WO2014050608A1 - 光学フィルム及びその製造方法、偏光板並びに液晶表示装置 - Google Patents
光学フィルム及びその製造方法、偏光板並びに液晶表示装置 Download PDFInfo
- Publication number
- WO2014050608A1 WO2014050608A1 PCT/JP2013/074822 JP2013074822W WO2014050608A1 WO 2014050608 A1 WO2014050608 A1 WO 2014050608A1 JP 2013074822 W JP2013074822 W JP 2013074822W WO 2014050608 A1 WO2014050608 A1 WO 2014050608A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- optical film
- group
- moisture permeability
- film
- resin
- 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
Links
- 0 CCC(*)(CC(*)(C(C)C)C(O1)=*)C1=O Chemical compound CCC(*)(CC(*)(C(C)C)C(O1)=*)C1=O 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- 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
- G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
- G02F1/133311—Environmental protection, e.g. against dust or humidity
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
- B29K2025/06—PS, i.e. polystyrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
- B29K2025/08—Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2267/00—Use of polyesters or derivatives thereof as reinforcement
- B29K2267/04—Polyesters derived from hydroxycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0068—Permeability to liquids; Adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0068—Permeability to liquids; Adsorption
- B29K2995/0069—Permeability to liquids; Adsorption non-permeable
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to an optical film and a method of manufacturing the same, a polarizing plate, and a liquid crystal display.
- a liquid crystal display device has a liquid crystal panel member in which polarizing plates are provided on both sides of a liquid crystal cell, and display is performed by controlling light from the backlight member with the liquid crystal panel member.
- the polarizing plate is composed of a polarizer and protective films on both sides thereof, and a general polarizer is obtained by staining a stretched polyvinyl alcohol (PVA) -based film with iodine or a dichroic dye, and protection As the film, a cellulose ester film or the like is used.
- PVA stretched polyvinyl alcohol
- a polymer film used as an optical compensation film (retardation film) in order to widen a viewing angle, improve image coloring, and improve contrast.
- the optical properties of the film for example, the retardation value Re in the film plane and the film thickness
- birefringence such as retardation value Rth in the longitudinal direction
- Recent liquid crystal display devices have been diversified in applications along with higher quality, and the demand for durability has become severe.
- durability stability against environmental changes is required for use in outdoor applications, and optical films such as the above polarizing plate protective films and optical compensation films used in liquid crystal displays are also resistant to temperature and humidity changes. It is required to suppress changes in dimensions and optical characteristics.
- the problems of liquid crystal display devices exposed to high temperature and high humidity environments include warping of liquid crystal cells of liquid crystal display devices and generation of display unevenness, which causes moisture to penetrate the polarizing plate and the optical film constituting it.
- Desorption causes a difference in the balance of contraction of the polarizing plates on the front and back of the liquid crystal cell of the liquid crystal display device, causing the liquid crystal cell to warp, and the four corners and four sides of the liquid crystal cell contact the housing and the member on the back side. It is considered that the cause of display unevenness is a cause.
- the protective film of polarizing plate, optical compensation film, etc. improvement of humidity dependency and wet heat durability has been required, but for drastic improvement, soaking of water by environmental change and It is necessary to suppress desorption, and in particular, the optical film on the outermost surface of the polarizing plate is required to have a performance to prevent moisture permeation, that is, a reduction in moisture permeability.
- Patent Document 1 discloses an optical system in which a large amount of acrylic resin such as polymethyl methacrylate (PMMA) is added to a cellulose ester for the purpose of providing an optical film having high transparency, low hygroscopicity, high heat resistance, and high mechanical strength. A film is disclosed.
- PMMA polymethyl methacrylate
- Liquid crystal display devices are used not only in conventional indoor applications, but also in harsher environments such as outdoors, and the optical film on the outermost surface of the liquid crystal display device is important for its ability not to transmit moisture. ing.
- This problem is influenced by the tendency of the glass of the liquid crystal cell to become thinner in TV applications, which are increasing in size in recent years, and the warpage tends to be large, and the influence on the black display unevenness after high temperature and high humidity environment is concerned .
- the solution of black display unevenness problem after aging in high temperature and high humidity environment is strongly desired There is.
- an object of the present invention is to provide an optical film which is excellent in durability and can reduce water permeation and desorption, and a method for producing the same.
- Another object of the present invention is to provide a polarizing plate using the above-mentioned optical film.
- Still another object of the present invention is to provide a liquid crystal display device in which the unevenness of black display after aging under high temperature and high humidity environment is improved.
- the object of the present invention can be achieved by the following means.
- An optical film containing a thermoplastic resin which is The moisture permeability of the optical film is 70 g / m 2 / day or less in terms of a film thickness of 40 ⁇ m
- A represents the moisture permeability of the optical film when 10% by mass of the moisture permeability reducing compound is added with respect to the mass of the thermoplastic resin
- B includes the thermoplastic resin and the permeability
- the moisture permeability of the optical film when the humidity reducing compound is not added is shown, except that the moisture permeability is 40 ⁇ m thickness after passing for 24 hours at 40 ° C and 90% relative humidity by the method of JIS Z-0208. It is a converted value.
- [2] It is preferable that the optical film as described in [1] satisfy
- Formula (2) a / B ⁇ 0.9 (In the formula (2), a represents the moisture permeability of the optical film in the case of containing the thermoplastic resin and the moisture permeability reducing compound, B contains the thermoplastic resin and does not add the moisture permeability reducing compound
- the moisture permeability is the value obtained by converting the moisture permeability after a lapse of 24 hours at 40 ° C., 90% relative humidity by the method of JIS Z-0208 into a film thickness of 40 ⁇ m.
- the moisture permeability reducing compound preferably contains one or more aromatic rings.
- R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 23 , R 24 , R 25 , R 32 , R 33 , R 34 , R 35 , R 36 are And each independently represents a hydrogen atom or a substituent, and R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 23 , R 24 , R 25 , R 32 , R 33 , R 34 , R At least one of 35 and R 36 is an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a hydroxy group, a mercapto group or a carboxyl group.) [5] In the optical film according to any one of [1] to [4], the moisture permeability reducing compound is preferably a novolac type phenolic resin, a
- the moisture permeability reducing compound is preferably a novolac type phenol resin, a hydrogenated terpene resin or a xylene resin.
- the moisture permeability reducing compound preferably contains three or more aromatic rings.
- the moisture permeability reducing compound is preferably represented by the following general formula (C).
- n 1 to 10
- m independently represents an integer of 1 to 4
- R may independently have a hydrogen atom, -OH group or a substituent group represents an alkyl group having a carbon number of 1 ⁇ 10, L 1 and L 2 each independently a methylene group or -CH 2 -O-CH 2 -. represents the proviso that at least one -OH group of R Represents a group
- the moisture permeability reducing compound is preferably a novolac type phenolic resin or a xylene resin.
- the optical film according to any one of [1] to [9] preferably contains 1% by mass or more of the moisture permeability reducing compound based on the mass of the thermoplastic resin.
- the optical film according to any one of [1] to [10] preferably has a thickness of 60 ⁇ m or less.
- the optical film according to any one of [1] to [11] has Re and Rth defined by the following formula (I) and the following formula (II) at the wavelength of 590 nm and the following formula (III) and It is preferable to satisfy the formula (IV).
- nx is the refractive index in the slow axis direction in the optical film plane
- ny is the refractive index in the fast axis direction in the optical film plane
- nz is the optical film It is a refractive index in the film thickness direction
- d is the thickness (nm) of the optical film.
- the optical film according to any one of [1] to [12] is formed by casting a polymer solution containing the thermoplastic resin, the moisture permeability reducing compound, and a solvent on a support. It is preferable that [14]
- the optical film according to any one of [1] to [13] preferably has a functional layer with a film thickness of 0.1 to 20 ⁇ m on at least one surface of the optical film.
- the optical film according to [14] comprises the moisture permeability (C) of the optical film when the functional layer is laminated, and the moisture permeability (D) of the optical film when the functional layer is not laminated. It is preferable that C / D ⁇ 0.9.
- A represents the moisture permeability of the optical film when 10% by mass of the moisture permeability reducing compound is added with respect to the mass of the thermoplastic resin
- B includes the thermoplastic resin and the permeability
- the optical film preferably satisfies the following formula (2).
- a represents the moisture permeability of the optical film in the case of containing the thermoplastic resin and the moisture permeability reducing compound
- B contains the thermoplastic resin and does not add the moisture permeability reducing compound
- the moisture permeability is the value obtained by converting the moisture permeability after a lapse of 24 hours at 40 ° C., 90% relative humidity by the method of JIS Z-0208 into a film thickness of 40 ⁇ m.
- the method for producing an optical film described in [16] or [17] preferably includes the step of stretching the optical film.
- a polarizing plate comprising at least one of the optical films according to any one of [1] to [15] as a protective film of a polarizer.
- the liquid crystal display device arrange
- the present invention it is possible to provide an optical film excellent in durability and capable of reducing water permeation and desorption, and a method for producing the same.
- the optical film of the present invention it is possible to provide a liquid crystal display device in which the occurrence of black display unevenness after high temperature and high humidity environment is suppressed.
- optical film of the present invention It is a top view of an example of the optical film of the present invention.
- the optical film of this invention has a pattern optically anisotropic layer as a functional layer, it is an upper surface schematic diagram of an example of a pattern optically anisotropic layer.
- polarizing plate of the present invention the method for producing the same, the additive used for the same, and the like will be described in detail.
- a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
- acrylic resin refers to a resin obtained by polymerizing a derivative of methacrylic acid or acrylic acid, and a resin containing the derivative.
- (meth) acrylate represents an acrylate and a methacrylate
- (meth) acryl represents an acryl and methacryl
- the “slow axis direction” of the film means the direction in which the refractive index is maximum in the film plane
- the “fast axis direction” means the direction orthogonal to the slow axis in the film plane.
- the optical film of the present invention is an optical film containing a thermoplastic resin, and the moisture permeability of the optical film is 70 g / m 2 / day or less (film thickness 40 ⁇ m equivalent), and the molecular weight is 200 or more, and It is characterized by including a moisture permeability reducing compound that satisfies the formula (1).
- A represents the moisture permeability of the optical film when 10% by mass of the moisture permeability reducing compound is added with respect to the mass of the thermoplastic resin
- B includes the thermoplastic resin and the permeability
- the moisture permeability of the optical film when the humidity reducing compound is not added is shown, except that the moisture permeability is 40 ⁇ m thickness after passing for 24 hours at 40 ° C and 90% relative humidity by the method of JIS Z-0208. It is a converted value.
- the optical film of this invention satisfy
- a represents the moisture permeability of the optical film in the case of containing the thermoplastic resin and the moisture permeability reducing compound
- B contains the thermoplastic resin and does not contain the moisture permeability reducing compound
- the moisture permeability is the value obtained by converting the moisture permeability after a lapse of 24 hours at 40 ° C., 90% relative humidity by the method of JIS Z-0208 into a film thickness of 40 ⁇ m.
- the a / B is preferably 0.8 or less, more preferably 0.6 or less, and particularly preferably 0.4 or less.
- thermoplastic resin used in the present invention will be described below.
- (meth) acrylic resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin can be mentioned, and from these resins and mixed resins of these plural types of resins You can choose.
- (meth) acrylic-type resin is the concept containing both methacrylic resin and acrylic resin.
- the (meth) acrylic resin also includes acrylate / methacrylate derivatives, in particular (co) polymers of acrylate ester / methacrylate ester.
- the repeating structural unit of the (meth) acrylic acid based resin is not particularly limited.
- the (meth) acrylic acid based resin preferably has a repeating structural unit derived from a (meth) acrylic acid ester monomer as the repeating structural unit.
- the (meth) acrylic acid-based resin further polymerizes at least one selected from a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and a monomer represented by the following general formula (201) as a repeating structural unit.
- the repeating structural unit may be included.
- R 201 represents a hydrogen atom or a methyl group
- X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a -CN group, a -CO-R 202 group, or -O-CO-R
- R 202 and R 203 represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the (meth) acrylic acid ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, and benzyl acrylate.
- methyl methacrylate is particularly preferable in terms of excellent heat resistance and transparency.
- its content in the monomer component to be subjected to the polymerization step is preferably 10 to 100% by weight, more preferably 10, in order to sufficiently exert the effects of the present invention.
- % To 100% by weight more preferably 40 to 100% by weight, particularly preferably 50 to 100% by weight.
- the hydroxyl group-containing monomer is not particularly limited, and examples thereof include 2- (hydroxyalkyl) acrylic acid esters such as ⁇ -hydroxymethylstyrene, ⁇ -hydroxyethylstyrene, and methyl 2- (hydroxyethyl) acrylate; And 2- (hydroxyalkyl) acrylic acid such as-(hydroxyethyl) acrylic acid; and the like. These may be used alone or in combination of two or more.
- the content thereof in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by weight, and more preferably 0 to 30 to fully exhibit the effects of the present invention. It is 20% by weight, more preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight.
- the unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, crotonic acid, ⁇ -substituted acrylic acid, ⁇ -substituted methacrylic acid, etc. Only one of them may be used, or two or more of them may be used. You may use together. Among these, acrylic acid and methacrylic acid are particularly preferable in that the effects of the present invention can be sufficiently exhibited.
- the content thereof in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by weight, more preferably 0 to 20, in order to sufficiently exert the effects of the present invention. % By weight, more preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight.
- Examples of the monomer represented by the general formula (201) include styrene, vinyl toluene, ⁇ -methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like, and only one of them is mentioned. You may use and you may use 2 or more types together. Among these, styrene and ⁇ -methylstyrene are particularly preferable in that the effects of the present invention can be sufficiently exhibited.
- the content ratio thereof in the monomer component to be subjected to the polymerization step is preferably 0 to 30 weight in order to sufficiently exhibit the effects of the present invention. %, More preferably 0 to 20% by weight, still more preferably 0 to 15% by weight, and particularly preferably 0 to 10% by weight.
- the monomer component may form a lactone ring after polymerization. In that case, it is preferable to polymerize the monomer component to obtain a polymer having a hydroxyl group and an ester group in the molecular chain.
- a polymerization reaction for polymerizing the monomer component to obtain a polymer having a hydroxyl group and an ester group in a molecular chain a polymerization form using a solvent is preferable, and solution polymerization is particularly preferable. .
- lactone ring structures described in JP 2007-316366 A, JP 2005-189623 A, WO 2007/032304 A and WO 2006/025445 A preferable one having a cyclic structure described in the following publication are also preferable. It is.
- the lactone ring-containing polymer is not particularly limited as long as it has a lactone ring, but preferably has a lactone ring structure represented by the following general formula (401).
- R 401 , R 402 and R 403 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms, and the organic residue may contain an oxygen atom .
- the organic residue having 1 to 20 carbon atoms a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like are preferable.
- the content ratio of the lactone ring structure represented by the above general formula (401) in the structure of the lactone ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 10 to 60%. %, Particularly preferably 10 to 50% by mass.
- the method for producing the lactone ring-containing polymer is not particularly limited, but preferably has a hydroxyl group and an ester group in the molecular chain described in paragraphs [0027] to [0030] of JP-A-2007-316366.
- a polymer (p) having a hydroxyl group and an ester group in its molecular chain is obtained by a polymerization step containing a monomer, the resulting polymer (p) is heat treated to form a lactone ring structure into a polymer It is obtained by carrying out the lactone cyclization condensation step to be introduced.
- the weight average molecular weight of the lactone ring-containing polymer is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably 50,000 to 500,000.
- the weight-average molecular weight Mw of the acrylic resin used in the present invention is preferably 80,000 or more.
- the weight average molecular weight Mw of the acrylic resin is 80,000 or more, the mechanical strength is high, and the handling suitability at the time of film production is excellent.
- the weight average molecular weight Mw of the acrylic resin is preferably 100,000 or more.
- the weight average molecular weight Mw of the acrylic resin is preferably 3,000,000 or less, and more preferably 2,000,000 or less.
- a commercially available thing can also be used as an acrylic resin used for this invention.
- Delpet 60N, 80N manufactured by Asahi Kasei Chemicals Co., Ltd.
- Dianal BR80, BR85, BR88, BR102 manufactured by Mitsubishi Rayon Co., Ltd.
- KT75 manufactured by Denki Kagaku Kogyo Co., Ltd.
- An acrylic resin can also use 2 or more types together.
- thermoplastic resin which can be used in the present invention can be used by adding an additive to a polycarbonate resin to control the peeling force and the toughness appropriately.
- Any appropriate polycarbonate may be employed as the polycarbonate resin.
- an aromatic polycarbonate comprising an aromatic dihydric phenol component and a carbonate component is preferred.
- the aromatic polycarbonate can preferably be obtained by the reaction of an aromatic dihydric phenol compound with a carbonate precursor.
- the aromatic dihydric phenol compound is not particularly limited, and, for example, 2,2-bis (4-hydroxyphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4′-biphenol, 4,4'-dihydroxybiphenyl ether, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dipropylphenyl) And propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohe
- the carbonate precursor is not particularly limited.
- phosgene, bischloroformate of the above dihydric phenol compound diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate And dinaphthyl carbonate etc., among which phosgene and diphenyl carbonate are preferable.
- the polycarbonate has a weight average molecular weight of 10000 or more, more preferably 50000 or more.
- the weight average molecular weight is less than 10000, a film excellent in strength and elongation characteristics and heat resistance can not be obtained.
- the upper limit of the weight average molecular weight is not particularly limited, but if it is 1.500000 or more, the occurrence of breakage or the like due to the increase in the drawing tension is not preferable.
- the weight average molecular weight is in the above range, the mechanical strength is excellent, and the solubility, the moldability, the operability of casting, etc. become good.
- the thermoplastic resin that can be used in the present invention can be used by adding an additive to the polystyrene resin to control the peel strength and toughness as appropriate.
- the polystyrene-based resin include polystyrene, poly (p-, m- or o-methylstyrene), poly (2,4-, 2, 5-, 3,4- or 3,5-dimethylstyrene), poly ( poly (alkyl styrene) such as p-tertiary butyl styrene), poly (p-, m- or o-chlorostyrene), poly (p-, m- or o-bromostyrene), poly (p-, m- Or poly (halogenated styrene) such as o-fluorostyrene), poly (o-methyl-p-fluorostyrene), poly (halogen-substituted alkylstyrene) such as poly (p-
- polystyrene is particularly preferred.
- the polystyrene polymer used in the present invention is not necessarily a single compound, and may be a mixture with another polystyrene polymer, a copolymer, and a mixture thereof.
- vinyl toluene, ⁇ -methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate, maleic anhydride and the like may be copolymerized.
- a commercially available thing can be used as a polystyrene-type resin used for this invention.
- polystyrene resins polystyrene G9504, G9401, G9305, SGP-10 (polystyrene Japan) manufactured by PS Japan Ltd., High Branch XC-540 HB, XC-520, Dick Styrene CR-250, CR-350, CR-450 (Manufactured by DIC), as a styrene-acrylonitrile copolymer, sebian N020SF, 050SF, 070SF, 080SF (manufactured by Daicel Polymer), and as a styrene-maleic anhydride copolymer, it is XIRAN SZ28110, SZ26180, SZ26120, SZ26120, SZ26080, SZ23110, SZ15170, SZ08250 (manufactured by Polyscope Polymers B.
- the polystyrene polymer used in the present invention has a weight average molecular weight of 10000 or more, more preferably 50000 or more. If the weight average molecular weight is less than 10000, a film excellent in strength and elongation characteristics and heat resistance can not be obtained.
- the upper limit of the weight average molecular weight is not particularly limited, but if it is 1.500000 or more, the occurrence of breakage or the like due to the increase in the drawing tension is not preferable.
- cyclic polyolefin resin As thermoplastic resin which can be used for this invention, cyclic
- cyclic polyolefin resin represents a polymer resin having a cyclic olefin structure.
- the polymer resin having a cyclic olefin structure used in the present invention include (1) norbornene polymers, (2) polymers of monocyclic olefins, (3) polymers of cyclic conjugated dienes, There are vinyl alicyclic hydrocarbon polymers and hydrides of (1) to (4).
- the polymer preferable for the present invention is an addition (co) polymer cyclic polyolefin resin containing at least one or more repeating units represented by the following general formula (II) and, if necessary, a repeat represented by It is an addition (co) polymer cyclic polyolefin resin further comprising at least one or more units.
- a ring-opened (co) polymer containing at least one cyclic repeating unit represented by the general formula (III) can also be suitably used.
- R 1 to R 6 each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- X 1 to X 3 and Y 1 to Y 3 each represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom or a halogen atom -Substituted hydrocarbon group having 1 to 10 carbon atoms,-(CH 2 ) n COOR 11 ,-(CH 2 ) n OCOR 12 ,-(CH 2 ) n NCO,-(CH 2 ) n NO 2 ,-( CH 2 ) n CN,-(CH 2 ) n CONR 13 R 14 ,-(CH 2 ) n NR 13 R 14 ,-(CH 2 ) n OZ,-(CH 2 ) n W, or X 1 and Y 1 Or (—CO) 2 O, (—CO) 2 NR 15 composed
- R 11 , R 12 , R 13 , R 14 and R 15 each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms
- Z represents a hydrocarbon group or a hydrocarbon group substituted with halogen
- W represents SiR 16 p D 3-p
- R 16 is a hydrocarbon group having 1 to 10 carbon atoms
- D is a halogen atom
- n is an integer of 0 to 10 Show.
- the retardation in the thickness direction (Rth) of the optical film is increased, and in-plane retardation (Re) Expressivity can be increased.
- a film having a large Re expression can be increased in Re value by stretching in the film forming process.
- the hydrogenated norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-1159767 or JP-A 2004-309979 As disclosed in U.S. Pat. No. 5,015,015, it is produced by addition polymerization or metathesis ring-opening polymerization of a polycyclic unsaturated compound followed by hydrogenation.
- R 5 to R 6 are preferably a hydrogen atom or -CH 3
- X 3 and Y 3 are preferably a hydrogen atom, Cl and -COOCH 3 , and other groups are appropriately selected.
- Ru This norbornene-based resin is marketed by JSR Corporation under the trade name Arton G or Arton F (such as Arton F 5023). It is commercially available under the trade name Zeonex 250 or Zeonex 280, and these can be used.
