dried by circulating dehumidified air at a temperature of 70 ° C. for 5 hours or more, and then put into a single screw extruder while maintaining the temperature at 100 ° C.
  • the moisture content of the pellets charged into the single screw extruder was 120 ppm.
  • a film was produced using a melt casting film production apparatus. Specifically, after the above-obtained pellet was melt-kneaded at 200 ° C. with a single screw extruder, it was extruded from a casting die onto a cooling roller having a surface temperature of 90 ° C. And after pressing the resin extruded by the cooling roller with the elastic touch roller whose thickness of the metal layer of a surface is 2 mm, it cooled further with the cooling roller and the cooling roller, and obtained the web of thickness 60 micrometers.
  • protective film A-1 an acrylic resin film having a thickness of 60 ⁇ m, which was designated as protective film A-1.
  • the web was made to have a thickness of 81 ⁇ m, and the cooled and solidified web was peeled off with a peeling roller, and then 175 ° C. in the web transport direction (MD direction) with a roller-type stretching device. And it extended
  • the obtained film was introduced into a tenter stretching machine having a preheating zone, a stretching zone, a holding zone, and a cooling zone, and further having a neutral zone between each zone. And it extended
  • protective film A-2 an acrylic resin film having a thickness of 60 ⁇ m, which was designated as protective film A-2.
  • the protective film A-2 was manufactured except that the acrylic resin (Technoloy S001) was filtered using five stainless steel sintered filters having a 7-inch size and a filtration accuracy of 25 ⁇ m.
  • An acrylic resin film was obtained in the same manner as in the preparation of -2, and was designated as protective film A-3.
  • protective films A-4 to A-12 In the production of the protective film A-2, the protective film A-2 was prepared except that the stretch ratio in the web conveyance direction (MD direction), the stretch ratio in the width direction (TD direction), and the film thickness were changed as shown in Table 1. Acrylic resin films A-4 to A-12 were produced in the same manner as in the production.
  • a polymer of stearyl phosphate / distearyl phosphate mixture (“Phoslex A-18” manufactured by Sakai Chemical Co., Ltd.) in an amount of 0.005 g with respect to 1 g of the polymer (1a) in the polymer solution obtained as described above.
  • a cyclization condensation reaction was performed under reflux (about 80 to 100 ° C.) for 5 hours while introducing nitrogen.
  • the lactone ring containing acrylic resin of the shape of a transparent pellet was obtained by performing and extruding.
  • the polycondensate is filtered using five stainless steel sintered filters with a 12-inch size and a filtration accuracy of 25 ⁇ m, extruded into a strand from a nozzle, and filtered in advance (pore size). 1 ⁇ m or less) was cooled and solidified, and cut into pellets (the obtained one is also referred to as “PET (A)”).
  • PET (B) 10 parts by weight of dried UV absorber (2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), 90 parts by weight of PET (A) containing no particles And a polyethylene terephthalate resin (B) containing an ultraviolet absorber was obtained using a kneading extruder (the obtained one is also referred to as “PET (B)”).
  • a transesterification reaction and a polycondensation reaction were carried out by a conventional method, and as a dicarboxylic acid component (based on the total dicarboxylic acid component) 46 mol% terephthalic acid, 46 mol% isophthalic acid and 8 mol% sodium 5-sulfonatoisophthalate, A water-dispersible sulfonic acid metal base-containing copolymer polyester resin having a composition of 50 mol% ethylene glycol and 50 mol% neopentyl glycol as a glycol component (based on the entire glycol component) was prepared.
