WO2022210197A1 - Stratifié et procédé de fabrication de celui-ci - Google Patents

Stratifié et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2022210197A1
WO2022210197A1 PCT/JP2022/013674 JP2022013674W WO2022210197A1 WO 2022210197 A1 WO2022210197 A1 WO 2022210197A1 JP 2022013674 W JP2022013674 W JP 2022013674W WO 2022210197 A1 WO2022210197 A1 WO 2022210197A1
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Prior art keywords
laminate
film
protective film
base material
polymer
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PCT/JP2022/013674
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English (en)
Japanese (ja)
Inventor
絢子 加藤
浩成 摺出寺
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日本ゼオン株式会社
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Priority to JP2023511081A priority Critical patent/JPWO2022210197A1/ja
Publication of WO2022210197A1 publication Critical patent/WO2022210197A1/fr

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    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • 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
    • 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

Definitions

  • the present invention relates to a laminate comprising a base material that can be used as an optical film or the like and a protective film that protects the base material, and a method for producing the same.
  • Optical films are widely used as components of optical devices such as liquid crystal display devices and organic electroluminescence display devices. Examples include films used as substrates in devices. Specifically, it is common practice to form other layers on such a base material to obtain a component comprising a plurality of layers constituting a device.
  • Optical films are required to have good optical properties and high durability against heat in the usage environment. For example, even when subjected to a heat load such as heating at 200° C. for 10 minutes or heating at 145° C. for 60 minutes, it is desirable not to cause shape change such as shrinkage.
  • a crystalline resin particularly a resin containing a crystalline alicyclic structure-containing polymer, may be used as a material for such an optical film.
  • various treatments such as stretching and heat setting may be performed in order to adjust optical anisotropy, heat resistance and other various properties (for example, Patent Document 1 ⁇ 2).
  • the optical film When processing a crystalline resin film, wrinkles may occur on the surface, causing undesirable phenomena such as damage to the flatness of the film, which may reduce the quality of the product.
  • the optical film may not have sufficient heat resistance. For example, it may not be possible to suppress shape change when subjected to a heat load such as heating at 200° C. for 10 minutes or heating at 145° C. for 60 minutes.
  • an object of the present invention is to provide a base material that suppresses the occurrence of wrinkles, maintains flatness when used as a base material, and has high heat resistance, and a method for producing the same.
  • the base material As a measure for suppressing the generation of wrinkles and maintaining flatness when used as a base material, it is conceivable to make the base material a laminate with a protective film. As a result of investigations by the present inventors on this point, it was found that high wrinkle suppression and heat resistance can be obtained by adopting a substrate and a protective film that have a specific physical property relationship to form a laminate. It was found that such a laminate can be produced by laminating a specific pre-annealing base material and a pre-annealing protective film to form a pre-annealing laminate, which is then annealed in the state of the laminate. The inventors found that it can be obtained, and completed the present invention. That is, the present invention provides the following.
  • a laminate having a long shape comprising a substrate and a protective film provided on one surface of the substrate,
  • the substrate is a resin layer containing a crystalline alicyclic structure-containing polymer
  • a production method comprising: a step of forming a resin layer containing a cyclic structure-containing polymer; and a step of annealing the pre-annealed laminate.
  • the resin containing the crystalline alicyclic structure-containing polymer constituting the base material before annealing is a hydride of a ring-opening polymer of dicyclopentadiene; Method of manufacture as described.
  • a laminate that suppresses the occurrence of wrinkles, maintains flatness when used as a substrate, and can easily supply a substrate with high heat resistance at the time of use, and a method for producing the same are provided. be done.
  • FIG. 1 is a cross-sectional view schematically showing the laminate of the present invention.
  • the term "long-shaped" film refers to a film having a length of 5 times or more, preferably 10 times or more, of its width.
  • the upper limit of the length of the film is not particularly limited, and can be, for example, 100,000 times or less the width.
  • the adhesive is not only an adhesive in a narrow sense (an adhesive having a shear storage elastic modulus of 1 MPa to 500 MPa at 23 ° C. after energy beam irradiation or after heat treatment), but also shear storage at 23 ° C. Adhesives with an elastic modulus of less than 1 MPa are also included.
  • the terms “parallel”, “perpendicular” and “perpendicular” in the directions of the elements are within a range that does not impair the effects of the present invention, such as ⁇ 3°, ⁇ 2° or ⁇ 1°, unless otherwise specified. may contain an error within the range of
  • the laminate of the present invention comprises a substrate and a protective film provided on one surface of the substrate. That is, the laminate includes a substrate and a protective film as layers constituting the laminate.
