WO2019208512A1 - Film de longueur d'onde à large bande, procédé de production dudit film, et procédé de production d'un film à polarisation circulaire - Google Patents

Film de longueur d'onde à large bande, procédé de production dudit film, et procédé de production d'un film à polarisation circulaire Download PDF

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Publication number
WO2019208512A1
WO2019208512A1 PCT/JP2019/017070 JP2019017070W WO2019208512A1 WO 2019208512 A1 WO2019208512 A1 WO 2019208512A1 JP 2019017070 W JP2019017070 W JP 2019017070W WO 2019208512 A1 WO2019208512 A1 WO 2019208512A1
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Prior art keywords
layer
film
broadband wavelength
stretching
resin
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PCT/JP2019/017070
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English (en)
Japanese (ja)
Inventor
次郎 石原
和弘 大里
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日本ゼオン株式会社
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Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to KR1020207029811A priority Critical patent/KR20210004985A/ko
Priority to CN201980026053.1A priority patent/CN112105970B/zh
Priority to JP2020516349A priority patent/JP7413997B2/ja
Publication of WO2019208512A1 publication Critical patent/WO2019208512A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

Definitions

  • the present invention relates to a broadband wavelength film, a method for producing the same, and a method for producing a circularly polarizing film.
  • a film including a combination of a ⁇ / 2 plate and a ⁇ / 4 plate is known.
  • a broadband wavelength film includes a step of stretching a film to obtain a ⁇ / 2 plate, a step of stretching another film to obtain a ⁇ / 4 plate, and the ⁇ / 2 plate and ⁇ / plate. It is common to manufacture by the manufacturing method including the process of bonding 4 plates and obtaining a broadband wavelength film.
  • a technique for obtaining a circularly polarizing film by combining the broadband wavelength film with a linearly polarizing film as a film that can function as a linearly polarizing plate is known.
  • a long linearly polarizing film has an absorption axis in the longitudinal direction or the width direction.
  • the slow axis of the ⁇ / 2 plate is required to be in an oblique direction that is neither parallel nor perpendicular to the longitudinal direction. .
  • the present invention was devised in view of the above problems, and a broadband wavelength film that can be efficiently manufactured with a small number of steps and a method for manufacturing the same; and a method for manufacturing a circularly polarizing film including the method for manufacturing the broadband wavelength film
  • the purpose is to provide;
  • the inventor has intensively studied to solve the above problems.
  • the inventor prepared a first step of preparing a layer (A) as a resin film having a slow axis parallel or perpendicular to the longitudinal direction; a resin having a negative intrinsic birefringence on the layer (A)
  • a second step of obtaining a multilayer film by stretching the multilayer film in an oblique direction that is neither parallel nor perpendicular to the longitudinal direction of the multilayer film And a third step of obtaining a long broadband wavelength film having two layers and a ⁇ / 4 layer, in this order, and found that a broadband wavelength film can be efficiently manufactured with a small number of steps.
  • the present invention includes the following.
  • a first step of preparing a layer (A) as a long resin film A second step of obtaining a multilayer film by forming a resin layer (B) having a negative intrinsic birefringence on the layer (A);
  • the multilayer film is stretched in an oblique direction that is neither parallel nor perpendicular to the longitudinal direction of the multilayer film to obtain a long broadband wavelength film having a ⁇ / 2 layer and a ⁇ / 4 layer.
  • the layer (A) prepared in the first step has a slow axis parallel or perpendicular to the longitudinal direction of the layer (A),
  • ⁇ ( ⁇ / 2) represents the angle formed by the slow axis of the ⁇ / 2 layer with respect to the longitudinal direction of the broadband wavelength film
  • ⁇ ( ⁇ / 4) represents an angle formed by the slow axis of the ⁇ / 4 layer with respect to the longitudinal direction of the broadband wavelength film.
  • [5] The method for producing a broadband wavelength film according to any one of [1] to [4], wherein the ⁇ / 2 layer is a layer obtained by stretching the layer (A).
  • [6] The method for producing a broadband wavelength film according to any one of [1] to [5], wherein the ⁇ / 4 layer is a layer obtained by stretching the layer (B).
  • the present invention it is possible to provide a broadband wavelength film that can be efficiently manufactured with a small number of steps and a method for manufacturing the same; and a method for manufacturing a circularly polarizing film including the method for manufacturing the broadband wavelength film.
  • FIG. 1 is a perspective view schematically showing a layer (A) as a resin film prepared in the first step of the method for producing a broadband wavelength film according to one embodiment of the present invention.
  • FIG. 2 is a perspective view schematically showing a multilayer film obtained in the second step of the method for producing a broadband wavelength film according to one embodiment of the present invention.
  • FIG. 3 is a perspective view schematically showing a broadband wavelength film obtained in the third step of the method for manufacturing a broadband wavelength film according to an embodiment of the present invention.
  • the “long” film means a film having a length of 5 times or more, preferably 10 times or more, and specifically a roll.
  • the upper limit of the film length is not particularly limited, and can be, for example, 100,000 times or less with respect to the width.
  • the slow axis of the film or layer represents the slow axis in the plane of the film or layer.
  • the orientation angle of the film or layer represents the angle formed by the slow axis of the film or layer with respect to the longitudinal direction of the film or layer.
  • the angle formed by the optical axis (slow axis, transmission axis, absorption axis, etc.) of each layer in a member having a plurality of layers is the angle when the layer is viewed from the thickness direction unless otherwise specified. Represents.
  • the direction and geometric direction (the longitudinal direction and width of the film) of the optical axis (slow axis, transmission axis, absorption axis, etc.) in the plane of a certain product broadband wavelength film, circularly polarizing film, etc.
  • the angle relationship of the direction is defined as positive in one direction and negative in the other direction, and the positive and negative directions are defined in common in the components in the product.
  • the angle formed by the slow axis of the ⁇ / 2 layer with respect to the longitudinal direction of the broadband wavelength film is 27.5 °
  • “An angle formed by the slow axis of 100” is the following two cases: When the broadband wavelength film is observed from one side thereof, the slow axis of the ⁇ / 2 layer is shifted 27.5 ° clockwise from the longitudinal direction of the broadband wavelength film, and the ⁇ / 4 layer The slow axis is shifted 100 ° clockwise from the longitudinal direction of the broadband wavelength film.
  • the slow axis of the ⁇ / 2 layer is shifted 27.5 ° counterclockwise from the longitudinal direction of the broadband wavelength film, and the ⁇ / 4 layer Is shifted 100 ° counterclockwise from the longitudinal direction of the broadband wavelength film.
  • the oblique direction of a long film refers to the in-plane direction of the film, which is neither parallel nor perpendicular to the longitudinal direction of the film.
  • the front direction of a film means the normal direction of the main surface of the film, specifically, the direction of the polar angle 0 ° and the azimuth angle 0 ° of the main surface. Point to.
  • the inclination direction of a film means a direction that is neither parallel nor perpendicular to the main surface of the film, and specifically, the polar angle of the main surface is larger than 0 ° and 90 °. Point in a direction smaller than °.
  • a material having a positive intrinsic birefringence means a material in which the refractive index in the stretching direction is larger than the refractive index in the direction perpendicular thereto unless otherwise specified.
  • a material having a negative intrinsic birefringence means a material in which the refractive index in the stretching direction is smaller than the refractive index in the direction perpendicular thereto unless otherwise specified.
  • the value of intrinsic birefringence can be calculated from the dielectric constant distribution.
  • (meth) acryl includes “acryl”, “methacryl”, and combinations thereof.