- the norbornene addition (co) polymer is disclosed in, for example, JP-A-10-7732, JP-A-2002-504184, US Published Patent 2004229157 A1 or WO 2004/070463 A1. It is obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds.
- a norbornene type polycyclic unsaturated compound ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; nonconjugated dienes such as ethylidene norbornene; acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride
- This norbornene addition (co) polymer is marketed by Mitsui Chemicals, Inc.
- Tg glass transition temperature
- APL 8008 T Tg 70 ° C.
- APL 6013 T Tg 125 ° C.
- APL 6015 T There are grades such as Tg 145 ° C).
- Pellets such as TOPAS 8007, 6013 and 6015 are commercially available from Polyplastics Co., Ltd. Furthermore, the Appear 3000 has been marketed by Ferrania.
- the glass transition temperature (Tg) of the cyclic polyolefin resin is not limited, but for example, a high Tg cyclic polyolefin resin such as 200 to 400 ° C. can also be used.
- thermoplastic resins examples include glutaric anhydride resins.
- glutaric anhydride resin refers to a polymer resin having glutaric anhydride units.
- the polymer having a glutaric anhydride unit preferably has a glutaric anhydride unit represented by the following general formula (101) (hereinafter referred to as a glutaric anhydride unit).
- R 31 and R 32 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom.
- R 31 and R 32 particularly preferably represent the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the polymer having glutaric anhydride units is preferably an acrylic copolymer containing glutaric anhydride units.
- the acrylic thermoplastic copolymer preferably has a glass transition temperature (Tg) of 120 ° C. or higher from the viewpoint of heat resistance.
- the content of the glutaric anhydride unit with respect to the acrylic thermoplastic copolymer is preferably 5 to 50% by mass, more preferably 10 to 45% by mass.
- the content is preferably 5 to 50% by mass, more preferably 10 to 45% by mass.
- the above-mentioned acrylic thermoplastic copolymer preferably further contains a repeating unit based on an unsaturated carboxylic acid alkyl ester.
- a repeating unit based on unsaturated carboxylic acid alkyl ester for example, one represented by the following general formula (102) is preferable.
- R 41 represents hydrogen or an alkyl group having 1 to 5 carbon atoms
- R 42 represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, or one or more carbon atoms or less
- Preferred specific examples of such monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylate t-Butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) 3-hydroxypropyl acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate, etc., among which methacryl Methyl acid is most preferably used. One of these may be used alone, or two or more may be used in combination.
- the content of the unsaturated carboxylic acid alkyl ester unit with respect to the above-mentioned acrylic thermoplastic copolymer is preferably 50 to 95% by mass, more preferably 55 to 90% by mass.
- an acrylic thermoplastic copolymer having a glutaric anhydride unit and an unsaturated carboxylic acid alkyl ester unit polymerizes a copolymer having an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit. It can be obtained by cyclization.
- R 51 represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
- Preferred specific examples of the monomer for deriving the unsaturated carboxylic acid unit include a compound represented by the following general formula (105), which is a monomer corresponding to the repeating unit represented by the general formula (104), and Although maleic acid and a hydrolyzate of maleic anhydride and the like may be mentioned, acrylic acid and methacrylic acid are preferable, and methacrylic acid is more preferable, from the viewpoint of excellent thermal stability.
- Formula (105): CH 2 C (R 51) (COOH)
- an acrylic thermoplastic copolymer having a glutaric anhydride unit and an unsaturated carboxylic acid alkyl ester unit is, for example, a co-polymer having an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit. Since they can be obtained by polymerizing and cyclizing a polymer, they may have unsaturated carboxylic acid units remaining in their constituent units.
- content of the unsaturated carboxylic acid unit to said acrylic thermoplastic copolymer 10 mass% or less is preferable, More preferably, it is 5 mass% or less. By setting the content to 10% by mass or less, it is possible to prevent a decrease in colorless transparency and retention stability.
- the acrylic thermoplastic copolymer may have other vinyl monomer units not containing an aromatic ring, as long as the effects of the present invention are not impaired.
- the other vinyl-based monomer units not containing an aromatic ring include vinyl cyanide-based monomers such as acrylonitrile, methacrylonitrile and ethacrylonitrile as the corresponding monomers; allyl glycidyl ether Maleic anhydride, itaconic anhydride; N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, acrylamide, methacrylamide, N-methyl acrylamide, butoxymethyl acrylamide, N-propyl methacrylamide, aminoethyl acrylate, acrylic Propylaminoethyl methacrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, cyclohexylaminoethyl methacrylate; N-vinyl
- As content of the other vinyl-type monomer unit which does not contain an aromatic ring with respect to said acrylic thermoplastic copolymer 35 mass% or less is preferable.
- the vinyl monomer unit containing an aromatic ring (N-phenylmaleimide, phenylaminoethyl methacrylate, p-glycidylstyrene, p-aminostyrene, 2-styryl-oxazoline, etc.) has scratch resistance and weather resistance. Since the content tends to decrease, the content of the above-mentioned acrylic thermoplastic copolymer is preferably limited to 1% by mass or less.
- thermoplastic resins examples include glutarimide resins.
- the glutarimide resin represents a polymer resin having a glutarimide unit.
- the glutarimide resin is a thermoplastic resin having a substituted or unsubstituted imide group in a side chain. By having a substituted or unsubstituted imide group in the side chain, it is possible to express a preferable balance of properties in terms of optical properties, heat resistance and the like.
- the glutarimide resin has at least the following general formula (301):
- each of R 301 , R 302 and R 303 independently represents hydrogen or an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or an aryl group ) Is preferably contained in an amount of 20% by weight or more.
- R 301 and R 302 are hydrogen or a methyl group
- R 303 is a methyl group or a cyclohexyl group.
- the glutarimide unit may be of a single type, or R 301 , R 302 and R 303 may contain a plurality of different types.
- 2nd structural unit which comprises glutar imide type-resin used for this invention is a unit which consists of acrylic acid ester or methacrylic acid ester.
- acrylic ester or methacrylic ester structural unit methyl acrylate, ethyl acrylate, methyl methacrylate, methyl methacrylate and the like can be mentioned.
- another preferable imidizable unit includes N-alkyl methacrylamides such as N-methyl methacrylamide and N-ethyl methacrylamide. These second constitutional units may be of a single type or may contain a plurality of types.
- the content of the glutarimide unit represented by the general formula (301) of the glutarimide resin is 20% by weight or more based on the total repeating units of the glutarimide resin.
- the preferred content of glutarimide units is 20% to 95% by weight, more preferably 50 to 90% by weight, and still more preferably 60 to 80% by weight. If the glutarimide unit is smaller than this range, the heat resistance of the resulting film may be insufficient or the transparency may be impaired. Moreover, if it exceeds this range, the heat resistance may be unnecessarily increased to make it difficult to form a film, and the mechanical strength of the obtained film may be extremely brittle and the transparency may be impaired.
- the glutarimide resin may further be copolymerized with a third structural unit, if necessary.
- the third structural unit include styrene-based monomers such as styrene, substituted styrene and ⁇ -methylstyrene, acrylic monomers such as butyl acrylate, and nitrile-based monomers such as acrylonitrile and methacrylonitrile
- a structural unit formed by copolymerizing a maleimide-based monomer such as maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide and the like can be used.
- the glutarimide unit and the imidizable unit in the glutarimide resin may be directly copolymerized with the glutarimide unit and the imidizable unit in the glutarimide resin, and the graft copolymer may be carried out to the resin having the glutarimide unit and the imidizable unit. It may be polymerized.
- the content in the glutarimide resin is preferably 5 mol% or more and 30 mol% or less based on the total repeating units in the glutarimide resin.
- Glutarimide-based resins are described in U.S. Pat. No. 3,284,425, U.S. Pat. No. 4,246,374, JP-A-2-153904, etc., and can be obtained using methacrylic acid methyl ester or the like as the main raw material as a resin having imidizable units. It can be obtained by imidating a resin having the imidizable unit using ammonia or a substituted amine. When a glutarimide resin is obtained, a unit composed of acrylic acid, methacrylic acid or an anhydride thereof may be introduced into the glutarimide resin as a reaction by-product.
- the presence of such a structural unit, in particular an acid anhydride, is not preferable because it reduces the total light transmittance and haze of the obtained film of the present invention.
- the content of acrylic acid or methacrylic acid is preferably 0.5 milliequivalent or less, preferably 0.3 milliequivalent or less, more preferably 0.1 milliequivalent or less, per gram of the resin.
- JP-A 02-153904 it is also possible to obtain a glutarimide resin by imidation using a resin mainly composed of N-methyl acrylamide and methacrylic acid methyl ester.
- the glutarimide resin preferably has a weight average molecular weight of 10000 or more, more preferably 50000 or more, from the viewpoint of maintaining strength and elongation properties and heat resistance.
- the upper limit of the weight average molecular weight is not particularly limited, but is preferably less than 500,000 from the viewpoint that the stretching tension does not increase excessively.
- thermoplastic resin that can be used in the present invention may contain other thermoplastic resins other than the above-mentioned resins.
- the other thermoplastic resins are not particularly limited as long as they do not contradict the purpose of the present invention, but thermoplastic resins compatible thermodynamically are preferable in terms of improving mechanical strength and desired physical properties.
- thermoplastic resins examples include olefinic thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene) and the like; halogen-containing ones such as vinyl chloride and chlorinated vinyl resin Thermoplastics; acrylic thermoplastics such as polymethyl methacrylate; polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer (manufactured by Daicel Polymer, Cebian N series, etc.), acrylonitrile-butadiene-styrene block Styrene thermoplastics such as copolymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polyamides such as nylon 6, nylon 66, nylon 610; polyacetal; polycarbonate; Phenylene oxide; polyphenylene sulfide; polyether ether ether
- the rubbery polymer preferably has on its surface a graph ridge portion of a composition compatible with the lactone ring polymer which can be used in the present invention, and the average particle diameter of the rubbery polymer is a film From the viewpoint of improving the transparency at that time, the thickness is preferably 100 nm or less, and more preferably 70 nm or less.
- Copolymer containing vinyl cyanide monomer unit and aromatic vinyl monomer unit specifically 50% by weight or more of acrylonitrile-styrene copolymer, polyvinyl chloride resin and methacrylic acid ester It is good to use the polymer to contain. Among them, when an acrylonitrile-styrene copolymer is used, a film having a glass transition temperature of 120 ° C. or more, a phase difference of 100 nm or less per 100 ⁇ m in the plane direction and a total light transmittance of 85% or more is easily obtained. It becomes possible.
- the optical film of the present invention is characterized by containing a moisture permeability reducing compound having a molecular weight of 200 or more and satisfying the following formula (1) in order to reduce permeation and desorption of water.
- Formula (1) A / B ⁇ 0.9
- A represents the moisture permeability of the optical film when 10% by mass of the moisture permeability reducing compound is added with respect to the mass of the thermoplastic resin
- B includes the thermoplastic resin and the permeability
- the moisture permeability of the optical film when the humidity reducing compound is not added is shown, except that the moisture permeability is 40 ⁇ m thickness after passing for 24 hours at 40 ° C and 90% relative humidity by the method of JIS Z-0208.
- the moisture permeability reducing compound preferably has an A / B of 0.8 or less, and more preferably an A / B of 0.7 or less.
- a / B is 0.60 or less.
- a / B is 0.5 or less.
- the above-mentioned moisture permeability reducing compound may have a structure containing one or more aromatic rings.
- the aromatic ring can impart hydrophobic properties to the film and can suppress the permeation and desorption of water.
- the moisture permeability reducing compound more preferably has a structure containing three or more aromatic rings.
- the moisture permeability reducing compound preferably contains one or more -OH groups, more preferably contains three or more aromatic rings, and more preferably contains one or more -OH groups.
- the moisture permeability reducing compound As the moisture permeability reducing compound, the compound represented by the general formula (B), the phenol resin, the terpene resin, the aromatic hydrocarbon formaldehyde resin, and the barbituric acid or phosphoric acid ester are preferable, and the general formula The compound represented by B), the phenol resin, the terpene resin, the aromatic hydrocarbon formaldehyde resin or the barbituric acid are more preferable, and the moisture permeability reducing compound is a novolac type phenol resin, a hydrogenated terpene resin, a xylene resin Or barbituric acids are particularly preferred.
- aromatic hydrocarbon formaldehyde resin is particularly preferable, and from the viewpoint of further improving the unevenness of black display after aging under high temperature and high humidity environment when the optical film of the present invention is incorporated in a liquid crystal display, Type phenolic resins are preferred) or the aforementioned aromatic hydrocarbon formaldehyde resins (of which xylene resins are preferred) are even more particularly preferred.
- n 1 to 10
- m independently represents an integer of 1 to 4
- R may independently have a hydrogen atom, -OH group or a substituent
- It represents an alkyl group having 1 to 10 carbon atoms
- L 1 and L 2 each independently represent a methylene group or —CH 2 —O—CH 2 —.
- at least one of R represents a group containing an —OH group.
- n is preferably 1 to 7.
- m is preferably 1 to 3, and more preferably 1 or 2.
- R is preferably each independently a hydrogen atom, an —OH group, or a methyl group or ethyl group which may have a substituent.
- the substituent which the alkyl group represented by R may have is not particularly limited, but is preferably -OH.
- the moisture permeability reducing compound represented by the above general formula (C) a compound satisfying the above general formula (C) among a phenol resin and an aromatic hydrocarbon formaldehyde resin described later is preferable.
- moisture permeability reducing compound petroleum resin, terpene resin, terpene phenol resin, rosin resin, coumarone resin, resin using formaldehyde as a raw material (phenol resin such as phenol formaldehyde resin and its derivative, aromatic hydrocarbon formaldehyde resin, Derivatives thereof and the like, as well as their hydrides can preferably be used.
- the novolac type phenol resin used in the present invention is a normal novolac type phenol resin obtained by reacting phenol and formaldehyde (formalin) under an acidic catalyst such as oxalic acid.
- the raw material of the phenol is not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-octylphenol, p-nonylphenol and the like Mixtures can be used.
- p-cresol is preferable.
- formalin, paraform, acetal and the like and mixtures thereof can be used as a source of formaldehyde.
- the structure of the novolac type phenolic resin is represented by the following general formula (1).
- n represents an average of 1 to 10
- R independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, among which an alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of durability, and a methyl group More preferable.
- the position of R substituted on each benzene ring of R is not particularly limited, but is preferably the para-position to the —OH group.
- n is preferably 1 to 7.
- the bonding position of the methylene group connecting each benzene ring is not particularly limited, but is preferably ortho to the —OH group.
- novolak-type phenolic resin represented by the general formula (1) Specific examples of the novolak-type phenolic resin represented by the general formula (1) are listed below, but the present invention is not limited thereto. Moreover, n in the following specific examples is synonymous with n in General formula (1). Among the following specific examples, A-4 is preferable.
- a phenolic resin (Sumilite resin PR-HF-3 or the like) manufactured by Sumitomo Bakelite Co., Ltd. can be suitably used.
- the novolak type phenolic resin preferably has a weight average molecular weight of 200 to 10,000, more preferably 200 to 5,000, and particularly preferably 200 to 3,000.
- aromatic hydrocarbon formaldehyde resin As the aromatic hydrocarbon formaldehyde resin used in the present invention, a common aromatic hydrocarbon formaldehyde resin which can be generally obtained by reacting an aromatic hydrocarbon with formaldehyde (formalin) can be used.
- the raw material of the aromatic hydrocarbon is not particularly limited, and, for example, toluene, three isomers of xylene, mesitylene, a monocyclic aromatic hydrocarbon compound having 10 or more carbon atoms, and the like and mixtures thereof can be used.
- xylene is preferable, and m-xylene is more preferable.
- formalin, paraform, acetal and the like and mixtures thereof can be used as a source of formaldehyde.
- the structure of the aromatic hydrocarbon formaldehyde resin is preferably represented by the following general formula (2).
- n represents an average of 1 to 10
- m independently represents an integer of 1 to 3
- R independently represents a methyl group or an ethyl group
- L 1 and L 2 represent Each independently represents a methylene group or -CH 2 -O-CH 2- .
- R is preferably a methyl group.
- the number of R substituted on each benzene ring of R is not particularly limited, but is preferably 0 to 2, and more preferably 2.
- the position of R substituted on each benzene ring of R is not particularly limited.
- n is preferably 1 to 7.
- the bonding position of the methylene group or —CH 2 O— group linked to each benzene ring is not particularly limited, but it is preferable that they have a relation of meta position to each other.
- aromatic hydrocarbon formaldehyde resin represented by the general formula (2) Specific examples of the aromatic hydrocarbon formaldehyde resin represented by the general formula (2) are listed below, but the present invention is not limited thereto. Moreover, n is synonymous with n in General formula (2).
- the xylene resin (Nicanol Y1000 grade
- the molecular weight of the aromatic hydrocarbon formaldehyde resin is preferably 200 to 10,000, more preferably 200 to 5,000, and particularly preferably 200 to 3,000.
- the aromatic hydrocarbon formaldehyde resin can be preferably used when the thermoplastic resin of the optical film of the present invention is a norbornene resin.
- the terpene resin used in the present invention is preferably a hydrogenated terpene resin.
- the hydrogenated terpene resin used in the present invention is generally a compound obtained by partially hydrogenating a terpene resin obtained by subjecting a terpene compound to cationic polymerization under Friedel-Crafts catalyst.
- terpene compounds examples include ⁇ -pinene, ⁇ -pinene, dipentene, d-limonene, myrcene, alloocimene, ocimene, ⁇ -ferandrene, ⁇ -terpinene, ⁇ -terpinene, terpinorene, 1,8-cineole, -Cineole, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol, sabinene, paramentadienes, carenes, etc., and ⁇ -pinene, ⁇ -pinene, dipentene, d-limonene are preferably used.
- terpene compounds and aromatic compounds and terpene compounds and phenol compounds may be used as raw materials.
- hydrogenated terpene resin hydrogenated terpene resin (CLEARON P150, CLEARON P135, CLEARON P125, CLEARON) 115 manufactured by Yasuhara Chemical Co., Ltd., CLEARON P105, CLEARON P85, aromatic modified hydrogenated terpene resin (CLEARON M125, Clearon M115 and Clearon M105) can be suitably used.
- R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 23 , R 24 , R 25 , R 32 , R 33 , R 34 , R 35 , and R 36 are Each represents a hydrogen atom or a substituent, and a substituent T described later can be applied as the substituent.
- the substituent T is, for example, an alkyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 12, particularly preferably a carbon number of 1 to 8, and for example, a methyl group, an ethyl group, an isopropyl group, tert-butyl Group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group etc., alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 carbon atoms) And particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl and 3-pentenyl groups, and alkynyl groups (preferably 2 to 20 carbon atoms, more preferably Is 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-penty
- carbon atoms Preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyl, p-methylphenyl and naphthyl), and amino groups (Preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.
- amino groups Preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.
- an alkoxy group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 12, particularly preferably a carbon number of 1 to 8, and examples thereof include a methoxy group, an ethoxy group and a butoxy group.
- An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms;
- an acyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 12, for example, an acetyl group, And benzoyl, formyl, pivaloyl and the like) and alkoxycarbonyl groups (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, particularly preferably a carbon number of 2 to 12, for example, methoxycarbonyl Group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (preferably having 7 to 20 carbon
- an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and in particular The carbon number is preferably 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group.
- An acylamino group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 16, particularly preferably a carbon number of 2 to 10, and examples include an acetylamino group, a benzoylamino group and the like), and alkoxycarbonyl
- An amino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group etc.), an aryloxycarbonylamino group (preferably, Is preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group and the like, a sulfonylamino group (preferably 1 to carbon atoms) 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms; And sulfamoyl groups (preferably
- sulfamoyl group dimethylsulfamoyl group, phenylsulfamoyl group and the like
- carbamoyl group preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 20.
- carbamoyl group includes, for example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc., alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon).
- the number 1 to 12, and examples thereof include a methylthio group and an ethylthio group.
- An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples include a phenylthio group), a sulfonyl group (preferably, The carbon number is preferably 1 to 20, more preferably 1 to 16 and particularly preferably 1 to 12, and examples thereof include a mesyl group and a tosyl group), and a sulfinyl group (preferably 1 to 20 carbon atoms).
- the carbon number is more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group, and a ureido group (preferably a carbon number of 1 to 20, more preferably carbon).
- the number is 1 to 16, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido group, methyl ureido group and phenyl ureido group.
- phosphoric acid amide group (preferably having a carbon number of 1 to 20, more preferably having a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 12, and examples thereof include diethyl phosphoric acid amide group and phenyl phosphoric acid amide group Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino Group, heterocyclic group (preferably having a carbon number of 1 to 30, more preferably 1 to 12, and as a hetero atom, for example, nitrogen atom, oxygen atom, sulfur atom, specifically, for example, imidazolyl group, pyridyl group, quinolyl Group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimi
- Silyl group (preferably having a carbon number of 3 to 40, more preferably having a carbon number of 3 to 30, particularly preferably a carbon number of 3 to 24, and examples thereof include a trimethylsilyl group and a triphenylsilyl group And the like).
- substituents may be further substituted by a substituent T. When two or more substituents are present, they may be the same or different. Moreover, when possible, they may be linked to each other to form a ring.
- at least one of them is an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a hydroxy group, a mercapto group or a carboxyl group, more preferably an amino group or a hydroxy group Preferably it is a hydroxy group.
- these groups may be substituted by a substituent.
- the substituent in this case the above-mentioned substituent T can be applied, and the preferred range is also the same.
- Barbituric acids can also be used as the moisture permeability reducing compound.
- barbituric acids used in the present invention compounds represented by the following general formula (3) can be used.
- R 1 , R 3 and R 5 each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or 6 carbon atoms Represents an aromatic group of -20.
- the alkyl group having 1 to 20 carbon atoms that can be adopted as R 1 , R 3 and R 5 preferably has 1 to 10 carbon atoms, and is 1 to 5 More preferably, it is more preferably 1 to 3, and still more preferably a methyl group or an ethyl group.
- the cycloalkyl group having 3 to 20 carbon atoms which can be adopted as R 1 , R 3 and R 5 preferably has 3 to 10 carbon atoms, and is 4 to 8 Is more preferred.
