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WO2014065294A1 - Stratifié, procédé permettant de produire ce dernier, film de retard, plaque de polarisation et panneau à cristaux liquides à mode de commutation dans le plan - Google Patents

Stratifié, procédé permettant de produire ce dernier, film de retard, plaque de polarisation et panneau à cristaux liquides à mode de commutation dans le plan Download PDF

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Publication number
WO2014065294A1
WO2014065294A1 PCT/JP2013/078615 JP2013078615W WO2014065294A1 WO 2014065294 A1 WO2014065294 A1 WO 2014065294A1 JP 2013078615 W JP2013078615 W JP 2013078615W WO 2014065294 A1 WO2014065294 A1 WO 2014065294A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
liquid crystalline
crystalline material
intrinsic birefringence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/078615
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English (en)
Japanese (ja)
Inventor
仁志 大石
宏晃 周
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
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Zeon Corp
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Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2014543312A priority Critical patent/JPWO2014065294A1/ja
Priority to KR1020157010481A priority patent/KR20150079630A/ko
Publication of WO2014065294A1 publication Critical patent/WO2014065294A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • G02F1/13338—Input devices, e.g. touch panels
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133635—Multifunctional compensators
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/02—Number of plates being 2
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/05—Single plate on one side of the LC cell
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/13—Positive birefingence
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/14—Negative birefingence

Definitions

  • the present invention relates to a laminate including an optical element, a manufacturing method thereof, a retardation film, a polarizing plate, and an IPS liquid crystal panel.
  • Liquid crystal display devices have advantages such as high image quality, thinness, light weight, and low power consumption, and are widely used in televisions, personal computers, car navigators, and the like.
  • a liquid crystal display device a liquid crystal cell is disposed between two polarizers (that is, an incident side polarizer and an output side polarizer) arranged so that transmission axes are orthogonal to each other, and a voltage is applied to the liquid crystal cell. The orientation of the liquid crystal molecules is changed to display an image on the screen.
  • a liquid crystal display device In a liquid crystal display device, sufficient contrast is usually obtained when viewing the screen from a direction parallel to the transmission axis of the polarizer. However, when the screen is viewed obliquely from a direction that is not parallel to the transmission axis, the transmission axis of the incident-side polarizer and the transmission axis of the output-side polarizer are apparently not orthogonal, so that linearly polarized light is not completely blocked. Light leakage may occur. When light leakage occurs, sufficient black cannot be obtained and the contrast decreases. Therefore, in a liquid crystal display device, an attempt has been made to provide an optical compensation film in order to prevent a reduction in screen contrast.
  • a retardation film is usually used as the optical compensation film.
  • various techniques have been conventionally developed as shown in Patent Documents 1 to 10, for example.
  • touch panels have been widely used in portable terminals such as mobile phones and tablet personal computers.
  • a display using an IPS (in-plane switching) type liquid crystal cell is preferable because there is no occurrence of display unevenness during use.
  • an optical compensation film used in a liquid crystal display device having an IPS type liquid crystal cell a retardation film in which a plurality of retardation films having different optical characteristics are combined is usually used.
  • optical compensation films are also required to be thinner.
  • an optical compensation film used in a liquid crystal display device including an IPS type liquid crystal cell is a retardation film in which a plurality of retardation films are combined, it is difficult to reduce the thickness.
  • the retardation film is generally easily damaged when the thickness of the retardation film is reduced, it is difficult to stably produce a thin optical compensation film.
  • the present invention was devised in view of the above-described problems, and provides a laminate and a method for producing the same that can achieve a retardation film having desired optical performance, a thin thickness, and capable of stable production.
  • An object of the present invention is to provide a retardation film having a desired optical performance, a thin thickness and capable of stable production, and a polarizing plate and an IPS liquid crystal panel provided with the retardation film.
  • the present inventor has found that the base film (A1) and the multilayer film (A) including the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence, A multilayer film (B) comprising a negative non-liquid crystalline material layer (B1) and a resin layer (B2), a surface of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence, and the intrinsic birefringence Is a laminate having a single adhesive layer interposed between the surface of the negative non-liquid crystalline material layer (B1) and having a desired optical performance, a thin thickness, and a stable production.
  • the present inventors have found that a possible retardation film can be realized and completed the present invention. That is, the present invention is as follows.
  • a multilayer film (A) comprising a substrate (A1) and a layer (A2) of a non-liquid crystalline material having a positive intrinsic birefringence in contact with the substrate (A1);
  • a multilayer film (B1) comprising a non-liquid crystalline material layer (B1) having a negative intrinsic birefringence and a resin layer (B2) in contact with the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence )
  • the surface of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence opposite to the base (A1) and the resin in the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence A single adhesive layer interposed between the surface opposite to the layer (B2);
  • a laminate comprising: [2] The laminate according to [1], wherein a peeling force between the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence and the resin layer (B2) is 0.5 N
  • the peel force between the substrate (A1) and the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence is 0.05 N / 20 mm or less, [1] or [2] The laminated body of description.
  • the difference between the glass transition temperature of the material of the base material (A1) and the glass transition temperature of the non-liquid crystalline material having a positive intrinsic birefringence is in the range of + 15 ° C. to ⁇ 15 ° C.
  • the laminated body according to any one of to [3].
  • a polymer obtained by polymerizing one or more monomers selected from the group consisting of styrenes, styrenes-maleic acid, maleimides, and (meth) acrylic acid esters with the non-liquid crystalline material having a negative intrinsic birefringence The mixture, and a mixture containing one or more polymers selected from the group consisting of a polycarbonate polymer, a polyester polymer, and a polyarylene ether polymer, according to any one of [1] to [8] Laminated body.
  • the resin layer (B2) is a polymer resin having an alicyclic structure, (meth) acrylic resin, polycarbonate resin, (meth) acrylic acid ester-vinyl aromatic compound copolymer resin, and polyethersulfone.
  • the non-liquid crystalline material having a negative intrinsic birefringence and the resin forming the resin layer (B2) are coextruded to form the resin layer (B2) and the non-liquid crystalline material layer having a negative intrinsic birefringence (B1).
  • a polarizing plate comprising a polarizer and the retardation film according to [14].
  • An IPS liquid crystal panel comprising an IPS liquid crystal cell and the polarizing plate according to [15].
  • a laminate having a desired optical performance, a thin thickness, and capable of realizing a retardation film that can be stably produced, and a method for producing the same have a desired optical performance, It is possible to provide a retardation film having a thin thickness and capable of stable production, and a polarizing plate and an IPS liquid crystal panel including the retardation film.
  • FIG. 1 is a diagram schematically showing a cross section of a laminated body according to an embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • FIG. 2 is a schematic view schematically showing an example of a production apparatus for producing the multilayer film (A).
  • FIG. 3 is a schematic view schematically showing an example of a production apparatus for producing the multilayer film (b).
  • FIG. 4 is a schematic view schematically showing an example of an apparatus for producing a laminate by laminating a multilayer film (A) and a multilayer film (B).
  • FIG. 5 is a diagram schematically showing a cross section of the polarizing plate according to one embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • FIG. 6 is a diagram schematically showing a cross section of the liquid crystal panel according to one embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • “long” means one having a length of at least 5 times the width, preferably 10 times or more, specifically a roll shape. It has a length enough to be wound up and stored or transported.
  • the “base material” and the “polarizing plate” include not only rigid members but also flexible members such as resin films.
  • the retardation in the in-plane direction of the film is a value represented by (nx ⁇ ny) ⁇ d unless otherwise specified.
  • the retardation in the thickness direction of the film is a value represented by ⁇
  • nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the film and giving the maximum refractive index.
  • ny represents the refractive index in the in-plane direction and orthogonal to the nx direction.
  • nz represents the refractive index in the thickness direction.
  • d represents the thickness of the film.
  • (meth) acrylate means “acrylate” or “methacrylate”
  • (meth) acryl means “acryl” or “methacryl”
  • (meth) acrylonitrile means.
  • Ultraviolet light means light having a wavelength of 1 nm or more and 400 nm or less.
  • the directions of the elements “parallel”, “vertical”, and “orthogonal” may include errors within a range that does not impair the effects of the present invention, for example, ⁇ 5 °, unless otherwise specified. Good. Further, “along” in a certain direction means “in parallel” in a certain direction.
  • the MD direction is the film flow direction in the production line, and is usually parallel to the longitudinal direction and the longitudinal direction of the long film.
  • the TD direction is a direction parallel to the film surface and perpendicular to the MD direction, and is usually parallel to the width direction and the lateral direction of the long film.
  • positive intrinsic birefringence means that the refractive index in the stretching direction is larger than the refractive index in the direction orthogonal to the stretching direction
  • negative intrinsic birefringence means that the refractive index in the stretching direction is negative. It means that the refractive index is smaller than the refractive index in the direction orthogonal to the stretching direction.
  • the value of intrinsic birefringence can also be calculated from the dielectric constant distribution.
  • the proportion of the structural unit contained in the polymer is usually the ratio of the monomer corresponding to the structural unit in all monomers of the polymer ( It matches the charging ratio).
  • FIG. 1 is a diagram schematically showing a cross section of a laminated body according to an embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • the laminate 100 includes a multilayer film (A) 10, a multilayer film (B) 20, an adhesive layer that bonds the multilayer film (A) 10 and the multilayer film (B) 20. 30.
  • the multilayer film (A) 10 includes a base material (A1) 11 and a layer (A2) 12 of a non-liquid crystalline material. Since the non-liquid crystal material layer (A2) 12 is in contact with the base material (A1) 11, other layers are provided between the base material (A1) 11 and the non-liquid crystal material layer (A2) 12. It is not done.
  • a resin film is usually used as the substrate (A1).
  • the kind of resin which forms a base material (A1) is not specifically limited, Transparent resin is preferable.
  • the term “transparent” means that it has a light transmittance suitable for use in an optical member.
  • the total light transmittance measured using a test piece having a thickness of 1 mm is usually 70% or more, preferably 80. % Or more, particularly preferably 90% or more.
  • the upper limit of the total light transmittance is usually 100%.
  • the total light transmittance can be measured using a spectrophotometer (manufactured by JASCO Corporation, ultraviolet-visible near-infrared spectrophotometer “V-570”) according to JIS K0115.
  • Examples of the resin that forms the base material (A1) include polyolefin resins such as polyethylene resins and polypropylene resins; polymer resins having an alicyclic structure such as norbornene-based resins; polyimide resins, polyamideimide resins, and polyamides.
  • polyetherimide resin polyether ether ketone resin, polyether ketone resin, polyketone sulfide resin, polyether sulfone resin, polysulfone resin, polyphenylene sulfide resin, polyphenylene oxide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate Resin, polyacetal resin, polycarbonate resin, polyarylate resin, (meth) acrylic resin, polyvinyl alcohol resin, polypropylene resin, cellulose Scan resins, epoxy resins, phenol resins, (meth) acrylic acid ester - vinyl aromatic compound copolymer resins, isobutene / N- methylmaleimide copolymer resins, styrene / acrylonitrile copolymer resins.
  • isobutene / N-methylmaleimide copolymer resin and styrene / acrylonitrile copolymer resin are preferably used in combination as a mixture.
  • a polymer resin having an alicyclic structure a (meth) acrylic resin, a polycarbonate resin, a (meth) acrylic acid ester-vinyl aromatic compound copolymer resin, and a polyethersulfone resin are selected.
  • Preferred is a resin. These resins are excellent in mechanical strength and can reduce the retardation developed by stretching.
  • the polymer resin having an alicyclic structure is a resin containing a polymer having an alicyclic structure.
  • the polymer having an alicyclic structure is a polymer having a structural unit containing an alicyclic structure as a structural unit of the polymer, a polymer having an alicyclic structure in the main chain, and a side chain. Any polymer having an alicyclic structure can be used.
  • the polymer which has an alicyclic structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Among these, a polymer containing an alicyclic structure in the main chain is preferable from the viewpoint of mechanical strength, heat resistance, and the like.
  • Examples of the alicyclic structure include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
  • a saturated alicyclic hydrocarbon cycloalkane
  • an unsaturated alicyclic hydrocarbon cycloalkene, cycloalkyne
  • a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is particularly preferable.
  • the number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably per alicyclic structure. Is a range of 15 or less. Thereby, mechanical strength, heat resistance, and film formability are highly balanced, which is preferable.
  • the ratio of the structural unit containing the alicyclic structure in the polymer having the alicyclic structure can be appropriately selected according to the purpose of use. Specifically, this ratio is preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more, and usually 100% by weight or less. It is preferable from a heat resistant viewpoint that the ratio of the structural unit containing the alicyclic structure in the polymer which has an alicyclic structure exists in this range.
  • Examples of the polymer having an alicyclic structure include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and hydrides thereof. Can be mentioned. Among these, norbornene-based polymers are preferable because of good moldability.
  • Examples of the norbornene-based polymer include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof;
  • An addition polymer of a monomer having a norbornene structure, an addition copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof can be given.
  • a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like.
  • (co) polymer refers to a polymer and a copolymer.
  • Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] deca-3,7- Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 12, 5.17,10] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).
  • examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different, and a plurality thereof may be bonded to the ring. Moreover, the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • optional monomers capable of ring-opening copolymerization with a monomer having a norbornene structure include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; and cyclic conjugates such as cyclohexadiene and cycloheptadiene. Dienes and derivatives thereof; and the like.
  • the optional monomer capable of ring-opening copolymerization with a monomer having a norbornene structure one type may be used alone, or two or more types may be used in combination at any ratio.
  • a ring-opening polymer of a monomer having a norbornene structure, and a ring-opening copolymer of any monomer copolymerizable with a monomer having a norbornene structure are, for example, a known ring-opening monomer. It can be produced by polymerization or copolymerization in the presence of a polymerization catalyst.
  • ⁇ -olefin is preferable, and ethylene is more preferable.
  • the arbitrary monomer which can carry out addition copolymerization with the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • An addition copolymer of a monomer having a norbornene structure and an addition copolymer of any monomer that can be copolymerized with a monomer having a norbornene structure include, for example, a monomer of a known addition polymerization catalyst. It can be produced by polymerization or copolymerization in the presence.
  • Examples of monocyclic olefin polymers include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.
  • cyclic conjugated diene polymer examples include polymers obtained by cyclization reaction of addition polymers of conjugated diene monomers such as 1,3-butadiene, isoprene and chloroprene; cyclic conjugated such as cyclopentadiene and cyclohexadiene. And 1,2- or 1,4-addition polymers of diene monomers; and their hydrides.
  • vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides; vinyl aromatic hydrocarbons such as styrene and ⁇ -methylstyrene. Hydrogenated product obtained by hydrogenating an aromatic ring portion contained in a polymer obtained by polymerizing a monomer, a vinyl alicyclic hydrocarbon monomer, or a vinyl aromatic hydrocarbon monomer and these vinyl aromatic hydrocarbon monomers.
  • a hydride of an aromatic ring of a copolymer such as a random copolymer or a block copolymer with an arbitrary copolymerizable monomer can be used.