  • the NZ coefficient of the layer is a value represented by (nx ⁇ nz) / (nx ⁇ ny) unless otherwise specified.
  • nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the layer and giving the maximum refractive index.
  • ny represents the refractive index in the in-plane direction of the layer and perpendicular to the nx direction.
  • nz represents the refractive index in the thickness direction of the layer.
  • d represents the thickness of the layer. The measurement wavelength is 590 nm unless otherwise specified.
  • FIG. 1 is a perspective view schematically showing a layer (A) 100 as a resin film prepared in the first step of the method for producing a broadband wavelength film according to one embodiment of the present invention.
  • FIG. 2 is a perspective view schematically showing a multilayer film 200 obtained in the second step of the method for producing a broadband wavelength film according to an embodiment of the present invention.
  • FIG. 3 is a perspective view schematically showing a broadband wavelength film 300 obtained in the third step of the method for manufacturing a broadband wavelength film according to an embodiment of the present invention.
  • the method for manufacturing the broadband wavelength film 300 includes: (1) As shown in FIG. 1, a first step of preparing a layer (A) 100 as a long resin film; (2) a second step of forming a resin layer (B) 210 having a negative intrinsic birefringence on the layer (A) 100 to obtain a multilayer film 200 shown in FIG. 2; (3) a third step of stretching the multilayer film 200 to obtain the long broadband wavelength film 300 shown in FIG. 3; Are included in this order.
  • the layer (A) 100 prepared in the first step has a slow axis A 100 that is parallel or perpendicular to the longitudinal direction of the layer (A) 100.
  • the multilayer film 200 is stretched in the third step. This stretching is performed in an oblique direction that is neither parallel nor perpendicular to the longitudinal direction of the multilayer film 200 so as to obtain a ⁇ / 2 layer and a ⁇ / 4 layer having a slow axis in a desired direction.
  • the layer (A) 100 By stretching in the third step, co-stretching for stretching the layer (A) 100 and the layer (B) 210 at the same time is performed. Therefore, as shown in FIG. 3, the layer (A) 100, the direction of adjustment of the slow axis A 100, and the adjustment of the optical properties is performed. On the other hand, the slow axis A 210 appears in the layer (B) 210, and optical characteristics are exhibited.
  • the stretched layer (A) 100 functions as one of the ⁇ / 2 layer and the ⁇ / 4 layer
  • the stretched layer (B) 210 functions as the other of the ⁇ / 2 layer and the ⁇ / 4 layer.
  • the broadband wavelength film 300 having the ⁇ / 2 layer and the ⁇ / 4 layer can be obtained by the above manufacturing method.
  • FIG. 3 shows an example in which the stretched layer (A) 100 functions as a ⁇ / 2 layer and the stretched layer (B) 210 functions as a ⁇ / 4 layer. It is not limited to examples.
  • Equation (1) shows that ⁇ ( ⁇ / 4) is a range where “ ⁇ 45 ° + 2 ⁇ ⁇ ( ⁇ / 2) ⁇ ⁇ 5 °” or more and “ ⁇ 45 ° + 2 ⁇ ⁇ ( ⁇ / 2) ⁇ + 5 °” or less. It means that there is.
  • ⁇ ( ⁇ / 2) represents an angle formed by the slow axis A 100 of the ⁇ / 2 layer with respect to the longitudinal direction A 300 of the broadband wavelength film 300.
  • ⁇ ( ⁇ / 4) represents an angle formed by the slow axis A 210 of the ⁇ / 4 layer with respect to the longitudinal direction A 300 of the broadband wavelength film 300.
  • the broadband wavelength film 300 can transmit light that passes through the film in a wide wavelength range to approximately 1 ⁇ 4 wavelength of the wavelength of the light. It can function as a broadband wavelength film capable of providing in-plane retardation.
  • the longitudinal A 300 of the broadband wave film 300, lambda / 4 layers of longitudinal (not shown), and, lambda / 2 layer in the longitudinal direction (not shown) is consistent. Therefore, the angle ⁇ ( ⁇ / 2) represents the orientation angle formed by the slow axis A 100 of the ⁇ / 2 layer with respect to the longitudinal direction of the ⁇ / 2 layer. ) ". Further, the angle ⁇ ( ⁇ / 4) represents the orientation angle formed by the slow axis A 210 of the ⁇ / 4 layer with respect to the longitudinal direction of the ⁇ / 4 layer. ) ".
  • a layer (A) as a long resin film having a slow axis in a predetermined direction in the plane is prepared.
  • this layer (A) a resin film having a multilayer structure including two or more layers may be used, but a resin film having a single layer structure including only one layer is usually used.
  • thermoplastic resin containing a polymer and further containing optional components as required can be used as the resin for forming the resin film.
  • a resin having a negative intrinsic birefringence may be used as the resin contained in the layer (A).
  • a resin having a positive intrinsic birefringence should be used because a broadband wavelength film can be manufactured particularly easily. Is preferred.
  • the resin having a positive intrinsic birefringence usually contains a polymer having a positive intrinsic birefringence.
  • polymers having a positive intrinsic birefringence include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyarylene sulfides such as polyphenylene sulfide; polyvinyl alcohol; polycarbonate; polyarylate; Polysulfone; Polysulfone; Polyallyl sulfone; Polyvinyl chloride; Cyclic olefin polymer such as norbornene polymer; Rod-like liquid crystal polymer.
  • polymers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymer may be a homopolymer or a copolymer.
  • a polycarbonate polymer is preferable because it is excellent in expression of retardation and stretchability at low temperature.
  • a cyclic olefin polymer is preferable because of excellent mechanical properties, heat resistance, transparency, low moisture absorption, dimensional stability, and light weight.
  • the proportion of the polymer in the resin contained in the layer (A) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight.
  • the layer (A) and the broadband wavelength film can obtain sufficient heat resistance and transparency.
  • the resin contained in the layer (A) may further contain any component other than the polymer in combination with the polymer.
  • Optional components include, for example, colorants such as pigments and dyes; plasticizers; fluorescent brighteners; dispersants; thermal stabilizers; light stabilizers; ultraviolet absorbers; antistatic agents; Examples include activators. These components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the glass transition temperature TgA of the resin contained in the layer (A) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher, preferably 190 ° C. or lower, more preferably 180 ° C. or lower, Especially preferably, it is 170 degrees C or less.
  • the layer ( ⁇ / 2 layer or ⁇ / 4 layer) obtained by stretching the layer (A) in a high temperature environment Durability can be increased.
  • the stretching treatment can be easily performed.
  • the slow axis of the layer (A) prepared in the first step is parallel or perpendicular to the longitudinal direction of the layer (A). Therefore, the orientation angle formed by the slow axis of the layer (A) with respect to the longitudinal direction of the layer preferably satisfies any of the following (a1) and (a2).
  • the orientation angle of the layer (A) is preferably ⁇ 3 ° or more, more preferably ⁇ 2 ° or more, particularly preferably ⁇ 1 ° or more, preferably 3 ° or less, more preferably 2 ° or less. Particularly preferably, it is 1 ° or less.
  • the orientation angle of the layer (A) is preferably 87 ° or more, more preferably 88 ° or more, particularly preferably 89 ° or more, preferably 93 ° or less, more preferably 92 ° or less, particularly preferably. Is 91 ° or less.
  • optical properties such as retardation and NZ coefficient of the layer (A) prepared in the first step can be set according to the optical properties of the layer obtained by stretching the layer (A).
  • the in-plane retardation of the layer (A) is preferably 150 nm or more, more preferably 180 nm or more, and particularly preferably 200 nm or more. , Preferably 400 nm or less, more preferably 380 nm or less, particularly preferably 350 nm or less.