- the alkenyl group having 2 to 20 carbon atoms which can be adopted as R 1 , R 3 and R 5 preferably has 2 to 10 carbon atoms, and is 2 to 5 Is more preferred.
- the above-mentioned 6 to 20 aromatic groups which can be adopted as R 1 , R 3 and R 5 may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
- aromatic hydrocarbon groups are preferable.
- the aromatic hydrocarbon group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
- R 1 , R 3 and R 5 may have a substituent, but the substituent is not particularly limited, and an alkyl group (preferably having 1 to 10 carbon atoms, for example, Methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl etc., alkenyl group (preferably having a carbon number of 2 to 20), for example, vinyl, allyl , Oleyl and the like), alkynyl group (preferably having a carbon number of 2 to 20, for example, ethynyl, butadiynyl, phenylethynyl and the like), and a cycloalkyl group (preferably having a carbon number of 3 to 20, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl
- the ring may be a saturated ring, an unsaturated ring, or an aromatic ring, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2 -Benzoimidazolyl, 2-thiazolyl, 2-oxazolyl etc., an alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably having 6 to 26 carbon atoms) For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), an alkylthio group (preferably carbon) 1 to 20, for example, methylthio, ethylthio, isopropylthio, benzylthio etc., an arylthio group (preferably having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylpheny
- An acyl group (including an alkylcarbonyl group, an alkenylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and preferably having a carbon number of 20 or less), for example, acetyl, pivaloyl, acryloyl, metachloroyl, benzoyl, nicotinoyl, etc., aryloyl Alkyl group, alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl etc.), aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, for example, phenyloxy group And an amino group (amino group, alkylamino group, arylamino group, heterocyclic amino group, preferably containing 0 to 20 carbon atoms); for example, amino, N, N-dimethylamino, N , N-die
- the aralkyl group is a compound in which an aryl group is substituted with an alkyl group, and among aralkyl groups, one or two alkyl groups Those substituted by the aryl group of (wherein two aryl groups are substituted, it is preferable to substitute at the same carbon atom) are preferable.
- an alkyl group is substituted with an aryl group and an acyl group (preferably an aryloyl group) is also preferable.
- -A compound wherein any one of R 1 , R 3 and R 5 is a group containing a cycloalkyl group, preferably, the group containing a cycloalkyl group is a cycloalkyl group
- the compound represented by the general formula (3) is an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms, from the viewpoint of dissolution stability when forming a film
- R 1 , R 3 and R 5 are More preferably, it is an aryl group having 6 to 20 carbon atoms. More preferably, each of R 1 , R 3 and R 5 has one or more ring structures, and more preferably one ring structure.
- the compound represented by the above general formula (3) is represented by the following general formula (3-a).
- L 1 to L 3 each represent a single bond or a divalent linking group having one or more carbon atoms.
- the above L 1 to L 3 are more preferably a single bond or an alkylene group having 1 to 6 carbon atoms, still more preferably a single bond, a methylene group or an ethylene group, and particularly preferably a single bond or a methylene group preferable.
- at least one of L 1 ⁇ L 3 is preferably an alkylene group having 1 to 6 carbon atoms, at least two of L 1 ⁇ L 3 has 1 to 6 carbon It is more preferable that it is an alkylene group.
- at least one of L 1 to L 3 is a single bond.
- the divalent linking group which can be represented by L 1 to L 3 may have a substituent, and the substituent has the same meaning as the substituent which may be possessed by R 1 , R 3 and R 5 described above. It is.
- Ar 1 to Ar 3 each represent an aryl group having a carbon number of 6 to 20, preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- Ar 1 to Ar 3 may have a substituent, and the substituent is the same as the substituent which the above R 1 , R 3 and R 5 may have.
- Ar 1 to Ar 3 do not have a substituent or have a substituent, it is preferable that the substituent does not have a ring structure.
- the molecular weight of the compound represented by the general formula (3) and the general formula (3-a) is preferably 250 to 1200, more preferably 300 to 800, and particularly preferably 350 to 600. If the molecular weight is too small, volatilization from the film may be a problem, and if too large, the haze may be high.
- the compound represented by the above general formula (3) can be synthesized using a synthesis method of barbituric acid in which a urea derivative and a malonic acid derivative are condensed.
- Barbituric acid having two substituents on N can be prepared by heating N, N ′ disubstituted urea and malonic acid chloride, or by combining and heating malonic acid and an activating agent such as acetic anhydride
- an activating agent such as acetic anhydride
- malonic acid used for condensation may be unsubstituted one or one having a substituent, and if malonic acid having a substituent corresponding to R 5 is used, the general formula of the present invention can be obtained by constructing barbituric acid.
- the compound represented by (3) can be synthesized.
- condensation of unsubstituted malonic acid with a urea derivative gives barbituric acid which is unsubstituted at position 5. Therefore, by modifying this, the compound represented by the general formula (3) of the present invention is synthesized. May be In addition, the synthesis method of the compound represented by General formula (3) used for this invention is not limited above.
- a phosphate ester can also be used as the moisture permeability reducing compound.
- the phosphate ester used in the present invention include low molecular phosphate esters known as additives to cellulose acylate films such as TPP (triphenyl phosphate).
- TPP triphenyl phosphate
- the phosphate ester preferably has a molecular weight of 200 to 1,000.
- the optimum moisture permeability reducing compound can be selected according to the type of the thermoplastic resin.
- the thermoplastic resin of the optical film of the present invention is an acrylic resin
- the compound represented by the general formula (B) and the phenol resin can be preferably used as the moisture permeability reducing compound.
- the thermoplastic resin of the optical film of the present invention is a polystyrene resin or a styrene-acrylonitrile resin
- the compound represented by the general formula (B) or a phosphoric acid ester can be preferably used as the moisture permeability reducing compound.
- the compound represented by the above general formula (B) is more preferably used.
- thermoplastic resin of the optical film of the present invention is a norbornene resin, the compound represented by the general formula (B), the phenol resin, the terpene resin, the aromatic hydrocarbon as the moisture permeability reducing compound
- a formaldehyde resin or barbituric acid more preferably to use the terpene resin, the aromatic hydrocarbon formaldehyde resin or the barbituric acid, and using the terpene resin or the aromatic hydrocarbon formaldehyde resin.
- the above-mentioned moisture permeability reducing compound is preferably contained in an amount of 10% by mass to 100% by mass with respect to the mass of the thermoplastic resin. More preferably, it is 15% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass.
- Fine particles can be added as a matting agent to the optical film of the present invention.
- fine particles used as a matting agent silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate can be mentioned.
- the fine particles containing silicon are preferable in that the haze of the film is low, and silicon dioxide is particularly preferable.
- the fine particles of silicon dioxide preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more.
- a primary particle having a small average diameter of 5 to 16 nm is more preferable because the haze of the film can be lowered.
- the apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. As the apparent specific gravity is larger, it is possible to make a dispersion with a high concentration, and the haze and the aggregates are improved, which is preferable.
- These fine particles usually form secondary particles having an average particle size of 0.1 to 3.0 ⁇ m, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to An unevenness of 3.0 ⁇ m is formed.
- the average particle diameter of the secondary particles is preferably 0.2 ⁇ m to 1.5 ⁇ m, more preferably 0.4 ⁇ m to 1.2 ⁇ m, and most preferably 0.6 ⁇ m to 1.1 ⁇ m.
- the particle diameter of the primary particles and secondary particles was determined by observing the particles in the film with a scanning electron microscope, and the diameter of the circle circumscribing the particles was taken as the particle diameter. Further, 200 particles were observed at different places, and the average value was taken as the average particle diameter.
- fine particles of silicon dioxide for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200 V, 300, R202, OX50, TT600 (all manufactured by Nippon Aerosil Co., Ltd.) can be used.
- fine particles of zirconium oxide are commercially available under the trade name of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used.
- Aerosil 200 V and Aerosil R 972 V are fine particles of silicon dioxide having an average particle diameter of primary particles of 20 nm or less and an apparent specific gravity of 70 g / liter or more, while keeping the turbidity of the optical film low. It is particularly preferable because the effect of lowering the coefficient of friction is large.
- solvent used for dispersion lower alcohols are preferable, and methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like can be mentioned. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of an optical film.
- the optical film of the present invention may contain various other additives (for example, a retardation developing agent, a plasticizer, an ultraviolet absorber, an antidegradant, a release agent, an infrared absorber, wavelength dispersion adjustment Agents), which may be solid or oily. That is, the melting point and the boiling point thereof are not particularly limited. For example, mixing of ultraviolet absorbing materials at 20 ° C. or less and 20 ° C. or more, mixing of plasticizers, and the like are also described, for example, in JP-A-2001-151901. Furthermore, infrared absorbing dyes are described, for example, in JP-A-2001-194522.
- additives for example, a retardation developing agent, a plasticizer, an ultraviolet absorber, an antidegradant, a release agent, an infrared absorber, wavelength dispersion adjustment Agents
- the melting point and the boiling point thereof are not particularly limited.
- the addition may be performed at any time in the dope preparation step, but may be performed by adding an additive and preparing step to the final preparation step of the dope preparation step.
- the addition amount of each material is not particularly limited as long as the function is exhibited.
- the kind and addition amount of the additive of each layer may differ.
- these are the techniques conventionally known.
- the materials described in detail in pages 16 to 22 of the Japan Institute of Invention and Innovation Technical Bulletin Publication No. 2001-1745, published on March 15, 2001, Japan Institute of Invention and Invention
- the optical film of the present invention may also contain acrylic particles.
- Japanese Patent Publication No. 60-17406, Japanese Patent Publication No. 3-39095, etc. disclose that the impact resistance and the stress whitening resistance are improved by adding an acrylic particle, particularly a multilayer structure acrylic granular composite.
- the total amount of the additives is preferably 50% by mass or less and preferably 30% by mass or less with respect to the optical film.
- Re and Rth (defined by the following formulas (I) and (II)) measured at a wavelength of 590 nm satisfy the formulas (III) and (IV).
- Formula (I) Re (nx-ny) x d
- Rth ⁇ (nx + ny) / 2-nz ⁇ ⁇ d
- n x is the refractive index in the slow axis direction in the film plane of the optical film
- ny is the refractive index in the fast axis direction in the optical film plane
- nz is the film thickness of the optical film Is the refractive index of the direction
- d is the thickness (nm) of the optical film.
- the above formulas (III) and (IV) may be satisfied at at least one point in the film plane, but the above formulas (III) and Is preferably satisfied.
- Re, Rth and Nz at the wavelength ⁇ nm can be measured as follows. Re is measured by causing light of wavelength ⁇ nm to be incident in the film normal direction in KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.).
- Rth was measured by making light of wavelength ⁇ nm incident from a direction inclined by + 40 ° with respect to the film normal direction with Re and an in-plane slow axis (as judged by KOBRA 21ADH) as a tilt axis (rotational axis) Retardation value and a total of three retardation values measured by making light of wavelength ⁇ nm incident from the direction inclined at -40 ° to the film normal direction with the in-plane slow axis as the inclined axis (rotation axis) Calculated by KOBRA 21ADH based on the retardation value measured in the direction.
- thermoplastic handbooks JOHN WILEY & SONS, INC
- catalogs of various optical films are exemplified below: cellulose acylate (1.48), cyclic polyolefin (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).
- Nz is calculated by equation (VI) based on Re and Rth.
- nx, ny, nz by KOBRA 21ADH based on the hypothetical value of the average refractive index and the film thickness, and to calculate Nz by equation (II) from the values of nx, ny, nz.
- the above Re, Rth and Nz can be adjusted by the addition of a retardation developer, the film thickness of the film, the stretching direction and the stretching ratio of the film, and the like.
- thickness of film 100 micrometers or less are preferable, as for the thickness of the optical film of this invention, 60 micrometers or less are more preferable, 40 micrometers or less are still more preferable, and 25 micrometers or less are especially preferable. If it is 60 ⁇ m or less, the environment in which the liquid crystal display device is placed, that is, the unevenness of the panel due to the change in temperature and humidity can be reduced.
- the moisture permeability of the film is measured under the conditions of 40 ° C. and 90% relative humidity based on JIS Z-0208.
- the moisture permeability was determined as the moisture permeability of the sample by correcting the zero point by subtracting the moisture permeability measurement value using an aluminum foil of 10 ⁇ m thickness instead of each sample from the measurement value of each sample.
- the moisture permeability decreases as the film thickness of the film increases, and increases as the film thickness decreases. Therefore, for samples with different film thicknesses, it is necessary to set the reference at 40 ⁇ m and convert.
- the conversion of the film thickness can be performed according to the following formula.
- the moisture permeability of the optical film of the present invention is more preferably 70 g / m 2 / day or less, still more preferably 50 g / m 2 / day, and still more preferably 40 g / m 2 / day or less Preferably, it is even more particularly preferably 30 g / m 2 / day or less. If the moisture permeability is 70 g / m 2 / day or less, it is possible to suppress the warping of the liquid crystal cell and the display unevenness at the time of black display after the normal temperature, high humidity and high temperature / high humidity environment aging of the liquid crystal display device.
- the oxygen permeation coefficient of the optical film of the present invention is preferably 100 cc ⁇ mm / (m 2 ⁇ day ⁇ atm) or less, and more preferably 30 cc ⁇ mm / (m 2 ⁇ day ⁇ atm) or less. In the case of the solvent casting method, 5 cc ⁇ mm / (m 2 ⁇ day ⁇ atm) or more is preferable in order to reduce the load of the drying process.
- the oxygen transmission rate of the film was measured by attaching a test piece cut to a diameter of 1.5 cm through a silicone grease thinly applied to an oxygen electrode (Obisphere Laboratories, MODEL 3600, PFA), and steady-state oxygen reduction current The oxygen permeation was determined from the output value.
- the conversion of the output current value to the oxygen permeation amount was obtained by preparing a calibration curve using a sample of which the permeation amount was known. The measurement was performed at 25 ° C. under a 50% relative humidity environment.
- the surface hardness is high, and in that case, as the characteristics of the optical film of the present invention, it is preferable that the Knoop hardness is high.
- the Knoop hardness is preferably 100 N / mm 2 or more, and more preferably 150 N / mm 2 or more.
- the direction of the short axis of the indenter is parallel to the transport direction (longitudinal direction; test direction in pencil hardness test) at film formation using "Fusher Scope H100 Vp hardness tester” manufactured by Fisher Instruments Co., Ltd.
- the sample surface fixed to the glass substrate was measured under the conditions of a loading time of 10 sec, a creep time of 5 sec, an unloading time of 10 sec, and a maximum load of 100 mN by the arranged Knoop indenter.
- the hardness was calculated from the relationship between the contact area between the indenter and the sample determined from the indentation depth and the maximum load, and the average value of these five points was taken as the surface hardness.
- the optical film of the present invention preferably has a total haze value (unit of haze value:%, hereinafter the same) is 2.00 or less.
- a total haze value (unit of haze value:%, hereinafter the same) is 2.00 or less.
- the total haze value is more preferably 1.00 or less, further preferably 0.50 or less, particularly preferably 0.30 or less, and most preferably 0.20 or less.
- the internal haze value of the optical film of the present invention is preferably 1.00 or less.
- the contrast ratio of the liquid crystal display device can be improved, and excellent display characteristics can be realized.
- the internal haze value is more preferably 0.50 or less, further preferably 0.20 or less, particularly preferably 0.10 or less, and most preferably 0.05 or less. It is preferable that it is 0.01 or more from a viewpoint of raw material selection, manufacturing control, etc.
- the total haze value is preferably 0.30 or less, and the internal haze value is preferably 0.10 or less.
- the total haze value and the internal haze value are the type and amount of resin of the film material, the selection of additives (in particular, the particle diameter of the matting agent particles, the refractive index, the amount added) and further the film manufacturing conditions (at the time of stretching It can adjust by temperature, a draw ratio, etc.).
- the haze can be measured according to JIS K-6714 with a haze meter (HGM-2DP, Suga Test Instruments) at 25 ° C. and a relative humidity of 60% of the film sample 40 mm ⁇ 80 mm of the present invention.
- the elastic modulus of the optical film of the present invention is preferably 1800 to 7000 MPa in the width direction (TD direction).
- TD direction width direction
- the elastic modulus in the TD direction is in the above-mentioned range, display unevenness at the time of black display after high humidity and high temperature high humidity environment aging, transportability at the time of film preparation, edge slit property and difficulty in breaking It is preferable from the viewpoint of production aptitudes such as the length. If the TD elastic modulus is too small, display unevenness at the time of black display after high humidity and high temperature and high humidity environment aging tends to occur, and a problem occurs in manufacturing suitability, and if it is too large, the film processability is inferior.
- the elastic modulus is more preferably 1800 to 5000 MPa, and still more preferably 1800 to 4000 MPa. Further, the elastic modulus of the optical film of the present invention in the transport direction (MD direction) is preferably 1800 to 4000 MPa, and more preferably 1800 to 3000 MPa.
- the film transport direction (longitudinal direction) is the transport direction (MD direction) at the time of film production
- the width direction is the direction (TD direction) perpendicular to the transport direction at the film production.
- the elastic modulus of the film is adjusted by the type and amount of resin of the film material, the selection of additives (in particular, the particle diameter of the matting agent particles, the refractive index and the amount added), and further the film manufacturing conditions (stretching ratio etc.) can do.
- the modulus of elasticity is measured at an elongation rate of 0.5% at a tensile rate of 10% / min in an atmosphere at a relative humidity of 70%. Can be asked.
- the glass transition temperature Tg of the optical film of the present invention is preferably 100 ° C. or more and 200 ° C. or less, and more preferably 100 ° C. or more and 150 ° C. or less, from the viewpoint of production suitability and heat resistance. Moreover, the measurement of a glass transition temperature can also be calculated
- a dynamic viscoelasticity measuring apparatus Vibron: DVA-225 (manufactured by IT Measurement & Control Co., Ltd.)
- a grip distance of 20 mm With a grip distance of 20 mm, a heating rate of 2 ° C./min, a measurement temperature range of 30 ° C.
- the moisture content (equilibrium moisture content) of the optical film of the present invention when used as a protective film of a polarizing plate, does not impair the adhesiveness to water-soluble thermoplasticity such as polyvinyl alcohol, regardless of the film thickness.
- the water content at 25 ° C. and 80% relative humidity is preferably 0 to 4% by mass.
- the content is more preferably 0.1 to 2.5% by mass, still more preferably 0.5 to 1.5% by mass.
- the equilibrium moisture content is 4% by mass or less, the dependency of retardation on humidity change does not become too large, and display unevenness during black display after normal temperature, high humidity and high temperature high humidity environment of liquid crystal display device is suppressed It is preferable from the point of The moisture content was measured by using a film sample of 7 mm ⁇ 35 mm by the Karl Fischer method with a moisture measuring device and sample drying devices “CA-03” and “VA-05” ⁇ both manufactured by Mitsubishi Chemical Co., Ltd. ⁇ . It can be calculated by dividing the water content (g) by the sample mass (g).
- the dimensional stability of the optical film of the present invention is as follows: dimensional change when left to stand under conditions of 60 ° C., relative humidity 90% (high humidity), and 80 ° C., DRY environment (relative humidity 5%) It is preferable that the dimensional change rate in each case (high temperature) after standing for 24 hours under the following conditions is 0.5% or less. More preferably, it is 0.3% or less, still more preferably 0.15% or less.
- birefringence When the optical film of the present invention is used as a protective film for a polarizing plate, birefringence (Re, Rth) may change due to stress due to shrinkage of a polarizer.
- the change in birefringence accompanying such stress can be measured as a photoelastic coefficient, but the range is preferably 30 Br or less, more preferably -3 to 12 Br, and further preferably 0 to 11 Br. preferable.
- the method for producing an optical film of the present invention comprises the step of casting a thermoplastic resin and a moisture permeability reducing compound on a support to form a polymer film, and the molecular weight of the moisture permeability reducing compound is 200 or more.
- the moisture permeability reducing compound satisfies the following formula (1).
- A represents the moisture permeability of the optical film when 10% by mass of the moisture permeability reducing compound is added with respect to the mass of the thermoplastic resin
- B includes the thermoplastic resin and the permeability
- Tg of the unstretched polymer film after drying is preferably 100 to 200 ° C., and more preferably 100 to 150 ° C.
- the polymer film (dried film) after drying refers to one in which the amount of residual solvent in the film is 3.0% by mass or less. It refers to a polymer membrane which is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, particularly preferably 0.2% by mass or less.
- the glass transition temperature can be adjusted by the type and mass ratio of the thermoplastic resin.
- the film forming method of the polymer film manufacturing methods such as inflation method, T-die method, calendar method, cutting method, casting method, emulsion method, hot press method and the like can be used. From the viewpoints of suppression, suppression of optical defects such as die lines, and the like, solution film formation by a casting method is preferable.
- the method for producing an optical film of the present invention may use a solution casting method or a melt casting method.
- the step of casting the thermoplastic resin and the moisture permeability reducing compound on a support to form a polymer film is obtained by melting the thermoplastic resin and the moisture permeability reducing compound as a support It is preferable to be a step of forming a polymer film by casting on the top.
- the melt casting method the method described in detail in JP-A-2009-154301 can be used.
- the step of casting the thermoplastic resin and the moisture permeability reducing compound on a support to form a polymer film comprises the thermoplastic resin, the moisture permeability reducing compound, and a solvent.
- the polymer film is formed by casting a polymer solution (dope) containing the thermoplastic resin, the moisture permeability reducing compound, and a solvent on a support.
- a solvent useful for forming a dope can be used without limitation as long as it can simultaneously dissolve the thermoplastic resin, the moisture permeability reducing compound and other additives.
- the organic solvent any of a chlorine-based solvent containing a chlorine-based organic solvent as a main solvent and a non-chlorine-based solvent not containing a chlorine-based organic solvent can be used. Two or more organic solvents may be mixed and used.
- a chlorine-based organic solvent is preferably used as a main solvent.
- the type of the chlorine-based organic solvent is not particularly limited as long as the purpose can be achieved as long as the thermoplastic resin can be dissolved, cast, and formed into a film.
- These chlorinated organic solvents are preferably dichloromethane and chloroform. In particular, dichloromethane is preferred.
- dichloromethane is preferred.
- the other organic solvents used in combination with the chlorine-based organic solvent in the present invention are described below.