  • the block copolymer include a diblock copolymer, a triblock copolymer or a multi-block copolymer having more than that, a gradient block copolymer, and the like.
  • the (meth) acrylic resin is a resin containing a (meth) acrylic polymer.
  • the (meth) acrylic polymer means a polymer of (meth) acrylic acid or a (meth) acrylic acid derivative.
  • examples of the (meth) acrylic polymer include homopolymers and copolymers such as acrylic acid, acrylic acid ester, acrylamide, acrylonitrile, methacrylic acid, and methacrylic acid ester.
  • a (meth) acrylic polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Since the (meth) acrylic resin has high strength and is hard, the strength of the laminate can be increased.
  • (meth) acrylic polymer a polymer containing a structural unit formed by polymerizing (meth) acrylic acid ester is preferable.
  • (meth) acrylic acid esters include alkyl esters of (meth) acrylic acid. Among them, those having a structure derived from (meth) acrylic acid and an alkanol having 1 to 15 carbon atoms or cycloalkanol are preferable, and those having a structure derived from an alkanol having 1 to 8 carbon atoms are more preferable. .
  • the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, and t-acrylate.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • methacrylic acid ester examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, methacrylic acid.
  • methacrylic acid examples thereof include t-butyl acid, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, and n-dodecyl methacrylate.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the (meth) acrylic acid ester may have a substituent such as a hydroxyl group or a halogen atom as long as the effects of the present invention are not significantly impaired.
  • a substituent such as a hydroxyl group or a halogen atom
  • Examples of (meth) acrylic acid ester having such a substituent include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethacrylate. Examples thereof include hydroxypropyl, 4-hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, glycidyl methacrylate and the like.
  • these substituents may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the (meth) acrylic polymer may be a polymer of only (meth) acrylic acid or (meth) acrylic acid derivatives, and can be copolymerized with (meth) acrylic acid or (meth) acrylic acid derivatives. It may be a copolymer with any arbitrary monomer.
  • Optional monomers include, for example, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomers other than (meth) acrylic acid esters, as well as ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomers, alkenyls Aromatic monomers, conjugated diene monomers, non-conjugated diene monomers, carboxylic acid unsaturated alcohol esters, olefin monomers, and the like can be mentioned. Moreover, arbitrary monomers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the proportion of structural units having a structure formed by polymerizing (meth) acrylic acid or (meth) acrylic acid derivatives in the (meth) acrylic polymer is preferably 55% by weight or more, more preferably 70% by weight. % Or more, particularly preferably 90% by weight or more, and usually 100% by weight or less.
  • acrylic polymers polymethacrylate is preferred, and polymethyl methacrylate is more preferred.
  • Polycarbonate resin is a resin containing a polycarbonate polymer.
  • the polycarbonate polymer is a polymer having structural units bonded by a carbonate bond (—O—C ( ⁇ O) —O—).
  • a polycarbonate polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • polycarbonate polymer those containing a structural unit represented by the following formula (I) are preferable.
  • the structural unit represented by the following formula (I) can be formed by polymerizing bisphenol Z, for example.
  • Examples of such a resin containing a polycarbonate polymer include Lexan manufactured by SABIC.
  • R 1 to R 8 each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group, cycloalkyl group, and aryl group may be substituted or unsubstituted.
  • the alkyl group, cycloalkyl group, or aryl group usually has 1 to 10 carbon atoms.
  • R 9 represents a hydrogen atom, an alkyl group or an aryl group.
  • the alkyl group and the aryl group usually have 1 to 9 carbon atoms.
  • Z is a residue that, together with the carbon atom to which it is attached, forms a saturated or unsaturated carbocycle having from 4 to 11 carbon atoms.
  • Z is preferably a saturated carbocyclic ring having 6 carbon atoms.
  • R 1 or R 3 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.
  • R 6 or R 8 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.
  • the structural unit represented by the formula (I) is particularly preferably a structural unit represented by the chemical formula (II) (bisphenol Z unit).
  • the polycarbonate polymer preferably includes a structural unit represented by the following formula (III) in addition to the structural unit represented by the formula (I).
  • the structural unit represented by the following formula (III) can be formed by polymerizing bisphenol A, for example.
  • the structural unit represented by the formula (III) is more preferably a structural unit represented by the formula (IV) or (V).
  • R 10 to R 17 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group, cycloalkyl group, and aryl group may be substituted or unsubstituted.
  • the alkyl group, cycloalkyl group and aryl group usually have 1 to 10 carbon atoms.
  • the amount of the structural unit represented by the formula (III) is preferably 0 with respect to 1 mol of the structural unit represented by the formula (I). .6 mol or more, and preferably 1.5 mol or less. Thereby, a film excellent in heat resistance and flexibility can be formed as the substrate (A1).
  • the polycarbonate polymer may contain an arbitrary structural unit other than the structural unit represented by the formula (I) or the formula (III).
  • the proportion of the structural unit represented by formula (I) or formula (III) is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. Usually, it is 100% by weight or less.
  • (Meth) acrylic acid ester-vinyl aromatic compound copolymer resin is a resin containing a copolymer of (meth) acrylic acid ester and vinyl aromatic compound.
  • the (meth) acrylic acid ester and the vinyl aromatic compound may be used one by one or may be copolymerized by combining two or more of them at an arbitrary ratio.
  • the said copolymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • (meth) acrylic acid ester examples include the same examples as those exemplified in the description of the (meth) acrylic resin. Moreover, (meth) acrylic acid ester may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • vinyl aromatic compounds include aromatic monomers having an ethylenically unsaturated bond. Specific examples include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, ⁇ -methylstyrene, vinylnaphthalene, and vinylanthracene. Can be mentioned. Moreover, a vinyl aromatic compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymerization ratio of (meth) acrylic acid ester to vinyl aromatic compound is 1% to 80% by weight of (meth) acrylic acid ester and vinyl aromatic compound from the viewpoint of heat resistance, transparency and strength of the copolymer. It may be 20% to 99% by weight.
  • the amount of (meth) acrylic acid ester 1% by weight or more the strength, heat resistance and transparency of the copolymer can be sufficiently increased, and by making it 80% by weight or less, (meth) acrylic acid ester -The moldability of the vinyl aromatic compound copolymer resin can be improved.
  • the copolymer of (meth) acrylic acid ester and vinyl aromatic compound may be a copolymer obtained by further polymerizing any monomer other than (meth) acrylic acid ester and vinyl aromatic compound.
  • a conjugated diene compound can be mentioned, for example.
  • Specific examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- Examples include hexadiene, and particularly preferred are 1,3-butadiene and isoprene. One of these may be used alone, or two or more thereof may be used in combination at any ratio.
  • the proportion of structural units having a structure formed by polymerizing (meth) acrylic acid ester or vinyl aromatic compound is preferably 55% by weight or more, more preferably 70% by weight or more, Particularly preferred is 90% by weight or more, and usually 100% by weight or less.
  • the polyethersulfone resin is a resin containing a polyethersulfone polymer.
  • the polyethersulfone polymer is a polymer in which the main chain is linked by a condensed structure of aromatic bisphenol and dihalogenoarylsulfone.
  • the polyethersulfone polymer can be obtained, for example, by polycondensing aromatic bisphenol and dihalogenoarylsulfone in the presence of a basic catalyst by a polymerization method such as a solution polymerization method or a melt polymerization method.
  • a polyether sulfone polymer may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • aromatic bisphenol examples include hydroquinone, 4,4′-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl.
  • Cyclohexane bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1 -Phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3-tert-butylphenyl) propane, 9,9-bis (4-hydride) Xylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene, 1,4-bis ⁇ 2- (4- Hydroxyphenyl) propyl ⁇ benzene, 2,2-bis (4-hydroxyphenyl) -1,1,1-3,3,3-hexafluoro
  • dihalogenoarylsulfone examples include bis (4-chlorophenyl) sulfone, bis (4-fluorophenyl) sulfone, bis (4-bromophenyl) sulfone, and 4-chloro-4 ′-(p-chlorophenyl) diphenyl.
  • the polyethersulfone polymer may contain any structural unit having a structure formed by polymerizing monomers other than aromatic bisphenol and dihalogenoarylsulfone.
  • the proportion of structural units having a structure formed by polymerizing aromatic bisphenol and dihalogenoaryl sulfone is preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably. It is 90% by weight or more and usually 100% by weight or less.
  • Resin that is a material for forming the base material (A1) may contain an optional component in addition to the above-described polymer.
  • the ratio of the above-mentioned polymer in the resin that is a material for forming the substrate (A1) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more, and is usually 100%. % By weight or less.
  • the substrate (A1) is a (meth) acrylic resin
  • the (meth) acrylic resin may contain rubber particles.
  • the flexibility of the (meth) acrylic resin can be increased, and the impact resistance of the laminate can be improved.
  • the surface roughness of the (meth) acrylic resin layer can be increased with rubber particles, the contact area on the surface can be reduced, and the slipperiness of the surface can be enhanced.
  • the surface of the non-liquid crystalline material layer (A2) side has a small surface roughness, and therefore the surface roughness of the surface opposite to the non-liquid crystalline material layer (A2). It is preferable to roughen the thickness.
  • Examples of the rubber forming the rubber particles include acrylate polymer rubber, polymer rubber mainly composed of butadiene, and ethylene-vinyl acetate copolymer rubber.
  • Examples of the acrylate polymer rubber include those having butyl acrylate, 2-ethylhexyl acrylate, or the like as a main component of monomer units. Among these, acrylic acid ester polymer rubber mainly composed of butyl acrylate and polymer rubber mainly composed of butadiene are preferable.
  • the rubber particles may contain one type of rubber alone or two or more types of rubber. Further, these rubbers may be mixed uniformly, but may be layered.
  • rubber particles in which rubber is layered include particles in which a core made of a rubber elastic component and a hard resin layer (shell) form a core-shell structure.
  • the rubber elastic component include a rubber elastic component obtained by grafting an alkyl acrylate such as butyl acrylate and styrene.
  • the hard resin layer include a hard resin layer made of a copolymer of one or both of polymethyl methacrylate and methyl methacrylate and an alkyl acrylate.
  • the rubber particles preferably have a number average particle diameter of 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and preferably 0.3 ⁇ m or less, and 0.25 ⁇ m or less. Is more preferable. By setting the number average particle diameter within the above range, moderate unevenness can be formed on the surface of the (meth) acrylic resin layer, and the slipperiness of the laminate can be improved.
  • the amount of rubber particles is preferably 5 parts by weight or more and preferably 50 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer.
  • a compounding agent can be mentioned.
  • compounding agents are layered crystal compounds; fine particles; antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, UV absorbers, near infrared absorbers and other stabilizers; plasticizers: dyes and pigments, etc. Colorants; antistatic agents; and the like.
  • a compounding agent may use one type and may use it combining two or more types by arbitrary ratios.
  • the amount of the compounding agent can be appropriately determined within a range that does not significantly impair the effects of the present invention.
  • the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the polymer.
  • it is more preferably 3 parts by weight or less, and usually 0 part by weight or more.
  • the difference between the glass transition temperature of the material of the base material (A1) and the glass transition temperature of the non-liquid crystalline material forming the layer (A2) is preferably ⁇ 15 ° C. or more, more preferably ⁇ 10 ° C or higher, particularly preferably ⁇ 5 ° C. or higher, preferably + 15 ° C. or lower, more preferably + 10 ° C. or lower, and particularly preferably + 5 ° C. or lower.
  • the followability of the layer (A2) of the non-liquid crystalline material with respect to the base material (A1) during the stretching treatment can be improved. Stretching can be performed without loss. Thereby, uniform stretching treatment can be performed on the layer (A2) of the non-liquid crystalline material in both the MD direction and the TD direction.
  • the substrate (A1) has an in-plane retardation Re A1 (550) at a wavelength of 550 nm, preferably 300 nm or less, more preferably 200 nm or less, particularly preferably 100 nm or less, and usually 0 nm or more.
  • Re A1 in-plane retardation Re A1
  • the substrate (A1) is preferably one having optical isotropy.
  • the base material (A1) a material subjected to a surface treatment such as a hydrophilization treatment, a hydrophobization treatment, or a treatment for reducing the solubility of the base material (A1) can be used as necessary.
  • the substrate (A1) may have a single layer structure formed of only one layer, or may have a multilayer structure including two or more layers.
  • the thickness of the substrate (A1) is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, particularly preferably 30 ⁇ m or more, preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
  • the layer (A2) of non-liquid crystalline material is a layer of non-liquid crystalline material having a positive intrinsic birefringence. Unlike the liquid crystalline material, the non-liquid crystalline material is transparent when applied to the surface of the base material (A1) due to the properties of the non-liquid crystalline material itself, regardless of the orientation of the base material (A1). A non-oriented layer can be formed. Thereafter, by stretching the multilayer film (A), a layer (A2) of a non-liquid crystalline material oriented in the same direction as an arbitrary stretching direction can be formed. For this reason, even if the said base material (A1) is a non-orientation thing, the process of coating an orientation film, the process of laminating an orientation film, etc. are not required, for example.
  • a resin having a positive intrinsic birefringence is usually used as the non-liquid crystalline material having a positive intrinsic birefringence. Further, as this resin, a transparent resin is usually used.
  • resins include polyamide resins, polyimide resins, maleimide resins, polyester resins, polyetherketone resins, polyamideimides because of their excellent heat resistance, chemical resistance, transparency, and rigidity.
  • Resins, polycarbonate resins, polyester imide resins, polyurethane urea resins and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • resins having different functional groups such as a mixture of a polyether ketone resin and a polyamide resin may be used in combination.
  • resins polyimide resin, maleimide resin, polyamideimide resin, polycarbonate resin and polyester resin, and polyurethane urea resin are preferable. Specific examples include those described in Japanese Patent No. 3962034, Japanese Patent No. 3897743, Japanese Patent No. 3838522, and Japanese Patent No. 3811175.
  • a resin containing polyimide having high in-plane orientation and soluble in an organic solvent is preferable.
  • it includes a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and an aromatic tetracarboxylic dianhydride disclosed in JP 2000-511296 A, and has the following formula ( A resin containing polyimide containing at least one structural unit shown in VI) per molecule is preferred.
  • each R 1a independently represents a hydrogen atom; a halogen atom; a phenyl group; a phenyl group substituted with 1 to 4 halogen atoms or an alkyl group having 1 to 10 carbon atoms; and And a group selected from the group consisting of: an alkyl group having 1 to 10 carbon atoms; Among them, as R 1a , a halogen atom; a phenyl group; a phenyl group substituted with 1 to 4 halogen atoms or an alkyl group having 1 to 10 carbon atoms; and an alkyl group having 1 to 10 carbon atoms; Are preferably selected from.
  • a a represents a tetrasubstituted aromatic group having 6 to 20 carbon atoms.
  • a a is preferably any of the following groups (1) to (3).
  • (1) A tetravalent group having a structure in which a hydrogen atom is removed from each of four carboxyl groups of pyromellitic acid.