  • the NZ coefficient of the layer (A) is preferably 1.0 or more, more preferably 1.1 or more, particularly preferably 1.15 or more, preferably 1.7 or less, more preferably 1.65 or less. Especially preferably, it is 1.6 or less.
  • the thickness of the layer (A) prepared in the first step can be arbitrarily set within a range where a desired broadband wavelength film can be obtained.
  • the specific thickness of the layer (A) is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, particularly preferably 30 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 95 ⁇ m or less, and particularly preferably 90 ⁇ m or less.
  • a ⁇ / 2 layer or a ⁇ / 4 layer having desired optical properties can be easily obtained by stretching in the third step.
  • the layer (A) can be obtained by a production method including drawing an appropriate long resin film and developing a slow axis in the resin film.
  • the resin film before being subjected to the stretching treatment may be referred to as “film before stretching”, and the resin film obtained after stretching may be referred to as “stretched film”.
  • the film before stretching can be produced by, for example, a melt molding method or a solution casting method.
  • the melt molding method include an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method.
  • an extrusion molding method, an inflation molding method or a press molding method is preferable.
  • the extrusion method is particularly preferred.
  • the long unstretched film After preparing a long unstretched film, the long unstretched film can be stretched to obtain a layer (A) as a stretched film.
  • the slow axis of the layer (A) is usually expressed by stretching the film before stretching. Therefore, the stretching direction of the film before stretching is preferably set according to the direction of the slow axis of the layer (A).
  • the stretch direction of the pre-stretch film is set in a direction parallel to the slow axis of the layer (A) to be prepared in the first step. It is preferable to do.
  • the stretching direction of the film before stretching is the direction perpendicular to the slow axis of the layer (A) to be prepared in the first step.
  • the stretching direction of the pre-stretching film is preferably a direction parallel or perpendicular to the longitudinal direction of the pre-stretching film.
  • the stretching direction of the film before stretching is preferably a direction perpendicular to the longitudinal direction of the film before stretching.
  • the stretch ratio of the pre-stretch film is preferably 1.1 times or more, more preferably 1.2 times or more, preferably 4.0 times or less, more preferably 3.0 times or less.
  • the draw ratio is not less than the lower limit of the above range, the refractive index in the drawing direction can be increased.
  • a draw ratio is below the upper limit of the said range, the direction of the slow axis of the layer obtained by extending
  • the stretching temperature of the film before stretching is preferably TgA or higher, more preferably “TgA + 2 ° C.” or higher, particularly preferably “TgA + 5 ° C.” or higher, preferably “TgA + 40 ° C.” or lower, more preferably “TgA + 35 ° C.” or lower, Especially preferably, it is “TgA + 30 ° C.” or less.
  • TgA refers to the glass transition temperature of the resin contained in the layer (A).
  • the above-described stretching can usually be performed using an appropriate stretching machine such as a roll stretching machine or a tenter stretching machine while continuously transporting the film before stretching in the longitudinal direction.
  • an appropriate stretching machine such as a roll stretching machine or a tenter stretching machine while continuously transporting the film before stretching in the longitudinal direction.
  • a roll stretching machine When a film before stretching is stretched in the longitudinal direction of the film before stretching, it is preferable to use a roll stretching machine.
  • free uniaxial stretching can be easily performed. Free uniaxial stretching refers to stretching in a certain direction and not applying a restraining force in a direction other than the direction in which the film is stretched.
  • these stretching machines for example, the one described in Patent Document 1 can be used.
  • the method for producing a broadband wavelength film may include a step of forming a thin film layer on the layer (A), if necessary, after preparing the layer (A) in the first step.
  • the thin film layer functions as an easy adhesion layer, and the binding force between the layer (A) and the layer (B) can be increased.
  • a thin film layer has solvent resistance.
  • Such a thin film layer is usually formed of a resin.
  • Examples of the material for the thin film layer include acrylic resin, urethane resin, acrylic urethane resin, ester resin, and ethyleneimine resin.
  • the acrylic resin is a resin containing an acrylic polymer.
  • the urethane resin is a resin containing polyurethane.
  • a polymer such as an acrylic polymer and polyurethane usually has a high binding force for a wide variety of resins, so that the binding force between the layer (A) and the layer (B) can be increased.
  • these polymers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Resin as a material of the thin film layer is combined with a polymer, heat stabilizer, weather stabilizer, leveling agent, antistatic agent, slip agent, antiblocking agent, antifogging agent, lubricant, dye, pigment, natural oil, Arbitrary components such as synthetic oil, wax, and particles may be included.
  • Arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the glass transition temperature of the resin as the material of the thin film layer is higher than the glass transition temperature TgA of the resin contained in the layer (A) and the glass transition temperature TgB of the resin having a negative intrinsic birefringence contained in the layer (B). Preferably it is low.
  • the difference between the glass transition temperature of the resin as the material of the thin film layer and the lower one of the glass transition temperatures TgA and TgB is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. preferable.
  • the thin film layer in a broadband wavelength film can have optical isotropy. Therefore, it is possible to easily adjust the optical characteristics of the broadband wavelength film.
  • the thin film layer can be formed, for example, by a method including coating a coating liquid containing a resin as a material for the thin film layer and a solvent on the layer (A).
  • a solvent water or an organic solvent may be used.
  • an organic solvent the thing similar to the solvent which can be used for formation of the layer (B) mentioned later is mentioned, for example.
  • a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the coating liquid may contain a crosslinking agent.
  • a crosslinking agent By using a crosslinking agent, the mechanical strength of the thin film layer can be increased, and the binding property of the thin film layer to the layer (A) and the layer (B) can be increased.
  • a crosslinking agent an epoxy compound, an amino compound, an isocyanate compound, a carbodiimide compound, an oxazoline compound, etc. can be used, for example. Moreover, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the amount of the crosslinking agent is preferably 1 part by weight or more, more preferably 5 parts by weight or more, preferably 70 parts by weight or less, more preferably 65 parts by weight with respect to 100 parts by weight of the polymer in the coating liquid. It is as follows.
  • Examples of the coating method of the coating liquid include the same methods as the coating method that can be used for forming the layer (B) described later.
  • a thin film layer can be formed by applying a coating solution on the layer (A).
  • This thin film layer may be subjected to a curing treatment such as drying and crosslinking as necessary.
  • a curing treatment such as drying and crosslinking as necessary.
  • the drying method include heat drying using an oven.
  • crosslinking method methods, such as heat processing, irradiation processing of active energy rays, such as an ultraviolet-ray, are mentioned, for example.
  • Second step In the first step, after preparing the layer (A) and forming a thin film layer as necessary, the second step of forming a resin layer (B) having a negative intrinsic birefringence to obtain a multilayer film Do.
  • the layer (B) is formed directly on the layer (A) or indirectly via an arbitrary layer such as a thin film layer.
  • “directly” means that there is no arbitrary layer between the layer (A) and the layer (B).
  • the resin having a negative intrinsic birefringence is usually a thermoplastic resin and includes a polymer having a negative intrinsic birefringence.
  • polymers having a negative intrinsic birefringence include homopolymers and copolymers of styrene or styrene derivatives, and polystyrene-based polymers including copolymers of styrene or styrene derivatives and arbitrary monomers; Examples thereof include acrylonitrile polymers; polymethyl methacrylate polymers; or multicomponent copolymers thereof; and cellulose compounds such as cellulose esters.