  • the base material is a film for use as a component of optical devices such as display devices.
  • a protective film is a film that is attached to a substrate for the purpose of protecting the substrate, and that can be peeled off when the substrate is used for manufacturing a device or in any subsequent process.
  • the protective film may be provided in direct contact with the base material, it is usually provided on the base material via an adhesive layer. That is, the base material and the protective film are adhered via the adhesive layer, thereby forming a laminate in which the base material, the adhesive layer and the protective film layer are provided in this order.
  • FIG. 1 is a cross-sectional view schematically showing the laminate of the present invention.
  • the laminate 10 includes a base material 110 and a composite film 120 provided on one surface thereof, and the composite film includes a protective film 121 and an adhesive layer 122 .
  • the protective film is provided only on one of the front surface and the back surface of the substrate, but the present invention is not limited to this. A film may be provided.
  • the protective film 121 is a layer for exhibiting mechanical strength and other desired physical properties as a protective film, while the adhesive layer 122 exhibits the function of adhesion between the substrate 110 and the protective film 121. layer.
  • the adhesive layer 122 is generally thinner and more flexible than the protective film 121, and therefore does not substantially affect the mechanical strength of the composite film 120 as a whole with respect to the in-plane expansion and contraction.
  • the base material is a resin layer containing a crystalline alicyclic structure-containing polymer.
  • the resin may be particularly referred to as resin (a1) in order to distinguish it from common resins.
  • the resin that constitutes the protective film may be particularly referred to as resin (b1).
  • the base material may be a single-layer structure layer or a multi-layer structure layer consisting of a plurality of layers, but is usually a single-layer structure layer.
  • the protective film may also be a layer having a single layer structure, or a layer having a multi-layer structure consisting of a plurality of layers, but is usually a layer having a single layer structure.
  • E's is the storage modulus of the substrate at 180°C
  • E'p is the storage modulus of the protective film at 180°C.
  • elastic modulus means storage elastic modulus unless otherwise specified.
  • the value of E's/E'p is less than 1, preferably 0.95 or less, more preferably 0.90 or less. Although the lower limit of E's/E'p is not particularly limited, it can be 0.1 or more.
  • Each value of E's and E'p is not particularly limited, but can be, for example, 1.0 ⁇ 10 7 Pa or more and 1.0 ⁇ 10 9 Pa or less.
  • the elastic modulus is measured by peeling off the base material and the protective film of the laminate, using each as a sample film, and using a dynamic viscoelasticity measuring device (for example, manufactured by Hitachi High-Tech Science Co., Ltd., product name: DMA7100) at 180 ° C. It can be measured by stretching viscoelasticity measurement.
  • a dynamic viscoelasticity measuring device for example, manufactured by Hitachi High-Tech Science Co., Ltd., product name: DMA7100
  • Fs is the heat shrinkage rate of the base material in the longitudinal direction of the laminate at 180°C for 2 minutes
  • Fp is the heat shrinkage rate of the protective film in the laminate longitudinal direction at 180°C for 2 minutes
  • LB indicates the side length of the sample film before heating
  • LA indicates the side length of the sample film after heating.
  • a positive value of heat shrinkage indicates that the film shrinks due to heating
  • a negative value indicates that the film elongates due to heating.
  • Fs-Fp is the value of the difference between the percentages.
  • the value of Fs-Fp is -0.4% or more, preferably -0.3% or more, while it is 0.4% or less, preferably 0.3% or less.
  • Each value of Fs and Fp is not particularly limited, but can be, for example, -0.3% or more and 0.5% or less.
  • the long laminate comprises a base material that is a layer of the resin (a1) and a protective film, and the base material and the protective film have the above formulas (1) to When (2) is satisfied, the occurrence of wrinkles in the laminate can be suppressed, the laminate can be handled while maintaining its flatness, and the substrate can be easily manufactured as a substrate with high heat resistance. It can be done. Specifically, the curling of the laminate can be suppressed, so that the laminate can be conveyed in a state where it is not curled, and the 200 ° C. 10 minute substrate heat shrinkage rate of the obtained substrate and Physical properties, such as base material heat shrinkage at 145° C. for 60 minutes, which are required to be low as a product, can also be set to favorable low values.