  • (2) A tetravalent group having a structure in which four hydrogen atoms are removed from a polycyclic aromatic compound such as naphthylene, fluorenylene, benzofluorenylene, anthracenylene, or the like, and a substituted derivative thereof.
  • the substituent is an alkyl group having 1 to 10 carbon atoms and a fluorinated derivative thereof, and a halogen atom such as fluorine or chlorine.
  • (3) A group represented by the formula (VII).
  • R 2a independently represents a hydrogen atom or a C (R 4a ) 3 group.
  • R 3a independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 4a independently represents a hydrogen atom, a fluorine atom or a chlorine atom.
  • m represents an integer of 1 to 10.
  • a preferable maleimide resin includes, for example, a resin containing a polymer represented by the formula (VIII).
  • R b and Q b each independently represent a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, siloxane group or unsaturated hydrocarbon group.
  • Xb represents a maleimide group capable of active energy ray curing or heat curing.
  • n represents an integer of 1 or more and 10 or less.
  • n independently represents an integer of 1 or more and 10 or less.
  • maleimide resin examples include compounds described in US Patent Application Publication No. 2008/0075961. These maleimide resins can be obtained from, for example, Air Brown.
  • polyamideimide resin and the polyester resin examples include polyamide resins and polyester resins described in JP-T-10-508048.
  • the structural unit contained in the polyamideimide or polyester contained in these polyamideimide resin or polyester resin is represented, for example, by the following chemical formula (XI).
  • each E c is independently a covalent bond, an alkylene group having 2 carbon atoms, a halogenated alkylene group having 2 carbon atoms, a CH 2 group, a C (CX c 3 ) 2 group, At least one group selected from the group consisting of a CO group, an O atom, an S atom, a SO 2 group, a Si (R c ) 2 group, and an N (R c ) group is shown. Further, E c may be the same or different.
  • R c is at least one of an alkyl group having 1 to 3 carbon atoms and a halogenated alkyl group having 1 to 3 carbon atoms, and is in a meta position or a para group with respect to the carbonyl group or the Y c group. Is in place.
  • Xc is a halogen atom or a hydrogen atom.
  • a c is, for example, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, OR c (where R c is as defined above) A substituted aryl group obtained by halogenation, etc., an alkoxycarbonyl group having 1 to 9 carbon atoms, an alkylcarbonyloxy group having 1 to 9 carbon atoms, or 1 to 12 carbon atoms.
  • Aryloxycarbonyl group, arylcarbonyloxy group having 1 to 12 carbon atoms and substituted derivatives thereof, arylcarbamoyl group having 1 to 12 carbon atoms, and arylcarbonylamino group having 1 to 12 carbon atoms and substituted derivatives thereof Is mentioned. Further, if the A c there are multiple, A c may be respectively identical or different.
  • a c ′ represents a substituent.
  • a c ′ include a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a phenyl group, and a substituted phenyl group. Also, 'if there are a plurality, A c' A c respectively may be the same or may be different.
  • the substituent on the phenyl ring of the substituted phenyl group include a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, and combinations thereof.
  • t and z represent the number of substitutions for A c and A c ′, respectively.
  • T is an integer of 0 to 4.
  • Z is an integer of 0 to 3.
  • p is an integer of 0 to 3
  • q is an integer of 1 to 3
  • r is an integer of 0 to 3.
  • the polyester may include a structural unit represented by the following formula (XII) or formula (XIII).
  • X d and Y d represent a substituent.
  • X d each independently represents a group selected from the group consisting of a hydrogen atom, a chlorine atom and a bromine atom.
  • Y d represents a group represented by the following formula (XIV) or formula (XV).
  • N represents an integer of 1 or more.
  • polyester As specific examples of polyester, “Byron” manufactured by Toyobo Co., Ltd. and “Polyester” manufactured by Nippon Synthetic Chemical Co., Ltd. can be suitably used.
  • polyurethane urea resins include aliphatic cyclic structure-containing polyols, aliphatic cyclic structure-containing polyisocyanates, aliphatic cyclic structure-containing polyamines, and heavy compounds obtained by reacting acrylic compounds having active hydrogen atom-containing groups.
  • the resin include coalescence. Specific examples thereof include materials described in JP 2011-132548 A and resins containing polymers synthesized by the production method.
  • “Tie Force” manufactured by DIC can be suitably used.
  • polycarbonate resin examples include the same examples as mentioned in the description of the material forming the base material (A1). Specific examples thereof include Iupizeta PCZ series manufactured by Mitsubishi Gas Chemical Company, “FPC2136” manufactured by Mitsubishi Gas Chemical Company, and “Toughzet” manufactured by Idemitsu Kosan Co., Ltd.
  • the resin that can be used as a non-liquid crystalline material having a positive intrinsic birefringence can contain an optional component in addition to the above-described polymer.
  • the proportion of the above-mentioned polymer in the resin that can be used as a non-liquid crystalline material having a positive intrinsic birefringence is preferably 55% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Further, it is usually 100% by weight or less.
  • the glass transition temperature of the non-liquid crystalline material having a positive intrinsic birefringence forming the layer (A2) of the non-liquid crystalline material is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 110 ° C. or higher. Preferably it is 180 degrees C or less, More preferably, it is 160 degrees C or less, Most preferably, it is 140 degrees C or less.
  • the layer (A2) of the non-liquid crystal material is preferably a negative biaxial layer in which the relationship between the refractive indexes nx, ny and nz satisfies nx> ny and nx> nz. Accordingly, the contrast of the IPS liquid crystal panel is effectively improved by using a retardation film in which the layer (A2) of the non-liquid crystal material and the layer (B1) of the non-liquid crystal material are combined as an optical compensation film. Is possible.
  • the layer (A2) of the non-liquid crystalline material has an in-plane retardation Re A2 (550) at a wavelength of 550 nm, preferably 50 nm or more, more preferably 70 nm or more, preferably 150 nm or less, more preferably 120 nm or less. It is.
  • the retardation Re A2 (550) in the in-plane direction of the layer (A2) of the non-liquid crystalline material is within this range, the multilayer film (A) can be easily produced by stretching.
  • the layer (A2) of the non-liquid crystalline material has a retardation Rth A2 (550) in the thickness direction at a wavelength of 550 nm, preferably 40 nm or more, more preferably 60 nm or more, preferably 150 nm or less, more preferably 120 nm or less.
  • the retardation Rth A2 (550) in the thickness direction of the layer (A2) of the non-liquid crystalline material is within this range, the multilayer film (A) can be easily produced by stretching.
  • a quotient obtained by dividing “retardation Re A1 (550) of substrate (A1) at wavelength 550 nm” by “thickness of substrate (A1)” is “I”.
  • a quotient obtained by dividing “retardation Re A2 (550) of the non-liquid crystalline material layer (A2) at a wavelength of 550 nm” by “the thickness of the non-liquid crystalline material layer (A2)” is “J”.
  • I ⁇ J is preferable, 3I ⁇ J is more preferable, 5I ⁇ J is further preferable, and 10I ⁇ J is particularly preferable.
  • the retardation of only the layer (A2) of the non-liquid crystalline material is accurately performed while performing a stretching process when the multilayer film (A) is produced. It becomes possible to measure.
  • the thickness of the layer (A2) of the non-liquid crystalline material is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 40 ⁇ m or less, more preferably from the viewpoint of improving scratch resistance, handling properties and thin film properties. 30 ⁇ m or less.
  • the variation in the thickness of the layer (A2) of the non-liquid crystal material is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less of the average thickness of the layer (A2). Specifically, it is 0%.
  • the thickness variation means a difference between the maximum value and the minimum value of the thickness.
  • the peel force between the substrate (A1) and the non-liquid crystalline material layer (A2) is preferably 0.05 N / 20 mm or less, more preferably 0.03 N / 20 mm or less, and particularly preferably 0.01 N / 20 mm. It is as follows.
  • the peeling force can be measured according to JIS K6855-2. By reducing the peeling force in this manner, the substrate (A1) can be peeled from the laminate, and the retardation film can be easily produced.
  • the lower limit of the peeling force is preferably 0.001 N / 20 mm or more, more preferably 0.003 N / 20 mm or more, and particularly preferably 0.005 N / 20 mm or more. Such a small peeling force can be realized, for example, by appropriately selecting a combination of materials of the base material (A1) and the non-liquid crystalline material layer (A2) using materials that are not compatible with each other.
  • the multilayer film (A) may include an arbitrary layer on the side of the base material (A1) opposite to the non-liquid crystalline material layer (A2).
  • the multilayer film (B) 20 includes a layer (B1) 21 and a resin layer (B2) 22 of a non-liquid crystalline material. Since the resin layer (B2) 22 is in contact with the layer (B1) 21 of the non-liquid crystal material, another layer is provided between the layer (B1) 21 of the non-liquid crystal material and the resin layer (B2) 22. It is not done.
  • the layer (B1) of non-liquid crystalline material is a layer of non-liquid crystalline material having a negative intrinsic birefringence.
  • a resin having a negative intrinsic birefringence is usually used.
  • a transparent resin is usually used.
  • a resin containing a polymer obtained by polymerizing one or more monomers selected from the group consisting of styrenes, styrenes-maleic acid, maleimides, and (meth) acrylic acid esters is preferable.
  • the polymer may be a homopolymer or a copolymer. Since such a polymer usually has a negative intrinsic birefringence, the intrinsic birefringence of the resin containing it can also be made negative.
  • styrenes mean styrene and styrene derivatives.
  • the styrene derivative include those in which a substituent is substituted at the benzene ring or ⁇ -position of styrene.
  • Specific examples of styrene derivatives include alkyl styrene such as methyl styrene and 2,4-dimethyl styrene; halogenated styrene such as chlorostyrene; halogen-substituted alkyl styrene such as chloromethyl styrene; alkoxy styrene such as methoxy styrene; Can be mentioned.
  • one kind of styrene may be used alone, or two or more kinds may be used in combination at any ratio.
  • polymerization using styrenes-maleic acid as a monomer means copolymerization of styrenes and maleic acid.
  • maleic acid may be polymerized in the form of maleic anhydride.
  • maleimides include compounds represented by the following formula (XVI).
  • R 1e and R 2e each independently represent a hydrogen atom or an alkyl group.
  • X e represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group, a cyano group or a hydroxyl group.
  • maleimides examples include maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tertiarybutylmaleimide, N-cyclohexylmaleimide, N-phenyl Maleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N-hydroxylethylmaleimide, N-hydroxylphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitro Examples thereof include phenylmaleimide and N-tribromophenylmaleimide.
  • maleimides may be used alone or in combinations of two or more in any ratio.
  • examples of the (meth) acrylic acid ester include the same examples as mentioned in the description of the material forming the base material (A1).
  • (meth) acrylic acid ester may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymer obtained by polymerizing the above monomer is copolymerized with any monomer other than styrenes, styrenes-maleic acid, maleimides and (meth) acrylic acid esters, as long as the effects of the present invention are not significantly impaired. It may be made.
  • the proportion of structural units having a structure formed by polymerizing a monomer selected from the group consisting of styrenes, styrenes-maleic acid, maleimides and (meth) acrylic acid esters is preferably It is 55% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more, and usually 100% by weight or less.
  • a polymer using styrene as a monomer and a copolymer of maleimides and styrene are preferable. That is, a resin containing a polymer obtained by polymerizing styrenes or styrenes-maleic acid and a resin containing a copolymer of maleimides and styrene are preferable as resins having a negative intrinsic birefringence.
  • a polymer using styrene as a monomer is a polystyrene polymer, and by using a resin containing a polystyrene polymer, a desired retardation can be stably expressed in the layer (B1) of the non-liquid crystalline material.
  • copolymer of maleimides and styrene polymers described in JP-A Nos. 2001-31710 and 2000-204126 can be preferably used. “Polyimilex” and “Denka IP” manufactured by Denka are preferably used.
  • the polystyrene polymer is preferably a polystyrene polymer having a syndiotactic structure.
  • the polystyrene-based polymer having a syndiotactic structure has high heat resistance, can suppress heat shrinkability, and can stably develop desired retardation by stretching.
  • the syndiotactic structure is a three-dimensional structure in which phenyl groups as side chains are regularly arranged alternately in opposite directions in the Fischer projection formula with respect to the main chain formed by carbon-carbon bonds.
  • a polystyrene polymer having a syndiotactic structure has a low specific gravity and excellent properties such as hydrolysis resistance, heat resistance and chemical resistance as compared with a conventional atactic polystyrene polymer.
  • the tacticity (stericity) of the polystyrene-based polymer can be quantified by an isotope carbon nuclear magnetic resonance method ( 13 C-NMR method).
  • the tacticity measured by the 13 C-NMR method can be indicated by the abundance ratio of a plurality of consecutive structural units. Generally, for example, when there are two consecutive structural units, it is a dyad, when it is three, it is a triad, and when it is five, it is a pentad.
  • the polystyrene polymer having the syndiotactic structure refers to a polymer that satisfies the following (x) or (y).
  • the racemic dyad usually has a syndiotacticity of 75% or more, preferably 85% or more and 100% or less.
  • the racemic pentad generally has a syndiotacticity of 30% or more, preferably 50% or more and 100% or less.
  • a polystyrene polymer having a syndiotactic structure can polymerize styrenes using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent.
  • Poly (halogenated alkylstyrene) may be produced, for example, by the method described in JP-A-1-46912.
  • the weight average molecular weight of a polymer obtained by polymerizing one or more monomers selected from the group consisting of styrenes, styrenes-maleic acid, maleimides and (meth) acrylic acid esters is preferably 130,000 or more, more preferably It is 140,000 or more, particularly preferably 150,000 or more, preferably 300,000 or less, more preferably 270,000 or less, and particularly preferably 250,000 or less. With such a weight average molecular weight, the glass transition temperature of the polymer can be increased, and the heat resistance of the laminate can be stably improved.
  • the glass transition temperature of a polymer obtained by polymerizing one or more monomers selected from the group consisting of styrenes, styrenes-maleic acid, maleimides and (meth) acrylic acid esters is preferably 85 ° C. or more, more preferably 90 ° C or higher, particularly preferably 95 ° C or higher.
  • the glass transition temperature of the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1) is effectively increased, and thus the heat resistance of the retardation film is stably improved. can do.
  • the glass transition temperature is preferably 160 ° C. or lower, more preferably 155 ° C. or lower, and particularly preferably 150 ° C. or lower.
  • the non-liquid crystalline material having a negative intrinsic birefringence and forming the layer (B1) of the non-liquid crystalline material is selected from the group consisting of styrene, styrene-maleic acid, maleimides and (meth) acrylic acid esters. It is preferably a mixture containing one or more polymers selected from the group consisting of a polycarbonate polymer, a polyester polymer and a polyarylene ether polymer in combination with a polymer obtained by polymerizing one or more monomers.
  • the strength of the layer (B1) of the non-liquid crystalline material can be increased, the glass transition temperature can be controlled, and the optical properties can be controlled. It becomes possible.