- solvents selected from esters having 3 to 12 carbon atoms, ketones, ethers, alcohols, hydrocarbons and the like are preferable.
- the ester, ketone, ether and alcohol may have a cyclic structure.
- Compounds having two or more functional groups of ester, ketone and ether ie, -O-, -CO- and -COO- can also be used as a solvent, for example, other functional groups such as alcoholic hydroxyl group It may have a group simultaneously.
- the number of carbon atoms may be within the specified range of the compound having any of the functional groups.
- solvents described in JP-A-2007-140497 can be used.
- the dope can be prepared by a general method comprising treatment at a temperature of 0 ° C. or more (normal temperature or high temperature). Preparation of the dope which can be used for this invention can be implemented using the preparation method and apparatus of dope in the usual solvent casting method.
- the total amount of the thermoplastic resin is preferably adjusted to be 10 to 40% by mass in the polymer solution to be obtained. More preferably, the amount of the thermoplastic resin is 10 to 30% by mass.
- the organic solvent main solvent
- an optional additive described later may be added.
- the solution can be prepared by stirring the thermoplastic resin and the organic solvent at normal temperature (0 to 40 ° C.). The highly concentrated solution may be stirred under pressure and heat conditions.
- thermoplastic resin and the organic solvent are put in a pressure vessel and sealed, and the mixture is stirred under pressure while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil.
- the heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.
- the optical film can achieve improved adhesion between the optical film and other layers (for example, a polarizer, an undercoat layer, and a back layer) by optionally performing surface treatment.
- glow discharge treatment ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used.
- the glow discharge treatment referred to here may be low temperature plasma generated under a low pressure gas of 10 -3 to 20 Torr, and plasma treatment under atmospheric pressure is also preferable.
- Plasma-exciting gas refers to a gas excited by plasma under the above conditions, such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, fluorocarbons such as tetrafluoromethane, and mixtures thereof. Be These are described in detail in the Japan Institute of Invention and Innovation Technical Bulletin (Publication No. 2001-1745, published on March 15, 2001, the Japan Institute of Invention and Innovation) on pages 30 to 32 and preferably used in the present invention. be able to.
- a functional layer having a thickness of 0.1 to 20 ⁇ m on at least one surface.
- the type of this functional layer is not particularly limited, but hard coat layers, antireflection layers (layers with adjusted refractive index such as low refractive index layer, medium refractive index layer, high refractive index layer), antiglare layer, antistatic layer An ultraviolet absorption layer, a low moisture-permeable layer (a moisture-permeability reduction layer), etc. are mentioned.
- the functional layer may be a single layer or a plurality of layers.
- the method of laminating the functional layer is not particularly limited, but co-casting of a thermoplastic resin and an optical film containing the moisture permeability reducing compound, or coating on an optical film containing a thermoplastic resin and the moisture permeability reducing compound Is preferably provided.
- the functional layer is formed by coating and drying, it is preferable to use a monomer having an ethylenically unsaturated group as a binder.
- the monomer may be monofunctional or polyfunctional.
- a polymerizable polyfunctional monomer it is more preferable to use a photopolymerizable polyfunctional monomer, and it is particularly preferable to use a coating solution containing a monomer having two or more (meth) acryloyl groups. .
- the monomer having two or more (meth) acryloyl groups include (meth) alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate and propylene glycol di (meth) acrylate.
- Acrylic acid diesters (Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; (Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis ⁇ 4- (acryloxy.diethoxy) phenyl ⁇ propane and 2-2-bis ⁇ 4- (acryloxy polypropoxy) phenyl ⁇ propane ; Etc. can be mentioned.
- polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (
- epoxy (meth) acrylates, urethane (meth) acrylates and polyester (meth) acrylates are also preferably used as photopolymerizable polyfunctional monomers.
- esters of polyhydric alcohol and (meth) acrylic acid are preferred.
- Polyhydric alcohol means alcohol having two or more valences. More preferably, polyfunctional monomers having three or more (meth) acryloyl groups in one molecule are preferable.
- pentaerythritol tetra (meth) acrylate pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, Ethylene oxide modified phosphoric acid tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexamer (Meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, Li ester polyacrylate, caprolactone-
- resins having three or more (meth) acryloyl groups such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.
- dendrimers described in JP-A-2005-76005 and JP-A-2005-36105 can also be used.
- esters of polyhydric alcohol and (meth) acrylic acid, and amides of polyhydric alcohol and isocyanate containing plural (meth) acryloyl groups are also preferably used.
- the polyhydric alcohol is not particularly limited, but is preferably an aliphatic alcohol, and more preferably an alcohol having a cyclic aliphatic hydrocarbon group.
- the aliphatic group of the monocyclic alicyclic alcohol is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group.
- Examples of the aliphatic group of the polycyclic alicyclic alcohol include groups having a carbon number of 5 or more and having a bicyclo, tricyclo, tetracyclo structure or the like, and a cycloalkyl group having a carbon number of 6 to 20 is preferable.
- a part of carbon atom in a cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom.
- polycyclic alcohol an adamantyl group, a norbornyl group, a dicyclopentyl group, a tricyclodecanyl group, a tetracyclododecyl group, and a central skeleton of a compound described in JP-A-2006-215096.
- Polyhydric alcohols having a central skeleton of the compound described in JP-A-2001-10999 are particularly preferable from the viewpoint of reducing the moisture permeability.
- Two or more types of polymerizable polyfunctional monomers may be used in combination.
- the polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
- a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer.
- a photopolymerization initiator a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
- a monomer having one (meth) acryloyl group is preferable, and a monomer having one (meth) acryloyl group is generally obtained from a monohydric alcohol and acrylic acid.
- the monohydric alcohol may be an aromatic alcohol or an aliphatic alcohol.
- the aliphatic portion of the aliphatic alcohol may be cycloaliphatic.
- the cycloaliphatic may be monocyclic or polycyclic, and in the case of polycyclic, it may be bridged.
- the monocyclic type is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group.
- groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms can be mentioned, and a cycloalkyl group having 6 to 20 carbon atoms is preferable.
- a part of carbon atom in a cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom.
- the monovalent alcohol is preferably an aromatic alcohol or an aliphatic alcohol, and preferably has 6 or more carbon atoms.
- acrylic acid acrylic acid and methacrylic acid are preferable.
- an antireflection layer (a layer having a controlled refractive index, such as a low refractive index layer, a middle refractive index layer, a high refractive index layer), an antiglare layer, an antistatic layer, an ultraviolet absorbing layer, a low moisture permeation layer
- a humidity reduction layer a layer having a controlled refractive index, such as a low refractive index layer, a middle refractive index layer, a high refractive index layer
- an antiglare layer a layer having a controlled refractive index, such as a low refractive index layer, a middle refractive index layer, a high refractive index layer
- an antiglare layer such as a low refractive index layer, a middle refractive index layer, a high refractive index layer
- an antiglare layer such as a low refractive index layer, a middle refractive index layer, a high refractive index layer
- an antiglare layer such as a low refractive index layer,
- the thickness of the functional layer is more preferably 0.01 to 100 ⁇ m, and particularly preferably 0.02 to 50 ⁇ m. Furthermore, as the functional layer for reducing the moisture permeability, the thickness is more preferably 0.1 to 20 ⁇ m.
- the moisture permeability (C) of the optical film on which the functional layer is laminated and the moisture permeability (D) of the optical film on which the functional layer is not laminated have a C / D of 0. .9 or less is preferable. It is more preferably 0.85 or less, still more preferably 0.8 or less.
- a low moisture-permeable layer can be preferably used as the functional layer.
- the low moisture-permeable layer that can be used for the optical film of the present invention is a layer formed of a composition containing a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond in the molecule, or a chlorine-containing vinyl
- the layer is preferably a layer having a resin containing a repeating unit derived from a monomer, and is a layer formed from a composition containing a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond in the molecule. It is more preferable that
- the layer formed from the composition having as a main component a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in the molecule will be described.
- a layer formed from a composition containing as a main component a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in the molecule is a cyclic aliphatic to provide low moisture permeability. It contains a compound having a hydrocarbon group and an unsaturated double bond group in the molecule, and further contains, if necessary, a polymerization initiator, light transmitting particles, a fluorine-containing or silicone compound, and a solvent
- the composition can be formed by coating, drying and curing directly on the support or through another layer. Each component will be described below.
- the main component of a composition or a layer means the component which occupies 50 mass% or more of the composition or that layer.
- a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in the molecule functions as a binder.
- a compound having a cyclic aliphatic hydrocarbon group and having an unsaturated double bond group can function as a curing agent, and it is possible to improve the strength and scratch resistance of the coating film, and at the same time, lower. Moisture permeability can be imparted. By using such a compound, low moisture permeability and high film strength can be realized.
- a hydrophobic cyclic aliphatic hydrocarbon group is introduced into the low moisture permeability layer and hydrophobized from the outside Prevent molecular uptake and reduce moisture permeability.
- the crosslink point density is increased and the diffusion path of water molecules in the low moisture permeable layer is restricted.
- Increasing the crosslink point density also has the effect of relatively increasing the density of cyclic aliphatic hydrocarbon groups, making the low moisture permeation layer more hydrophobic, preventing adsorption of water molecules, and reducing moisture permeability it is conceivable that.
- the number of unsaturated double bond groups in the molecule is more preferably 2 or more in order to increase the density of crosslinking points.
- the cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound having 7 or more carbon atoms, more preferably a group derived from an alicyclic compound having 10 or more carbon atoms, and further preferably Is a group derived from an alicyclic compound having 12 or more carbon atoms.
- the cyclic aliphatic hydrocarbon group is particularly preferably a group derived from a polycyclic compound such as bicyclic or tricyclic. More preferably, the central skeleton of the compound described in the claim of JP-A-2006-215096, the central skeleton of the compound described in JP-A-2001-10999, or the skeleton of an adamantane derivative may be mentioned.
- cyclic aliphatic hydrocarbon group examples include norbornyl, tricyclodecanyl, tetracyclododecanyl, pentacyclopentadecanyl, adamantyl, diamantanyl and the like.
- a compound containing three or more (meth) acryloyl groups in one molecule described below can be used.
- the above-mentioned cyclic aliphatic hydrocarbon group and a group having an unsaturated double bond have a linking group It is constituted by connecting via.
- the linking group a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted, an amido group having N-position which may be substituted on earth, a carbamoyl group having N-position which may be substituted, And an oxycarbonyl group, an ether group, etc., and a group obtained by combining these.
- These compounds are, for example, carboxylic acids, carboxylic acid derivatives of compounds having the above-mentioned cyclic aliphatic hydrocarbon group, polyols such as triol, etc., and compounds having (meth) acryloyl group, vinyl group, styryl group, allyl group etc. It can be easily synthesized by one-step or two-step reaction with an epoxy derivative, an isocyanate derivative or the like.
- compounds such as (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic acid anhydride, (meth) acrylic acid glycidyl, and compounds described in WO 2012/00316 A (eg, 1, 1-bis ( It can synthesize
- a composition containing a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in a molecule as a main component preferably contains a polymerization initiator, but a photopolymerization initiator is preferable as the polymerization initiator. .
- Photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, Fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
- photopolymerization initiator and preferable embodiments, commercial products, and the like are described in paragraphs [0133] to [0151] of JP-A-2009-098658, and they are also suitably used in the present invention as well. it can.
- the content of the photopolymerization initiator in the composition having as a main component a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in the molecule used in the present invention is the content of the polymerizable compound contained in the composition.
- Preferred is 0.5 to 8% by mass, based on the total solid content in the composition for forming a hardcoat layer, because the starting point is set so as not to increase excessively. % By mass is more preferred.
- composition having as a main component a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in a molecule used in the present invention can contain a solvent.
- a solvent various solvents can be used in consideration of the solubility of the monomer, the drying property at the time of coating, the dispersibility of the light transmitting particles, and the like.
- Such organic solvents include, for example, dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, carbonate Methyl ethyl, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, cyclohexanone, methyl cyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, Methyl propionate, ethyl propionate, ⁇ -butyrolactone,
- the concentration of the solid content of the composition having as a main component a compound having a cyclic aliphatic hydrocarbon group and an unsaturated double bond group in the molecule used in the present invention is in the range of 20 to 80% by mass. It is preferable to use, more preferably 30 to 75% by mass, and still more preferably 40 to 70% by mass.
- the coating layers described in [0042] to [0058] of JP-A No. 2008-230036 can be preferably used.
- a component for forming a layer formed of a composition containing vinylidene chloride as a main component among the materials of the coating layers described in [0042] to [0058] of JP-A-2008-230036, Asahi Kasei Corp. It is preferable to use "Saran Resin R 204" or the like manufactured by Life & Living Co., Ltd.
- the main component of a composition or a layer means the component which occupies 50 mass% or more of the composition or that layer.
- the low moisture-permeable layer may be a single layer or a plurality of layers.
- the method for laminating the low moisture-permeable layer is not particularly limited, but the low moisture-permeable layer may be formed by co-casting with a substrate film, or the low moisture-permeable layer may be coated on the substrate film by application. It is preferable that the low moisture-permeable layer be applied and laminated on the base film. That is, as for the optical film of this invention, it is more preferable that the said low moisture-permeable layer is laminated
- the thickness of the low moisture-permeable layer is preferably 1 to 20 ⁇ m, more preferably 2 to 18 ⁇ m, and particularly preferably 3 to 17 ⁇ m.
- the low moisture-permeable layer of the optical film of the present invention have a hard coat layer function, an antireflective function, an antifouling function and the like in combination.
- the optical film of the present invention may additionally have an optically anisotropic layer, and a cross-sectional schematic view is shown in FIG. 1 as an example of the preferred embodiment.
- An optical film 10 shown in FIG. 1 has a transparent support 14, an optically anisotropic layer 12, and a base material 16, and the optically anisotropic layer 12 is a layer that causes retardation, and has a fixed position.
- the film may be an optically anisotropic layer in which a film having a phase difference is uniformly formed in a plane, or a pattern optical anisotropy in which regions different from each other in slow axis or retardation are regularly arranged in a plane It may be a layer.
- the moisture permeability reducing compound having the molecular weight of 200 or more and satisfying the following formula (1) may be contained in the transparent support 14.
- a ⁇ / 4 film is preferable as the optically anisotropic layer in which a film having a constant retardation is uniformly formed in the plane, and a specific example of an optical film in which the ⁇ / 4 film is an optically anisotropic layer
- the optically anisotropic layer and the optical film described in JP 2012-098721 A, JP 2012-103689 A, and JP 2012-177894 A can be appropriately used.
- An optical film having a ⁇ / 4 film as an optically anisotropic layer can be used for a brightness enhancement plate, a 3D liquid crystal display device, etc., and is particularly useful as a member of an active 3D liquid crystal display device.
- FIG. 2 shows a schematic cross-sectional view as a representative example of the patterned optically anisotropic layer 12.
- the first and second retardation regions 12a and 12b are patterned optically anisotropic layers arranged evenly and symmetrically.
- the first and second retardation regions 12a and 12b preferably have in-plane slow axes a and b orthogonal to each other.
- the patterned optically anisotropic layer of this embodiment When the patterned optically anisotropic layer of this embodiment is combined with a polarizing film, the light passing through each of the first and second retardation regions becomes circularly polarized in opposite directions, and the circles for the right eye and the left eye, respectively. Form a polarized image.
- Specific embodiments of the optical film having the pattern ⁇ / 4 layer as the optically anisotropic layer include the optically anisotropic layer described in Japanese Patent No. 4825934 and Japanese Patent No. 4887463, and the optical film It can be used as appropriate.
- the optical film 10 is useful as a member of a 3D liquid crystal display device, particularly a passive 3D liquid crystal display device.
- the polarization image passing through each of the first and second retardation regions 12a and 12b is recognized as an image for right eye or left eye through polarization glasses or the like. Therefore, it is preferable that the first and second retardation regions 12a and 12b have the same shape and that their respective arrangements be uniform and symmetrical so that the left and right images do not become nonuniform. .
- the patterned optically anisotropic layer 12 is not limited to the embodiment shown in FIG. 2 and, for example, the in-plane retardation of one of the first and second retardation regions is ⁇ / 4, and the other is A display pixel area having an in-plane retardation of 3 ⁇ / 4 can be used. Furthermore, it is also possible to use a retardation region in which the in-plane retardation of one of the first and second retardation regions 12a and 12b is ⁇ / 2 and the other in-plane retardation is zero.
- the optical film of the present invention can also be used as an optical compensation film of a liquid crystal display device.
- liquid crystal display devices of TN, IPS, FLC, AFLC, OCB, STN, ECB, VA and HAN modes are preferable, and liquid crystal display devices of TN, OCB, IPS and VA modes are more preferable, and VA Mode liquid crystal display devices are more preferred.
- various functional layers may be provided to the optical film of the present invention.
- the functional layer include an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflective layer, an easily adhesive layer, an antiglare layer, an optically anisotropic layer, an alignment layer, a liquid crystal layer and the like.
- These functional layers and materials thereof include surfactants, slip agents, matting agents, antistatic layers, hard coat layers and the like, and are disclosed in Journal of the Japan Institute of Invention and Innovation No. 2001-1745 (March 15, 2001). The publication is described in detail on pages 32 to 45 of the Japan Institute of Invention and Innovation, and can be preferably used in the present invention.
- the polarizing plate of the present invention is characterized by including at least one optical film of the present invention as a protective film of a polarizer.
- the optical film of the present invention can be used as a polarizing plate protective film.
- the optical compensation film of the liquid crystal display device can be combined with the protective film for polarizing plate.
- the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method.
- the adhesive used to bond the protective film-treated surface to the polarizer examples include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl-based latexes such as butyl acrylate.
- the polarizing plate is composed of a polarizer and a protective film for protecting both sides of the polarizing plate, and a protective film is bonded to one side of the polarizing plate, and a separate film is bonded to the other side.
- the protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipment of the polarizing plate, at the time of product inspection and the like.
- the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface on which the polarizing plate is bonded to the liquid crystal plate.
- the separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the side of the polarizing plate to be bonded to the liquid crystal plate.
- a substrate including a liquid crystal cell is usually disposed between two polarizing plates, but the protective film for polarizing plate to which the optical film of the present invention is applied is any protective film of two polarizing plates. Although it can be used, it is preferable to be used as a protective film arrange
- the optical film of the present invention can be used in various applications, and is particularly effective when used as an optical compensation film of a liquid crystal display device.
- the optical compensation film generally refers to an optical material which is used in a liquid crystal display device and which compensates for retardation, and is synonymous with a retardation plate, an optical compensation sheet and the like.
- the optical compensation film has birefringence and is used for the purpose of removing the coloring of the display screen of the liquid crystal display device and improving the viewing angle characteristics.
- the optical film of the present invention may itself be used as an optical compensation film, or may be used as a support of the optical compensation film, and an optically anisotropic layer may be provided thereon.
- the optically anisotropic layer is not limited to the optical performance or driving system of the liquid crystal cell of the liquid crystal display device using the optical film of the present invention, and any optically anisotropic layer required as an optical compensation film It can be used together.
- the optically anisotropic layer to be used in combination may be formed of a composition containing a liquid crystalline compound, or may be formed of a thermoplastic film having birefringence.
- the liquid crystal display device of the present invention includes a liquid crystal cell and the polarizing plate of the present invention disposed in at least one of the liquid crystal cells, and the optical film of the present invention contained in the polarizing plate is the outermost layer. It is characterized in that it is arranged.
- the film of the present invention can be used in liquid crystal cells of various display modes.
- TN Transmission Nematic
- IPS In-Plane Switching
- FLC Fluoroelectric Liquid Crystal
- AFLC Anti-ferroelectric Liquid Crystal
- OCB Optically Compensatory Bend
- STN Super Twisted Nematic
- VA Vertically Aligned
- ECB Electrode Controlled Birefringence
- HAN Hybrid Aligned Nematic
- the optical film of the present invention is effective in liquid crystal displays of any display mode.
- the present invention is also effective in any of transmissive, reflective, and semi-transmissive liquid crystal displays.
- Thermoplastic resin The acrylic resin and thermoplastic resin described below were used. These acrylic resins and thermoplastic resins are commercially available or can be obtained by known synthesis methods. ⁇ PMMA, trade name Dianal BR88, Mitsubishi Rayon PS, trade name G9504, PS Japan, SAN, trade name Sebian 050SF, Daicel Polymer, norbornene (norbornene resin), trade name Arton F 5023, JSR -Lactone (acrylic resin which is a lactone ring-containing polymer, synthesized by a synthesis method described later)
- Example 3 in which the optical film of Example 1 in which 10% by mass of the moisture permeability reducing compound was added to the thermoplastic resin (PMMA) and the thermoplastic resin (PMMA) in Example 1 were changed to other thermoplastic resins.
- Optical films of ⁇ 5 were produced, and the moisture permeability A was determined by the method described later.
- UV absorber Tinuvin 328 (Ciba Specialty Chemicals Co., Ltd.)
- Brittle modifier 1 manufactured by Kuraray, LA 4285
- Example 1 ⁇ Production of Optical Film 101> (Dope preparation) The composition described below was introduced into a mixing tank and stirred while heating to dissolve each component to prepare a dope.
- Doping composition PMMA resin 100 parts by mass Moisture permeability reducing compound B-7 10 parts by mass UV agent 1 2.4 parts by mass Brittle modifier 1 5.0 parts by mass Dichloromethane 534 parts by mass Methanol 46 parts by mass
- the prepared dope was uniformly cast from a casting die onto a stainless steel endless band (casting support) having a width of 2000 mm.
- a stainless steel endless band casting support
- the amount of residual solvent in the dope reaches 15% by mass, it is exfoliated as a polymer film from the casting support, conveyed without actively stretching with a tenter, and dried at 120 ° C. in a drying zone.
- the sample film was conditioned at 25 ° C. and 60% relative humidity for 24 hours. Then, using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments), at 25 ° C. and 60% relative humidity, the film surface normal with the direction perpendicular to the film surface and the slow axis as the rotation axis.
- the in-plane retardation value (Re) and the retardation value (Rth) in the film thickness direction were calculated by measuring the retardation at a wavelength of 590 nm from a direction inclined by 10 ° from + 50 ° to -50 ° .
- the casting film forming conditions were the same as in the preparation of the optical film 101 of Example 1, and the optical films 102 to 107 and 110 to 115 of Examples 2 to 7 and 10 to 15 and the optical films 2 to 6 of Comparative Examples 2 to 6 6 was produced.