  • PET (A) resin pellets containing no particles and 10 parts by weight of PET (B) resin pellets containing an ultraviolet absorber were dried under reduced pressure (1 Torr) at 135 ° C. for 6 hours, and then an extruder (for intermediate layer)
  • PET (A) was dried by a conventional method and supplied to an extruder (for both outer layers) and dissolved at 285 ° C.
  • These two types of polymers were each filtered twice with a filter medium made of a sintered stainless steel (nominal filtration accuracy of 10 ⁇ m particles, 95% cut), laminated in a two-type, three-layer confluence block, and extruded into a sheet form from the die.
  • the film was wound around a casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method, and solidified by cooling to obtain an unstretched film.
  • the discharge amount of each extruder was adjusted so that the thickness ratio of each layer was 10 (outer layer): 80 (intermediate layer): 10 (outer layer).
  • the unstretched film on which this coating layer was formed was preheated to 145 ° C. using a heated roll group and an infrared heater, and then stretched 3 times in the running direction (MD direction) with a roll group having a difference in peripheral speed. Thereafter, the film was guided to a tenter stretching machine, guided to a hot air zone having a temperature of 135 ° C. while gripping the end of the film with a clip, and stretched 2.5 times in the width direction (TD direction). In this way, a biaxially oriented PET film having a thickness of 70 ⁇ m was obtained, and designated as protective film A-15.
  • the monomer composition in the obtained polycondensation reaction product (polyester resin) is as follows.
  • the obtained dope was uniformly cast on a stainless band support using a belt casting apparatus under the conditions of a dope liquid temperature of 35 ° C. and a width of 1.95 m.
  • membrane was evaporated until the amount of residual solvents became 30 mass%, and the web was formed, Then, the web was peeled from the stainless steel band support body.
  • the obtained web was further dried at 35 ° C. and then slit to have a width of 1.90 m. Thereafter, the web was stretched 1.3 times in the TD direction (the width direction of the film) using a tenter under the condition of 160 ° C.
  • the residual solvent amount of the web at the start of stretching in the TD direction was 3% by mass.
  • the obtained film was dried at 120 ° C. for 15 minutes while being conveyed by a number of rolls in the drying apparatus, and then slit to 1.6 m width to obtain a cellulose acetate film.
  • the end was knurled.
  • the long cellulose acetate film of width 1.6m, length 6000m, and thickness 40micrometer obtained in this way was wound up in the length direction, and the laminated roll body 1 of the cellulose acetate film was obtained. .
  • protective films B-2 to B-25 In the production of the protective film B-1, the same as the protective film B-1, except that the degree of substitution of cellulose acetate, the type of retardation increasing agent, the type of plasticizer, and the stretching ratio in the TD direction were changed as shown in Table 2.
  • Protective films B-2 to B-25 were produced by the method described above.
  • the raising agents 2 to 12 listed in Table 2 are the following compounds.
  • UV curable adhesive liquid 2 alicyclic epoxy compound
  • 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid (4- (4)) was used instead of 10.0 g of triglycidyl ether of trimethylolpropane.
  • Methyl-7-oxabicyclo [4.1.0] heptan-3-yl) methyl except that 10.0 g was used. 2 was prepared.
  • UV curable adhesive solution 3 (Preparation of UV curable adhesive solution 3: combined use of aliphatic and alicyclic epoxy compounds)
  • UV curable adhesive solution 1 5.0 g of triglycidyl ether of trimethylolpropane and 4-methyl-7-oxabicyclo [4.1.0] were used instead of 10.0 g of triglycidyl ether of trimethylolpropane.
  • An ultraviolet curable adhesive liquid 3 was prepared in the same manner as in the above.