  • polycarbonate polymer examples include the same examples as mentioned in the description of the material forming the base material (A1).
  • a polycarbonate polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polyester polymer is a polymer having structural units linked by an ester bond.
  • a polyester polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Examples of the polyester polymer are obtained by dehydration condensation or polymerization of a polyol having a plurality of hydroxyl groups such as glycol and diol, and a polyvalent carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid or its anhydride. Can be mentioned.
  • polystyrene resin examples include 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5- Pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2 -Methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,6-hexanediol and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • polyvalent carboxylic acid examples include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, and sebacic acid.
  • dicarboxylic acids such as trimellitic acid and pyromellitic acid, polyvalent carboxylic acids having a trivalent or higher valent carboxyl group, and anhydrides thereof. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the polyester polymer may be a polymer obtained by copolymerizing any monomer other than polyol, polyvalent carboxylic acid or anhydride thereof.
  • the proportion of structural units having a structure formed by polymerizing polyol, polyvalent carboxylic acid or anhydride thereof is preferably 55% by weight or more, more preferably 70% by weight or more, particularly preferably. Is 90% by weight or more.
  • polyester polymer “Byron” manufactured by Toyobo Co., Ltd. and “Polyester” manufactured by Nippon Synthetic Chemical Co., Ltd. can be suitably used.
  • the polyarylene ether polymer is a polymer having a structural unit having an arylene ether skeleton in the main chain.
  • a polyarylene ether polymer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymer containing the structural unit represented by a following formula (XVII) is preferable.
  • each Q 1 independently represents a halogen atom, a lower alkyl group (for example, an alkyl group having 7 or less carbon atoms), a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, or A halohydrocarbonoxy group (wherein the halogen atom and the oxygen atom are separated by at least two carbon atoms);
  • Q 1 is preferably an alkyl group or a phenyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • each Q 2 independently represents a hydrogen atom, a halogen atom, a lower alkyl group (for example, an alkyl group having 7 or less carbon atoms), a phenyl group, a haloalkyl group, a hydrocarbon oxy group, or a halo.
  • a hydrocarbon oxy group (wherein the halogen atom and the oxygen atom are separated by at least two carbon atoms). Among them, preferably a hydrogen atom Q 2.
  • the polyarylene ether polymer may be a homopolymer having one type of structural unit (homopolymer) or a copolymer having two or more types of structural units (copolymer).
  • the polyarylene ether polymer containing the structural unit represented by the formula (XVII) is a homopolymer
  • preferred examples of the homopolymer include 2,6-dimethyl-1,4-phenylene ether units ( That is, a homopolymer having “— (C 6 H 2 (CH 3 ) 2 —O) —”) is exemplified.
  • the polyarylene ether polymer containing the structural unit represented by the formula (XVII) is a copolymer
  • a preferred example of the copolymer is 2,6-dimethyl-1,4-phenylene ether.
  • a random copolymer having a unit and a 2,3,6-trimethyl-1,4-phenylene ether unit that is, a structural unit represented by “— (C 6 H (CH 3 ) 3 —O —) —”).
  • a polymer is mentioned.
  • the polyarylene ether polymer may contain a structural unit other than the arylene ether unit.
  • the polyarylene ether polymer is a copolymer having an arylene ether unit and other structural units.
  • the ratio of the arylene ether unit in the polyarylene ether polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
  • polystyrene polymer when combining a polystyrene polymer and a polyarylene ether polymer, because of the high expression of retardation and good compatibility with the polyarylene ether polymer, A homopolymer of styrenes is more preferable, and a polystyrene polymer having a syndiotactic structure is more preferable. Furthermore, even when the polystyrene polymer is a copolymer obtained by copolymerizing monomers other than styrenes, the proportion of monomers other than styrenes is less than 5% by weight from the viewpoint of compatibility with the polyarylene ether polymer. It is desirable.
  • the weight ratio with one or more polymers selected from the group consisting of is preferably 90:10 to 55:45, more preferably 85:15 to 60:40, and particularly preferably 80:20. ⁇ 65: 35. When the weight ratio is in this range, desired retardation and desired optical properties can be easily expressed in the layer (B1) of the non-liquid crystal material by stretching.
  • the non-liquid crystal material having a negative intrinsic birefringence and forming the layer (B1) of the non-liquid crystal material is selected from the group consisting of styrenes, styrenes-maleic acid, maleimides, and (meth) acrylic acid esters.
  • an optional component may be included. Examples of the optional component include an antioxidant, an ultraviolet absorber, a light stabilizer, and a crosslinking agent.
  • the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1) one or more kinds selected from the group consisting of styrenes, styrenes-maleic acid, maleimides and (meth) acrylic acid esters
  • the ratio of one or more polymers selected from the group consisting of a polymer obtained by polymerizing monomers and a polycarbonate polymer, a polyester polymer and a polyarylene ether polymer is preferably 50% by weight or more, more preferably 80%. % By weight or more, particularly preferably 90% by weight or more, and usually 100% by weight or less.
  • the glass transition temperature of the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1) of the non-liquid crystalline material is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher.
  • the glass transition temperature of a non-liquid crystalline material having a negative intrinsic birefringence is usually 200 ° C. or lower.
  • the tensile elongation at break of the layer (B1) of the non-liquid crystalline material is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less.
  • the tensile breaking elongation can be measured according to JIS K7162.
  • a non-liquid crystalline material having negative intrinsic birefringence has low mechanical strength.
  • the multilayer film (B) includes the resin layer (B2), even the non-liquid crystalline material layer (B1) having a low mechanical strength can be hardly damaged.
  • the laminate of the present invention has a laminate structure including a base material (A1), a non-liquid crystal material layer (A2), an adhesive layer, a non-liquid crystal material layer (B1), and a resin layer (B2) in this order. Therefore, even this laminated structure can effectively prevent the non-liquid crystalline material layer (B1) from being damaged. Therefore, the low tensile rupture elongation of the layer (B1) as described above prevents damage to the layer (B1), and makes the effects of improving handling and impact resistance more prominent. There is technical significance.
  • the layer (B1) of the non-liquid crystal material is preferably a positive biaxial layer in which the relationship between the refractive indexes nx, ny and nz satisfies nz> nx> ny. Accordingly, the contrast of the IPS liquid crystal panel is effectively improved by using a retardation film in which the layer (A2) of the non-liquid crystal material and the layer (B1) of the non-liquid crystal material are combined as an optical compensation film. Is possible.
  • the layer (B1) of the non-liquid crystalline material has an in-plane retardation Re B1 (550) at a wavelength of 550 nm, preferably 40 nm or more, more preferably 50 nm or more, preferably 150 nm or less, more preferably 100 nm or less. It is.
  • the retardation Re B1 (550) in the in-plane direction of the layer (B1) of the non-liquid crystalline material is within this range, the multilayer film (B) can be easily manufactured by stretching.
  • the layer of non-liquid material (B1) is retardation in the in-plane direction at a wavelength of 450nm Re B1 (450) and the in-plane direction at a wavelength of 550nm retardation Re B1 is (550), Re B1 (450 ) / It is preferable to satisfy Re B1 (550)> 1.00.
  • Re B1 (450) and Re B1 (550) satisfy this relationship, a retardation film capable of exhibiting a compensation effect for the IPS liquid crystal cell in a wide wavelength range can be obtained.
  • the layer (B1) of the non-liquid crystalline material has a retardation Rth B1 (550) in the thickness direction at a wavelength of 550 nm, preferably ⁇ 150 nm or more, more preferably ⁇ 130 nm or more, preferably ⁇ 50 nm or less. Preferably, it is ⁇ 60 nm or less.
  • the retardation Rth B1 (550) in the thickness direction of the layer (B1) of the non-liquid crystalline material is within this range, the multilayer film (B) can be easily produced by stretching.
  • the in-plane slow axis of the layer (B1) of the non-liquid crystalline material is usually parallel to the in-plane slow axis of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence of the multilayer film (A). To do. Thereby, optical compensation can be effectively performed in the IPS liquid crystal panel, and the contrast of the liquid crystal display device can be improved.
  • the thickness of the non-liquid crystalline material layer (B1) is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the variation in the thickness of the layer (B1) of the non-liquid crystalline material is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less of the average thickness of the layer (B1). 0%.
  • thickness accuracy By realizing such thickness accuracy, it is possible to obtain a laminate and a retardation film that exhibit uniform optical characteristics in the MD direction and the TD direction.
  • Such thickness accuracy can be realized, for example, by manufacturing the multilayer film (B) by a manufacturing method in which melt extrusion and stretching described later are combined.
  • the resin layer (B2) is a layer formed of a resin.
  • a thermoplastic resin is usually used.
  • a transparent resin is usually used.
  • resins include polymer resins having an alicyclic structure, (meth) acrylic resins, polycarbonate resins, (meth) acrylic acid ester-vinyl aromatic compound copolymer resins, and polyethersulfone resins.
  • a resin selected from is preferred. These resins are excellent in mechanical strength, can have a desired peel strength with respect to the non-liquid crystalline material layer (B1), and can reduce the retardation developed by stretching.
  • a polymer resin having an alicyclic structure capable of forming the resin layer (B2) a (meth) acrylic resin, a polycarbonate resin, a (meth) acrylic ester-vinyl aromatic compound copolymer resin, and a polyethersulfone resin
  • a (meth) acrylic resin a polycarbonate resin
  • a (meth) acrylic ester-vinyl aromatic compound copolymer resin a polyethersulfone resin
  • the same resins as those described as the material for forming the base material (A1) can be used.
  • the types and amounts of the polymer and optional components that can be contained in the resin can be the same as those of the resins described as materials for forming the base material (A1).
  • a polymer resin having a cycloaliphatic structure and a (meth) acrylic resin are preferable, and a (meth) acrylic resin is particularly preferable.
  • the glass transition temperature of the resin forming the resin layer (B2) is preferably set according to the glass transition temperature of the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1). Specifically, the glass transition temperature Tg (B1) of the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1), and the glass transition temperature Tg (B2) of the resin forming the resin layer (B2) However, it is preferable to satisfy
  • the glass transition temperature of the polymer resin having an alicyclic structure capable of forming the resin layer (B2) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 150 ° C. or lower, more preferably Is 120 ° C. or lower, more preferably 110 ° C. or lower.
  • the glass transition temperature of the (meth) acrylic resin capable of forming the resin layer (B2) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 120 ° C. or lower, more preferably 110 ° C. or lower. It is.
  • the glass transition temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 120 ° C. or lower, more preferably 110 ° C. or lower. It is.
  • the glass transition temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 120 ° C. or lower, more preferably 110 ° C. or lower. It is.
  • the glass transition temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, preferably 120 ° C. or lower, more preferably 110 ° C. or lower. It is.
  • the glass transition temperature of the polycarbonate resin capable of forming the resin layer (B2) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher. Is 160 ° C. or lower, more preferably 150 ° C. or lower.
  • the resin layer (B2) has an in-plane retardation Re B2 (550) at a wavelength of 550 nm, preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, and usually 0 nm or more.
  • a wavelength of 550 nm preferably 30 nm or less, more preferably 20 nm or less, particularly preferably 10 nm or less, and usually 0 nm or more.
  • the thickness of the resin layer (B2) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the peeling force between the layer (B1) of non-liquid crystalline material having a negative intrinsic birefringence and the resin layer (B2) is preferably 0.5 N / 20 mm or less, more preferably 0.3 N / 20 mm or less, particularly preferably. Is 0.15 N / 20 mm or less.
  • the peeling force can be measured according to JIS K6855-2. By reducing the peeling force in this way, the resin layer (B2) can be peeled from the laminate, and the retardation film can be easily produced.
  • the lower limit of the peeling force is preferably 0.01 N / 20 mm or more, more preferably 0.03 N / 20 mm or more, and particularly preferably 0.05 N / 20 mm or more. Such a small peeling force can be realized, for example, by appropriately selecting a combination of materials of the non-liquid crystal material layer (B1) and the resin layer (B2) with materials that are not compatible with each other.
  • the multilayer film (B) may include an arbitrary layer on the side of the resin layer (B2) opposite to the non-liquid crystalline material layer (B1).
  • Adhesive layer As shown in FIG. 1, a non-liquid crystalline material layer (A2) 12 having a positive intrinsic birefringence and a surface 12U opposite to the substrate (A1) 11 and a non-liquid crystalline material having a negative intrinsic birefringence.
  • a single adhesive layer 30 is provided between the layer (B1) 21 and the surface 21D opposite to the resin layer (B2) 22.
  • the fact that the adhesive layer 30 is interposed between the surface 12U and the surface 21D alone means that there is only the adhesive layer 30 between the surface 12U and the surface 21D, and there is no layer other than the adhesive layer 30. To do.
  • the adhesive layer is a layer formed by a cured product of an adhesive.
  • the adhesive includes a narrowly defined adhesive having a shear storage elastic modulus of 1 MPa to 500 MPa at 23 ° C. after curing, and a pressure-sensitive adhesive having a shear storage elastic modulus at 23 ° C. of less than 1 MPa.
  • the multi-layer film (A) and the multi-layer film (B) are bonded to each other, if the bonding is performed using the pressure-sensitive adhesive, it is possible to suppress the entrapment of bubbles and the inclusion of foreign substances.
  • the thickness of the pressure-sensitive adhesive layer tends to increase in order to ensure strong adhesive strength.
  • the thickness of the adhesive layer can be reduced. Therefore, as the adhesive, it is preferable to use a narrowly defined adhesive having a shear storage elastic modulus of 1 MPa to 500 MPa at 23 ° C. after curing.
  • an active energy ray curable adhesive is usually used.
  • the active energy ray-curable adhesive refers to an adhesive that can be cured when irradiated with active energy rays such as ultraviolet rays, X-rays, and electron beams.
  • active energy rays such as ultraviolet rays, X-rays, and electron beams.
  • an adhesive that can be cured by ultraviolet rays is preferable because an inexpensive device can be used.
  • the irradiated active energy rays may include arbitrary energy rays such as visible light, ultraviolet rays, infrared rays, and electron beams.
  • a suitable adhesive one containing (meth) acrylate in an uncured state can be used.
  • the (meth) acrylate (I) an oligomer-type polyfunctional (meth) acrylate and (II) a mono (meta) having at least one hydroxyl group having a viscosity of 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at a temperature of 20 ⁇ 1.0 ° C. )
  • a combination of acrylates is preferred.
  • the number of functional groups per molecule of the oligomer type polyfunctional (meth) acrylate is preferably 3 or less, more preferably 2 or 3.
  • the number of functional groups refers to the number of functional groups that can exhibit radical polymerizability.
  • the number of functional groups is 3 or less, the curing shrinkage of the cured product when the adhesive is cured can be reduced, and the glass transition temperature of the cured product can be lowered.
  • a layer film (B) can be favorably bonded.
  • Examples of (I) oligomer-type polyfunctional (meth) acrylates include radicals such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and silicone (meth) acrylate.