- pellets of a lactone ring-containing polymer were obtained according to the synthesis method described in [0230] to [0232] of International Publication WO2006 / 025445 A1. Next, this pellet was dissolved, and in the same manner as the optical film 101 of Example 1, an optical film 107 of Example 7 was produced. Also, using this pellet, an optical film 106 of Comparative Example 6 was produced in the same manner as the optical film 101 of Example 1 except that the moisture permeability reducing compound was not added.
- Example 8 In Example 6, a film having a thickness of 490 ⁇ m is produced in the same manner as in Example 6 except that the thickness at the time of casting film formation is changed, and 3.4 times and 3 in the conveying direction and width direction at 120 ° C.
- the optical film 108 of Example 8 having a thickness of 40 ⁇ m was produced by stretching 6 times.
- Example 9 A film having a thickness of 490 ⁇ m is produced in the same manner as in Example 6 except that in Example 6, the polymer is changed to a norbornene resin (trade name; Arton), and the thickness at the time of casting film formation is changed.
- the optical film 109 of Example 9 having a thickness of 40 ⁇ m was produced by stretching 3.4 times and 3.6 times in the transport direction and the width direction at 130 ° C., respectively.
- the liquid crystal display was allowed to stand for 48 hours in an environment of 60 ° C. and 90% relative humidity, and then conditioned for 24 hours in an environment of 25 ° C. and 60% relative humidity.
- the liquid crystal display after humidity control was turned on, the degree of color unevenness at the time of black display was observed visually, and the following criteria evaluated in four steps.
- C Weak color unevenness was observed at the four corners of the display surface.
- D Strong color unevenness was observed at one or two of the four corners of the display surface.
- E Strong color unevenness was observed at the four corners of the display surface.
- Example 12 was superior to Example 15 in terms of durability. Among them, it is clear that the unevenness improving effect is high particularly when the moisture permeability a / the moisture permeability B is 0.4 or less and the moisture permeability is 30 g / m 2 / day or less.
- optical film 12 patterned optically anisotropic layer 12a first retardation region 12b second retardation region 14 transparent support a first retardation region in-plane slow axis b surface of second retardation region Internal slow axis
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Materials Engineering (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Environmental Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Ecology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
また、液晶表示装置において、視野角の拡大、画像着色の改良、及びコントラストの向上のため、ポリマーフィルムを光学補償フィルム(位相差フィルム)として使用することが知られている。光学補償フィルムとして用いられるポリマーフィルムに対しては、VAモードやIPSモード等の液晶表示装置の液晶セルのモードに応じて、フィルムの光学特性(例えば、フィルム面内のレターデーション値Reやフィルム厚さ方向のレターデーション値Rthなどの複屈折性)を制御して所望の光学異方性を持たせることが求められる。
本発明の別の目的は、上記光学フィルムを用いた偏光板を提供することである。本発明の更に別の目的は、高温高湿環境経時後の黒表示ムラが改善された液晶表示装置を提供することである。
前記光学フィルムの透湿度が、膜厚40μm換算で70g/m2/day以下であり、
分子量が200以上であり、かつ下記式(1)を満たす透湿度低減化合物を前記光学フィルムが含む光学フィルム。
式(1) A/B≦0.9
(式(1)中、Aは前記熱可塑性樹脂の質量に対して前記透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度は、JIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
[2] [1]に記載の光学フィルムは、下記式(2)を満たすことが好ましい。
式(2) a/B≦0.9
(式(2)中、aは前記熱可塑性樹脂と前記透湿度低減化合物とを含有する場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
[3] [1]または[2]に記載の光学フィルムは、前記透湿度低減化合物が、芳香族環を1つ以上含むことが好ましい。
[4] [1]~[3]のいずれかに記載の光学フィルムは前記透湿度低減化合物が、下記一般式(B)で表される化合物、フェノール樹脂、テルペン樹脂、芳香族炭化水素ホルムアルデヒド樹脂またはバルビツール酸類であることが好ましい。
一般式(B)
[5] [1]~[4]のいずれかに記載の光学フィルムは、前記透湿度低減化合物が、ノボラック型フェノール樹脂、水添テルペン樹脂、キシレン樹脂またはバルビツール酸類であることが好ましい。
[6] [1]~[5]のいずれかに記載の光学フィルムは、前記透湿度低減化合物が、ノボラック型フェノール樹脂、水添テルペン樹脂またはキシレン樹脂であることが好ましい。
[7] [1]~[6]のいずれかに記載の光学フィルムは、前記透湿度低減化合物が、芳香族環を3つ以上含むことが好ましい。
[8] [1]~[7]のいずれかに記載の光学フィルムは、前記透湿度低減化合物が、下記一般式(C)で表されることが好ましい。
[9] [1]~[8]のいずれかに記載の光学フィルムは、前記透湿度低減化合物が、ノボラック型フェノール樹脂またはキシレン樹脂であることが好ましい。
[10] [1]~[9]のいずれかに記載の光学フィルムは、前記熱可塑性樹脂の質量に対し、前記透湿度低減化合物を1質量%以上含むことが好ましい。
[11] [1]~[10]のいずれかに記載の光学フィルムは、膜厚が60μm以下であることが好ましい。
[12] [1]~[11]のいずれかに記載の光学フィルムは、下記式(I)及び下記式(II)で定義されるRe及びRthが、波長590nmにおいて下記式(III)及び下記式(IV)を満たすことが好ましい。
式(I) Re=(nx-ny)×d
式(II) Rth={(nx+ny)/2-nz}×d
式(III)|Re|≦50nm
式(IV) |Rth|≦300nm
(式(I)~(IV)中、nxは光学フィルム面内の遅相軸方向の屈折率であり、nyは光学フィルム面内の進相軸方向の屈折率であり、nzは光学フィルムの膜厚方向の屈折率であり、dは光学フィルムの厚さ(nm)である。)
[13] [1]~[12]のいずれかに記載の光学フィルムは、前記熱可塑性樹脂、前記透湿度低減化合物および溶媒を含む高分子溶液を支持体上に流延して製膜されてなることが好ましい。
[14] [1]~[13]のいずれかに記載の光学フィルムは、前記光学フィルムの少なくとも一方の表面に、膜厚0.1~20μmの機能層を有することが好ましい。
[15] [14]に記載の光学フィルムは、前記機能層が積層された場合の光学フィルムの透湿度(C)と、前記機能層が積層されない場合の光学フィルムの透湿度(D)とが、C/D≦0.9となることが好ましい。
[16] 熱可塑性樹脂、および透湿度低減化合物を支持体上に流延して高分子膜を形成する工程を含み、
前記透湿度低減化合物の分子量が200以上であり、
前記透湿度低減化合物が下記式(1)を満たす光学フィルムの製造方法。
式(1) A/B≦0.9
(式(1)中、Aは前記熱可塑性樹脂の質量に対して前記透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
[17] [16]に記載の光学フィルムの製造方法は、前記光学フィルムが下記式(2)を満たすことが好ましい。
式(2) a/B≦0.9
(式(2)中、aは前記熱可塑性樹脂と前記透湿度低減化合物とを含有する場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
[18] [16]または[17]に記載の光学フィルムの製造方法は、前記光学フィルムを延伸する工程を含むことが好ましい。
[19] 偏光子の保護フィルムとして[1]~[15]のいずれかに記載の前記光学フィルムを少なくとも1枚含むことを特徴とする偏光板。
[20] 液晶セルと、
該液晶セルの少なくとも一方に配置された[19]に記載の前記偏光板とを含み、
前記光学フィルムが最表層となるように配置された液晶表示装置。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
「アクリル樹脂」とはメタクリル酸又はアクリル酸の誘導体を重合して得られる樹脂、及びその誘導体を含有する樹脂を意味するものとする。また、特に限定しない場合には、「(メタ)アクリレート」はアクリレート及びメタクリレートを表し、「(メタ)アクリル」はアクリル及びメタクリルを表す。
更に、フィルムの「遅相軸方向」とはフィルム面内で屈折率が最大となる方向で、「進相軸方向」とはフィルム面内で遅相軸と直交する方向を意味するものとする。
本発明の光学フィルムは、熱可塑性樹脂を含む光学フィルムであって、前記光学フィルムの透湿度が70g/m2/day以下(膜厚40μm換算)であり、分子量が200以上であり、かつ下記式(1)を満たす透湿度低減化合物を含むことを特徴とする。
式(1) A/B≦0.9
(式(1)中、Aは前記熱可塑性樹脂の質量に対して当該透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度は、JIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
上記構成により、耐久性に優れ、水分の透過および脱着を低減することが出来る。
式(2) a/B≦0.9
(式(2)中、aは前記熱可塑性樹脂と前記透湿度低減化合物とを含有する場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物の添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
前記a/Bは、0.8以下であることが好ましく、0.6以下であることがより好ましく、0.4以下であることが特に好ましい。
以下、本発明の光学フィルムの構成の好ましい態様について説明する。
下記に本発明で使用する熱可塑性樹脂に関し説明する。
本発明のフィルムにおいて、最適な熱可塑性樹脂としては、(メタ)アクリル系樹脂、ポリカーボネート系樹脂、ポリスチレン系樹脂、環状ポリオレフィン系樹脂が挙げられ、これらの樹脂及びこれら複数種の樹脂の混合樹脂から選ぶことができる。
前記(メタ)アクリル酸系樹脂の繰り返し構造単位は、特に限定されない。前記(メタ)アクリル酸系樹脂は、繰り返し構造単位として(メタ)アクリル酸エステル単量体由来の繰り返し構造単位を有することが好ましい。
CH2=C(X)R201
前記(メタ)アクリル酸エステルを用いる場合、重合工程に供する単量体成分中のその含有割合は、本発明の効果を十分に発揮させる上で、好ましくは10~100重量%、より好ましくは10~100重量%、更に好ましくは40~100重量%、特に好ましくは50~100重量%である。
前記水酸基含有単量体を用いる場合、重合工程に供する単量体成分中のその含有割合は、本発明の効果を十分に発揮させる上で、好ましくは0~30重量%、より好ましくは0~20重量%、更に好ましくは0~15重量%、特に好ましくは0~10重量%である。
前記不飽和カルボン酸を用いる場合、重合工程に供する単量体成分中のその含有割合は、本発明の効果を十分に発揮させる上で、好ましくは0~30重量%、より好ましくは0~20重量%、更に好ましくは0~15重量%、特に好ましくは0~10重量%である。
前記一般式(201)で表される単量体を用いる場合、重合工程に供する単量体成分中のその含有割合は、本発明の効果を十分に発揮させる上で、好ましくは0~30重量%、より好ましくは0~20重量%、更に好ましくは0~15重量%、特に好ましくは0~10重量%である。
前記単量体成分を重合して分子鎖中に水酸基とエステル基とを有する重合体を得るための重合反応の形態としては、溶剤を用いた重合形態であることが好ましく、溶液重合が特に好ましい。
たとえば、下記の公報に記載の環状構造を導入したものも好ましい、特開2007-316366号公報、特開2005-189623号公報、WO2007/032304号公報、WO2006/025445号公報に記載のラクトン環構造である。
ラクトン環含有重合体は、ラクトン環を有するものであれば特に限定されないが、好ましくは下記一般式(401)で示されるラクトン環構造を有する。
原子数1~20の有機残基を表し、有機残基は酸素原子を含有していてもよい。ここで、炭素原子数1~20の有機残基としては、メチル基、エチル基、イソプロピル基、n-ブチル基、t-ブチル基などが好ましい。
アクリル樹脂は2種以上を併用することもできる。
本発明に用いることができる熱可塑性樹脂は、ポリカーボネート系樹脂に、適宜剥離力や、靭性を制御するべく添加剤を入れて、用いることができる。
ポリカーボネート系樹脂としては、任意の適切なポリカーボネートが採用され得る。特に、芳香族2価フェノール成分とカーボネート成分とからなる芳香族ポリカーボネートが好ましい。芳香族ポリカーボネートは、好ましくは、芳香族2価フェノール化合物とカーボネート前駆物質との反応によって得ることができる。具体的には、芳香族2価フェノール化合物を苛性アルカリおよび溶剤の存在下でホスゲンを吹き込むホスゲン法、あるいは、芳香族2価フェノール化合物とビスアリールカーボネートとを触媒の存在下でエステル交換させるエステル交換法によって得ることができる。
上記芳香族2価フェノール化合物としては、特に限定されないが、例えば、2,2-ビス(4-ヒドロキシフェニル)プロパン、9,9-ビス(4-ヒドロキシフェニル)フルオレン、4,4´-ビフェノール、4,4´-ジヒドロキシビフェニルエーテル、2,2-ビス(3-メチル-4-ヒドロキシフェニル)プロパン、2,2-ビス(3-ブロモ-4-ヒドロキシフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、ビス(4-ヒドロキシフェニル)メタン、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)ブタン、2,2-ビス(4-ヒドロキシ-3,5-ジプロピルフェニル)プロパン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサン等が挙げられる。これらは、1種のみを用いても良いし、2種以上を併用しても良い。
上記カーボネート前駆物質としては、特に限定されないが、例えば、ホスゲン、上記2価フェノール化合物のビスクロロホーメート、ジフェニルカーボネート、ジ-p-トリルカーボネート、フェニル-p-トリルカーボネート、ジ-p-クロロフェニルカーボネート、ジナフチルカーボネート等が挙げられ、中でも、ホスゲン、ジフェニルカーボネートが好ましい。これらは、1種のみを用いても良いし、2種以上を併用しても良い。
上記ポリカーボネートは、重量平均分子量が10000以上、更に好ましくは50000以上である。重量平均分子量が10000未満のものでは、強伸度特性や耐熱性に優れたフィルムを得ることができない。重量平均分子量の上限については、特に限定されるものではないが、1500000以上では延伸張力の増加に伴う破断の発生などが生じるため余り好ましくない。重量平均分子量が上記範囲にあれば、機械的強度に優れ、溶解性、成形性、流延の操作性などが良好なものとなる。
本発明に用いることができる熱可塑性樹脂は、ポリスチレン系樹脂に、適宜剥離力や、靭性を制御するべく添加剤を入れて、用いることができる。
該ポリスチレン系樹脂としては、ポリスチレン、ポリ(p-、m-又はo-メチルスチレン)、ポリ(2,4-、2,5-、3,4-又は3,5-ジメチルスチレン)、ポリ(p-ターシャリーブチルスチレン)などのポリ(アルキルスチレン)、ポリ(p-、m-又はo-クロロスチレン)、ポリ(p-、m-又はo-ブロモスチレン)、ポリ(p-、m-又はo-フルオロスチレン)、ポリ(o-メチル-p-フルオロスチレン)などのポリ(ハロゲン化スチレン)、ポリ(p-、m-又はo-クロロメチルスチレン)などのポリ(ハロゲン置換アルキルスチレン)、ポリ(p-、m-又はo-メトキシスチレン)、ポリ(p-、m-又はo-エトキシスチレン)などのポリ(アルコキシスチレン)、ポリ(p-、m-又はo-カルボキシメチルスチレン)などのポリ(カルボキシアルキルスチレン)ポリ(p-ビニルベンジルプロピルエーテル)などのポリ(アルキルエーテルスチレン)、ポリ(p-トリメチルシリルスチレン)などのポリ(アルキルシリルスチレン)、さらにはポリ(ビニルベンジルジメトキシホスファイド)などが挙げられる。
本発明においては、前記ポリスチレン系重合体のなかで、特にポリスチレンが好適である。また、本発明で用いるポリスチレン系重合体は、必ずしも単一化合物である必要はなく、他のポリスチレン系重合体との混合物や、共重合体及びそれらの混合物でもよい。物性制御のため、ビニルトルエン、α-メチルスチレン、アクリロニトリル、メチルビニルケトン、エチレン、プロピレン、酢酸ビニル、無水マレイン酸などを共重合してもよい。
本発明に用いるポリスチレン系樹脂としては、市販のものが使用できる。例えば、ポリスチレン樹脂としては、PSジャパン社製ポリスチレンG9504、G9401、G9305、SGP-10(ポリスチレンジャパン製)、ハイブランチXC-540HB、XC-520、ディックスチレンCR―250、CR―350、CR-450(DIC製)、スチレン-アクリロニトリル共重合体としては、セビアンN020SF、050SF、070SF、080SF(ダイセルポリマー製)、スチレン-無水マレイン酸共重合体としては、XIRAN SZ28110、SZ26180、SZ26120、SZ26080、SZ23110、SZ15170、SZ08250(ポリスコープポリマーズB.V.製)等が挙げられる。
また本発明に用いるポリスチレン系重合体は、重量平均分子量が10000以上、更に好ましくは50000以上である。重量平均分子量が10000未満のものでは、強伸度特性や耐熱性に優れたフィルムを得ることができない。重量平均分子量の上限については、特に限定されるものではないが、1500000以上では延伸張力の増加に伴う破断の発生などが生じるため余り好ましくない。
本発明に用いることができる熱可塑性樹脂としては、環状ポリオレフィン系樹脂が挙げられる。ここで、環状ポリオレフィン系樹脂とは、環状オレフィン構造を有する重合体樹脂を表す。
本発明に用いる環状オレフィン構造を有する重合体樹脂の例には、(1)ノルボルネン系重合体、(2)単環の環状オレフィンの重合体、(3)環状共役ジエンの重合体、(4)ビニル脂環式炭化水素重合体、及び(1)~(4)の水素化物などがある。
本発明に好ましい重合体は下記一般式(II)で表される繰り返し単位を少なくとも1種以上含む付加(共)重合体環状ポリオレフィン系樹脂及び必要に応じ、一般式(I)で表される繰り返し単位の少なくとも1種以上を更に含んでなる付加(共)重合体環状ポリオレフィン系樹脂である。また、一般式(III)で表される環状繰り返し単位を少なくとも1種含む開環(共)重合体も好適に使用することができる。
本発明に用いることができる熱可塑性樹脂としては、グルタル酸無水物系樹脂が挙げられる。ここで、グルタル酸無水物系樹脂とは、グルタル酸無水物単位を有する重合体樹脂を表す。
一般式(102):-[CH2-C(R41)(COOR42)]-
一般式(103):CH2=C(R41)(COOR42)
一般式(104):-[CH2―C(R51)(COOH)]-
ここでR51は水素又は炭素数1~5のアルキル基を表す。
一般式(105):CH2=C(R51)(COOH)
本発明に用いることができる熱可塑性樹脂としては、グルタルイミド系樹脂が挙げられる。ここで、グルタルイミド系樹脂とは、グルタルイミド単位を有する重合体樹脂を表す。
炭素数1~12個の非置換のまたは置換のアルキル基、シクロアルキル基、アリール基である。)を20重量%以上有するグルタルイミド樹脂を含有することが好ましい。
本発明に用いることができる熱可塑性樹脂は、上記の樹脂以外のその他の熱可塑性樹脂を含んでいてもよい。その他の熱可塑性樹脂は、本発明の趣旨に反しない限りにおいて特に種類は問わないが、熱力学的に相溶する熱可塑性樹脂の方が、機械強度や所望の物性を向上させる点において好ましい。
本発明の光学フィルムは、水分の透過、脱着を低減するため、分子量が200以上であり、かつ下記式(1)を満たす透湿度低減化合物を含むことを特徴とする。
式(1) A/B≦0.9
(式(1)中、Aは前記熱可塑性樹脂の質量に対して当該透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度は、JIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
前記透湿度低減化合物は、好ましくはA/Bが0.8以下であり、A/Bが0.7以下であることがより好ましい。本発明の光学フィルムの前記熱可塑性樹脂がアクリル樹脂またはノルボルネン系樹脂であるときはA/Bが0.60以下であることがさらに好ましい。本発明の光学フィルムの前記熱可塑性樹脂がノルボルネン系樹脂であるときはA/Bが0.5以下であることがよりさらに好ましい。
前記透湿度低減化合物は、芳香族環を3つ以上含む構造であることがより好ましい。
また、前記透湿度低減化合物は、-OH基を1つ以上含むことが好ましく、芳香族環を3つ以上含み、かつ-OH基を1つ以上含むことがより好ましい。
本発明の光学フィルムの透湿度を低減し、本発明の光学フィルムを液晶表示装置に組み込んだときの高温高湿環境経時後の黒表示ムラを改善する観点からは前記フェノール樹脂、前記テルペン樹脂または前記芳香族炭化水素ホルムアルデヒド樹脂がより特に好ましく、本発明の光学フィルムを液晶表示装置に組み込んだときの高温高湿環境経時後の黒表示ムラをより改善する観点からは前記フェノール樹脂(その中でもノボラック型フェノール樹脂が好ましい)または前記芳香族炭化水素ホルムアルデヒド樹脂(その中でもキシレン樹脂が好ましい)がよりさらに特に好ましい。