  • UV-curable adhesive solution 4 radical polymerizable compound
  • Hydroxyethyl acrylamide manufactured by Kojin Co., Ltd.
  • Aronix M-220 tripropylene glycol diacrylate, manufactured by Toagosei Co., Ltd.
  • acryloylmorpholine manufactured by Kojin Co., Ltd.
  • photopolymerization initiator KAYACUREDETX-S diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.
  • IRGACURE907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 (ON, manufactured by BASF) 1.4 g was measured, mixed and defoamed to prepare an ultraviolet curable adhesive liquid 4 comprising a curable resin composition containing a radical polymerizable compound.
  • adhesive solution 5 polyvinyl alcohol aqueous solution
  • a 2.5% by mass aqueous solution of polyvinyl alcohol was prepared and used as an adhesive solution 5.
  • the protective film B-16 produced above was used as the protective film B (105), and the surface thereof was subjected to corona discharge treatment.
  • the corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min.
  • the UV curable adhesive liquid 1 prepared above is applied to the corona discharge-treated surface of the protective film B (105) with a bar coater so that the film thickness after curing is about 3 ⁇ m.
  • a resin layer (103B) was formed.
  • the polyvinyl alcohol-iodine polarizer (104, thickness 10 ⁇ m) produced above was bonded to the obtained photocurable resin layer (103B).
  • the protective film A-1 (acrylic resin film) prepared above was used as the protective film A (102), and the surface thereof was subjected to corona discharge treatment.
  • the conditions of the corona discharge treatment were a corona output intensity of 2.0 kW and a speed of 18 m / min.
  • the ultraviolet curable adhesive liquid 1 prepared above is applied to the corona discharge treated surface of the protective film A (102) with a bar coater so that the film thickness after curing is about 3 ⁇ m.
  • An adhesive layer (103A) was formed.
  • the polarizer (104) bonded to one surface of the protective film B (105) is bonded to the ultraviolet curable adhesive layer (103A), and the protective film A (acrylic resin film, 102) / UV curable type is bonded.
  • a laminate in which the adhesive layer (103A) / polarizer (104) / ultraviolet curable adhesive layer (103B) / protective film B (cellulose acetate film, 105) was laminated was obtained. In that case, it bonded so that the slow axis of protective film B (105) and the absorption axis of polarizer (104) might mutually orthogonally cross.
  • UV curable adhesive layers (103A, 103B) were cured to produce polarizing plate 1 (101).
  • VA type liquid crystal display devices 1 to 54 corresponding to the respective polarizing plates 1 to 54 were produced by bonding them with an adhesive mainly composed of butyl acrylate.
  • the display device was placed in a thermostatic chamber, and 50 cycles were performed with -40 ° C. (30 minutes) ⁇ 90 ° C. (30 minutes) as one cycle.
  • the display device was placed under conditions of 75 ° C. and 95% for 100 hours.
  • the polarizing plate of the present invention having the structure defined in the present invention is mainly composed of an acrylic resin or polyester as the protective film A (viewing side protective film) with respect to the comparative example.
  • the film is used, problems such as light leakage at the in-plane end of the polarizing plate and warping of the panel due to the curling of the polarizing plate even after the heat shock durability test and the high temperature and high humidity durability test Can be suppressed.
  • Polarizers 55 to 60 were produced in the same manner as in the production of the polarizing plate 5 except that the protective film B was changed to the protective films B-26 to B-31 produced above.
  • the thickness of the protective film B is preferably 12 to 60 ⁇ m, more preferably 15 to 40 ⁇ m, and most preferably 15 to 30 ⁇ m.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Liquid Crystal (AREA)