  • An acrylic oligomer having 3 or less functional groups capable of exhibiting polymerizability is exemplified. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • Polyester (meth) acrylate is obtained, for example, as a reaction product obtained by reacting a terminal hydroxyl group of a polyester obtained from a polybasic acid and a polyhydric alcohol with acrylic acid or methacrylic acid.
  • the polybasic acid include phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, terephthalic acid and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the polyhydric alcohol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like.
  • polyester (meth) acrylates include EBECRYL 851,852,853,884,885 (manufactured by Daicel Cytec); Olester (manufactured by Mitsui Chemicals); Aronix M-6100,6200,6250,6500 ( Toagosei Co., Ltd.).
  • Epoxy (meth) acrylate is obtained, for example, as a reaction product obtained by ring-opening addition reaction of acrylic acid or methacrylic acid to an epoxy polymer.
  • the epoxy polymer include bisphenol A type composed of bisphenol A and epichlorohydrin, novolac type composed of phenol novolac and epichlorohydrin, aliphatic type, and alicyclic type.
  • the aliphatic epoxy polymer include ethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.
  • Trimethylolpropane diglycidyl ether Trimethylolpropane diglycidyl ether, polyethylene glycol diglycidyl ether, and the like.
  • unsaturated fatty acid epoxy polymers such as butadiene-based epoxy polymers and isoprene-based epoxy polymers can also be used.
  • the alicyclic epoxy polymer include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9-diepoxysilimonene, and 3,4-epoxycyclohexenylmethyl-3 ′. 4,4′-epoxycyclohexenecarboxylate and the like can be used.
  • epoxy (meth) acrylates include EBECRYL 600, 860, 3105, 3420, 3700, 3701, 3702, 3703, 3708, 6040 (manufactured by Daicel Cytec); Neopole 8101, 8250, 8260, 8270, 8355, 8351, 8335, 8414, 8190, 8195, 8316, 8317, 8318, 8319, 8371 (manufactured by Iupika Japan); Denacol acrylate DA212, 250, 314, 721, 722, DM201 (manufactured by Nagase ChemteX); Van Beam ( Harima Chemicals, Inc.); Miramer PE210, PE230, EA2280 (manufactured by Toyo Chemicals), and the like.
  • Urethane (meth) acrylate is obtained as a reactant having a urethane skeleton at the center, for example, by reacting a (meth) acrylic monomer having a hydroxyl group, a polyfunctional isocyanate and a polyhydric alcohol.
  • the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylolpropane tolylene diisocyanate, and diphenylmethane triisocyanate.
  • hexamethylene diisocyanate having good weather resistance is preferably used. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • polyester (meth) acrylate As a polyhydric alcohol, what can be used for polyester (meth) acrylate, for example can be used.
  • urethane (meth) acrylate are EBECRYL 204, 210, 220, 230, 270, 4858, 8200, 8201, 8402, 8804, 8807, 9260, 9270, KRM 8098, 7735, 8296 (manufactured by Daicel Cytec) UX2201, 2301, 3204, 3301, 4101, 6101, 7101, 8101, 0937 (manufactured by Nippon Kayaku Co., Ltd.); UV6640B, 6100B, 3700B, 3500BA, 3520TL, 3200B, 3000B, 3310B, 3210EA, 7000B, 6630B, 7461TE ( Nippon Synthetic Chemical Co., Ltd.); Iupica 8921, 8932, 8940, 8936, 8937,
  • Polyether (meth) acrylate is obtained, for example, as a reaction product of polyether polyol and acrylic acid or methacrylic acid.
  • examples of the polyether (meth) acrylate include ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate.
  • EBECRYL81 manufactured by Daicel Cytec Co., Ltd.
  • Silicone (meth) acrylate is obtained, for example, as a reaction product obtained by further reacting an addition reaction product of an organopolysiloxane and an alkenyl group-containing epoxy polymer with acrylic acid or methacrylic acid.
  • organopolysiloxane include, for example, a trimethylsiloxy group-capped methylhydrogen polysiloxane having both molecular chains, a trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer having both molecular chains, and a trimethylsiloxy group-capped dimethyl with both molecular chains.
  • Siloxane / Methylhydrogensiloxane / Methylphenylsiloxane copolymer dimethylhydrogensiloxy group-blocked dimethylpolysiloxane with both molecular chains, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane / methylhydrogensiloxane copolymer with both ends of molecular chain, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked In addition to ruthenyl polysiloxane, dimethylpolysiloxane whose molecular chain end is blocked with a dimethylhydrogensiloxy group and other molecular chain end is blocked with a trimethylsiloxy group, it is basically not only of linear structure but also partially Also included are those containing a branched siloxane structure.
  • the alkenyl group-containing epoxy polymer for example, one having an epoxy group such as a glycidyloxy group and having an alkenyl group can be used.
  • the number of epoxy groups contained in the alkenyl group-containing epoxy polymer is usually 2 or more, preferably 2 to 7, more preferably 2 to 3 per molecule.
  • the number of alkenyl groups contained in the alkenyl group-containing epoxy polymer is usually 1 or more, preferably 1 to 5, more preferably 1 to 2, particularly preferably 1 per molecule.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 6, more preferably 2 to 4.
  • Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group. Among these, an allyl group is particularly preferable.
  • Silicone (meth) acrylate can be obtained by reacting the epoxy group in the addition reaction product of the organopolysiloxane and the alkenyl group-containing epoxy polymer with (meth) acrylic acid.
  • Examples of silicone (meth) acrylates include compounds exemplified in JP-A No. 2004-189942; “TEGO” manufactured by Evonik Degussa Japan; SQ series manufactured by Tokushiki, and the like.
  • oligomer-type polyfunctional (meth) acrylates polyester (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate are preferable.
  • oligomer type polyfunctional (meth) acrylate may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the molecular weight of the oligomer type polyfunctional (meth) acrylate is a polyisoprene-converted weight average molecular weight (Mw) measured by gel permeation chromatography, and is usually 500 or more and 10,000 or less.
  • the amount of oligomer type polyfunctional (meth) acrylate is preferably 15 to 65 parts by weight with respect to 100 parts by weight of (meth) acrylate contained in the uncured adhesive. By being within this range, a stronger adhesive force can be obtained.
  • Examples of mono (meth) acrylate having at least one hydroxyl group having a viscosity of 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at a temperature of 20 ⁇ 1.0 ° C. include the following. Moreover, in the following illustration, the viscosity in parenthesis represents the viscosity in 20 +/- 1.0 degreeC of the example thing. Examples of mono (meth) acrylate having at least one hydroxyl group having a viscosity of 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at a temperature of 20 ⁇ 1.0 ° C.
  • the adhesive coating suitability is improved and adhesion is achieved. This is preferred because the layer exhibits stronger adhesion.
  • the viscosity range at the temperature of 20 ⁇ 1.0 ° C. is more preferably 50 mPa ⁇ s or more, particularly preferably 70 mPa ⁇ s or more, more preferably 400 mPa ⁇ s or less, and particularly preferably 350 mPa ⁇ s or less. .
  • the amount of mono (meth) acrylate having at least one hydroxyl group having a viscosity of 10 mPa ⁇ s or more and less than 500 mPa ⁇ s at a temperature of 20 ⁇ 1.0 ° C. is (meth) acrylate 100 contained in the uncured adhesive.
  • the amount is preferably 35 to 85 parts by weight with respect to parts by weight. By being within this range, a stronger adhesive force can be obtained.
  • the adhesive may contain any component other than (meth) acrylate as long as the effects of the present invention are not significantly impaired.
  • Optional components include, for example, a polymerization initiator, a crosslinking agent, an inorganic filler, a polymerization inhibitor, a color pigment, a dye, an antifoaming agent, a leveling agent, a dispersing agent, a light diffusing agent, a plasticizer, an antistatic agent, and a surface activity.
  • the type of the polymerization initiator can be selected according to the mode of curing of the adhesive. For example, when the adhesive can be cured by irradiation with active energy rays, a photopolymerization initiator can be used. In this case, a photosensitizer may be used in combination with the photopolymerization initiator.
  • the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl.
  • the amount of the polymerization initiator is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight with respect to 100 parts by weight of (meth) acrylate contained in the uncured adhesive. Part or less, more preferably 5 parts by weight or less.
  • the photosensitizer include n-butylamine, triethylamine, and poly-n-butylphosphine.
  • antifoaming agent examples include BYK051,052,055,057,1790,065,070,088,354,392 manufactured by Big Chemie Japan; LR-20R, OP-80R, OP-83RAT, OP manufactured by Nippon Oil & Fats Co., Ltd. -85R, PP-40R, SO-80R, SP-60R, BP-70R, CP-08R, DS-60HN, and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the antifoaming agent can be used in an amount within a range in which the adhesive force of the adhesive layer does not decrease.
  • the antifoaming agent is preferably 0.1 parts by weight with respect to 100 parts by weight of the solid content of the uncured adhesive. It is above, Preferably it is 1.0 weight part or less, More preferably, it is 0.5 weight part or less.
  • crosslinking agent for example, a bifunctional or higher functional (meth) acrylate monomer having a molecular weight of less than 500 can be used.
  • specific examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, tetraethylene diacrylate, Polyethylene glycol # 400 diacrylate, tricyclodecane dimethanol di (meth) acrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol di (meth) acrylate, hydroxypentane phosphate neopentyl glycol diacrylate, 1,9 -Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaery
  • the amount of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight with respect to 100 parts by weight of (meth) acrylate contained in the uncured adhesive. Below, more preferably 5 parts by weight or less.
  • the amount of the crosslinking agent By setting the amount of the crosslinking agent to be equal to or more than the lower limit of the above range, the mechanical strength of the adhesive layer can be effectively increased.
  • the adhesive force of a multilayer film (A) and a multilayer film (B) can be made high by setting it as below an upper limit.
  • the viscosity modifier for example, a slurry in which metal oxide particles having a particle diameter of several nm to several hundred nm are dispersed in a solvent can be used.
  • the metal oxide include silica, aluminum hydroxide, aluminum oxide, titanium oxide, zinc oxide, barium sulfate, magnesium silicate, and a mixture thereof.
  • viscosity modifiers include: organosilica sol, methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, MEK- ST, MIBK-ST, XBA-ST, PMA-ST, PGM-ST; PL-1-IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK manufactured by Fuso Chemical it can. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the amount of the viscosity modifier is an amount of the metal oxide with respect to 100 parts by weight of (meth) acrylate contained in the uncured adhesive, preferably 1 part by weight or more, more preferably 5 parts by weight or more, preferably 15 parts by weight or less, more preferably 10 parts by weight or less.
  • Specific examples of the adhesive include those described in JP-A-7-82544.
  • the thickness of the adhesive layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence and the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence have desired optical properties (particularly, retardation). Have. Therefore, the phase difference which combined the layer (A2) of non-liquid crystalline material with a positive intrinsic birefringence and the layer (B1) of non-liquid crystalline material with a negative intrinsic birefringence by peeling an unnecessary layer from this laminated body. A film can be obtained easily.
  • the thickness of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence and the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence can be reduced.
  • the non-liquid crystalline material layer (B1) is generally easily damaged because the mechanical strength of the non-liquid crystalline material having a negative intrinsic birefringence is weak.
  • the non-liquid crystalline material layer ( The damage of B1) can be stably prevented.
  • the thickness of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence and the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence is usually reduced, the variation in thickness is reduced. Is possible. Therefore, a thin retardation film can be easily obtained by peeling off unnecessary layers from the laminate.
  • the laminate 100 shown in FIG. 1 includes, for example, a step of manufacturing a multilayer film (A) 10, a step of manufacturing a multilayer film (B) 20, and a multilayer film (A) 10 and a multilayer film (B ) 20 can be manufactured by a manufacturing method including a step of bonding through the adhesive layer 30.
  • this manufacturing method will be described.
  • FIG. 2 is a schematic view schematically showing an example of a production apparatus 200 for producing the multilayer film (A) 10.
  • the manufacturing apparatus 200 provided with the expansion
  • the developing unit 210 is a device that can develop (cast) a solution 240 obtained by dissolving a non-liquid crystalline material having a positive intrinsic birefringence in a solvent onto the base material (A1) 11.
  • a solvent for dissolving the non-liquid crystalline material having a positive intrinsic birefringence a solvent capable of dissolving the non-liquid crystalline material having a positive intrinsic birefringence and not extremely eroding the substrate (A1) can be used.
  • an appropriate solvent can be selected according to the non-liquid crystalline material having a positive intrinsic birefringence and the base material (A1).
  • the solvent include: halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene; phenols such as phenol and parachlorophenol; benzene, Aromatic hydrocarbons such as toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene; acetone, ethyl acetate, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol , Dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl cellosolve, butyl cellosolve, 2-pyrrolidone, N- Chill-2-
  • the concentration of the non-liquid crystalline material having a positive intrinsic birefringence takes into consideration the coating property (for example, the degree of foreign matter contamination, unevenness or streaks during coating) on the base material (A1) 11. , Preferably 0.5% by weight or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, particularly preferably 30% by weight or less. It is.
  • the concentration By setting the concentration to be equal to or higher than the lower limit of the above range, the viscosity of the solution 240 can be increased and the solution 240 can be developed with a desired thickness. Moreover, by making it into the upper limit value or less, the viscosity of the solution 240 can be lowered, and deterioration of the surface state of the layer of the solution 240 can be prevented.
  • the solution 240 may contain a compounding agent such as a surfactant in addition to the non-liquid crystalline material having positive intrinsic birefringence and the solvent.
  • a compounding agent such as a surfactant in addition to the non-liquid crystalline material having positive intrinsic birefringence and the solvent.
  • a coating method is usually used as a developing method in the developing unit 210.
  • Specific examples of the coating method include spin coating, roll coating, die coating, and blade coating.
  • the drying unit 220 is a device that can dry the solution 240 developed on the base material (A1) 11. By drying the solution 240, the pre-stretching film 250 including the base material (A1) 11 and the layer (A2) of the non-liquid crystalline material having positive intrinsic birefringence in this order is obtained.
  • the drying section is preferably an apparatus capable of adjusting the temperature in the range of 30 ° C. to 200 ° C., and preferably has a mechanism for actively sending temperature-controlled hot air on the film surface.
  • the stretching unit 230 is a device that can stretch the base material (A1) 11 after drying the solution 240.
  • the layer (A2) of the positive non-liquid crystalline material formed thereon is also stretched. Since this stretching causes retardation, a layer (A2) of a non-liquid crystalline material having a desired retardation can be obtained.
  • a tenter stretching machine can be used.
  • the tenter stretching machine generally includes a pair of rails and a gripper that can move along the rails.
  • the rail has a rail widening portion in which the rail width is increased in a taper shape in the TD direction toward the downstream side in the MD direction of the belt-like film.
  • the belt-shaped film can be stretched in the TD direction by gripping both ends of the film in the TD direction with a gripper and running the gripper along the rail.
  • manufacture by a roll toe roll method is possible using the elongate film-form base material (A1) 11.