前記透湿度低減化合物としては、下記一般式(C)で表される化合物がより好ましい。
一般式(C)中、mは1~3であることが好ましく、1または2であることがより好ましい。
一般式(C)中、Rはそれぞれ独立に水素原子、-OH基または置換基を有していてもよいメチル基もしくはエチルであることが好ましい。一般式(C)中、Rが表すアルキル基が有していてもよい置換基としては特に制限はないが、-OH基が好ましい。
一般式(C)中、Rのうち少なくとも1つは-OH基を含む基を表し、分子末端のベンゼン環が-OH基を少なくとも1つ含む基を有することが好ましい。
前記一般式(C)で表される透湿度低減化合物としては、後述のフェノール樹脂および芳香族炭化水素ホルムアルデヒド樹脂のうち前記一般式(C)を満たす化合物が好ましい。
本発明に用いるフェノール系樹脂としては、ノボラック型フェノール樹脂が好ましい。
本発明に用いるノボラック型フェノール樹脂としては、一般にフェノールとホルムアルデヒド(ホルマリン)とをシュウ酸などの酸性触媒下で反応し得られる通常のノボラック型フェノール樹脂である。該フェノールの原料として、特に制限はなく、例えば、フェノール、o-クレゾール、m-クレゾール、p-クレゾール、p-tert-ブチルフェノール、p-tert-オクチルフェノール、p-オクチルフェノール、p-ノニルフェノールなど及びそれらの混合物が使用できる。前記フェノールの原料としては、p-クレゾールが好ましい。
また、ホルムアルデヒドの原料としては、ホルマリン、パラホルム、アセタールなど及びそれらの混合物が使用できる。
一般式(1)中、Rの各ベンゼン環に置換しているRの位置は特に制限はないが、-OH基に対してパラ位であることが好ましい。
一般式(1)中、nは1~7であることが好ましい。
一般式(1)中、各ベンゼン環を連結するメチレン基の結合位置は特に制限はないが、-OH基に対してオルト位であることが好ましい。
本発明に用いる芳香族炭化水素ホルムアルデヒド樹脂としては、一般に芳香族炭化水素とホルムアルデヒド(ホルマリン)を反応し得られる通常の芳香族炭化水素ホルムアルデヒド樹脂が使用できる。該芳香族炭化水素の原料として、特に制限はなく、例えば、トルエン、キシレンの3異性体、メシチレン、炭素数が10以上の単環芳香族炭化水素化合物など及びそれらの混合物が使用できる。前記芳香族炭化水素の中でも、キシレンであることが好ましく、m-キシレンであることがより好ましい。
また、ホルムアルデヒドの原料としては、ホルマリン、パラホルム、アセタールなど及びそれらの混合物が使用できる。
一般式(2)中、Rの各ベンゼン環に置換しているRの数は特に制限はないが、0~2個であることが好ましく、2個であることがより好ましい。
一般式(2)中、Rの各ベンゼン環に置換しているRの位置は特に制限はない。
一般式(2)中、nは1~7であることが好ましい。
一般式(2)中、各ベンゼン環に連結するメチレン基または-CH2O-基の結合位置は特に制限はないが、互いにメタ位の関係であることが好ましい。
本発明に用いるテルペン樹脂は、水添テルペン樹脂であることが好ましい。
本発明に用いる水添テルペン樹脂とは、一般にテルペン化合物をフリーデルクラフト触媒下、カチオン重合することにより得られるテルペン樹脂を部分水素添加した化合物である。該テルペン化合物としては、α-ピネン、β-ピネン、ジペンテン、d-リモネン、ミルセン、アロオシメン、オシメン、α-フェランドレン、α-テルピネン、γ-テルピネン、テルピノーレン、1,8-シネオール、1,4-シネオール、α-テルピネオール、β-テルピネオール、γ-テルピネオール、サビネン、パラメンタジエン類、カレン類などが挙げられ、α-ピネン、β-ピネン、ジペンテン、d-リモネンが好ましく用いられる。また、原料としてテルペン化合物のほか、テルペン化合物と芳香族化合物、テルペン化合物とフェノール系化合物を使用しても良い。
これらの置換基は更に置換基Tで置換されてもよい。また、置換基が二つ以上ある場合は、同じでも異なってもよい。また、可能な場合には互いに連結して環を形成してもよい。
前記透湿度低減化合物としては、バルビツール酸類も用いることができる。
本発明に用いるバルビツール酸類としては、下記一般式(3)で表される化合物を使用できる。
上記一般式(3)中、R1、R3およびR5として採用しうる上記炭素数3~20のシクロアルキル基は、その炭素数が3~10であることが好ましく、4~8であることがより好ましい。当該シクロアルキル基の具体例として、例えば、シクロプロピル基、シクロペンチル基、シクロへキシル基が挙げられ、シクロヘキシル基が特に好ましい。
上記一般式(3)中、R1、R3およびR5として採用しうる上記炭素数2~20のアルケニル基は、その炭素数が2~10であることが好ましく、2~5であることがより好ましい。
上記一般式(3)中、R1、R3およびR5として採用しうる上記6~20の芳香族基は、芳香族炭化水素基であっても芳香族複素環基であってもよいが、芳香族炭化水素基であることが好ましい。当該芳香族炭化水素基としては、フェニル基、ナフチル基が好ましく、フェニル基がより好ましい。
・R1、R3およびR5のいずれか1つがアラルキル基である化合物
なお、アラルキル基はアルキル基にアリール基が置換した化合物であり、アラルキル基のなかでも、アルキル基に1個または2個のアリール基が置換したもの(2個のアリール基が置換した場合、同一炭素原子に置換していることが好ましい。)が好ましい。さらに、アルキル基にアリール基とアシル基(好ましくはアリーロイル基)が置換したものも好ましい。
・R1、R3およびR5のいずれか1つが、シクロアルキル基を含む基で、好ましくは、シクロアルキル基を含む基がシクロアルキル基である化合物
分子量が小さすぎると、フィルムからの揮散が問題となることがあり、大きすぎると、ヘイズが高くなることがある。
また、縮合に用いるマロン酸は、無置換のものでも置換基を有するものでもよく、R5に相当する置換基を有するマロン酸を用いれば、バルビツール酸を構築することにより本発明の一般式(3)で表される化合物を合成することができる。また、無置換のマロン酸と尿素誘導体を縮合させると5位が無置換のバルビツール酸が得られるので、これを修飾することにより本発明の一般式(3)で表される化合物を合成してもよい。
なお、本発明に用いる一般式(3)で表される化合物の合成法は上記に限定されるものではない。
前記透湿度低減化合物としては、リン酸エステルも用いることができる。
本発明に用いるリン酸エステルとしては、TPP(りん酸トリフェニル)などのセルロースアシレートフィルムへの添加剤として公知の低分子のリン酸エステルなどを挙げることができる。
前記リン酸エステルは、分子量が200~1000であることが好ましい。
本発明の光学フィルムの前記熱可塑性樹脂がアクリル樹脂であるとき、前記透湿度低減化合物として、前記一般式(B)で表される化合物および前記フェノール樹脂を好ましく用いることができる。
本発明の光学フィルムの前記熱可塑性樹脂がポリスチレン樹脂またはスチレン-アクリロニトリル樹脂であるとき、前記透湿度低減化合物として、前記一般式(B)で表される化合物またはリン酸エステルを好ましく用いることができ、前記一般式(B)で表される化合物がより好ましく用いられる。
本発明の光学フィルムの前記熱可塑性樹脂がノルボルネン系樹脂であるとき、前記透湿度低減化合物として、前記一般式(B)で表される化合物、前記フェノール樹脂、前記テルペン樹脂、前記芳香族炭化水素ホルムアルデヒド樹脂またはバルビツール酸類を用いることが好ましく、前記テルペン樹脂、前記芳香族炭化水素ホルムアルデヒド樹脂またはバルビツール酸類を用いることがより好ましく、前記テルペン樹脂または前記芳香族炭化水素ホルムアルデヒド樹脂を用いることが前記熱可塑性樹脂との極性を考慮すると特に好ましく、前記芳香族炭化水素ホルムアルデヒド樹脂を用いることがより特に好ましい。
(マット剤微粒子)
本発明の光学フィルムには、マット剤として微粒子を加えることができる。マット剤として使用される微粒子としては、二酸化珪素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、タルク、クレイ、焼成カオリン、焼成珪酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム及びリン酸カルシウムを挙げることができる。微粒子はケイ素を含むものがフィルムのヘイズが低くなる点で好ましく、特に二酸化珪素が好ましい。二酸化珪素の微粒子は、1次平均粒子径が20nm以下であり、かつ見かけ比重が70g/リットル以上であるものが好ましい。1次粒子の平均径が5~16nmと小さいものがフィルムのヘイズを下げることができより好ましい。見かけ比重は90~200g/リットル以上が好ましく、100~200g/リットル以上が更に好ましい。見かけ比重が大きい程、高濃度の分散液を作ることが可能になり、ヘイズ、凝集物が良化するため好ましい。
上記マット粒子の他に、本発明の光学フィルムには、その他の種々の添加剤(例えば、レターデーション発現剤、可塑剤、紫外線吸収剤、劣化防止剤、剥離剤、赤外線吸収剤、波長分散調整剤など)を加えることができ、それらは固体でもよく油状物でもよい。すなわち、その融点や沸点において特に限定されるものではない。例えば20℃以下と20℃以上の紫外線吸収材料の混合や、同様に可塑剤の混合などであり、例えば特開2001-151901号などに記載されている。更にまた、赤外吸収染料としては例えば特開2001-194522号に記載されている。またその添加する時期はドープ作製工程において何れで添加しても良いが、ドープ調製工程の最後の調製工程に添加剤を添加し調製する工程を加えて行ってもよい。更にまた、各素材の添加量は機能が発現する限りにおいて特に限定されない。また、光学フィルムが多層から形成される場合、各層の添加物の種類や添加量が異なってもよい。例えば特開2001-151902号などに記載されているが、これらは従来から知られている技術である。これらの詳細は、発明協会公開技報(公技番号2001-1745、2001年3月15日発行、発明協会)にて16頁~22頁に詳細に記載されている素材が好ましく用いられる。
(レターデーション)
本発明の光学フィルムは、波長590nmで測定したRe及びRth(下記式(I)及び(II)にて定義される)が、式(III)及び(IV)を満たす。
式(I) Re=(nx-ny)×d
式(II) Rth={(nx+ny)/2-nz}×d
式(III) |Re|≦50nm
式(IV) |Rth|≦300nm
(式中、nxは前記光学フィルムのフィルム面内の遅相軸方向の屈折率であり、nyは前記光学フィルム面内の進相軸方向の屈折率であり、nzは前記光学フィルムの膜厚方向の屈折率であり、dは前記光学フィルムの厚さ(nm)である。)
なお、本発明の光学フィルムでは、上記式(III)及び(IV)がフィルム面内の少なくとも1点において満足されればよいが、フィルム面内の任意の点で上記式(III)及び(IV)が満足されることが好ましい。
ReはKOBRA 21ADH(王子計測機器(株)製)において波長λnmの光をフィルム法線方向に入射させて測定される。
Rthは前記Re、面内の遅相軸(KOBRA 21ADHにより判断される)を傾斜軸(回転軸)としてフィルム法線方向に対して+40°傾斜した方向から波長λnmの光を入射させて測定したレターデーション値、及び面内の遅相軸を傾斜軸(回転軸)としてフィルム法線方向に対して-40°傾斜した方向から波長λnmの光を入射させて測定したレターデーション値の計3つの方向で測定したレターデーション値を基にKOBRA 21ADHにより算出する。ここで平均屈折率の仮定値は熱可塑性ハンドブック(JOHN WILEY&SONS,INC)、各種光学フィルムのカタログの値を使用することができる。平均屈折率の値が既知でないものについてはアッベ屈折計で測定することができる。主な光学フィルムの平均屈折率の値を以下に例示する:セルロースアシレート(1.48)、環状ポリオレフィン(1.52)、ポリカーボネート(1.59)、ポリメチルメタクリレート(1.49)、ポリスチレン(1.59)である。
Nzは、Re及びRthに基づいて式(VI)により算出する。なお、平均屈折率の仮定値と膜厚に基づいて、KOBRA 21ADHによりnx、ny、nzを算出し、これらのnx、ny、nzの値から式(II)によりNzを算出することもできる。
本発明の光学フィルムの厚さは、100μm以下が好ましく、60μm以下がより好ましく、40μm以下が更に好ましく、25μm以下が特に好ましい。60μm以下であれば液晶表示装置の置かれる環境、すなわち温湿度変化に伴うパネルのムラ小さくすることができる。
フィルムの透湿度は、JIS Z-0208をもとに、40℃、相対湿度90%の条件において測定される。
透湿度は、各サンプルの替わりに10μm厚のアルミ箔を用いた透湿度測定値を各サンプルの測定値から引くことにより0点補正を行いサンプルの透湿度とした。また、透湿度はフィルムの膜厚が厚ければ小さくなり、膜厚が薄ければ大きくなる。そこで膜厚の異なるサンプルでは、基準を40μmに設けて換算する必要がある。膜厚の換算は、下記数式に従って行うことができる。
数式:40μm換算の透湿度=実測の透湿度×実測の膜厚(μm)/40(μm)。
本発明の光学フィルムの透湿度は、70g/m2/day以下であることがより好ましく、50g/m2/dayであることが更に好ましく、40g/m2/day以下であることがより更に好ましく、30g/m2/day以下であることがより更に特に好ましい。
透湿度が70g/m2/day以下であれば、液晶表示装置の常温、高湿及び高温高湿環境経時後の、液晶セルの反りや、黒表示時の表示ムラを抑制できる。
透湿度を低減するためには、フィルム中の水の拡散を抑える事が好ましく、すなわちフィルムの自由体積を下げる事が好ましい。一般的にフィルムの自由体積はフィルムの酸素透過係数と相関する。
本発明の光学フィルムの酸素透過係数は、100cc・mm/(m2・day・atm)以下が好ましく、30cc・mm/(m2・day・atm)以下がより好ましい。
溶剤流延方式の場合には、乾燥プロセスの負荷低減のため、5cc・mm/(m2・day・atm)以上が好ましい。
フィルムの酸素透過量測定は、酸素電極(オービスフェア・ラボラトリーズ社製MODEL3600、PFA)に薄く塗布したシリコングリスを介して直径1.5cmに裁断した試験片を貼り付け、定常状態での酸素還元電流出力値より、酸素透過量を求めた。
出力電流値の酸素透過量への換算は、透過量既知のサンプルを用いて検量線を作成することにより求めた。測定は、25℃、相対湿度50%環境下で行った。
最表面に用いる偏光板保護膜では、表面硬度が高いことが好ましく、その場合、本発明の光学フィルムの特性としては、ヌープ硬度が高いことが好ましい。ヌープ硬度は、100N/mm2以上が好ましく、150N/mm2以上が更に好ましく用いられる。
フィッシャーインスツルメンツ(株)社製"フッシャースコープH100Vp型硬度計"を用い、圧子の短軸の向きをフィルム製膜時の搬送方向(長手方向;鉛筆硬度試験での試験方向)に対して平行に配置したヌープ圧子により、ガラス基板に固定したサンプル表面を負荷時間10sec、クリープ時間5sec、除荷時間10sec、最大荷重100mNの条件で測定した。押し込み深さから求められる圧子とサンプルとの接触面積と最大荷重の関係より硬度を算出し、この5点の平均値を表面硬度とした。
本発明の光学フィルムは、全ヘイズ値(ヘイズ値の単位:%、以下同じ。)が2.00以下であることが好ましい。全ヘイズ値が2.00以下であると、フィルムの透明性が高く、液晶表示装置のコントラスト比や輝度向上に効果がある。全ヘイズ値は、1.00以下がより好ましく、0.50以下であることが更に好ましく、0.30以下が特に好ましく、0.20以下が最も好ましい。全ヘイズ値は低いほど光学的性能が優れるが原料選択や製造管理やロールフィルムのハンドリング性も考慮すると0.01以上であることが好ましい。
本発明の光学フィルムの内部ヘイズ値は、1.00以下であることが好ましい。内部ヘイズ値を1.00以下とすることで、液晶表示装置のコントラスト比を向上させ、優れた表示特性を実現することができる。内部ヘイズ値は、0.50以下がより好ましく、0.20以下が更に好ましく、0.10以下が特に好ましく、0.05以下が最も好ましい。原料選択や製造管理等の観点からは0.01以上であることが好ましい。
本発明の光学フィルムとしては、特に、全ヘイズ値が0.30以下であり、内部ヘイズ値が0.10以下であることが好ましい。
全ヘイズ値及び内部ヘイズ値は、フィルム材料の樹脂の種類や添加量、添加剤の選択(特に、マット剤粒子の粒径、屈折率、添加量)や、更にはフィルム製造条件(延伸時の温度や延伸倍率など)により調整することができる。
なおヘイズの測定は、本発明のフィルム試料40mm×80mmを、25℃、相対湿度60%で、ヘイズメーター(HGM-2DP、スガ試験機)でJIS K-6714に従って測定することができる。
本発明の光学フィルムの弾性率は、幅方向(TD方向)で1800~7000MPaであることが好ましい。
本発明において、TD方向の弾性率が上記範囲とすることにより、高湿及び高温高湿環境経時後の黒表示時の表示ムラやフィルム作製時の搬送性、端部スリット性や破断のし難さ等の製造適性の観点で好ましい。TD弾性率が小さすぎると高湿及び高温高湿環境経時後の黒表示時の表示ムラが発生し易くなり、また製造適性に問題が生じ、大きすぎるとフィルム加工性に劣る為、TD方向の弾性率は、1800~5000MPaがより好ましく、1800~4000MPaであることが更に好ましい。
また、本発明の光学フィルムの搬送方向の(MD方向)の弾性率は、1800~4000MPaが好ましく、1800~3000MPaであることがより好ましい。
ここで、フィルムの搬送方向(長手方向)とは、フィルム作製時の搬送方向(MD方向)であり、幅方向とはフィルム作製時の搬送方向に対して垂直な方向(TD方向)である。
フィルムの弾性率は、フィルム材料の樹脂の種類や添加量、添加剤の選択(特に、マット剤粒子の粒径、屈折率、添加量)や、更にはフィルム製造条件(延伸倍率など)により調整することができる。
弾性率は、例えば、東洋ボールドウィン(株)製万能引っ張り試験機“STM T50BP”を用い、23℃、相対湿度70%雰囲気中、引張速度10%/分で0.5%伸びにおける応力を測定して求めることができる。
本発明の光学フィルムのガラス転移温度Tgは製造適性と耐熱性の観点より、100℃以上200℃以下が好ましく、更に100℃以上150℃以下が好ましい。
また、ガラス転移温度の測定は、以下の動的粘弾性測定装置を用いて求めることもできる。本発明のフィルム試料(未延伸)5mm×30mmを、25℃、相対湿度60%で2時間以上調湿した後に動的粘弾性測定装置(バイブロン:DVA-225(アイティー計測制御(株)製))で、つかみ間距離20mm、昇温速度2℃/分、測定温度範囲30℃~250℃、周波数1Hzで測定し、縦軸に対数軸で貯蔵弾性率、横軸に線形軸で温度(℃)をとった時に、貯蔵弾性率が固体領域からガラス転移領域へ移行する際に見受けられる貯蔵弾性率の急激な減少を固体領域で直線1を引き、ガラス転移領域で直線2を引いたときの直線1と直線2の交点を、昇温時に貯蔵弾性率が急激に減少しフィルムが軟化し始める温度であり、ガラス転移領域に移行し始める温度であるため、ガラス転移温度Tg(動的粘弾性)とする。
本発明の光学フィルムの含水率(平衡含水率)は、偏光板の保護フィルムとして用いる際、ポリビニルアルコールなどの水溶性熱可塑性との接着性を損なわないために、膜厚のいかんに関わらず、25℃、相対湿度80%における含水率が、0~4質量%であることが好ましい。0.1~2.5質量%であることがより好ましく、0.5~1.5質量%であることが更に好ましい。平衡含水率が4質量%以下であれば、レターデーションの湿度変化による依存性が大きくなり過ぎず、液晶表示装置の常温、高湿及び高温高湿環境経時後の黒表示時の表示ムラを抑止の点からも好ましい。
含水率の測定法は、フィルム試料7mm×35mmを水分測定器、試料乾燥装置“CA-03”及び“VA-05”{共に三菱化学(株)製}にてカールフィッシャー法で測定した。水分量(g)を試料質量(g)で除して算出できる。
本発明の光学フィルムの寸度安定性は、60℃、相対湿度90%の条件下に24時間静置した場合(高湿)の寸度変化率、及び80℃、DRY環境(相対湿度5%以下)の条件下に24時間静置した場合(高温)の寸度変化率が、いずれも0.5%以下であることが好ましい。
より好ましくは0.3%以下であり、更に好ましくは0.15%以下である。
本発明の光学フィルムを偏光板用保護フィルムとして使用した場合には、偏光子の収縮による応力などにより複屈折(Re、Rth)が変化する場合がある。このような応力に伴う複屈折の変化は光弾性係数として測定できるが、その範囲は、30Br以下であることが好ましく、-3~12Brであることがより好ましく、0~11Brであることが更に好ましい。
本発明の光学フィルムの製造方法は、熱可塑性樹脂、および透湿度低減化合物を支持体上に流延して高分子膜を形成する工程を含み、前記透湿度低減化合物の分子量が200以上であり、前記透湿度低減化合物が下記式(1)を満たす。
式(1) A/B≦0.9
(式(1)中、Aは前記熱可塑性樹脂の質量に対して前記透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。)
延伸に用いる高分子膜としては、乾燥後の未延伸の高分子膜のガラス転移温度Tgは100~200℃が好ましく、100~150℃がより好ましい。
ここで、乾燥後の高分子膜(乾燥フィルム)とは、膜中の残留溶剤量が3.0質量%以下のものをいう。
好ましくは1.0質量%以下、より好ましくは0.5質量%以下、更に好ましくは0.3質量%以下、特に好ましくは0.2質量%以下である高分子膜を指す。ガラス転移温度は、前記熱可塑性樹脂の種類や質量比により調整することができる。
溶融流延法の場合、前記熱可塑性樹脂、および透湿度低減化合物を支持体上に流延して高分子膜を形成する工程が、熱可塑性樹脂および透湿度低減化合物を溶融したものを支持体上に流延して高分子膜を形成する工程であることが好ましい。溶融流延法としては、特開2009-154301号に詳しく記載されている方法を用いることが出来る。
溶液流延法の場合、前記熱可塑性樹脂、および透湿度低減化合物を支持体上に流延して高分子膜を形成する工程が、前記熱可塑性樹脂、前記透湿度低減化合物および溶媒を含む高分子溶液(ドープ)を支持体上に流延して高分子膜を形成する工程であることが好ましい。前記熱可塑性樹脂、前記透湿度低減化合物及び溶媒を含む高分子溶液(ドープ)を支持体上に流延することで前記高分子膜が形成される。
ドープを形成するのに有用な溶媒は、前記熱可塑性樹脂、前記透湿度低減化合物及びその他の添加剤を同時に溶解するものであれば、制限なく用いることができる。
本発明においては、有機溶媒として、塩素系有機溶媒を主溶媒とする塩素系溶媒と塩素系有機溶媒を含まない非塩素系溶媒とのいずれをも用いることができる。2種類以上の有機溶媒を混合して用いてもよい。
ドープは、0℃以上の温度(常温又は高温)で処理することからなる一般的な方法で調製することができる。本発明に用いることができるドープの調製は、通常のソルベントキャスト法におけるドープの調製方法及び装置を用いて実施することができる。
前記熱可塑性樹脂の合計量は、得られる高分子溶液中に10~40質量%含まれるように調整することが好ましい。
前記熱可塑性樹脂の量は、10~30質量%であることが更に好ましい。有機溶媒(主溶媒)中には、後述する任意の添加剤を添加しておいてもよい。
溶液は、常温(0~40℃)で前記熱可塑性樹脂と有機溶媒とを攪拌することにより調製することができる。高濃度の溶液は、加圧及び加熱条件下で攪拌してもよい。具体的には、前記熱可塑性樹脂と有機溶媒とを加圧容器に入れて密閉し、加圧下で溶媒の常温における沸点以上、かつ溶媒が沸騰しない範囲の温度に加熱しながら攪拌する。
加熱温度は、通常は40℃以上であり、好ましくは60~200℃であり、更に好ましくは80~110℃である。
光学フィルムは、場合により表面処理を行うことによって、光学フィルムと他の層(例えば、偏光子、下塗層及びバック層)との接着の向上を達成することができる。例えばグロー放電処理、紫外線照射処理、コロナ処理、火炎処理、酸又はアルカリ処理を用いることができる。ここでいうグロー放電処理とは、10-3~20Torrの低圧ガス下でおこる低温プラズマでもよく、更にまた大気圧下でのプラズマ処理も好ましい。プラズマ励起性気体とは上記のような条件においてプラズマ励起される気体をいい、アルゴン、ヘリウム、ネオン、クリプトン、キセノン、窒素、二酸化炭素、テトラフルオロメタンの様なフロン類及びそれらの混合物などがあげられる。これらについては、詳細が発明協会公開技報(公技番号 2001-1745、2001年3月15日発行、発明協会)にて30頁~32頁に詳細に記載されており、本発明において好ましく用いることができる。
また本発明の光学フィルムは、少なくとも一方の表面に、膜厚0.1~20μmの機能層を積層することが好ましい。この機能層の種類は特に限定されないが、ハードコート層、反射防止層(低屈折率層、中屈折率層、高屈折率層など屈折率を調整した層)、防眩層、帯電防止層、紫外線吸収層、低透湿層(透湿度低減層)などが挙げられる。