Abstract

Le problème décrit par l'invention est de fournir un moyen de minimiser l'apparition de problèmes tels que la fuite de lumière à partir d'une partie extrémité dans le plan d'une plaque polarisante et la déformation d'un panneau à cause du tuilage de la plaque polarisante même après un essai de résistance aux chocs thermiques ou un essai d'endurance à haute température et haute humidité, ladite plaque polarisante étant obtenue en agençant, en tant que film protecteur, un film qui est constitué principalement d'une résine acrylique ou d'un polyester sur une surface d'un polariseur. La solution de l'invention est une plaque polarisante qui comprend un film protecteur (A), un polariseur et un film protecteur (B) dans cet ordre, et qui est obtenue en faisant adhérer le film protecteur (A) et le film protecteur (B) au polariseur en utilisant un adhésif à séchage par ultraviolets. Cette plaque polarisante est caractérisée comme suit : le film protecteur (A) est un film qui est constitué principalement d'une résine acrylique ou d'un polyester ; le film protecteur (B) est un film d'acétate de cellulose qui est constitué principalement d'un acétate de cellulose ayant un degré de substitution moyen de groupe acétyle de 2,1-2,7 ; et la différence entre le coefficient photoélastique du film d'acétate de cellulose dans la direction de la machine et du coefficient photoélastique du film d'acétate de cellulose dans la direction transversale (la valeur absolue de la différence obtenue en soustrayant le coefficient photoélastique dans la direction TD au coefficient photoélastique dans la direction MD) est inférieure ou égale à 5,0.
PCT/JP2014/079294 2013-11-19 2014-11-05 Plaque polarisante et dispositif d'affichage à cristaux liquides l'utilisant Ceased WO2015076101A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2015549059A JPWO2015076101A1 (ja) 2013-11-19 2014-11-05 偏光板およびこれを用いた液晶表示装置
KR1020167012463A KR20160070810A (ko) 2013-11-19 2014-11-05 편광판 및 이것을 사용한 액정 표시 장치
CN201480062796.1A CN105745561B (zh) 2013-11-19 2014-11-05 偏振片及使用其的液晶显示装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-239352 2013-11-19
JP2013239352 2013-11-19