  • arbitrary monomer which can be copolymerized with styrene or a styrene derivative acrylonitrile, maleic anhydride, methyl methacrylate, and butadiene are mentioned as a preferable thing, for example.
  • polystyrene polymers and cellulose compounds are preferred.
  • these polymers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the ratio of the polymer in the resin having a negative intrinsic birefringence is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight.
  • a layer ( ⁇ / 2 layer or ⁇ / 4 layer) obtained by stretching the layer (B) can exhibit appropriate optical properties.
  • the resin having a negative intrinsic birefringence contained in the layer (B) preferably contains a plasticizer.
  • a plasticizer By using a plasticizer, the glass transition temperature TgB of the resin contained in the layer (B) can be adjusted appropriately.
  • the plasticizer include phthalate esters, fatty acid esters, phosphate esters, and epoxy derivatives. Specific examples of the plasticizer include those described in JP-A-2007-233114.
  • a plasticizer may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • phosphate esters are preferable because they are easily available and inexpensive.
  • phosphate esters include trialkyl phosphates such as triethyl phosphate, tributyl phosphate, trioctyl phosphate; halogen-containing trialkyl phosphates such as trichloroethyl phosphate; triphenyl phosphate, tricresyl Triaryl phosphates such as phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate; alkyl-diaryl phosphates such as octyl diphenyl phosphate; tri (alkoxy) such as tri (butoxyethyl) phosphate Alkyl) phosphate; and the like.
  • the amount of the plasticizer is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and particularly preferably with respect to 100% by weight of the resin having a negative intrinsic birefringence contained in the layer (B). Is 0.1% by weight or more, preferably 20% by weight or less, more preferably 18% by weight or less, and particularly preferably 15% by weight or less.
  • the glass transition temperature TgB of the resin contained in the layer (B) can be appropriately adjusted, so that appropriate stretching that can provide a desired broadband wavelength film can be easily performed in the third step. Is possible.
  • the resin having a negative intrinsic birefringence may further contain an optional component other than the polymer and the plasticizer in combination with the polymer and the plasticizer.
  • an optional component the same example as the arbitrary component which the resin contained in a layer (A) can contain is mentioned, for example.
  • Arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the glass transition temperature TgB of the resin having a negative intrinsic birefringence contained in the layer (B) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 110 ° C. or higher, particularly preferably. Is 120 ° C. or higher.
  • the glass transition temperature TgB of the resin having a negative intrinsic birefringence is high as described above, the orientation relaxation of the resin having a negative intrinsic birefringence can be reduced.
  • limiting in particular in the upper limit of glass transition temperature TgB of resin with a negative intrinsic birefringence Usually, it is 200 degrees C or less.
  • the glass transition temperature TgA of the resin contained in the layer (A) and the layer (B) is preferably close.
  • of the difference between the glass transition temperature TgA and the glass transition temperature TgB is preferably 20 ° C. or less, more preferably 15 ° C. or less, and particularly preferably 10 ° C. or less.
  • the layer (B) may have in-plane retardation and a slow axis.
  • the in-plane retardation and the slow axis direction of the layer (B) are adjusted by stretching in the third step.
  • the setting of the stretching conditions for performing such adjustment tends to be complicated. Therefore, from the viewpoint of easily obtaining the desired optical characteristics and slow axis direction in the layer (B) after stretching in the third step, the layer (B) formed in the second step has in-plane retardation and slow phase. It is preferable that the in-plane retardation is small even if it does not have an axis.
  • the in-plane retardation of the layer (B) is preferably 0 nm to 20 nm, more preferably 0 nm to 15 nm, and particularly preferably 0 nm to 10 nm.
  • the thickness of the layer (B) formed in the second step can be arbitrarily set within a range where a desired broadband wavelength film can be obtained.
  • the specific thickness of the layer (B) is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably 7 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • a ⁇ / 2 layer or ⁇ / 4 layer having desired optical properties can be easily obtained by stretching.
  • a layer (B) There is no special restriction
  • formation methods such as a coating method, an extrusion method, and the bonding method, can be used.
  • the second step includes coating a composition containing a resin having a negative intrinsic birefringence on the layer (A).
  • the above composition is usually a liquid composition containing a solvent in combination with a resin having a negative intrinsic birefringence.
  • the solvent examples include methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, 3-methyl-2-butanone, methyl isobutyl ketone, tetrahydrofuran, cyclopentyl methyl ether, acetylacetone, cyclohexanone, 2-methylcyclohexanone, 1,3-dioxolane, 1 , 4-dioxane, 2-pentanone, N, N-dimethylformamide and the like.
  • a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the solvent may cause a phenomenon such as dissolution and orientation relaxation in the layer (A).
  • the coating thickness of the liquid composition is thin, and the coating is dried quickly after coating. The degree of this phenomenon is negligibly small.
  • Examples of the coating method of the composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, and gravure.
  • Examples of the method include a coating method, a die coating method, a gap coating method, and a dipping method.
  • the second step includes drying the coated composition as necessary after coating the composition on the layer (A).
  • a resin layer (B) having a negative intrinsic birefringence can be formed on the layer (A). Drying can be performed by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying.
  • the second step includes extruding a resin having a negative intrinsic birefringence on the layer (A).
  • the extrusion of the resin is usually performed in a state where the resin is melted.
  • resin is normally extruded to a film form using die
  • a resin (B) having a negative intrinsic birefringence may be formed on the layer (A) by adhering the extruded resin having a negative intrinsic birefringence to the layer (A) or the thin film layer. it can.
  • the second step usually includes cooling and curing the resin having a negative intrinsic birefringence that has been extruded and attached to the layer (A).
  • a 2nd process includes bonding the film of resin with a negative intrinsic birefringence to a layer (A).
  • the method for producing a resin film having a negative intrinsic birefringence include melt molding methods such as an extrusion molding method, an inflation molding method, and a press molding method; and a solution casting method.
  • the coating method is preferable.
  • a resin having a negative intrinsic birefringence tends to have a low mechanical strength.
  • the layer (B) can be easily formed while using a resin having low mechanical strength.
  • a bonding method forming a layer (B) on an appropriate support film, and bonding this layer (B) to the layer (A), while suppressing damage to the layer (B) It is possible to form the layer (B) on the layer (A).
  • the coating method is the layer (B).
  • the number of steps required to form the film can be reduced.
  • an adhesive and a pressure-sensitive adhesive are unnecessary.
  • the thickness of the layer (B) itself can be made thinner than in the extrusion method. Therefore, from the viewpoint of obtaining a thin broadband wavelength film with a small number of steps, it is preferable to form the layer (B) by a coating method.
  • the third step of stretching the multilayer film to obtain a long broadband wavelength film is performed.
  • the direction of the slow axis of the layer (A) is adjusted, and the optical characteristics of the layer (A) are adjusted to obtain one of the ⁇ / 2 layer and the ⁇ / 4 layer.
  • the slow axis appears in the layer (B), and the optical characteristics appear in the layer (B), and the other of the ⁇ / 2 layer and the ⁇ / 4 layer is obtained.
  • the stretching of the multilayer film in the third step is performed in an oblique direction that is neither parallel nor perpendicular to the longitudinal direction of the multilayer film.
  • the specific stretching direction is set so that a desired broadband wavelength film can be obtained from the in-plane direction of the multilayer film.
  • the direction of the slow axis of the layer (A) changes so as to approach the stretching direction by stretching in the third step.
  • the layer (A) is a resin layer having a negative intrinsic birefringence
  • the slow axis direction of the layer (A) is perpendicular to the stretching direction by stretching in the third step. It changes to approach the direction.