  • FIG. For example, the base material (A1) 11 is pulled out from the roll of the base material (A1) 11, and the pulled out base material (A1) 11 is continuously sent to the developing unit 210.
  • the thickness of the base material (A1) 11 before stretching is preferably 40 ⁇ m or more, more preferably 60 ⁇ m or more from the viewpoint of improving handling properties and mechanical strength, and preferably 500 ⁇ m or less from the viewpoint of improving handling properties. More preferably, it is 150 ⁇ m or less.
  • the developing unit 210 performs a process of developing (casting) the solution 240 on the base material (A1) 11. At this time, the amount of the solution 240 to be developed is such that the thickness of the solution 240 formed by the development is such that the non-liquid crystalline material layer (A2) 12 having a desired thickness can be obtained in the multilayer film (A) 10. It can be set as follows.
  • the region where the solution 240 is developed on the surface 11U of the base material (A1) 11 is preferably not the entire base material (A1) 11 but the region excluding the gripped portion at the time of stretching.
  • the base material (A1) 11 is strip-shaped and the strip-shaped base material (A1) 11 is stretched in the TD direction, both end portions in the width direction of the base material (A1) 11 that are gripped portions at the time of stretching It is preferable to spread the solution 240 on the central portion of the substrate (A1) 11 except for the above.
  • the base material (A1) 11 on which the solution 240 is developed on the surface 11U is sent to the drying unit 220.
  • a process of drying the solution 240 developed on the surface of the base material (A1) 11 is performed.
  • the drying temperature may be set according to the type of solvent of the solution 240, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Drying may be performed at a constant temperature, or may be performed by increasing the temperature stepwise or continuously.
  • the drying time is preferably 10 seconds or more, more preferably 30 seconds or more, preferably 60 minutes or less, more preferably 30 minutes or less.
  • a layer (A2) of a non-liquid crystalline material having a positive intrinsic birefringence is formed on the surface of the substrate (A1) 11.
  • the thickness of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence before stretching thus obtained is preferably smaller than the thickness of the substrate (A1) 11 before stretching, and the substrate (A1). More preferably, it is smaller than half of the thickness of 11.
  • the specific thickness of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence before stretching can be set according to the thickness of the non-liquid crystalline material layer (A2) obtained after stretching. Yes, preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the thickness By setting the thickness to be equal to or more than the lower limit of the above range, sufficient retardation and mechanical strength can be obtained in the layer (A2) 12 of the non-liquid crystalline material of the multilayer film (A) 10.
  • the scratch resistance and handling properties of the non-liquid crystalline material layer (A2) 12 of the multilayer film (A) 10 can be improved, the thickness can be reduced, and further the thickness Variations can be suppressed.
  • the base material (A1) 11 on which the layer (A2) of the non-liquid crystalline material having positive intrinsic birefringence is formed by drying is sent to the stretching unit 230.
  • stretching part 230 the process of extending
  • the base material (A1) 11 plays a role like a relaxation layer, the stretching stress from the gripping portion of the base material (A1) 11 to the layer (A2) of the non-liquid crystalline material having positive intrinsic birefringence The way of transmission becomes gentle, and as a result, uniform stretching in the width direction becomes possible.
  • the base material (A1) 11 mainly This is particularly preferable because tension can be imposed and the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence can be stretched more uniformly.
  • the stretching temperature is preferably in the range of the glass transition temperature ⁇ 20 ° C. of the material forming the base material (A1) 11, and is preferably not more than the glass transition temperature of the non-liquid crystalline material having a positive intrinsic birefringence.
  • the specific stretching temperature is preferably 40 ° C. or higher, more preferably 80 ° C. or higher, particularly preferably 100 ° C. or higher, preferably 250 ° C. or lower, more preferably 220 ° C. or lower, particularly preferably 200 ° C. or lower. .
  • the concentration of stress at the boundary between the region where the layer (A2) of the non-liquid crystalline material having positive intrinsic birefringence is positive and the region where the layer is not formed can be suppressed. Damage to the material (A1) can be prevented.
  • the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence can be reliably stretched by stretching at a glass transition temperature of the substrate (A1) 11 of 20 ° C. or lower.
  • the stretching can be controlled stably, and a desired retardation can be obtained without adding a load to the manufacturing process. Can do.
  • the draw ratio is preferably 1.01 times or more, more preferably 1.03 times or more, particularly preferably 1.05 times or more, preferably 2 times or less, more preferably 1.7 times or less, particularly preferably. 1.5 times or less.
  • the multilayer film (A) 10 having desired optical characteristics is obtained.
  • the in-plane slow axis of the layer (A 2) 12 of the non-liquid crystalline material having a positive intrinsic birefringence is usually parallel to the direction stretched by the stretching portion 230. .
  • a relaxation step may be performed as necessary.
  • the stretched base material (A1) 11 is held at a predetermined temperature for a predetermined time, and the base material (A1) 11 is contracted.
  • the relaxation rate is preferably within 20%
  • the holding temperature is preferably in the range of the glass transition temperature ⁇ 30 ° C. of the material forming the substrate (A1) 11, and the holding time is 1 second to 60 seconds. Is preferred.
  • the obtained multilayer film (A) 10 is cooled to room temperature as necessary.
  • the cooling rate and the cooling means are not particularly limited. However, if the tension at the time of stretching is suddenly released before cooling, the resulting multilayer film (A) 10 is likely to wrinkle. Therefore, before releasing the tension, some or all of the cooling process should be performed. Is preferred.
  • the obtained multilayer film (A) 10 is usually wound into a roll and stored.
  • the thickness variation of the layer (A2) 12 of the non-liquid crystal material is small, and the letter of the layer (A2) 12 of the non-liquid crystal material is small.
  • the foundation is uniform.
  • the multilayer film (B) usually has a step of obtaining a multilayer film comprising a resin layer (B2) and a layer (B1) of a non-liquid crystalline material having a negative intrinsic birefringence in this order, and the multilayer film is stretched. It can manufacture by the manufacturing method including a process.
  • a multilayer film (b) comprising a resin layer (B2), a non-liquid crystalline material layer (B1) having a negative intrinsic birefringence and a resin layer (B2) in this order is produced, and the multilayer film (b) After stretching the film, it is preferable to peel off one resin layer (B2) from the stretched multilayer film (b) to obtain a multilayer film (B).
  • the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence generally has a low mechanical strength. However, the both sides of the layer (B1) of the non-liquid crystalline material are covered with the resin layer (B2), so that Breakage of the liquid crystal material layer (B1) can be reliably prevented.
  • the non-liquid crystalline material layer (B1) can be protected by being sandwiched from both sides by the high-strength resin layer (B2), bleeding out from the non-liquid crystalline material layer (B1) can be effectively prevented.
  • the bleed out from the non-liquid crystalline material layer (B1) means that a part of the components (for example, a compounding agent) contained in the non-liquid crystalline material layer (B1) is the non-liquid crystalline material layer (B1). A phenomenon that exudes to the surface.
  • FIG. 3 is a schematic view schematically showing an example of a production apparatus 300 for producing the multilayer film (b) 310.
  • a manufacturing apparatus 300 including a film molding unit 320 and a stretching unit 330 can be used.
  • the film molding unit 320 is an apparatus for manufacturing a multilayer film (b) including a resin layer (B2), a non-liquid crystalline material layer (B1) having a negative intrinsic birefringence, and a resin layer (B2) in this order.
  • Production methods include, for example, coextrusion molding methods such as coextrusion T-die method, coextrusion inflation method and coextrusion lamination method; film lamination molding methods such as dry lamination; co-casting method; and resin solution on the resin film surface And the like, such as coating molding method such as coating.
  • the coextrusion molding method is preferable from the viewpoint of manufacturing efficiency and preventing a volatile component such as a solvent from remaining in the film.
  • the multilayer film (b) is obtained, for example, by coextruding a non-liquid crystalline material having a negative intrinsic birefringence and a resin that forms the resin layer (B2).
  • the co-extrusion molding method include a co-extrusion T-die method, a co-extrusion inflation method, and a co-extrusion lamination method, and among them, the co-extrusion T-die method is preferable.
  • the coextrusion T-die method includes a feed block method and a multi-manifold method, but the multi-manifold method is particularly preferable in that variation in thickness can be reduced. In FIG. 3, description will be made assuming that the multilayer film (b) 340 before stretching is manufactured by co-extruding the material from the die 321 onto the cooling roll 322.
  • the stretching unit 330 is a device that can stretch the multilayer film (b) 340 before stretching.
  • the multilayer film (b) 340 before stretching is stretched, retardation is developed in the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence, and a desired multilayer film (b) is obtained. It is like that.
  • Examples of the stretching performed in the stretching unit 330 include a method of uniaxial stretching in the MD direction using a difference in peripheral speed between rolls (longitudinal uniaxial stretching); uniaxial stretching in the TD direction using a tenter stretching machine.
  • lateral uniaxial stretching method of performing longitudinal uniaxial stretching and transverse uniaxial stretching in order (sequential biaxial stretching); method of performing longitudinal uniaxial stretching and transverse uniaxial stretching simultaneously (simultaneous biaxial stretching); oblique to the MD direction
  • oblique direction means a direction that is neither parallel nor orthogonal.
  • the film forming part 320 coextrudes a non-liquid crystalline material having a negative intrinsic birefringence and a resin forming the resin layer (B2). Perform the process.
  • the melting temperature of the non-liquid crystalline material having a negative intrinsic birefringence and the resin forming the resin layer (B2) is the glass transition temperature of these non-liquid crystalline material and resin. It is preferable that the temperature is higher than 80 ° C, more preferably higher than 100 ° C, more preferably lower than 180 ° C, more preferably lower than 150 ° C. .
  • a multilayer film (b) 340 before stretching provided with a resin layer (B2), a layer (B1) of a non-liquid crystalline material having a negative intrinsic birefringence and a resin layer (B2) in this order is obtained. It is done.
  • the thickness of the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence is the non-liquid crystalline material layer (B1) in the finally obtained laminate.
  • the thickness ratio of the resin layer (B2) is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more from the viewpoint of obtaining sufficient retardation and mechanical strength. From a viewpoint of making it favorable, Preferably it is 800 micrometers or less, More preferably, it is 600 micrometers or less.
  • the thickness per layer of the resin layer (B2) is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of obtaining sufficient mechanical strength. Moreover, from a viewpoint which makes a softness
  • the total thickness of the multilayer film (b) 340 before stretching is preferably 20 ⁇ m or more, more preferably 70 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 700 ⁇ m or less.
  • the obtained multilayer film (b) 340 before stretching is sent to the stretching section 330.
  • stretching is performed.
  • the stretching temperature is preferably Tg (B1) ⁇ 20 ° C. or higher when expressed using the glass transition temperature Tg (B1) of the non-liquid crystalline material having a negative intrinsic birefringence forming the layer (B1).
  • (B1) ⁇ 15 ° C. or higher is more preferable, and Tg (B1) ⁇ 13 ° C. or higher is further preferable.
  • Tg (B1) + 20 ° C. or lower is preferable, Tg (B1) + 2 ° C. or lower is more preferable, Tg (B1) ⁇ 2 ° C. or lower is further preferable, and Tg (B1) -11. It is particularly preferable that the temperature is not higher than ° C.
  • the draw ratio is preferably 1.2 times or more, more preferably 2.5 times or more, preferably 6 times or less, more preferably 5.0 times or less.
  • a non-liquid crystalline material layer (B1) having a small thickness and a desired retardation can be obtained.
  • the number of stretching may be one time or two or more times.
  • the in-plane slow axis of the layer (B 1) of the non-liquid crystalline material having a negative intrinsic birefringence is usually perpendicular to the direction stretched by the stretching portion 330.
  • a preheat treatment may be performed on the multilayer film (b) 340 before stretching.
  • the obtained multilayer film (b) 310 is usually wound into a roll and stored.
  • the mechanical strength of the non-liquid crystalline material layer (B1) is low, but it is protected by the resin layer (B2), and is not easily damaged. It has become.
  • FIG. 4 is a schematic view schematically showing an example of an apparatus 400 for manufacturing the laminate 100 by laminating the multilayer film (A) 10 and the multilayer film (B) 20.
  • the manufacturing apparatus 400 provided with the peeling part 410, the coating part 420, the bonding part 430, and the hardening process part 440 can be used.
  • the peeling part 410 is an apparatus which peels one resin layer (B2) 450 from the multilayer film (b) 310 extended as shown in FIG.
  • one resin layer (B2) 450 is peeled, one surface of the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence is exposed, and the non-liquid crystalline material layer (B1) and the resin layer are exposed.
  • a multilayer film (B) 20 provided with (B2) is obtained.
  • the coating unit 420 is an apparatus that can apply an adhesive layer to the exposed surface of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the multilayer film (B) 20. That is, the coating part 420 applies the adhesive 460 to the surface 21D opposite to the resin layer (B2) of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the multilayer film (B). Can be crafted.
  • Examples of the method for applying the adhesive layer include, but are not particularly limited to, a die coating method such as a roll coating method, a curtain coating method, and a slot coating method, a spray coating method, and the like.
  • the bonding portion 430 includes an adhesive layer formed on the multilayer film (B) and a base material (A1) of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence of the multilayer film (A).
  • This is an apparatus capable of bonding the opposite surface 12U.
  • the laminating method by the laminating unit 430 can be performed by any laminating means. However, it is preferable to eliminate the air bubbles mixed during the bonding. For example, in the continuous laminating process such as the roll-to-roll method shown in FIG.
  • the multilayer film (A) is so thick that the total thickness of the multilayer film (B) 20 is larger than the total thickness of the multilayer film (A) 10.
  • the mixing of bubbles can be suppressed by a method such as selecting 10 base materials (A1). Further, in the batch laminating process, for example, by adopting a technique such as (iv) increasing the surface pressure or (v) applying a vacuum, it is possible to suppress the mixing of bubbles.
  • the curing processing unit 440 is a device that can perform a process of curing the adhesive included in the adhesive layer.
  • the specific curing process can be performed appropriately according to the adhesive used.
  • an active energy ray-curable adhesive such as ultraviolet rays
  • an apparatus that can uniformly irradiate the active energy rays in the TD direction can be used.
  • the ultraviolet light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.
  • manufacture by the roll toe roll method is possible using the elongate multilayer film (A) 10 and multilayer film (b) 310.
  • FIG. For example, the multilayer film (b) 310 is pulled out from the roll of the multilayer film (b) 310, and the pulled multilayer film (b) 310 is sent to the peeling unit 410.
  • the process which peels one said resin layer (B2) 450 from the multilayer film (b) 310, and obtains the multilayer film (B) 20 is performed.
  • the obtained multilayer film (B) 20 is sent to the coating unit 420.
  • the resin layer (B2) 450 peeled from the multilayer film (b) 310 is usually wound up and collected in a roll shape.
  • an adhesive layer is applied to the surface 21D opposite to the resin layer (B2) of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the multilayer film (B) 20. . That is, the adhesive 460 is applied to the surface 21D of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence exposed by peeling off the resin layer (B2) 450, and the uncured adhesive 460 is removed.