Publications (1)

Publication Number Publication Date
WO2015076101A1 true WO2015076101A1 (fr) 2015-05-28

Family

ID=53179368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/079294 Ceased WO2015076101A1 (fr) 2013-11-19 2014-11-05 Plaque polarisante et dispositif d'affichage à cristaux liquides l'utilisant

Country Status (5)

Country Link
JP (1) JPWO2015076101A1 (fr)
KR (1) KR20160070810A (fr)
CN (1) CN105745561B (fr)
TW (1) TWI569967B (fr)
WO (1) WO2015076101A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017168807A1 (fr) * 2016-03-31 2017-10-05 コニカミノルタ株式会社 Film à différence de phase, plaque polarisante, et dispositif d'affichage à cristaux liquides
JP2017181865A (ja) * 2016-03-31 2017-10-05 コニカミノルタ株式会社 位相差フィルム、偏光板および液晶表示装置
JP2017191153A (ja) * 2016-04-12 2017-10-19 コニカミノルタ株式会社 偏光板および液晶表示装置
JP2017194620A (ja) * 2016-04-22 2017-10-26 コニカミノルタ株式会社 偏光板および液晶表示装置
TWI619975B (zh) * 2015-06-18 2018-04-01 南韓商三星Ｓｄｉ股份有限公司 偏光板、偏光板的製造方法以及包括偏光板的光學顯示器
WO2018074102A1 (fr) * 2016-10-18 2018-04-26 コニカミノルタ株式会社 Film de retard, plaque de polarisation et dispositif d'affichage à cristaux liquides
JPWO2017078086A1 (ja) * 2015-11-05 2018-08-23 住友化学株式会社 偏光板及びこれを含む画像表示装置
WO2019069756A1 (fr) * 2017-10-03 2019-04-11 日東電工株式会社 Plaque polarisante, dispositif d'affichage d'image et procédé de production de plaque polarisante
WO2019069755A1 (fr) * 2017-10-03 2019-04-11 日東電工株式会社 Plaque polarisante, dispositif d'affichage d'image et procédé de production de plaque polarisante
JP2019518241A (ja) * 2016-05-31 2019-06-27 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． 偏光子用保護フィルム、それを含む偏光板、およびそれらを用いて提供される表示
JP2020104513A (ja) * 2018-11-22 2020-07-09 住友化学株式会社 積層フィルム巻回体、ハードコートフィルム付き積層体、及び偏光板
JP2021033058A (ja) * 2019-08-23 2021-03-01 コニカミノルタ株式会社 光学フィルム用ドープの製造方法、光学フィルム用ドープ、光学フィルム、偏光板および光学フィルムの製造方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102394679B1 (ko) * 2016-07-28 2022-05-09 스미또모 가가꾸 가부시키가이샤 편광판
CN110446955B (zh) * 2017-04-03 2022-03-08 日东电工株式会社 起偏镜及偏振片
TWI702248B (zh) 2017-05-26 2020-08-21 南韓商Ｓｋｃ股份有限公司 光學聚酯薄膜及包含其之偏光反射片或稜鏡片
JP6470828B1 (ja) * 2017-12-04 2019-02-13 住友化学株式会社 プロテクトフィルム付偏光板枚葉体の製造方法
JP6470829B1 (ja) * 2017-12-04 2019-02-13 住友化学株式会社 光学積層体及びその製造方法
IT201900011502A1 (it) * 2019-07-11 2021-01-11 Ind Termoplastica Pavese S P A Sistema per la produzione mediante estrusione in bolla di un film contenente almeno uno strato di polimero hot melt e/o ad elevato melt flow index
KR20220154458A (ko) * 2021-05-13 2022-11-22 동우 화인켐 주식회사 편광판 및 이를 구비한 화상표시장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007061041A1 (fr) * 2005-11-28 2007-05-31 Asahi Kasei Chemicals Corporation Film optique
JP2009086047A (ja) * 2007-09-27 2009-04-23 Fujifilm Corp 偏光板及び液晶表示装置
JP2011118370A (ja) * 2009-10-28 2011-06-16 Fujifilm Corp 液晶表示装置
JP2012203284A (ja) * 2011-03-28 2012-10-22 Fujifilm Corp 偏光板、及びそれを有する液晶表示装置
JP2013057706A (ja) * 2011-09-07 2013-03-28 Konica Minolta Advanced Layers Inc 液晶表示装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101699497B1 (ko) * 2010-06-22 2017-01-24 도요보 가부시키가이샤 액정표시장치, 편광판 및 편광자 보호 필름
JP2012018341A (ja) * 2010-07-09 2012-01-26 Konica Minolta Opto Inc 偏光板、及びそれを用いた液晶表示装置
US9151870B2 (en) * 2010-12-08 2015-10-06 Konica Minolta, Inc. Optical film, and polarizing plate and liquid crystal display device using same
JP2012181277A (ja) * 2011-02-28 2012-09-20 Sumitomo Chemical Co Ltd 偏光板並びに偏光板のセット、液晶パネル及び液晶表示装置
JP6024662B2 (ja) * 2011-09-05 2016-11-16 コニカミノルタ株式会社 光学フィルムの製造方法
JP5146628B1 (ja) * 2012-05-01 2013-02-20 コニカミノルタアドバンストレイヤー株式会社 位相差フィルム、偏光板の製造方法および液晶表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007061041A1 (fr) * 2005-11-28 2007-05-31 Asahi Kasei Chemicals Corporation Film optique
JP2009086047A (ja) * 2007-09-27 2009-04-23 Fujifilm Corp 偏光板及び液晶表示装置
JP2011118370A (ja) * 2009-10-28 2011-06-16 Fujifilm Corp 液晶表示装置
JP2012203284A (ja) * 2011-03-28 2012-10-22 Fujifilm Corp 偏光板、及びそれを有する液晶表示装置
JP2013057706A (ja) * 2011-09-07 2013-03-28 Konica Minolta Advanced Layers Inc 液晶表示装置