  • the direction of the slow axis of a layer (A) changes with extending
  • a slow axis usually appears in a direction perpendicular to the stretching direction by stretching in the third step.
  • the stretching direction in the third step is delayed in the desired direction by the change in the direction of the slow axis in the layer (A) and the development of the slow axis in the layer (B). It is preferable to set so that ⁇ / 2 layers and ⁇ / 4 layers having axes are obtained.
  • the specific angle formed by the stretching direction of the multilayer film in the third step with respect to the longitudinal direction of the multilayer film is preferably 4 ° or more, particularly preferably 5 ° or more, preferably 45 ° or less, More preferably, it is 30 ° or less, and particularly preferably 20 ° or less.
  • the multilayer film is stretched in such a stretching direction, the slow axis directions of the ⁇ / 2 layer and the ⁇ / 4 layer can be easily controlled.
  • the size of the angle formed by the stretching direction of the multilayer film in the third step and the slow axis of the layer (A) is preferably 45 ° or more, more preferably 60 ° or more, particularly preferably. Is 70 ° or more, preferably 86 ° or less, particularly preferably 85 ° or less.
  • the draw ratio in the third step is preferably 1.1 times or more, more preferably 1.15 times or more, particularly preferably 1.2 times or more, preferably 2.5 times or less, more preferably 2.2 times. 2 times or less, particularly preferably 2.0 times or less.
  • the draw ratio in the third step is not less than the lower limit of the above range, the generation of wrinkles can be suppressed.
  • the draw ratio in the third step is not more than the upper limit of the above range, the slow axis directions of the ⁇ / 2 layer and the ⁇ / 4 layer can be easily controlled.
  • the stretching temperature in the third step is the following condition (C1) with respect to the glass transition temperature TgA of the resin contained in the layer (A) and the glass transition temperature TgB of the resin having a negative intrinsic birefringence contained in the layer (B). ) And (C2) are preferably satisfied.
  • the stretching temperature is preferably TgA-20 ° C or higher, more preferably TgA-10 ° C or higher, particularly preferably TgA-5 ° C or higher, preferably TgA + 30 ° C or lower, more preferably TgA + 25 ° C or lower, particularly preferably. Is a temperature of TgA + 20 ° C. or lower.
  • the stretching temperature is preferably TgB-20 ° C or higher, more preferably TgB-10 ° C or higher, particularly preferably TgB-5 ° C or higher, preferably TgB + 30 ° C or lower, more preferably TgB + 25 ° C or lower, particularly preferably. Is a temperature of TgB + 20 ° C. or lower.
  • the stretching in the third step described above can be performed using an arbitrary stretching machine, for example, a tenter stretching machine or a roll stretching machine. Stretching using these stretching machines is preferably performed while continuously transporting a long multilayer film in the longitudinal direction.
  • the above-described method for producing a broadband wavelength film may further include an optional step in combination with the above-described steps.
  • the method for producing a broadband wavelength film may include a step of providing a protective layer on the surface of the broadband wavelength film.
  • surface treatment such as corona treatment and plasma treatment is applied to one or more surfaces of the layer (A), the layer (B), and the thin film layer at an arbitrary time.
  • the process to apply may be included. Therefore, for example, after the surface treatment is performed on the surface of the layer (A), the layer (B) or the thin film layer may be formed on the treated surface. Further, for example, after the surface treatment is performed on the surface of the thin film layer, the layer (B) may be formed on the treated surface. By performing the surface treatment, it is possible to enhance the binding property between the layers on the surface-treated surface.
  • any of the first to fourth steps and the optional step described above can be performed while continuously transporting films such as the layer (A), the multilayer film, and the broadband wavelength film.
  • the conveyance direction of such a file conveyance is usually the longitudinal direction of the film. Therefore, in the case of the said conveyance, the longitudinal direction and the width direction of a film usually correspond to MD direction (Machine Direction) and TD direction (Transverse Direction) of conveyance.
  • a co-stretched film having a ⁇ / 2 layer and a ⁇ / 4 layer can be obtained.
  • the ⁇ / 2 layer and ⁇ / 4 layer of this co-stretched film satisfy the above formula (1).
  • the combination of the ⁇ / 2 layer and the ⁇ / 4 layer satisfying the relationship represented by the formula (1) is such that an in-plane letter having a wavelength that is approximately 1 ⁇ 4 wavelength of the light transmitted through the film in a wide wavelength range. It can function as a broadband wavelength film capable of providing a foundation (see JP 2007-004120 A).
  • a long broadband wavelength film can be obtained as a co-stretched film having a ⁇ / 2 layer and a ⁇ / 4 layer.
  • the ⁇ / 2 layer and the ⁇ / 4 layer preferably satisfy Expression (2), and more preferably satisfy Expression (3).
  • Formula (2) is a range in which ⁇ ( ⁇ / 4) is “ ⁇ + 45 ° + 2 ⁇ ⁇ ( ⁇ / 2) ⁇ ⁇ 4 °” or more and “ ⁇ + 45 ° + 2 ⁇ ⁇ ( ⁇ / 2) ⁇ + 4 °” or less. It means that there is.
  • the stretching of the layer (A) and the layer (B) is not performed separately as in the prior art, but is performed together in the third step. Therefore, since the number of stretching processes can be reduced as compared with the prior art, the number of steps required for producing a broadband wavelength film can be reduced, and thus efficient production can be realized. Further, in the above production method for obtaining a broadband wavelength film by co-stretching the layer (A) and the layer (B) by stretching a multilayer film, both the ⁇ / 2 layer and the ⁇ / 4 layer are produced after the production. As in the conventional manufacturing method of bonding, there is no shift in the slow axis direction due to bonding.
  • the ⁇ / 2 layer is a layer obtained by stretching one of the layer (A) and the layer (B), and the ⁇ / 4 layer is the layer (A) and the layer (B).
  • the other is a layer obtained by stretching.
  • the ⁇ / 2 layer is preferably a layer obtained by stretching the layer (A)
  • the ⁇ / 4 layer is preferably a layer (B ) Is preferably obtained by stretching. Therefore, the ⁇ / 2 layer is preferably a layer made of the same resin as the layer (A), and the ⁇ / 4 layer is preferably a layer made of the same resin as the layer (B).
  • the ⁇ / 2 layer is a layer having an in-plane retardation of usually 220 nm or more and usually 300 nm or less at a measurement wavelength of 590 nm.
  • a broadband wavelength film can be realized by combining the ⁇ / 2 layer and the ⁇ / 4 layer.
  • the in-plane retardation of the ⁇ / 2 layer at a measurement wavelength of 590 nm is preferably 230 nm or more, more preferably 240 nm or more, preferably It is 280 nm or less, more preferably 270 nm or less.
  • the retardation in the thickness direction of the ⁇ / 2 layer at a measurement wavelength of 590 nm is preferably 130 nm or more, more preferably 140 nm or more, particularly preferably 150 nm or more, preferably 300 nm or less, more preferably 280 nm or less, particularly preferably 270 nm. It is as follows. When the retardation in the thickness direction of the ⁇ / 2 layer is in the above range, it is possible to obtain a circularly polarizing film particularly excellent in the function of suppressing coloring in the tilt direction.
  • the NZ coefficient of the ⁇ / 2 layer is preferably 1.0 or more, more preferably 1.05 or more, particularly preferably 1.10 or more, preferably 1.6 or less, more preferably 1.55 or less, particularly Preferably it is 1.5 or less.