  • An adhesive layer is formed as a layer.
  • the multilayer film (B) 20 coated with the adhesive layer is sent to the bonding part 430. Further, the multilayer film (A) 10 drawn from the roll of the multilayer film (A) 10 has also been sent to the bonding portion 430. In the laminating portion 430, the multilayer film (B) 20 is sandwiched between the multilayer film (A) 10 and the multilayer film (B) 20 between the lami roll 431 and the counter roll 432, so that the intrinsic birefringence of the multilayer film (B) 20 is negative.
  • the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the multilayer film (B) 20 has a low mechanical strength, but is reinforced by the resin layer (B2), and thus is damaged during bonding. There is nothing.
  • the arithmetic average roughness Ra of the surface 12U on the side opposite to the base material (A1) of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence serving as a bonding surface in the multilayer film (A) 10. Is preferably 0.001 ⁇ m or more, more preferably 0.005 ⁇ m or more, preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
  • the arithmetic average roughness Ra is preferably 0.0005 ⁇ m or more, more preferably 0.001 ⁇ m or more, preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
  • the curing processing unit 440 irradiates the adhesive layer with ultraviolet rays, and the adhesive layer is cured.
  • the irradiation intensity of ultraviolet rays is preferably 50 mW / cm 2 or more, more preferably 100 mW / cm 2 or more, particularly preferably 300 mW / cm 2 or more in a wavelength region effective for activating the polymerization initiator. preferably 5000 mW / cm 2 or less, more preferably 3000 mW / cm 2 or less, particularly preferably 2000 mW / cm 2 or less.
  • irradiation intensity By making irradiation intensity more than the lower limit of the said range, processing time can be shortened and hardening reaction can fully advance. Moreover, by setting it as the upper limit value or less, for example, yellowing of the adhesive layer due to heat such as radiant heat from a light source or heat of polymerization reaction and a decrease in adhesive force due to curing shrinkage can be prevented. Further, the irradiation time can be set according to the curing state.
  • the integrated light amount expressed as the product of irradiation intensity and irradiation time is preferably 10 mJ / cm 2 or more, more preferably 100 mJ / cm 2 or more, particularly preferably 500 mJ / cm 2 or more, preferably 5000 mJ / cm 2 or less, more preferably 3000 mJ / cm 2 or less, particularly preferably 2000 mJ / cm 2 or less.
  • the adhesive layer is cured by the curing process. Therefore, the substrate (A1), the non-liquid crystalline material layer (A2) with positive intrinsic birefringence, the adhesive layer, the non-liquid crystalline material layer (B1) with negative intrinsic birefringence and the resin layer (B2)
  • the laminated body 100 provided in order is obtained.
  • the obtained laminate 100 is usually wound into a roll and stored.
  • the manufacturing method described above may further include an optional step.
  • a step of performing a surface treatment such as a corona treatment on the surface 21D opposite to the resin layer (B2) of (B1) may be included. Thereby, the adhesive force of a multilayer film (A) and a multilayer film (B) can be improved.
  • an adhesive layer is first applied to the surface 12U opposite to the base material (A1) of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence, and the adhesive layer is formed into a multilayer film.
  • the surface 21D opposite to the resin layer (B2) of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of 20 may be bonded. That is, the surface 12U opposite to the base material (A1) of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence of the multilayer film (A) and the intrinsic complex of the multilayer film (B).
  • a step of applying an adhesive layer to one surface of the surface 21D opposite to the resin layer (B2) of the non-liquid crystalline material layer (B1) having a negative refraction, an adhesive layer, and an adhesive layer are applied.
  • the adhesive layer may be applied to either the surface 12U or the surface 21D.
  • the laminate described above directly produces a multilayer film (B) having a non-liquid crystalline material layer (B1) and a resin layer (B2) one by one by coextrusion, and the multilayer film ( You may manufacture by bonding B) and a multilayer film (A) through an adhesive layer.
  • the retardation film of the present invention is obtained by peeling the substrate (A1) and the resin layer (B2) from the above-described laminate. Therefore, the retardation film includes a non-liquid crystalline material layer (A2) having a positive intrinsic birefringence, an adhesive layer, and a non-liquid crystalline material layer (B1) having a negative intrinsic birefringence in this order.
  • the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence and the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence are thin and have a desired retardation. Uniformly in the plane. Therefore, the retardation film obtained from this laminate has desired optical performance, is thin, and can be stably manufactured.
  • the retardation film has a total light transmittance of preferably 85% or more, more preferably 92% or more, and usually 100% or less from the viewpoint of use as an optical film.
  • the total light transmittance of the retardation film was measured at five locations using “turbidimeter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997, and the average value obtained therefrom. It is.
  • the haze of the retardation film is preferably 1% or less, more preferably 0.8% or less, particularly preferably 0.5% or less, and usually 0% or more.
  • haze is an average value obtained by measuring five points using “turbidity meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997.
  • ⁇ YI is preferably 5 or less, more preferably 3 or less, and usually 0 or more.
  • ⁇ YI is obtained as an arithmetic average value by performing the same measurement five times using “Spectral Color Difference Meter SE2000” manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM E313.
  • the thickness of the retardation film is usually 5 ⁇ m or more, preferably 8 ⁇ m or more, more preferably 10 ⁇ m or more, and usually 500 ⁇ m or less, preferably 80 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • FIG. 5 is a diagram schematically showing a cross section of the polarizing plate according to one embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • the polarizing plate 500 includes a polarizer 510 and the retardation film 520.
  • the basic structure of the polarizing plate 500 is obtained by bonding the retardation film 520 of the present invention serving as a protective layer to one or both sides of the polarizer 510 through an adhesive layer or an adhesive layer 530 as necessary. is there.
  • the direction of the retardation film 520 is arbitrary, and as shown in FIG.
  • the retardation film 520 is bonded to the polarizer 510 on the non-liquid crystalline material layer (A2) 12 side having a positive intrinsic birefringence.
  • it may be bonded to the polarizer 510 on the side of the layer (B1) 21 of the non-liquid crystalline material which is opposite and has a negative intrinsic birefringence.
  • the polarizer examples include, for example, an appropriate vinyl alcohol polymer film such as polyvinyl alcohol and partially formalized polyvinyl alcohol, a dyeing treatment with a dichroic substance such as iodine or a dichroic dye, a stretching treatment, a crosslinking treatment, and the like. Are applied in an appropriate order and manner.
  • a polarizer is capable of transmitting linearly polarized light when natural light is incident thereon, and in particular, a polarizer excellent in light transmittance and degree of polarization is preferable.
  • the thickness of the polarizer is generally 5 ⁇ m to 80 ⁇ m, but is not limited thereto.
  • the retardation film of the present invention is adhered to at least one side of the polarizer, but an optional protective layer may be provided on the other side.
  • Any transparent film can be used as the protective layer.
  • a resin film excellent in transparency, mechanical strength, thermal stability, moisture shielding properties and the like is preferable.
  • resins include acetate resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and polymers having an alicyclic structure. Examples thereof include resins and acrylic resins.
  • an acetate resin, a polymer resin having an alicyclic structure, and an acrylic resin are preferable in terms of low birefringence.
  • an alicyclic structure is preferable.
  • Particularly preferred are polymer resins having The thickness of the protective layer is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, particularly preferably 150 ⁇ m or less, and usually 5 ⁇ m or more, from the viewpoint of thinning the polarizing plate.
  • any adhesive or pressure-sensitive adhesive layer can be used.
  • the adhesive or pressure-sensitive adhesive include acrylic, silicone, polyester, polyurethane, polyether, rubber, and the like. Among these, an acrylic type is preferable from the viewpoint of heat resistance and transparency.
  • the slow axis in the plane of the retardation film and the transmission axis of the polarizer are usually parallel or orthogonal.
  • the thickness of the polarizing plate (the protective layer, the polarizer, the adhesive layer, the non-liquid crystalline material layer (A2) having positive intrinsic birefringence, the adhesive layer, the non-liquid crystalline material layer (B1) having negative intrinsic birefringence)
  • the thickness of the polarizing plate provided in order is preferably 70 ⁇ m or more, more preferably 80 ⁇ m or more, particularly preferably 90 ⁇ m or more, preferably 150 ⁇ m or less, more preferably 140 ⁇ m or less, and particularly preferably 120 ⁇ m or less.
  • Such a polarizing plate peels off the base material (A1) or the resin layer (B2) from the laminate of the present invention, and thereby the surface of the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence exposed. Or it can manufacture easily by sticking a polarizer on the surface of the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence, and further peeling off unnecessary layers as necessary. Bonding may be performed by batch-bonding films cut to a desired size, or by a roll-to-roll method using a long film.
  • FIG. 6 is a diagram schematically showing a cross section of the liquid crystal panel according to one embodiment of the present invention, taken along a plane perpendicular to the main surface.
  • the liquid crystal panel 600 includes a liquid crystal cell 610 and the polarizing plate 500.
  • the orientation of the polarizing plate 500 is arbitrary, and a retardation film 520 may be provided between the polarizer 510 and the liquid crystal cell 610 as shown in FIG.
  • Liquid crystal cells include in-plane switching (IPS) type, vertical alignment (VA) type, multi-domain vertical alignment (MVA) type, continuous spin wheel alignment (CPA) type, twisted nematic (TN) type, super twisted nematic ( STN) type, hybrid alignment nematic (HAN) type, optical compensated bend (OCB) type, and the like.
  • IPS in-plane switching
  • VA vertical alignment
  • MVA multi-domain vertical alignment
  • CPA continuous spin wheel alignment
  • TN twisted nematic
  • STN super twisted nematic
  • HAN hybrid alignment nematic
  • OOB optical compensated bend
  • an ISP type liquid crystal cell includes a liquid crystal layer including liquid crystal molecules having a homogeneous alignment in the horizontal direction.
  • an IPS liquid crystal panel including such an IPS liquid crystal cell generally includes two polarizers whose transmission axes point vertically and horizontally with respect to the front of the screen. . Accordingly, when the screen of the IPS liquid crystal panel is viewed obliquely from the top, bottom, left, and right directions, the two transmission axes of the polarizer are in a positional relationship that they appear to be orthogonal. Birefringence generated in the liquid crystal cell is reduced, and sufficient contrast can be obtained.
  • the retardation film of the present invention as an optical compensation film, compensation of retardation caused by the liquid crystal in the liquid crystal cell and orthogonal arrangement of the transmission axes of the two polarizers are achieved. Compensation can be performed. Therefore, it is possible to effectively compensate for the birefringence generated in the transmitted light to prevent light leakage and to obtain high contrast at all azimuth angles. This effect is considered to be obtained in other types of liquid crystal panels as well, but the effect is particularly remarkable in the IPS type.
  • the retardation film of the present invention can be applied to a liquid crystal panel having an arbitrary structure such as a transmission type, a reflection type, or a transmission / reflection type in which a polarizer is disposed on one side or both sides of a liquid crystal cell.
  • a liquid crystal display device can be configured by combining the liquid crystal panel with components such as a prism array sheet, a lens array sheet, a light diffusion plate, a backlight, and a brightness enhancement film.
  • the value obtained by measuring the layer (B1) of the non-liquid crystalline material having a negative intrinsic birefringence obtained in this manner was taken as the measured value.
  • the layer (A2) of the non-liquid crystalline material having a positive intrinsic birefringence was measured by the following method.
  • the layer (A2) side of the non-liquid crystalline material having a positive intrinsic birefringence of the multilayer film (A) was attached to the glass substrate via an adhesive layer, and the base material (A1) was peeled off.
  • a composite of glass substrate / adhesive layer / non-liquid crystalline material layer (A2) having a positive intrinsic birefringence was prepared as a sample. The value measured with this sample was taken as the measured value.
  • the peeling force was measured at a peeling speed of 100 mm / min and a sample width of 20 mm in accordance with JIS K6855-2.
  • the tensile elongation at break was in accordance with JIS K7162, and the test piece was prepared in accordance with JIS K7127-1B. The tensile speed was measured as 5 mm / min.
  • Example 1 [1.1. Production of multilayer film comprising layer (B1) and layer (B2)] (Preparation of resin) 70 parts of amorphous polystyrene (PS Japan "HH102") and 30 parts of poly (2,6-dimethyl-1,4-phenylene oxide) (Aldrich) were kneaded with a twin screw extruder. Then, a transparent thermoplastic resin (X) pellet was produced.
  • This resin (X) is a non-liquid crystalline material having a negative intrinsic birefringence. The glass transition temperature of resin (X) was 134 ° C.
  • thermoplastic resin (Y) pellets of methacrylic resin (glass transition temperature 105 ° C.) containing polymethyl methacrylate and rubber particles were put into one uniaxial extruder of a film molding apparatus and melted.
  • the resin (X) pellets were charged into the other uniaxial extruder of the film molding apparatus and melted.
  • a film forming apparatus for coextrusion molding of two types and three layers was prepared.
  • the melted resin (X) was supplied to the other manifold of the film forming apparatus through a leaf disk-shaped polymer filter having an opening of 10 ⁇ m.
  • thermoplastic resin (Y) and the resin (X) are simultaneously extruded from the multi-manifold die at 260 ° C. while adjusting the extrusion conditions so that a resin layer having a desired thickness is obtained.
  • the film was formed into a film having a three-layer structure of layer (B2) / layer (B1) of resin (X) / layer (B2) of thermoplastic resin (Y).
  • the molten resin coextruded in the form of a film in this way was cast on a cooling roll adjusted to a surface temperature of 115 ° C., and then passed between two cooling rolls adjusted to a surface temperature of 120 ° C.
  • the layer (B2) of the thermoplastic resin (Y), the layer (B1) of the resin (X) as a non-liquid crystalline material having a negative intrinsic birefringence, and the layer (B2) of the thermoplastic resin (Y) A multilayer film (b) having a three-layer structure provided in this order was obtained.
  • the multi-layer film (b) is pulled up by 1.8 times in the longitudinal direction using a tenter stretching machine while adjusting the tension and the tenter chain tension so that an in-plane slow axis parallel to the TD direction can be obtained by stretching.
  • the film was biaxially stretched 1.1 times in the transverse direction.
  • the temperature during stretching was 131 ° C., which is 3 ° C. lower than the glass transition temperature of the resin (X) as a non-liquid crystalline material having a negative intrinsic birefringence.
  • base film (A1) (“Zeonor film” manufactured by Nippon Zeon Co., Ltd., thickness 80 ⁇ m, glass transition temperature 138 ° C.) formed of a norbornene-based resin as a polymer resin having an alicyclic structure was applied so that the dry film thickness was 6 ⁇ m to form a resin solution film.
  • the membrane of this resin solution was dried at 80 ° C. for 2 minutes to obtain a multilayer film (a) comprising a base film (A1) and a polycarbonate resin layer (A2).