  • the laminate of the present invention preferably has a small amount of curl.
  • the amount of curl was determined by cutting the laminate into a 50 mm ⁇ 50 mm square sample film under an environment of 23 ° C. (room temperature), placing it on a horizontal and flat surface, and raising the four corners of the sample film from the horizontal surface. It is obtained by measuring the amount (amount of curl) and calculating the average value of the four corners.
  • the amount of curl can be preferably 8.5 mm or less, more preferably 7.5 mm or less. Although the lower limit of curl amount is not particularly limited, it is ideally 0.0 mm.
  • the substrate is a layer of resin (a1), that is, a resin layer containing a crystalline alicyclic structure-containing polymer.
  • the base material can be a layer consisting only of the resin (a1). By using the resin (a1) as the base material, the base material can exhibit good mechanical strength, heat resistance, and moldability.
  • a polymer that "has crystallinity” refers to a polymer that has a melting point Tm. "Have a melting point Tm” means that the melting point can be observed with a differential scanning calorimeter (DSC).
  • a polymer having crystallinity may be simply referred to as a "crystalline polymer”.
  • a resin containing a polymer having crystallinity may be simply referred to as a “crystalline resin”.
  • the alicyclic structure-containing polymer is a polymer containing an alicyclic structure in the molecule. It is a polymer containing structures.
  • the alicyclic structure-containing polymer can be a polymer or a hydride thereof that can be obtained by a polymerization reaction using a cyclic olefin as a monomer.
  • One type of the alicyclic structure-containing polymer may be used alone, or two or more types may be used in combination at an arbitrary ratio.
  • Examples of the alicyclic structure possessed by the alicyclic structure-containing polymer include a cycloalkane structure and a cycloalkene structure. Among these, a cycloalkane structure is preferable because an optical film having excellent properties such as thermal stability can be easily obtained.
  • the number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. be. When the number of carbon atoms contained in one alicyclic structure is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.
  • the ratio of structural units having an alicyclic structure to all structural units is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more.
  • Heat resistance can be improved by increasing the ratio of structural units having an alicyclic structure in the alicyclic structure-containing polymer as described above.
  • the remainder other than structural units having an alicyclic structure is not particularly limited and can be appropriately selected according to the purpose of use.
  • Examples of the crystalline alicyclic structure-containing polymer include the following polymers ( ⁇ ) to ( ⁇ ). Among these, the polymer ( ⁇ ) is preferable as the crystalline alicyclic structure-containing polymer because a base material having excellent heat resistance can be easily obtained.
  • Polymer ( ⁇ ) A crystalline addition polymer of cyclic olefin monomers.
  • Polymer ( ⁇ ) A hydride or the like of polymer ( ⁇ ) having crystallinity.
  • the crystalline alicyclic structure-containing polymer includes a ring-opening polymer of dicyclopentadiene having crystallinity, and a hydride of a ring-opening polymer of dicyclopentadiene. It is more preferable to have crystallinity, and particularly preferable is a hydrogenated ring-opening polymer of dicyclopentadiene having crystallinity.
  • the ring-opening polymer of dicyclopentadiene means that the ratio of structural units derived from dicyclopentadiene to all structural units is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, More preferably, it refers to 100% by weight of polymer.
  • the hydride of the ring-opening polymer of dicyclopentadiene preferably has a high ratio of racemo dyads.
  • the ratio of the racemo diad of repeating units in the hydrogenated ring-opening polymer of dicyclopentadiene is preferably 51% or more, more preferably 70% or more, and particularly preferably 85% or more.
  • a high proportion of racemo dyads indicates high syndiotactic stereoregularity. Therefore, the melting point of the hydride of the ring-opening polymer of dicyclopentadiene tends to be higher as the ratio of the racemo diad is higher.
  • the ratio of racemo dyads can be determined based on the 13 C-NMR spectrum analysis described in the Examples below.
  • crystalline alicyclic structure-containing polymer a polymer obtained by the production method disclosed in International Publication No. 2018/062067 can be used.
  • the melting point Tm of the crystalline alicyclic structure-containing polymer is preferably 200°C or higher, more preferably 230°C or higher, and preferably 290°C or lower.
  • a crystalline polymer such as a crystalline alicyclic structure-containing polymer has a glass transition temperature Tg.
  • Tg glass transition temperature
  • the specific glass transition temperature Tg of the crystalline polymer is not particularly limited, it is usually 85°C or higher and usually 170°C or lower.