  • the NZ coefficient of the ⁇ / 2 layer is in the above range, it is possible to obtain a circularly polarizing film particularly excellent in the function of suppressing coloring in the tilt direction. Further, the ⁇ / 2 layer having such an NZ coefficient can be easily manufactured.
  • the optical properties such as the retardation of the ⁇ / 2 layer and the NZ coefficient include, for example, the retardation and thickness of the layer (A) prepared in the first step; and the stretching temperature, stretching ratio, stretching direction, etc. in the third step.
  • the stretching conditions can be adjusted.
  • the orientation angle ⁇ ( ⁇ / 2) of the ⁇ / 2 layer is preferably in the range of 27.5 ° ⁇ 10 ° (that is, in the range of 17.5 ° to 37.5 °). More preferably in the range of 8 ° (ie in the range of 19.5 ° to 35.5 °), in the range of 27.5 ° ⁇ 5 ° (ie in the range of 22.5 ° to 32.5 °). It is particularly preferable that A general linearly polarizing film has a transmission axis in the width direction and an absorption axis in the longitudinal direction.
  • the orientation angle ⁇ ( ⁇ / 2) of the ⁇ / 2 layer is, for example, the direction of the slow axis of the layer (A) prepared in the first step; and the stretching conditions such as the stretching direction and the stretching ratio in the third step Can be adjusted.
  • the thickness of the ⁇ / 2 layer is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, further preferably 30 ⁇ m or more, preferably 80 ⁇ m or less, more preferably 70 ⁇ m or less, and even more preferably 60 ⁇ m or less. Thereby, the mechanical strength of the ⁇ / 2 layer can be increased.
  • the ⁇ / 4 layer is a layer having an in-plane retardation of usually 90 nm or more and usually 154 nm or less at a measurement wavelength of 590 nm.
  • a broadband wavelength film can be realized by combining the ⁇ / 2 layer and the ⁇ / 4 layer.
  • the in-plane retardation of the ⁇ / 4 layer at a measurement wavelength of 590 nm is preferably 100 nm or more, more preferably 110 nm or more, preferably 140 nm or less, more preferably 130 nm or less.
  • the retardation in the thickness direction of the ⁇ / 4 layer at a measurement wavelength of 590 nm is preferably ⁇ 150 nm or more, more preferably ⁇ 140 nm or more, particularly preferably ⁇ 130 nm or more, preferably ⁇ 80 nm or less, more preferably ⁇ 90 nm or less. Particularly preferably, it is ⁇ 100 nm or less.
  • the retardation in the thickness direction of the ⁇ / 4 layer is in the above range, it is possible to obtain a circularly polarizing film particularly excellent in the function of suppressing coloring in the tilt direction.
  • the NZ coefficient of the ⁇ / 4 layer is preferably ⁇ 1.0 or more, more preferably ⁇ 0.8 or more, particularly preferably ⁇ 0.7 or more, preferably 0.0 or less, more preferably ⁇ 0. 05 or less, particularly preferably ⁇ 0.1 or less.
  • the NZ coefficient of the ⁇ / 4 layer is in the above range, it is possible to obtain a circularly polarizing film particularly excellent in the function of suppressing coloring in the tilt direction.
  • the ⁇ / 4 layer having such an NZ coefficient can be easily manufactured.
  • optical properties such as retardation and NZ coefficient of the ⁇ / 4 layer are, for example, the thickness of the layer (B) formed in the second step; and the stretching conditions such as the stretching temperature, the stretching ratio and the stretching direction in the third step Can be adjusted.
  • the orientation angle ⁇ ( ⁇ / 4) of the ⁇ / 4 layer is preferably in the range of 100 ° ⁇ 20 ° (ie, in the range of 80 ° to 120 °), and in the range of 100 ° ⁇ 15 ° (ie, 85 °). It is more preferably in the range of ° to 115 °, particularly preferably in the range of 100 ° ⁇ 10 ° (that is, in the range of 90 ° to 110 °).
  • the orientation angle ⁇ ( ⁇ / 4) of the ⁇ / 4 layer is in the above range, it is combined with a general linearly polarizing film having a transmission axis in the width direction and an absorption axis in the longitudinal direction. A polarizing film can be easily realized.
  • the orientation angle ⁇ ( ⁇ / 4) of the ⁇ / 4 layer is in the above range, the function of suppressing coloring in the front direction and the tilt direction of the obtained circularly polarizing film can be improved.
  • the direction of the slow axis of the ⁇ / 4 layer can be adjusted by, for example, the stretching direction in the third step.
  • the thickness of the ⁇ / 4 layer is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 15 ⁇ m or less, more preferably 13 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the thickness of the ⁇ / 4 layer is not less than the lower limit of the above range, desired optical characteristics can be easily obtained.
  • the thickness of the ⁇ / 4 layer is not more than the upper limit of the above range, the thickness of the broadband wavelength film can be reduced.
  • the ⁇ / 2 layer and the ⁇ / 4 layer are preferably in direct contact with each other. Thereby, the thickness of the broadband wavelength film can be reduced.
  • the broadband wavelength film includes a thin film layer between the ⁇ / 2 layer and the ⁇ / 4 layer.
  • the thin film layer of the broadband wavelength film obtained by the manufacturing method described above is thicker than the adhesive layer used in the conventional manufacturing method in which the ⁇ / 2 layer and the ⁇ / 4 layer are bonded together after manufacturing each of the ⁇ / 2 layer and the ⁇ / 4 layer. Can be thinner than that.
  • the specific thickness of the thin film layer is preferably less than 2.0 ⁇ m, more preferably less than 1.8 ⁇ m, and particularly preferably less than 1.5 ⁇ m.
  • the lower limit of the thickness of the thin film layer is preferably as thin as possible, and may be, for example, 0.1 ⁇ m.
  • the broadband wavelength film may include an arbitrary layer in combination with the ⁇ / 2 layer, the ⁇ / 4 layer, and the thin film layer.
  • an adhesive layer or an adhesive layer for adhering the ⁇ / 2 layer and the ⁇ / 4 layer may be provided.
  • the total light transmittance of the broadband wavelength film is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
  • the light transmittance can be measured in a wavelength range of 400 nm to 700 nm using a spectrophotometer according to JIS K0115.
  • the haze of the broadband wavelength film is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and ideally 0%.
  • the haze can be measured at five locations using “turbidity meter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7361-1997, and the average value obtained therefrom can be adopted.
  • the thickness of the broadband wavelength film is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, particularly preferably 30 ⁇ m or more, preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less, and particularly preferably 90 ⁇ m or less. According to the manufacturing method described above, it is possible to easily manufacture such a thin broadband wavelength film.
  • a long circularly polarizing film can be manufactured using the broadband wavelength film manufactured by the manufacturing method described above.
  • Such a circularly polarizing film can be manufactured by a manufacturing method including a step of manufacturing a broadband wavelength film by the above-described manufacturing method and a step of bonding the broadband wavelength film and a long linear polarizing film. The pasting is usually performed so that the linearly polarizing film, the ⁇ / 2 layer, and the ⁇ / 4 layer are arranged in this order in the thickness direction. Moreover, you may use a contact bonding layer or an adhesion layer for bonding as needed.
  • the linearly polarizing film is a long film having an absorption axis, and has a function of absorbing linearly polarized light having a vibration direction parallel to the absorption axis and transmitting other polarized light.
  • the vibration direction of linearly polarized light means the vibration direction of the electric field of linearly polarized light.
  • the linearly polarizing film usually includes a polarizer layer, and a protective film layer for protecting the polarizer layer as necessary.
  • a polarizer layer for example, a film obtained by subjecting a suitable vinyl alcohol polymer film to appropriate treatment in an appropriate order and manner can be used.