  • the multilayer film (a) was stretched by a tenter stretching machine at a stretching temperature of 145 ° C. and a stretching ratio of 2.7 times in the TD direction. This obtained the multilayer film (A) of the 2 layer structure of base film (A1) / polycarbonate resin layer (A2). At this time, the thickness of the polycarbonate resin layer (A2) layer was 5 ⁇ m.
  • One layer (B2) is peeled from the multilayer film having a three-layer structure of layer (B2) / layer (B1) / layer (B2), and a multilayer having layers (B1) and (B2) is provided.
  • a film (B) was obtained.
  • the surface of the layer (B1) exposed by peeling off one of the layers (B2) was subjected to corona treatment (paint index 56 dyne / cm).
  • An active energy ray-curable adhesive (“Aronix M-6100” manufactured by Toagosei Co., Ltd.) was applied to the surface of the layer (B1) subjected to the corona treatment in a thickness of 5 ⁇ m to form an adhesive layer.
  • the surface of the polycarbonate resin layer (A2) of the multilayer film (A) was subjected to corona treatment (painting index 56 dyne / cm).
  • the surface of the polycarbonate resin layer (A2) subjected to this corona treatment was bonded to the adhesive layer.
  • the in-plane slow axis of the polycarbonate resin layer (A2) and the in-plane slow axis of the resin (X) layer (B1) were made parallel. By making them parallel, it is inevitably possible to perform roll-to-roll bonding.
  • the layer (B2) and the layer are irradiated by irradiating the surface on the layer (B2) side with an ultraviolet irradiation device (Conveyor UV, manufactured by Fusion UV Systems Japan Co., Ltd., integrated light quantity 350 mJ / cm 2 ).
  • the adhesive layer was irradiated with ultraviolet rays via (B1). Thereby, the adhesive layer is cured, and the base film (A1), the polycarbonate resin layer (A2), the adhesive layer, the resin (X) layer (B1), and the thermoplastic resin (Y) layer (B2) are arranged in this order.
  • the laminated body provided was obtained.
  • the base film (A1) was peeled from the produced laminate.
  • the surface of the polycarbonate resin layer (A2) exposed by peeling off the base film (A1) was subjected to corona treatment (paint index 56 dyne / cm).
  • a water-based adhesive was applied to the edge of the surface of the polycarbonate resin layer (A2) subjected to the corona treatment so as to have a dry film thickness of 0.1 ⁇ m.
  • This water-based adhesive is an aqueous solution in which 100 parts of “Gosephemer Z-200” manufactured by Nihon Gosei Co., Ltd. and 1 part of glyoxal GX are dissolved in 4949 parts of pure water.
  • a film comprising a triacetylcellulose layer with a hard coat (thickness 50 ⁇ m) and a polarizer (thickness 25 ⁇ m) is prepared, and the surface of the polarizer of this film and the surface of the polycarbonate resin layer (A2) are arranged to face each other. And laminated with a laminator.
  • the in-plane slow axis of the laminate comprising the polycarbonate resin layer (A2), the adhesive layer, the resin (X) layer (B1) and the thermoplastic resin (Y) layer (B2) in this order is: It was made to be parallel to the transmission axis of the polarizer.
  • thermoplastic resin (Y) layer (B2) is peeled off, and the triacetylcellulose layer, the polarizer, the adhesive layer, the polycarbonate resin layer (A2), the adhesive layer, and the resin (X) layer (B1) are peeled off.
  • a polarizing plate provided in this order was obtained.
  • the obtained polarizing plate had a thickness of 96 ⁇ m.
  • the exit side polarizing plate was peeled from the IPS liquid crystal panel of a commercially available IPS mode liquid crystal display device.
  • the polarizing plate from which the layer (B2) was peeled was bonded to the surface of the IPS liquid crystal panel from which the outgoing-side polarizing plate was peeled.
  • the surface of the resin (X) layer (B1) of the polarizing plate faced the liquid crystal cell.
  • the transmission axis of the polarizing plate to be bonded and the transmission axis of the incident side polarizing plate of the IPS liquid crystal panel were set to be crossed Nicols.
  • the bonding was performed using an adhesive layer (“MO-T006C” manufactured by Lintec Corporation, thickness 25 ⁇ m).
  • an adhesive layer (“MO-T006C” manufactured by Lintec Corporation, thickness 25 ⁇ m).
  • the display was good and uniform both when viewed from the front and when viewed from an oblique angle in the range of 0 ° to 80 ° in all directions.
  • Met In order to evaluate the light leakage of this liquid crystal display device, the screen during black display was measured at an azimuth angle of 45 ° and a polar angle of ⁇ 60 ° to 60 ° with respect to the transmission axis of the output side polarizing plate of the liquid crystal panel. As a result, the maximum value Ymax of the measured luminance was 0.55 (candela / m 2 ).
  • Example 2 As the non-liquid crystalline material having a negative intrinsic birefringence, a styrene-maleic anhydride copolymer (“Dairark D332” manufactured by Nova Chemical Japan, glass transition temperature 130 ° C.) was used instead of the resin (X). Further, the stretching temperature of the multilayer film (b) was changed to 127 ° C. A liquid crystal display device was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • a styrene-maleic anhydride copolymer (“Dairark D332” manufactured by Nova Chemical Japan, glass transition temperature 130 ° C.) was used instead of the resin (X). Further, the stretching temperature of the multilayer film (b) was changed to 127 ° C.
  • a liquid crystal display device was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Example 3 100 parts of bismaleimide resin (UV-cured product of “BMI 1500” manufactured by Air Brown; glass transition temperature 90 ° C.), 1 part of photopolymerization initiator (“Irg907” manufactured by BASF Japan), 202 parts of toluene, acetic acid
  • the resin solution was obtained by mixing 202 parts of ethyl.
  • this resin solution was used in place of the resin solution containing the polycarbonate resin as the resin solution containing the non-liquid crystalline material having a positive intrinsic birefringence.
  • the film thickness of the bismaleimide resin layer after stretching was 4 ⁇ m.
  • a norbornene-based resin film (A1) (“Zeonor Film” manufactured by Nippon Zeon Co., Ltd., thickness 80 ⁇ m, glass transition temperature 105 ° C.) was used as the base film.
  • a liquid crystal display device was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • the thickness of the polarizing plate was 95 ⁇ m.
  • Example 4 instead of the thermoplastic resin (Y), a norbornene resin (“Zeonor” manufactured by Nippon Zeon Co., Ltd .; glass transition temperature 105 ° C.) was used. A liquid crystal display device was manufactured and evaluated in the same manner as in Example 1 except for the above items.
  • Corona treatment (paint index 56 dyne / cm) was applied to the surface of one layer (B2) of the multilayer film having a three-layer structure of layer (B2) / layer (B1) / layer (B2).
  • An active energy ray curable adhesive (“Aronix M-6100” manufactured by Toagosei Co., Ltd.) was applied to the surface of the corona-treated layer (B2) to form an adhesive layer.
  • the surface of the polycarbonate resin layer (A2) of the multilayer film (A) similar to that in Example 1 was subjected to corona treatment (wetting index 56 dyne / cm). The surface of the polycarbonate resin layer (A2) subjected to this corona treatment was bonded to the adhesive layer.
  • the adhesive layer was irradiated with ultraviolet rays by an ultraviolet irradiation device under the same conditions as in Example 1. Thereby, the adhesive layer is cured, and the base film (A1), the polycarbonate resin layer (A2), the adhesive layer, the layer (B2) of the thermoplastic resin (Y), the layer (B1) of the resin (X), and the thermoplastic resin.
  • the laminated body provided with the layer (B2) of resin (Y) in this order was obtained.
  • a polarizing plate was produced in the same manner as in Step [1.4] of Example 1 except that the laminate thus obtained was used. The thickness of this polarizing plate was 102 ⁇ m.
  • a liquid crystal display device was produced and evaluated in the same manner as in Step [1.5] of Example 1 except that the polarizing plate thus obtained was used.
  • the display was good and uniform both when viewed from the front and when viewed from an oblique angle in the range of 0 ° to 80 ° in all directions.
  • Met In order to evaluate the light leakage of this liquid crystal display device, the screen during black display was measured at an azimuth angle of 45 ° and a polar angle of ⁇ 60 ° to 60 ° with respect to the transmission axis of the output side polarizing plate of the liquid crystal panel. As a result, the maximum value Ymax of the measured luminance was 0.60 (candela / m 2 ).
  • Tg difference of film (B) difference in glass transition temperature calculated by “glass transition temperature of layer (B1) of non-liquid crystalline material having negative intrinsic birefringence ⁇ glass transition temperature of resin layer (B2)”.
  • Tg difference of film (A) difference in glass transition temperature calculated by “glass transition temperature of layer (A2) of non-liquid crystalline material having positive intrinsic birefringence ⁇ glass transition temperature of substrate (A1)”.
  • Re (550 nm) In-plane retardation measured at a wavelength of 550 nm.
  • Rth (550 nm) retardation in the thickness direction measured at a wavelength of 550 nm.
  • MAA resin Methacrylic resin
  • NBR resin Norbornene resin
  • PC resin Polycarbonate resin
  • BMI resin Bismaleimide resin
  • the contrast of the IPS liquid crystal panel can be improved. Therefore, it was confirmed that the retardation films according to Examples 1 to 4 have optical characteristics that enable optical compensation of the IPS liquid crystal panel.
  • the retardation films according to Examples 1 to 4 each have a base material (A1), a non-liquid crystal material layer (A2), an adhesive layer, a non-liquid crystal material layer (B1), and a resin layer (B2). It was confirmed that the laminate can be easily manufactured from the provided laminate and that the thickness can be reduced.
  • Multi-layer film (A) 11 Substrate (A1) 11U Surface of base material (A1) 12 Layer of non-liquid crystalline material with positive intrinsic birefringence (A2) 12U Surface of the non-liquid crystalline material layer (A2) having a positive intrinsic birefringence on the side opposite to the base material (A1) 20 Multilayer film (B) 21 Layer of non-liquid crystalline material with negative intrinsic birefringence (B1) 21D Surface of the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence opposite to the resin layer (B2) 22 Resin layer (B2) DESCRIPTION OF SYMBOLS 30 Adhesive layer 100 Laminated body 200 Manufacturing apparatus of multilayer film (A) 210 Expanding section 220 Drying section 230 Stretching section 240 Solution 250 Film before stretching 300 Manufacturing apparatus of multilayer film (b) 310 Multilayer film after stretching (b ) 320 Film forming part 321 Die 322 Cooling roll 330 Stretching part 340 Multilayer film (b) before stretching DESCRIPTION

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

Abstract

La présente invention se rapporte à un stratifié qui comprend : un film multicouche (A) qui comprend une base (A1) et une couche (A2) d'un matériau à cristaux non liquides qui présente une biréfringence intrinsèque positive, ladite couche (A2) étant en contact avec la base (A1) ; un film multicouche (B) qui comprend une couche (B1) d'un matériau à cristaux non liquides qui présente une biréfringence intrinsèque négative, et une couche de résine (B2) qui est en contact avec la couche (B1) d'un matériau à cristaux non liquides qui présente une biréfringence intrinsèque négative ; et une couche adhésive qui intervient entre une surface de la couche (A2) d'un matériau à cristaux non liquides qui présente une biréfringence intrinsèque positive, ladite surface se trouvant sur le côté opposé de la surface côté base (A1), et une surface de la couche (B1) d'un matériau à cristaux non liquides qui présente une biréfringence intrinsèque négative, ladite surface se trouvant sur le côté opposé de la surface côté couche de résine (B2).
PCT/JP2013/078615 2012-10-26 2013-10-22 Stratifié, procédé permettant de produire ce dernier, film de retard, plaque de polarisation et panneau à cristaux liquides à mode de commutation dans le plan Ceased WO2014065294A1 (fr)

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JP2014543312A JPWO2014065294A1 (ja) 2012-10-26 2013-10-22 積層体及びその製造方法、位相差フィルム、偏光板並びにｉｐｓ液晶パネル
KR1020157010481A KR20150079630A (ko) 2012-10-26 2013-10-22 적층체 및 그의 제조 방법, 위상차 필름, 편광판, 및 ips 액정 패널

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KR20150141142A (ko) * 2014-06-09 2015-12-17 스미또모 가가꾸 가부시키가이샤 위상차 필름
WO2017135336A1 (fr) * 2016-02-05 2017-08-10 三菱瓦斯化学株式会社 Film de résine thermoplastique multicouche étiré
JP2017196816A (ja) * 2016-04-28 2017-11-02 三菱ケミカル株式会社 熱可塑性樹脂延伸シートの製造方法
CN110720062A (zh) * 2017-06-05 2020-01-21 3M创新有限公司 包括多层光学膜和薄粘合剂层的光学主体
CN114207067A (zh) * 2019-08-09 2022-03-18 三菱瓦斯化学株式会社 贴合用粘接片材、多层体和多层体的制造方法
JP2023049870A (ja) * 2021-09-29 2023-04-10 富士フイルム株式会社 転写フィルム、転写フィルムの製造方法、偏光板、画像表示装置

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EP3412449B1 (fr) * 2016-02-05 2020-11-04 Mitsubishi Gas Chemical Company, Inc. Film de résine thermoplastique multicouche étiré
JP7040462B2 (ja) * 2016-11-30 2022-03-23 日本ゼオン株式会社 偏光板、及び、偏光板の製造方法

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KR20150141142A (ko) * 2014-06-09 2015-12-17 스미또모 가가꾸 가부시키가이샤 위상차 필름
KR102477375B1 (ko) * 2014-06-09 2022-12-13 스미또모 가가꾸 가부시키가이샤 위상차 필름
WO2017135336A1 (fr) * 2016-02-05 2017-08-10 三菱瓦斯化学株式会社 Film de résine thermoplastique multicouche étiré
JPWO2017135336A1 (ja) * 2016-02-05 2018-12-06 三菱瓦斯化学株式会社 熱可塑性樹脂積層延伸フィルム
JP2017196816A (ja) * 2016-04-28 2017-11-02 三菱ケミカル株式会社 熱可塑性樹脂延伸シートの製造方法
CN110720062A (zh) * 2017-06-05 2020-01-21 3M创新有限公司 包括多层光学膜和薄粘合剂层的光学主体
JP2020522752A (ja) * 2017-06-05 2020-07-30 スリーエム イノベイティブ プロパティズ カンパニー 多層光学フィルム及び薄い接着剤層を含む光学体
EP3635455A4 (fr) * 2017-06-05 2021-02-24 3M Innovative Properties Company Corps optique comprenant un film optique multicouche et une couche mince adhésive
US12001042B2 (en) 2017-06-05 2024-06-04 3M Innovative Properties Company Optical body including multilayer optical film and thin adhesive layer
CN114207067A (zh) * 2019-08-09 2022-03-18 三菱瓦斯化学株式会社 贴合用粘接片材、多层体和多层体的制造方法
JP2023049870A (ja) * 2021-09-29 2023-04-10 富士フイルム株式会社 転写フィルム、転写フィルムの製造方法、偏光板、画像表示装置

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KR20150079630A (ko) 2015-07-08
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TW201423172A (zh) 2014-06-16

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