前記機能層は、1層であってもよいし、複数層設けてもよい。前記機能層の積層方法は特に限定されないが、熱可塑性樹脂と前記透湿度低減化合物を含む光学フィルムとの共流延、あるいは、熱可塑性樹脂と前記透湿度低減化合物を含む光学フィルム上に塗設して設けることが好ましい。
機能層を塗布・乾燥にて形成する場合には、バインダーとしてエチレン性不飽和基をもつモノマーを用いることが好ましい。前記モノマーは、単官能であっても多官能であっても良い。なかでも重合性の多官能モノマーを用いることが好ましく、光重合性多官能モノマーを用いることがより好ましく、2個以上の(メタ)アクリロイル基を有するモノマーを含有した塗布液を用いることが特に好ましい。
トリエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート等のポリオキシアルキレングリコールの(メタ)アクリル酸ジエステル類;
ペンタエリスリトールジ(メタ)アクリレート等の多価アルコールの(メタ)アクリル酸ジエステル類;
2,2-ビス{4-(アクリロキシ・ジエトキシ)フェニル}プロパン、2-2-ビス{4-(アクリロキシ・ポリプロポキシ)フェニル}プロパン等のエチレンオキシドあるいはプロピレンオキシド付加物の(メタ)アクリル酸ジエステル類;
等を挙げることができる。
更に好ましくは、1分子中に3個以上の(メタ)アクリロイル基を有する多官能モノマーが好ましい。例えば、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、エチレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、プロピレンオキシド変性トリメチロールプロパントリ(メタ)アクリレート、エチレンオキシド変性リン酸トリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,2,3-シクロヘキサンテトラメタクリレート、ポリウレタンポリアクリレート、ポリエステルポリアクリレート、カプロラクトン変性トリス(アクリロキシエチル)イソシアヌレート等が挙げられる。
多価アルコールとしては、特に制限されないが、脂肪族アルコールが好ましく、なかでも環状脂肪族炭化水素基を持つアルコールがより好ましい。単環式の脂環式アルコールの脂肪族基としては、炭素数3~8のシクロアルキル基が好ましく、例えば、シクロペンチル基、シクロヘキシル基、シクロブチル基、シクロオクチル基等を挙げることができる。
多環式の脂環式アルコールの脂肪族基としては、炭素数5以上のビシクロ、トリシクロ、テトラシクロ構造等を有する基を挙げることができ、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、ジシクロペンチル基、トリシクロデカニル基、テトラシクロドデシル基、特開2006-215096号公報の特許請求の範囲記載の化合物の中心骨格、特開2001-10999号公報記載の化合物の中心骨格等を挙げることができる。なお、シクロアルキル基中の炭素原子の一部が、酸素原子等のヘテロ原子によって置換されていてもよい。
なかでも、多環式のアルコールとしては、アダマンチル基、ノルボルニル基、ジシクロペンチル基、トリシクロデカニル基、テトラシクロドデシル基、特開2006-215096号公報の特許請求の範囲記載の化合物の中心骨格、特開2001-10999号公報記載の化合物の中心骨格を持つ多価アルコール類が、透湿度を低下させる観点から特に好ましい。
1価のアルコールとしては、メチルアルコール、n-プロピルアルコール、iso-プロピルアルコール、n-ブチルアルコール、tert-ブチルアルコール、n-アミルアルコール、ジアセトンアルコール、1-メトキシ-2-プロパノール、フルフリルアルコール、2-オクタノール、2-エチルヘキサノール、ノナノール、n-デカノール、ウンデカノール、n-ドデカノール、トリメチルノニルアルコール、ベンジルアルコール、フェネチルアルコール、エチレングリコールモノイソアミルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノヘキシルエーテルが挙げられる。
また、脂肪族アルコールの脂肪族部分については、環状脂肪族であってもよい。環状脂肪族としては単環型でもよく、多環型でもよく、多環型の場合は有橋式であってもよい。単環型としては、炭素数3~8のシクロアルキル基が好ましく、例えば、シクロペンチル基、シクロヘキシル基、シクロブチル基、シクロオクチル基等を挙げることができる。多環型としては、炭素数5以上のビシクロ、トリシクロ、テトラシクロ構造等を有する基を挙げることができ、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、ジシクロペンチル基、トリシクロデカニル基、テトラシクロドデシル基、特開2006-215096号公報の特許請求の範囲記載の化合物の中心骨格、特開2001-10999号公報記載の化合物の中心骨格等を挙げることができる。なお、シクロアルキル基中の炭素原子の一部が、酸素原子等のヘテロ原子によって置換されていてもよい。
前記機能層として、低透湿層を好ましく用いることができる。
本発明の光学フィルムに用いることができる低透湿層は、分子内に環状脂肪族炭化水素基と不飽和二重結合を有する化合物を含む組成物から形成されてなる層、または、塩素含有ビニル単量体から誘導される繰り返し単位を含む樹脂を有する層であることが好ましく、分子内に環状脂肪族炭化水素基と不飽和二重結合を有する化合物を含む組成物から形成されてなる層であることがより好ましい。
本発明において、分子内に環状脂肪族炭化水素基と不飽和二重結合基を有する化合物を主成分とする組成物から形成されてなる層は、低透湿性を付与するために、環状脂肪族炭化水素基を有し、かつ分子内に不飽和二重結合基を有する化合物を含有し、必要に応じて更に、重合開始剤、透光性粒子、含フッ素又はシリコーン系化合物、溶剤を含有する組成物を、支持体上に直接又は他の層を介して塗布・乾燥・硬化することにより形成することができる。以下各成分について説明する。なお、組成物または層の主成分とは、その組成物またはその層の50質量%以上を占める成分のことを言う。
分子内に環状脂肪族炭化水素基と不飽和二重結合基を有する化合物はバインダーとして機能する。また、環状脂肪族炭化水素基を有し、不飽和二重結合基を有する化合物は、硬化剤として機能することができ、塗膜の強度や耐擦傷性を向上させることが可能となると同時に低透湿性を付与することができる。
このような化合物を用いることによって、低透湿性と高い膜強度を実現できる。詳細は明らかではないが、分子内に環状脂肪族炭化水素基を有する化合物を用いることで、低透湿層に疎水的な環状脂肪族炭化水素基を導入し、疎水化することで、外部から分子の取り込みを防止し、透湿度を低下させる。また、分子内に不飽和二重結合基を有することで、架橋点密度を上げ、低透湿層中の水分子の拡散経路を制限する。架橋点密度を上げることは、環状脂肪族炭化水素基の密度を相対的に上昇させる効果も有り、低透湿層内をより疎水的にし、水分子の吸着を防止し、透湿度を低下させると考えられる。
架橋点密度を上げるために分子内に有する不飽和二重結合基の数は2以上であることがより好ましい。
環状脂肪族炭化水素基としては、特に好ましくは、二環式、三環式等の、多環式化合物から誘導される基である。
より好ましくは、特開2006-215096号公報の特許請求の範囲記載の化合物の中心骨格、特開昭2001-10999号公報記載の化合物の中心骨格、あるいは、アダマンタン誘導体の骨格等が挙げられる。
連結基としては、単結合、炭素数1~6の置換されていてもよいアルキレン基、N位が地置換されていてもよいアミド基、N位が置換されていてもよいカルバモイル基、エステル基、オキシカルボニル基、エーテル基等、及びこれらを組み合わせて得られる基が挙げられる。
分子内に環状脂肪族炭化水素基と不飽和二重結合基を有する化合物を主成分とする組成物には、重合開始剤を含むことが好ましいが、重合開始剤としては光重合開始剤が好ましい。
光重合開始剤としては、アセトフェノン類、ベンゾイン類、ベンゾフェノン類、ホスフィンオキシド類、ケタール類、アントラキノン類、チオキサントン類、アゾ化合物、過酸化物類、2,3-ジアルキルジオン化合物類、ジスルフィド化合物類、フルオロアミン化合物類、芳香族スルホニウム類、ロフィンダイマー類、オニウム塩類、ボレート塩類、活性エステル類、活性ハロゲン類、無機錯体、クマリン類などが挙げられる。光重合開始剤の具体例、及び好ましい態様、市販品などは、特開2009-098658号公報の段落[0133]~[0151]に記載されており、本発明においても同様に好適に用いることができる。
本発明に用いられる分子内に環状脂肪族炭化水素基と不飽和二重結合基を有する化合物を主成分とする組成物は、溶剤を含有することができる。溶剤としては、モノマーの溶解性、塗工時の乾燥性、透光性粒子の分散性等を考慮し、各種溶剤を用いることができる。係る有機溶剤としては、例えばジブチルエーテル、ジメトキシエタン、ジエトキシエタン、プロピレンオキシド、1,4-ジオキサン、1,3-ジオキソラン、1,3,5-トリオキサン、テトラヒドロフラン、アニソール、フェネトール、炭酸ジメチル、炭酸メチルエチル、炭酸ジエチル、アセトン、メチルエチルケトン(MEK)、ジエチルケトン、ジプロピルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノン、メチルシクロヘキサノン、蟻酸エチル、蟻酸プロピル、蟻酸ペンチル、酢酸メチル、酢酸エチル、酢酸プロピル、プロピオン酸メチル、プロピオン酸エチル、γ-プチロラクトン、2-メトキシ酢酸メチル、2-エトキシ酢酸メチル、2-エトキシ酢酸エチル、2-エトキシプロピオン酸エチル、2-メトキシエタノール、2-プロポキシエタノール、2-ブトキシエタノール、1,2-ジアセトキシアセトン、アセチルアセトン、ジアセトンアルコール、アセト酢酸メチル、アセト酢酸エチル等メチルアルコール、エチルアルコール、イソプロピルアルコール、n-ブチルアルコール、シクロヘキシルアルコール、酢酸イソブチル、メチルイソブチルケトン(MIBK)、2-オクタノン、2-ペンタノン、2-ヘキサノン、エチレングリコールエチルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールブチルエーテル、プロピレングリコールメチルエーテル、エチルカルビトール、ブチルカルビトール、ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ベンゼン、トルエン、キシレン等が挙げられ、1種単独であるいは2種以上を組み合わせて用いることができる。
なお、組成物または層の主成分とは、その組成物またはその層の50質量%以上を占める成分のことを言う。
前記低透湿層は、1層であってもよいし、複数層設けてもよい。前記低透湿層の積層方法は特に限定されないが、前記低透湿層を基材フィルムとの共流延として作成すること、または、前記低透湿層を前記基材フィルム上に塗布で積層して設けることが好ましく、前記低透湿層を前記基材フィルム上に塗布で積層して設けることがより好ましい。すなわち、本発明の光学フィルムは、前記低透湿層が、前記基材フィルム上に塗布により積層されてなることがより好ましい。
前記低透湿層の膜厚は、1~20μmであることが好ましく、2~18μmであることがより好ましく、3~17μmであることが特に好ましい。
本発明の光学フィルムは、他に光学異方性層を有していてもよく、その好ましい態様の一例として断面模式図を図1に示す。
図1に示す光学フィルム10は、透明支持体14、光学異方性層12、及び基材16を有し、光学異方性層12は、位相差を生じさせる層であって、一定の位相差を有する膜が面内均一に形成された光学異方性層であってもよいし、遅相軸や位相差等が互いに異なる領域が規則的に面内に配置されたパターン光学異方性層であってもよい。
図1の態様の光学フィルムでは、前記分子量が200以上であり、かつ下記式(1)を満たす透湿度低減化合物は、透明支持体14に含まれていてもよい。
λ/4膜を光学異方性層とする光学フィルムは、輝度向上板、3D液晶表示装置等に使用でき、特にアクティブ方式の3D液晶表示装置の部材として有用である。
画像表示装置内に、第1及び第2の位相差領域12a及び12bが、均等且つ対称に配置されたパターン光学異方性層である。第1及び第2の位相差領域12a及び12bは、互いに直交する面内遅相軸a及びbをそれぞれ有することが好ましい。
さらに、第1及び第2位相差領域12a、12bの面内遅相軸a及びbが互いに直交するとともに、面内レターデーションReがλ/4であるパターンλ/4層であることが好ましい。この態様のパターン光学異方性層を偏光膜と組み合わせると、第1及び第2位相差領域のそれぞれを通過した光は互いに逆向きの円偏光状態になり、それぞれ右眼及び左眼用の円偏光画像を形成する。
前記のパターンλ/4層を光学異方性層とする光学フィルムの具体的な態様については、特許第4825934号公報、特許第4887463号公報に記載された光学異方性層、及び光学フィルムを適宜、使用することができる。
その際に、本発明の光学フィルムには各種の機能層を付与してもよい。機能層としては、例えば、帯電防止層、硬化樹脂層(透明ハードコート層)、反射防止層、易接着層、防眩層、光学異方性層、配向層、液晶層などである。これらの機能層及びその材料としては、界面活性剤、滑り剤、マット剤、帯電防止層、ハードコート層などが挙げられ、発明協会公開技報(公技番号2001-1745、2001年3月15日発行、発明協会)にて32頁~45頁に詳細に記載されており、本発明において好ましく用いることができる。
本発明の偏光板は、偏光子の保護フィルムとして本発明の光学フィルムを少なくとも1枚含むことを特徴とする。
本発明の光学フィルムは、偏光板用保護フィルムとして用いることができる。この場合、液晶表示装置の光学補償フィルムと偏光板用保護フィルムとを兼ねることができる。偏光板用保護フィルムとして用いる場合、偏光板の作製方法は特に限定されず、一般的な方法で作製することができる。得られた光学フィルムをアルカリ処理し、ポリビニルアルコールフィルムを沃素溶液中に浸漬延伸して作製した偏光子の両面に完全ケン化ポリビニルアルコール水溶液を用いて貼り合わせる方法がある。アルカリ処理の代わりに特開平6-94915号、特開平6-118232号に記載されているような易接着加工を施してもよい。また前記のような表面処理を行ってもよい。
保護フィルム処理面と偏光子を貼り合わせるのに使用される接着剤としては、例えば、ポリビニルアルコール、ポリビニルブチラール等のポリビニルアルコール系接着剤や、ブチルアクリレート等のビニル系ラテックス等が挙げられる。
偏光板は偏光子及びその両面を保護する保護フィルムで構成されており、更に該偏光板の一方の面にプロテクトフィルムを、反対面にセパレートフィルムを貼合して構成される。プロテクトフィルム及びセパレートフィルムは偏光板出荷時、製品検査時等において偏光板を保護する目的で用いられる。この場合、プロテクトフィルムは、偏光板の表面を保護する目的で貼合され、偏光板を液晶板へ貼合する面の反対面側に用いられる。又、セパレートフィルムは液晶板へ貼合する接着層をカバーする目的で用いられ、偏光板を液晶板へ貼合する面側に用いられる。
液晶表示装置には通常2枚の偏光板の間に液晶セルを含む基板が配置されているが、本発明の光学フィルムを適用した偏光板用保護フィルムは、2枚の偏光板のいずれの保護フィルムとして用いることができるが、各偏光板の2枚の保護フィルムのうち、偏光子に対して液晶セル側に配置される保護フィルムとして用いられることが好ましい。
本発明の光学フィルムは、様々な用途で用いることができ、液晶表示装置の光学補償フィルムとして用いると特に効果がある。なお、光学補償フィルムとは、一般に液晶表示装置に用いられ、位相差を補償する光学材料のことを指し、位相差板、光学補償シートなどと同義である。光学補償フィルムは複屈折性を有し、液晶表示装置の表示画面の着色を取り除いたり、視野角特性を改善したりする目的で用いられる。
本発明の液晶表示装置は、液晶セルと、該液晶セルの少なくとも一方に配置された本発明の偏光板とを含み、前記偏光板中に含まれる本発明の光学フィルムが最表層となるように配置されたことを特徴とする。
本発明のフィルムは、様々な表示モードの液晶セルに用いることができる。TN(Twisted Nematic)、IPS(In-Plane Switching)、FLC(Ferroelectric Liquid Crystal)、AFLC(Anti-ferroelectric Liquid Crystal)、OCB(Optically Compensatory Bend)、STN(Super Twisted Nematic)、VA(Vertically Aligned)、ECB(Electrically Controlled Birefringence)、及びHAN(Hybrid Aligned Nematic)のような様々な表示モードが提案されている。また、上記表示モードを配向分割した表示モードも提案されている。本発明の光学フィルムは、いずれの表示モードの液晶表示装置においても有効である。また、透過型、反射型、半透過型のいずれの液晶表示装置においても有効である。
下記に記載のアクリル樹脂および熱可塑性樹脂を使用した。これらのアクリル樹脂および熱可塑性樹脂は市販品や公知の合成方法により入手可能である。
・PMMA、商品名ダイヤナールBR88、三菱レイヨン社製
・PS、商品名G9504、PSジャパン社製
・SAN、商品名セビアン050SF、ダイセルポリマー社製
・ノルボルネン(ノルボルネン系樹脂)、商品名アートン F5023、JSR社製
・ラクトン(ラクトン環含有重合体であるアクリル樹脂、後述の合成方法により合成)
下記に示す構造の透湿度低減化合物を用いた。
用いた透湿度低減化合物のA/Bの値は、下記の方法で透湿度A及びBを算出することにより求めた。すなわち、透湿度低減化合物を熱可塑性樹脂(PMMA)に対し10質量%添加した実施例1の光学フィルム、および実施例1の熱可塑性樹脂(PMMA)を他の熱可塑性樹脂に変更した実施例3~5の光学フィルムを作製し、後述の方法により透湿度Aを求めた。別途、実施例1、及び3~5で用いた各種熱可塑性樹脂を含み、かつ透湿度低減化合物は含まない比較例2~5の光学フィルムを作製し、透湿度Aの測定方法と同様の方法で透湿度Bを求めた。
・C-4 フドー株式会社製、キシレン樹脂、ニカノールY1000(下記構造)
下記に記載の紫外線吸収剤を使用した。
UV剤1:チヌビン328(チバ・スペシャルティ・ケミカルズ(株)製)
脆性改良剤1:クラレ社製、LA4285
<光学フィルム101の作製>
(ドープ調製)
下記に記載の組成物をミキシングタンクに投入し、加熱しながら攪拌して、各成分を溶解し、ドープを調製した。
(ドープ組成)
PMMA樹脂 100質量部
透湿度低減化合物 B-7 10質量部
UV剤1 2.4質量部
脆性改良剤1 5.0質量部
ジクロロメタン 534質量部
メタノール 46質量部
作製したフィルムについて膜厚を測定し、下記の物性測定と評価を行った。結果は下記表1に示す。
JIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を、40μm膜厚に換算した。
また、得られた後述の各実施例の光学フィルムの透湿度をaとし、後述の比較例2~5の光学フィルムのうち、各実施例の光学フィルムで用いたポリマーの種類と同じ種類のポリマーを用いた各比較例の光学フィルムの透湿度の透湿度をBとして、a/Bの値を計算した。
サンプルフィルムを25℃、相対湿度60%にて24時間調湿した。次いで、自動複屈折計(KOBRA-21ADH:王子計測機器(株)製)を用いて、25℃、相対湿度60%において、フィルム表面に対し垂直方向及び遅相軸を回転軸としてフィルム面法線から+50°から-50°まで10°刻みで傾斜させた方向から波長590nmにおける位相差を測定して、面内レターデーション値(Re)と膜厚方向のレターデーション値(Rth)とを算出した。
(光学フィルム101を用いた偏光板の作製)
1)フィルムの鹸化
市販のセルローストリアセテートフィルム(フジタック ZRD40、富士フイルム(株)製)を、55℃に保った1.5mol/LのNaOH水溶液(鹸化液)に2分間浸漬した後、フィルムを水洗し、その後、25℃の0.05mol/Lの硫酸水溶液に30秒浸漬した後、更に水洗浴を30秒流水下に通して、フィルムを中性の状態にした。そして、エアナイフによる水切りを3回繰り返し、水を落とした後に70℃の乾燥ゾーンに15秒間滞留させて乾燥し、鹸化処理したフィルムを作製した。
特開2001-141926号公報の実施例1に従い、延伸したポリビニルアルコールフィルムにヨウ素を吸着させて膜厚20μmの偏光子を作製した。
この偏光子の片面に、コロナ処理を施したフィルム101を、アクリル接着剤を用いて貼合した。もう片側に、上記鹸化した市販のセルローストリアセテートフィルムを、ポリビニルアルコール系接着剤を用いて貼り付け、70℃で10分以上乾燥して、フィルム101を用いた偏光板を作製した。ここで、偏光子の透過軸とフィルムの搬送方向とが直交するように配置した。得られた偏光板を実施例1の偏光板とした。
(光学フィルム102~107および110~115、比較例の光学フィルム2~6の作製)
実施例1の光学フィルム101の作製において、熱可塑性樹脂(ポリマー)の種類、透湿度低減化合物の種類および量を表1のように変更し、溶剤としてジクロロメタンのみを用い、脆性改良剤1を用いなかった以外は光学フィルム101の作製と同様にして、ドープ(固形分濃度20質量%)を調製した。流延製膜条件は実施例1の光学フィルム101の作製と同様にして、実施例2~7および10~15の光学フィルム102~107および110~115、比較例2~6の光学フィルム2~6を作製した。
また、国際公開WO2006/025445A1の[0230]~[0232]に記載された合成方法に従い、ラクトン環含有重合体のペレットを得た。次いで、このペレットを溶解して、実施例1の光学フィルム101と同様にして実施例7の光学フィルム107を作製した。また、このペレットを用いて、透湿度低減化合物を添加しない以外は実施例1の光学フィルム101と同様にして比較例6の光学フィルム106を作製した。
実施例6において、流延製膜時の厚みを変更した以外は実施例6と同様の方法で厚み490μmのフィルムを作製し、120℃で搬送方向および幅手方向にそれぞれ3.4倍、3.6倍延伸し、厚み40μmの実施例8の光学フィルム108を作製した。
実施例6において、ポリマーをノルボルネン系樹脂(商品名;アートン)に変更し、かつ、流延製膜時の厚みを変更した以外は実施例6と同様な方法で厚み490μmのフィルムを作製し、130℃で搬送方向および幅手方向にそれぞれ3.4倍、3.6倍延伸し、厚み40μmの実施例9の光学フィルム109を作製した。
実施例1の偏光板と同様の方法で、実施例2~15の光学フィルム102~115を用いた偏光板および比較例2~6の光学フィルム2~6を用いた偏光板を作製した。
<IPSパネルへの実装>
IPSモード液晶セル(LGD製 42LS5600)の上下の偏光板を剥し、上記偏光板をZRD40が液晶セル側になるようにして貼りつけた。上側偏光板の透過軸が上下方向に、そして下側偏光板の透過軸が左右方向になるように、クロスニコル配置とした。
なお、IPSパネルへの実装時における、各実施例および比較例の偏光板の構成を下記表2に記載した。
液晶表示装置を60℃、相対湿度90%の環境下で48時間放置した後、25℃、相対湿度60%の環境下で24時間調湿した。調湿後の液晶表示装置を点灯させ、黒表示時の色ムラの程度を目視で観測し、以下の基準により4段階で評価した。
A:色ムラは観測されなかった。
B:表示面の四隅のうちの1または2箇所に弱い色ムラが観測された。
C:表示面の四隅に弱い色ムラが観測された。
D:表示面の四隅のうちの1または2箇所に強い色ムラが観測された。
E:表示面の四隅に強い色ムラが観測された。
その中でも特に透湿度a/透湿度Bが0.4以下、透湿度30g/m2/day以下のときにムラ改善効果が高いことが分る。
12 パターン光学異方性層
12a 第1の位相差領域
12b 第2の位相差領域
14 透明支持体
a 第1の位相差領域の面内遅相軸
b 第2の位相差領域の面内遅相軸
Claims (20)
- 熱可塑性樹脂を含む光学フィルムであって、
前記光学フィルムの透湿度が、膜厚40μm換算で70g/m2/day以下であり、
分子量が200以上であり、かつ下記式(1)を満たす透湿度低減化合物を前記光学フィルムが含むことを特徴とする光学フィルム。
式(1) A/B≦0.9
式(1)中、Aは前記熱可塑性樹脂の質量に対して前記透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度は、JIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。 - 下記式(2)を満たすことを特徴とする請求項1に記載の光学フィルム。
式(2) a/B≦0.9
式(2)中、aは前記熱可塑性樹脂と前記透湿度低減化合物とを含有する場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。 - 前記透湿度低減化合物が、芳香族環を1つ以上含むことを特徴とする請求項1または2に記載の光学フィルム。
- 前記透湿度低減化合物が、下記一般式(B)で表される化合物、フェノール樹脂、テルペン樹脂、芳香族炭化水素ホルムアルデヒド樹脂またはバルビツール酸類であることを特徴とする請求項1~3のいずれか一項に記載の光学フィルム。