  • vinyl alcohol polymers include polyvinyl alcohol and partially formalized polyvinyl alcohol.
  • the film treatment include dyeing treatment with dichroic substances such as iodine and dichroic dyes, stretching treatment, and crosslinking treatment.
  • the stretching treatment for producing the polarizer layer the film before stretching is stretched in the longitudinal direction, and therefore the obtained polarizer layer can exhibit an absorption axis parallel to the longitudinal direction of the polarizer layer.
  • This polarizer layer is capable of absorbing linearly polarized light having a vibration direction parallel to the absorption axis, and is particularly preferably excellent in polarization degree.
  • the thickness of the polarizer layer is generally 5 ⁇ m to 80 ⁇ m, but is not limited thereto.
  • any transparent film can be used as the protective film layer for protecting the polarizer 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, cyclic olefin resins, (meth) acrylic resins, and the like.
  • acetate resin, cyclic olefin resin, and (meth) acrylic resin are preferable in terms of low birefringence, and cyclic olefin resin is particularly preferable from the viewpoint of transparency, low moisture absorption, dimensional stability, lightness, and the like.
  • the linearly polarizing film can be manufactured, for example, by laminating a long polarizer layer and a long protective film layer. In bonding, an adhesive may be used as necessary.
  • the linearly polarizing film preferably has an absorption axis in the longitudinal direction of the linearly polarizing film.
  • Such a linearly polarizing film has a ⁇ / 2 layer having an orientation angle ⁇ ( ⁇ / 2) of 27.5 ° ⁇ 10 ° (ie, 17.5 ° to 37.5 °), and 100 ° ⁇ 20. It is preferable to produce a circularly polarizing film by laminating with a broadband wavelength film including a ⁇ / 4 layer having an orientation angle ⁇ ( ⁇ / 4) of ° (ie, 80 ° to 120 °).
  • the circularly polarizing film In the circularly polarizing film thus obtained, linearly polarized light in a wide wavelength range transmitted through the linearly polarizing film is converted into circularly polarized light by the broadband wavelength film. Therefore, the circularly polarizing film has a function of absorbing one of right circularly polarized light and left circularly polarized light and transmitting the remaining light in a wide wavelength range.
  • the circularly polarizing film may further include an arbitrary layer in combination with the linearly polarizing film and the broadband wavelength film.
  • the circularly polarizing film may include a protective film layer for suppressing damage.
  • the circularly polarizing film may include an adhesive layer or an adhesive layer for adhesion between the linearly polarizing film and the broadband wavelength film.
  • the circularly polarizing film When the circularly polarizing film is provided on a surface that can reflect light, reflection of external light can be effectively reduced.
  • the circularly polarizing film is useful in that reflection of external light can be effectively reduced in a wide wavelength range in the visible region. And since reflection of external light can be effectively reduced in such a wide wavelength range, the circularly polarizing film can suppress coloring due to an increase in the reflection intensity of light of some wavelengths.
  • This circularly polarizing film can obtain the above-described effects of reflection suppression and coloration suppression at least in the front direction, and more usually in the tilt direction.
  • the effects of reflection suppression and coloring suppression in the tilt direction can usually be obtained in all azimuth directions of the film main surface.
  • the circularly polarizing film can be used as a reflection suppressing film of an organic electroluminescence display device (hereinafter sometimes referred to as “organic EL display device” as appropriate). .
  • the organic EL display device includes a circularly polarizing film piece obtained by cutting out from a long circularly polarizing film.
  • the organic EL display device usually includes a circularly polarizing film piece on the display surface.
  • the circularly polarizing film may be provided in a liquid crystal display device.
  • a liquid crystal display device includes a circularly polarizing film piece obtained by cutting out from a long circularly polarizing film.
  • the liquid crystal display device includes a circularly polarizing film piece so that the surface on the linearly polarizing film side faces the viewing side, it is possible to prevent light incident from the outside of the device from being reflected inside the device and emitted to the outside of the device. As a result, glare and coloring of the display surface of the display device can be suppressed.
  • the liquid crystal display device includes a circularly polarizing film piece, a broadband wavelength film, a linearly polarizing film, and a liquid crystal cell of the liquid crystal display device arranged in this order from the viewing side, an image can be displayed in a circularly polarized light. . Therefore, it is possible to stably view the light emitted from the display surface with the polarized sunglasses, and the image visibility when wearing the polarized sunglasses can be enhanced.
  • an image display device includes a display panel including a display element such as an organic electroluminescence element and a liquid crystal cell.
  • This display panel includes a base material such as a glass base material in order to increase the mechanical strength of the display panel.
  • the substrate, the broadband wavelength film and the linearly polarizing film were usually provided in this order.
  • the polarizer layer of a linearly polarizing film generally tends to shrink in the in-plane direction in a high temperature environment.
  • a stress that tends to warp the display panel is generated in the display panel provided with the linearly polarizing film including the polarizer layer. Since warping of the display panel can cause deterioration in image quality, it is desirable to suppress it. With regard to this warp, it has been found that the warp tends to increase as the distance between the polarizer layer and the substrate of the display panel increases.
  • a broadband wavelength film manufactured as a co-stretched film as described above has a ⁇ / 2 layer and a ⁇ / 4 layer in direct contact with each other, or is provided between a ⁇ / 2 layer and a ⁇ / 4 layer.
  • the thin film layer can be made thin. Therefore, since the whole broadband wavelength film can be thinned, the distance between the polarizer layer and the substrate of the display panel can be reduced. Therefore, it is possible to suppress warping of the display panel.
  • the broadband wavelength film to be evaluated was placed on the stage of a phase difference meter (“AxoScan” manufactured by Axometrics). And the change of the polarization state of the polarized light which permeate
  • the multidirectional measurement was performed in each azimuth direction of 45 °, 90 °, 135 °, and 180 °, where the azimuth direction with the main surface of the broadband wavelength film was 0 °.
  • the measurement wavelength of the above measurement was 590 nm.
  • the in-plane retardation Re the thickness direction retardation Rth, the NZ coefficient and the orientation angle of each layer were determined by fitting calculation from the transmission polarization characteristics measured as described above.
  • the fitting calculation was performed by setting the three-dimensional refractive index and the orientation angle of each layer included in the broadband wavelength film as fitting parameters.
  • the attached software (“Multi-Layer Analysis” manufactured by Axometrics) of the phase difference meter (AxoScan) was used.
  • color difference (DELTA) E * ab when light was irradiated to a circularly-polarizing film from D65 light source was calculated in the front direction of the said circularly-polarizing film.
  • the color difference ⁇ E * ab the reflected light in the direction of the polar angle 0 ° and the azimuth angle 0 ° of the aluminum mirror not attached with the circularly polarizing film was used as a reference.
  • the surface reflection component actually generated on the surface of the circularly polarizing film is excluded from the calculation of the color difference ⁇ E * ab.
  • the value of the color difference ⁇ E * ab means that the smaller the value, the smaller the color change, which is preferable.
  • Example 1 (First step: production of layer (A)) A pellet-shaped norbornene resin (manufactured by Nippon Zeon Co., Ltd .; glass transition temperature 126 ° C.) was prepared as a resin having positive intrinsic birefringence and dried at 100 ° C. for 5 hours. The dried resin was supplied to an extruder, passed through a polymer pipe and a polymer filter, and extruded from a T-die onto a casting drum. The extruded resin was cooled to obtain a long unstretched film having a thickness of 160 ⁇ m. The obtained film before stretching was wound up on a roll and collected.