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10488571B2 (en) 2015-06-18 2019-11-26 Samsung Sdi Co., Ltd. Polarizing plate, method of manufacturing the same, and optical display comprising the same
TWI619975B (zh) * 2015-06-18 2018-04-01 南韓商三星Ｓｄｉ股份有限公司 偏光板、偏光板的製造方法以及包括偏光板的光學顯示器
JPWO2017078086A1 (ja) * 2015-11-05 2018-08-23 住友化学株式会社 偏光板及びこれを含む画像表示装置
JP2022017232A (ja) * 2015-11-05 2022-01-25 住友化学株式会社 偏光板及びこれを含む画像表示装置
JP2017181865A (ja) * 2016-03-31 2017-10-05 コニカミノルタ株式会社 位相差フィルム、偏光板および液晶表示装置
WO2017168807A1 (fr) * 2016-03-31 2017-10-05 コニカミノルタ株式会社 Film à différence de phase, plaque polarisante, et dispositif d'affichage à cristaux liquides
JP2017191153A (ja) * 2016-04-12 2017-10-19 コニカミノルタ株式会社 偏光板および液晶表示装置
JP2017194620A (ja) * 2016-04-22 2017-10-26 コニカミノルタ株式会社 偏光板および液晶表示装置
JP2019518241A (ja) * 2016-05-31 2019-06-27 エスケイシー・カンパニー・リミテッドＳｋｃ Ｃｏ．， Ｌｔｄ． 偏光子用保護フィルム、それを含む偏光板、およびそれらを用いて提供される表示
WO2018074102A1 (fr) * 2016-10-18 2018-04-26 コニカミノルタ株式会社 Film de retard, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2019066716A (ja) * 2017-10-03 2019-04-25 日東電工株式会社 偏光板、画像表示装置、および偏光板の製造方法
WO2019069755A1 (fr) * 2017-10-03 2019-04-11 日東電工株式会社 Plaque polarisante, dispositif d'affichage d'image et procédé de production de plaque polarisante
JP2019066715A (ja) * 2017-10-03 2019-04-25 日東電工株式会社 偏光板、画像表示装置、および偏光板の製造方法
WO2019069756A1 (fr) * 2017-10-03 2019-04-11 日東電工株式会社 Plaque polarisante, dispositif d'affichage d'image et procédé de production de plaque polarisante
JP2020104513A (ja) * 2018-11-22 2020-07-09 住友化学株式会社 積層フィルム巻回体、ハードコートフィルム付き積層体、及び偏光板
JP2021033058A (ja) * 2019-08-23 2021-03-01 コニカミノルタ株式会社 光学フィルム用ドープの製造方法、光学フィルム用ドープ、光学フィルム、偏光板および光学フィルムの製造方法
JP7379933B2 (ja) 2019-08-23 2023-11-15 コニカミノルタ株式会社 光学フィルム用ドープの製造方法および光学フィルムの製造方法

Also Published As

Publication number Publication date
CN105745561B (zh) 2018-12-14
CN105745561A (zh) 2016-07-06
TW201531404A (zh) 2015-08-16
TWI569967B (zh) 2017-02-11
KR20160070810A (ko) 2016-06-20
JPWO2015076101A1 (ja) 2017-03-16

Similar Documents

Publication Publication Date Title
WO2015076101A1 (fr) Plaque polarisante et dispositif d'affichage à cristaux liquides l'utilisant
JP6493213B2 (ja) 位相差フィルム、偏光板及び液晶表示装置
JP6245260B2 (ja) 位相差フィルム、偏光板および液晶表示装置
KR101778477B1 (ko) 편광판, 그것을 구비한 액정 표시 장치
TWI538944B (zh) A cellulose ester film, a method for producing the same, and a polarizing plate
JP6428621B2 (ja) セルロースアシレートフィルム、偏光板及び液晶表示装置
TW202041898A (zh) 偏光板、偏光板之製造方法及液晶顯示裝置
WO2015001980A1 (fr) Plaque polarisante et dispositif d'affichage à cristaux liquides l'utilisant
WO2014136529A1 (fr) Film optique, plaque de polarisation contenant ce film optique, et dispositif d'affichage à cristaux liquides à alignement vertical
JP7099440B2 (ja) 偏光板およびこれを具備する表示装置
TWI644131B (zh) Polarizing plate, manufacturing method of polarizing plate and liquid crystal display device
JP6081244B2 (ja) 偏光板および液晶表示装置
JP5655706B2 (ja) 液晶表示装置
WO2016111058A1 (fr) Dispositif d'affichage à cristaux liquides à alignement vertical
WO2015104940A1 (fr) Film d'ester de cellulose et procédé de fabrication de film d'ester de cellulose
WO2011077910A1 (fr) Plaque de polarisation et procédé de fabrication de celle-ci
TW202408915A (zh) 薄膜卷、其製造方法、偏光板及顯示裝置
JP2014167577A (ja) 偏光板および液晶表示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14863901

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015549059

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167012463

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14863901

Country of ref document: EP

Kind code of ref document: A1