一般式(B)
一般式(B)中、R12、R13、R14、R15、R16、R21、R23、R24、R25、R32、R33、R34、R35、R36は、それぞれ独立に、水素原子または置換基を表し、R12、R13、R14、R15、R16、R21、R23、R24、R25、R32、R33、R34、R35およびR36のうち少なくとも1つはアミノ基、アシルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホニルアミノ基、ヒドロキシ基、メルカプト基、カルボキシル基である。 - 前記透湿度低減化合物が、ノボラック型フェノール樹脂、水添テルペン樹脂、キシレン樹脂またはバルビツール酸類であることを特徴とする請求項1~4のいずれか一項に記載の光学フィルム。
- 前記透湿度低減化合物が、ノボラック型フェノール樹脂、水添テルペン樹脂またはキシレン樹脂であることを特徴とする請求項1~5のいずれか一項に記載の光学フィルム。
- 前記透湿度低減化合物が、芳香族環を3つ以上含むことを特徴とする請求項1~6のいずれか一項に記載の光学フィルム。
- 前記透湿度低減化合物が、ノボラック型フェノール樹脂またはキシレン樹脂であることを特徴とする請求項1~8のいずれか一項に記載の光学フィルム。
- 前記熱可塑性樹脂の質量に対し、前記透湿度低減化合物を1質量%以上含むことを特徴とする請求項1~9のいずれか一項に記載の光学フィルム。
- 膜厚が60μm以下であることを特徴とする請求項1~10のいずれか一項に記載の光学フィルム。
- 下記式(I)及び下記式(II)で定義されるRe及びRthが、波長590nmにおいて下記式(III)及び下記式(IV)を満たすことを特徴とする請求項1~11のいずれか一項に記載の光学フィルム。
式(I) Re=(nx-ny)×d
式(II) Rth={(nx+ny)/2-nz}×d
式(III)|Re|≦50nm
式(IV) |Rth|≦300nm
式(I)~(IV)中、nxは光学フィルム面内の遅相軸方向の屈折率であり、nyは光学フィルム面内の進相軸方向の屈折率であり、nzは光学フィルムの膜厚方向の屈折率であり、dは光学フィルムの厚さ(nm)である。 - 前記熱可塑性樹脂、前記透湿度低減化合物および溶媒を含む高分子溶液を支持体上に流延して製膜されてなることを特徴とする請求項1~12のいずれか一項に記載の光学フィルム。
- 前記光学フィルムの少なくとも一方の表面に、膜厚0.1~20μmの機能層を有することを特徴とする請求項1~13のいずれか一項に記載の光学フィルム。
- 前記機能層が積層された場合の光学フィルムの透湿度(C)と、前記機能層が積層されない場合の光学フィルムの透湿度(D)とが、C/D≦0.9となることを特徴とする請求項14に記載の光学フィルム。
- 熱可塑性樹脂、および透湿度低減化合物を支持体上に流延して高分子膜を形成する工程を含み、
前記透湿度低減化合物の分子量が200以上であり、
前記透湿度低減化合物が下記式(1)を満たすことを特徴とする光学フィルムの製造方法。
式(1) A/B≦0.9
式(1)中、Aは前記熱可塑性樹脂の質量に対して前記透湿度低減化合物を10質量%添加した場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。 - 前記光学フィルムが下記式(2)を満たすことを特徴とする請求項16に記載の光学フィルムの製造方法。
式(2) a/B≦0.9
式(2)中、aは前記熱可塑性樹脂と前記透湿度低減化合物とを含有する場合の光学フィルムの透湿度を表し、Bは前記熱可塑性樹脂を含みかつ前記透湿度低減化合物を添加しない場合の光学フィルムの透湿度を表す。ただし、透湿度はJIS Z-0208の手法で、40℃、相対湿度90%で24時間経過後の透湿度を40μm膜厚に換算した値である。 - 前記光学フィルムを延伸する工程を含むことを特徴とする請求項16または17に記載の光学フィルムの製造方法。
- 偏光子の保護フィルムとして請求項1~15のいずれか一項に記載の前記光学フィルムを少なくとも1枚含むことを特徴とする偏光板。
- 液晶セルと、
該液晶セルの少なくとも一方に配置された請求項19に記載の前記偏光板とを含み、
前記光学フィルムが最表層となるように配置されたことを特徴とする液晶表示装置。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020157002788A KR101688437B1 (ko) | 2012-09-28 | 2013-09-13 | 광학 필름 및 그 제조 방법, 편광판 그리고 액정 표시 장치 |
| JP2014538395A JP6043799B2 (ja) | 2012-09-28 | 2013-09-13 | 光学フィルム及びその製造方法、偏光板並びに液晶表示装置 |
| CN201380042653.XA CN104541189B (zh) | 2012-09-28 | 2013-09-13 | 光学膜及其制造方法、偏振片以及液晶显示装置 |
| US14/642,993 US10240033B2 (en) | 2012-09-28 | 2015-03-10 | Optical film and method for manufacturing same, polarization plate, and liquid crystal display apparatus |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012218701 | 2012-09-28 | ||
| JP2012-218701 | 2012-09-28 | ||
| JP2012232423 | 2012-10-19 | ||
| JP2012-232423 | 2012-10-19 | ||
| JP2012276873 | 2012-12-19 | ||
| JP2012-276873 | 2012-12-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/642,993 Continuation US10240033B2 (en) | 2012-09-28 | 2015-03-10 | Optical film and method for manufacturing same, polarization plate, and liquid crystal display apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014050608A1 true WO2014050608A1 (ja) | 2014-04-03 |
Family
ID=50388015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2013/074822 Ceased WO2014050608A1 (ja) | 2012-09-28 | 2013-09-13 | 光学フィルム及びその製造方法、偏光板並びに液晶表示装置 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US10240033B2 (ja) |
| JP (1) | JP6043799B2 (ja) |
| KR (1) | KR101688437B1 (ja) |
| CN (1) | CN104541189B (ja) |
| WO (1) | WO2014050608A1 (ja) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014132071A (ja) * | 2012-12-04 | 2014-07-17 | Fujifilm Corp | シクロオレフィン系樹脂フィルム、偏光板、および液晶表示装置 |
| US20150098046A1 (en) * | 2013-10-09 | 2015-04-09 | Fujifilm Corporation | Polarizing plate protective film, polarizing plate, liquid crystal display device, and production method of polarizing plate protective film |
| WO2016009743A1 (ja) * | 2014-07-16 | 2016-01-21 | コニカミノルタ株式会社 | 光学フィルム、偏光板および画像表示装置 |
| JP2019032401A (ja) * | 2017-08-07 | 2019-02-28 | 三菱瓦斯化学株式会社 | 積層光学フィルム、及び積層光学フィルムを有する位相差補償板 |
| WO2019131831A1 (ja) * | 2017-12-27 | 2019-07-04 | 株式会社クラレ | アクリル系樹脂フィルムおよびその製造方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI669809B (zh) | 2012-05-30 | 2019-08-21 | 日商新力股份有限公司 | Imaging element, imaging device, manufacturing device and method |
| JP6027214B1 (ja) * | 2015-06-11 | 2016-11-16 | 住友化学株式会社 | フィルム製造方法 |
| JP2017009795A (ja) * | 2015-06-22 | 2017-01-12 | 日東電工株式会社 | 偏光板及び偏光板の製造方法 |
| KR102066640B1 (ko) * | 2016-09-20 | 2020-01-15 | 주식회사 엘지화학 | 접착력이 우수한 광학 필름, 및 이를 포함하는 편광판 |
| KR101964436B1 (ko) * | 2016-09-20 | 2019-04-01 | 주식회사 엘지화학 | 접착력 및 자외선 차단 기능이 우수한 광학 필름, 및 이를 포함하는 편광판 |
| WO2018170371A1 (en) * | 2017-03-17 | 2018-09-20 | Henkel IP & Holding GmbH | Polyaromatic compounds and high refractive index, light stable, yellowing resistant resins containing same |
| WO2019003679A1 (ja) * | 2017-06-28 | 2019-01-03 | 日東電工株式会社 | 偏光板 |
| KR102363874B1 (ko) | 2018-10-18 | 2022-02-15 | 주식회사 엘지화학 | 편광판, 액정 패널 및 디스플레이 장치 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005338736A (ja) * | 2004-05-31 | 2005-12-08 | Fuji Photo Film Co Ltd | 偏光板、偏光板一体型光学補償フィルム、液晶表示装置および自発光型表示装置 |
| JP2007293301A (ja) * | 2006-03-29 | 2007-11-08 | Fujifilm Corp | 光学フィルム、偏光板、画像表示装置、及び光学フィルムの製造方法 |
| JP2008268658A (ja) * | 2007-04-23 | 2008-11-06 | Nitto Denko Corp | 連結組み合わせ型光学フィルムの製造方法、連結組み合わせ型光学フィルム、画像表示装置 |
| JP2009227917A (ja) * | 2008-03-25 | 2009-10-08 | Kuraray Co Ltd | フィルム |
| JP2010058411A (ja) * | 2008-09-04 | 2010-03-18 | Fujifilm Corp | 熱可塑性樹脂フィルム、その製造方法、偏光板および液晶表示装置 |
| JP2011098442A (ja) * | 2009-11-04 | 2011-05-19 | Konica Minolta Opto Inc | 光学フィルムの製造方法及び製造装置 |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW449612B (en) * | 1997-04-09 | 2001-08-11 | Chang Chun Plastics Co Ltd | An epoxy resin composition containing polyalkyl phenol resins and/or polyalkyl phenol epoxy resins |
| US6156865A (en) * | 1998-11-19 | 2000-12-05 | Nec Corporation | Flame retardant thermosetting resin composition |
| US7125918B2 (en) * | 2000-11-07 | 2006-10-24 | Konica Corporation | Protective film of a polarizing plate |
| TW200517436A (en) * | 2003-10-09 | 2005-06-01 | Nippon Kayaku Kk | Resin composition for protective film |
| US20070211334A1 (en) * | 2004-05-11 | 2007-09-13 | Nitto Denko Corporation | Polarizer protective film, polarizing plate and image display |
| JP4907881B2 (ja) * | 2004-09-09 | 2012-04-04 | 富士フイルム株式会社 | 液晶組成物、光学補償フィルム、及び液晶表示装置 |
| JP4681913B2 (ja) * | 2005-03-02 | 2011-05-11 | 富士フイルム株式会社 | 光学積層体、偏光板および液晶表示装置 |
| US7611760B2 (en) * | 2005-04-22 | 2009-11-03 | Fujifilm Corporation | Cellulose acylate film, optical compensation film, polarizing plate and liquid crystal display |
| JP5122982B2 (ja) | 2006-01-27 | 2013-01-16 | 出光興産株式会社 | アダマンタン誘導体、それを含む樹脂組成物、それらを用いた光学電子部材及び電子回路用封止剤 |
| US7960018B2 (en) * | 2006-03-29 | 2011-06-14 | Fujifilm Corporation | Optical film, polarizing plate, image display, and manufacturing method of optical film |
| KR20070114026A (ko) * | 2006-05-24 | 2007-11-29 | 후지필름 가부시키가이샤 | 셀룰로스 아실레이트 필름 및 셀룰로스 아실레이트 필름,광학 보상 필름, 편광판과 액정 디스플레이 장치의제조방법 |
| JP2009073960A (ja) * | 2007-09-21 | 2009-04-09 | Sumitomo Chemical Co Ltd | 光学用フィルム |
| JP4379547B2 (ja) | 2007-10-13 | 2009-12-09 | コニカミノルタオプト株式会社 | 光学フィルムの製造方法 |
| TW201207442A (en) * | 2009-12-25 | 2012-02-16 | Mitsui Chemicals Inc | Polarizing diffusion film, method for fabricating the same, and liquid crystal display apparatus including the same |
| JP5560943B2 (ja) * | 2010-06-18 | 2014-07-30 | Dic株式会社 | セルロースエステル樹脂組成物、それを用いたフィルム及び液晶表示装置用偏光板 |
| TW201213128A (en) * | 2010-07-05 | 2012-04-01 | Sumitomo Chemical Co | Laminate and process for preparing the same |
-
2013
- 2013-09-13 JP JP2014538395A patent/JP6043799B2/ja active Active
- 2013-09-13 KR KR1020157002788A patent/KR101688437B1/ko active Active
- 2013-09-13 WO PCT/JP2013/074822 patent/WO2014050608A1/ja not_active Ceased
- 2013-09-13 CN CN201380042653.XA patent/CN104541189B/zh active Active
-
2015
- 2015-03-10 US US14/642,993 patent/US10240033B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005338736A (ja) * | 2004-05-31 | 2005-12-08 | Fuji Photo Film Co Ltd | 偏光板、偏光板一体型光学補償フィルム、液晶表示装置および自発光型表示装置 |
| JP2007293301A (ja) * | 2006-03-29 | 2007-11-08 | Fujifilm Corp | 光学フィルム、偏光板、画像表示装置、及び光学フィルムの製造方法 |
| JP2008268658A (ja) * | 2007-04-23 | 2008-11-06 | Nitto Denko Corp | 連結組み合わせ型光学フィルムの製造方法、連結組み合わせ型光学フィルム、画像表示装置 |
| JP2009227917A (ja) * | 2008-03-25 | 2009-10-08 | Kuraray Co Ltd | フィルム |
| JP2010058411A (ja) * | 2008-09-04 | 2010-03-18 | Fujifilm Corp | 熱可塑性樹脂フィルム、その製造方法、偏光板および液晶表示装置 |
| JP2011098442A (ja) * | 2009-11-04 | 2011-05-19 | Konica Minolta Opto Inc | 光学フィルムの製造方法及び製造装置 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014132071A (ja) * | 2012-12-04 | 2014-07-17 | Fujifilm Corp | シクロオレフィン系樹脂フィルム、偏光板、および液晶表示装置 |
| US20150098046A1 (en) * | 2013-10-09 | 2015-04-09 | Fujifilm Corporation | Polarizing plate protective film, polarizing plate, liquid crystal display device, and production method of polarizing plate protective film |
| WO2016009743A1 (ja) * | 2014-07-16 | 2016-01-21 | コニカミノルタ株式会社 | 光学フィルム、偏光板および画像表示装置 |
| JP2019032401A (ja) * | 2017-08-07 | 2019-02-28 | 三菱瓦斯化学株式会社 | 積層光学フィルム、及び積層光学フィルムを有する位相差補償板 |
| JP7007832B2 (ja) | 2017-08-07 | 2022-01-25 | 三菱瓦斯化学株式会社 | 積層光学フィルム、及び積層光学フィルムを有する位相差補償板 |
| WO2019131831A1 (ja) * | 2017-12-27 | 2019-07-04 | 株式会社クラレ | アクリル系樹脂フィルムおよびその製造方法 |
| JPWO2019131831A1 (ja) * | 2017-12-27 | 2021-01-14 | 株式会社クラレ | アクリル系樹脂フィルムおよびその製造方法 |
| JP7096842B2 (ja) | 2017-12-27 | 2022-07-06 | 株式会社クラレ | アクリル系樹脂フィルムおよびその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104541189A (zh) | 2015-04-22 |
| CN104541189B (zh) | 2018-03-23 |
| US20150183977A1 (en) | 2015-07-02 |
| KR101688437B1 (ko) | 2016-12-21 |
| US10240033B2 (en) | 2019-03-26 |
| JPWO2014050608A1 (ja) | 2016-08-22 |
| KR20150041780A (ko) | 2015-04-17 |
| JP6043799B2 (ja) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6043799B2 (ja) | 光学フィルム及びその製造方法、偏光板並びに液晶表示装置 | |
| US9946110B2 (en) | Liquid crystal display | |
| US7875341B2 (en) | Antireflective film, polarizer plate and display | |
| JP6086629B2 (ja) | 光学フィルム、光学フィルムの製造方法、偏光板、及び画像表示装置 | |
| JP2014170202A (ja) | 液晶表示装置 | |
| JPWO2014119487A1 (ja) | 光学フィルム及びその製造方法、偏光板並びに液晶表示装置 | |
| JP2014219429A (ja) | 光学フィルム、偏光板及び液晶表示装置 | |
| JP2014119539A (ja) | 偏光板保護フィルム、偏光板および液晶表示装置 | |
| JP6267886B2 (ja) | 液晶表示装置 | |
| JP2017191203A (ja) | 積層体および液晶表示装置 | |
| WO2014057950A1 (ja) | 光学フィルム、光学フィルムの製造方法、偏光板、及び画像表示装置 | |
| US20080107832A1 (en) | Optical Film, Process of Producing the Same, Polarizing Plate Including the Same, and Liquid Crystal Display | |
| JP2014157284A (ja) | 偏光板保護フィルム、偏光板および液晶表示装置 | |
| JP2014102492A (ja) | 光学フィルム及びその製造方法、偏光板ならびに液晶表示装置 | |
| JP2023073124A (ja) | 位相差層付偏光板および該位相差層付偏光板を含む画像表示装置 | |
| JP2018018096A (ja) | 光学フィルム、偏光板及び液晶表示装置 | |
| JP2014119538A (ja) | 偏光板保護フィルム、偏光板および液晶表示装置 | |
| JP2014098893A (ja) | 光学フィルム及びその製造方法、偏光板ならびに液晶表示装置 | |
| JP7592662B2 (ja) | 位相差層付偏光板および画像表示装置 | |
| JP6329880B2 (ja) | 光学フィルム、光学フィルムの製造方法、偏光板、及び画像表示装置 | |
| CN118210094A (zh) | 光学层叠体和使用该光学层叠体的图像显示装置 | |
| JP2006195295A (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: 13841205 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 20157002788 Country of ref document: KR Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 2014538395 Country of ref document: JP 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: 13841205 Country of ref document: EP Kind code of ref document: A1 |