  • a pellet-shaped norbornene resin manufactured by Nippon Zeon Co., Ltd .; glass transition temperature 126 ° C.
  • the film before stretching was pulled out from the roll and continuously supplied to a tenter stretching machine. And the film before extending
  • the stretching angle formed by the stretching direction with respect to the longitudinal direction of the film before stretching was 90 °
  • the stretching temperature was 135 ° C.
  • the stretching ratio was 2.0 times.
  • the orientation angle of the obtained stretched film was 90 °
  • the obtained stretched film was wound up on a roll and collected.
  • a liquid composition containing a styrene-maleic anhydride copolymer (“Daylark D332” manufactured by Nova Chemical Co., glass transition temperature 130 ° C., oligomer component content 3% by weight) as a resin having a negative intrinsic birefringence was prepared.
  • This liquid composition contained methyl ethyl ketone as a solvent, and the concentration of the styrene-maleic anhydride copolymer in the liquid composition was 10% by weight.
  • the stretched film was pulled out from the roll, and the liquid composition was applied onto the stretched film. Thereafter, the coated liquid composition was dried to form a styrene-maleic anhydride copolymer layer (thickness 10 ⁇ m) as a layer (B) on the stretched film.
  • This obtained the multilayer film provided with a layer (A) and a layer (B).
  • the obtained multilayer film was wound up on a roll and collected.
  • the multilayer film was pulled out from the roll and continuously supplied to the tenter stretching machine. And it extended
  • the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was 15 °
  • the stretching temperature was 130 ° C.
  • the stretching ratio was 1.5 times.
  • a broadband wavelength film was obtained as a co-stretched film comprising a ⁇ / 2 layer obtained by stretching the layer (A) and a ⁇ / 4 layer obtained by stretching the layer (B).
  • the obtained broadband wavelength film was evaluated by the method described above.
  • Example 2 In the third step, the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was changed to 10 °. Except for the above, the same operations as in Example 1 were performed to produce and evaluate a broadband wavelength film and a circularly polarizing film.
  • Example 3 In the third step, the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was changed to 5 °. Except for the above, the same operations as in Example 1 were performed to produce and evaluate a broadband wavelength film and a circularly polarizing film.
  • a pellet-shaped norbornene resin (manufactured by Nippon Zeon Co., Ltd .; glass transition temperature 126 ° C.) was prepared as a resin having positive intrinsic birefringence and dried at 100 ° C. for 5 hours. The dried resin was supplied to an extruder, passed through a polymer pipe and a polymer filter, and extruded from a T-die onto a casting drum. The extruded resin was cooled to obtain a long unstretched film having a thickness of 110 ⁇ m. The obtained film before stretching was wound up on a roll and collected.
  • the film before stretching was pulled out from the roll and continuously supplied to a roll stretching machine. And by this roll extending machine, the film before extending
  • the stretching angle formed by the stretching direction with respect to the longitudinal direction of the film before stretching was 0 °
  • the stretching temperature was 135 ° C.
  • the stretching ratio was 1.9 times.
  • the orientation angle of the obtained stretched film was 0 °
  • the in-plane retardation Re was 350 nm
  • the thickness was 80 ⁇ m.
  • a wide-band wavelength film and a circularly polarizing film were produced and evaluated in the same manner as in Example 1 except that the stretched film thus obtained was used as the layer (A).
  • Example 2 In the third step, the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was changed to 0 °. In addition, the multilayer film in the third step was stretched by free uniaxial stretching using a roll stretching machine. Except for the above, the same operations as in Example 1 were performed to produce and evaluate a broadband wavelength film and a circularly polarizing film.
  • Example 3 In the third step, the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was changed to 45 °. Except for the above, the same operations as in Example 1 were performed to produce and evaluate a broadband wavelength film and a circularly polarizing film.
  • Example 4 In the third step, the stretching angle formed by the stretching direction with respect to the longitudinal direction of the multilayer film was changed to 60 °. Except for the above, the same operations as in Example 1 were performed to produce and evaluate a broadband wavelength film and a circularly polarizing film.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un procédé de production d'un film de longueur d'onde à large bande, le procédé de production comprenant, dans cet ordre, une première étape consistant à préparer une couche (A) qui est un film de résine qui présente un axe lent qui est orthogonal ou parallèle à la direction longitudinale, une deuxième étape consistant à obtenir un film multicouche en formant sur la couche (A) une couche (B) d'une résine qui présente une biréfringence intrinsèque négative, et une troisième étape consistant à obtenir un film de longueur d'onde à large bande qui présente une couche λ/2 et une couche λ/4 en étirant le film multicouche en diagonale. La couche λ/2 et la couche λ/4 du film de longueur d'onde à large bande répondent à la formule (1). Formule (1) : θ(λ/4)={45°+2×θ(λ/2)}±5° (θ(λ/2) est l'angle formé par l'axe lent de la couche λ/2 par rapport à la direction longitudinale du film de longueur d'onde à large bande, et θ(λ/4) est l'angle formé par l'axe lent de la couche λ/4 par rapport à la direction longitudinale du film de longueur d'onde à large bande.)
PCT/JP2019/017070 2018-04-27 2019-04-22 Film de longueur d'onde à large bande, procédé de production dudit film, et procédé de production d'un film à polarisation circulaire WO2019208512A1 (fr)

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KR1020207029811A KR20210004985A (ko) 2018-04-27 2019-04-22 광대역 파장 필름 및 그 제조 방법, 그리고 원 편광 필름의 제조 방법
CN201980026053.1A CN112105970B (zh) 2018-04-27 2019-04-22 宽带波长膜及其制造方法、以及圆偏振膜的制造方法
JP2020516349A JP7413997B2 (ja) 2018-04-27 2019-04-22 広帯域波長フィルムの製造方法、並びに円偏光フィルムの製造方法

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JP2018-087251 2018-04-27

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WO2022145171A1 (fr) * 2020-12-28 2022-07-07 日本ゼオン株式会社 Film multicouche, film optique et procédé de fabrication
WO2023074385A1 (fr) * 2021-10-25 2023-05-04 日本ゼオン株式会社 Film étiré multicouche et son procédé de production
WO2024004605A1 (fr) * 2022-06-30 2024-01-04 日本ゼオン株式会社 Procédé de fabrication de film à différence de phase et procédé de fabrication de plaque polarisante stratifiée
WO2024004601A1 (fr) * 2022-06-30 2024-01-04 日本ゼオン株式会社 Procédé de production d'un film à différence de phase et procédé de production d'une plaque à polarisation circulaire

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CN111308603A (zh) * 2020-04-09 2020-06-19 四川龙华光电薄膜股份有限公司 一种斜向光轴相位差膜

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WO2022145171A1 (fr) * 2020-12-28 2022-07-07 日本ゼオン株式会社 Film multicouche, film optique et procédé de fabrication
WO2023074385A1 (fr) * 2021-10-25 2023-05-04 日本ゼオン株式会社 Film étiré multicouche et son procédé de production
WO2024004605A1 (fr) * 2022-06-30 2024-01-04 日本ゼオン株式会社 Procédé de fabrication de film à différence de phase et procédé de fabrication de plaque polarisante stratifiée
WO2024004601A1 (fr) * 2022-06-30 2024-01-04 日本ゼオン株式会社 Procédé de production d'un film à différence de phase et procédé de production d'une plaque à polarisation circulaire

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JP7413997B2 (ja) 2024-01-16
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CN112105970A (zh) 2020-12-18
TW201945773A (zh) 2019-12-01
KR20210004985A (ko) 2021-01-13

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