  • the glass transition temperature Tg and melting point Tm of the polymer can be measured by the following methods. First, the polymer is melted by heating, and the melted polymer is quenched with dry ice. Subsequently, using this polymer as a test sample, a differential scanning calorimeter (DSC) was used to measure the glass transition temperature Tg and melting point Tm of the polymer at a heating rate of 10° C./min (heating mode). measurable.
  • DSC differential scanning calorimeter
  • the weight-average molecular weight (Mw) of the crystalline polymer such as a crystalline alicyclic structure-containing polymer is preferably 1,000 or more, more preferably 2,000 or more, and preferably 1,000,000. 500,000 or less, more preferably 500,000 or less.
  • a crystalline polymer having such a weight-average molecular weight has an excellent balance between moldability and heat resistance.
  • the molecular weight distribution (Mw/Mn) of the crystalline polymer such as a crystalline alicyclic structure-containing polymer is preferably 1.0 or more, more preferably 1.5 or more, and preferably 4.0 or less. , more preferably 3.5 or less.
  • Mn represents the number average molecular weight.
  • a crystalline polymer having such a molecular weight distribution is excellent in moldability.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the crystalline polymer can be measured as polystyrene equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.
  • the proportion of the crystalline alicyclic structure-containing polymer in the resin (a1) is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
  • the ratio of the crystalline alicyclic structure-containing polymer can be 100% by weight or less.
  • the crystalline alicyclic structure-containing polymer contained in the resin (a1) does not have to be crystallized before manufacturing the base material.
  • the crystalline polymer contained in the base material is preferably crystallized, and preferably has a high degree of crystallinity.
  • a specific crystallinity range is preferably 20% or higher, more preferably 25% or higher, and particularly preferably 30% or higher.
  • the upper limit of the crystallinity is not particularly limited, it can be 95% or less.
  • the degree of crystallinity of a crystalline polymer can be measured by a density method, an X-ray diffraction method, or a measurement method using a differential scanning calorimeter.
  • the resin (a1) may contain any component in addition to the crystalline alicyclic structure-containing polymer.
  • optional ingredients include antioxidants; light stabilizers; waxes; nucleating agents; fluorescent brighteners; near-infrared absorber; lubricant; filler; and any polymer other than crystalline polymer;
  • arbitrary components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • the thickness of the substrate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 160 ⁇ m or less, more preferably 150 ⁇ m or less.
  • the resin (b1) i.e., the resin constituting the protective film in the protective film, may have a resin layer containing a crystalline polymer from the viewpoint of easily obtaining a protective film having the specific physical properties described above. preferable.
  • the material constituting the protective film in the protective film can be a material different from the resin (a1) usually constituting the base material. Examples of such materials include a resin capable of exhibiting a lower storage elastic modulus than the one employed as a component of the base material among the examples of the resin (a1) described above, and a polymer containing an alicyclic structure having crystallinity. Resins, including crystalline polymers other than coalescence, and other materials are included.
  • Examples of the crystalline polymer that constitutes the resin (b1) include, among the examples of the polymer that constitutes the resin (a1) described above, a polymer different from that employed as a component of the base material. mentioned.
  • crystalline polymer constituting the resin (b1) include styrenic polymers (e.g., homopolymers of styrene or styrene derivatives or copolymers thereof with other polymerizable monomers); Cellulosic polymers such as triacyl cellulose; Polyolefins such as polyethylene and polypropylene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyarylene sulfides such as polyphenylene sulfide; Polyvinyl alcohol; polysulfone; polyarylsulfone; polyvinyl chloride; acrylic polymers such as polymethyl methacrylate and polyacrylonitrile; polyimide; These polymers may be homopolymers or copolymers.
  • styrenic polymers e.g., homopolymers of styrene or styrene derivatives or copolymers thereof with other polymerizable
  • examples of polystyrene-based polymers having crystallinity include those described in JP-A-2011-118137.
  • the resin (b1) may contain optional components in addition to the polymer.
  • optional components that can be contained in the resin (b1) include the same components as examples of optional components that can be contained in the resin (a1).
  • the resin (b1) may contain a polymer singly or in combination of two or more at any ratio.
  • the proportion of the polymer in 100% by weight of the resin (b1) is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 85% by weight or more, and is usually 100% by weight or less. may be
  • the glass transition temperature of the resin (b1) is preferably 60°C or higher, more preferably 70°C or higher, and preferably 180°C or lower, more preferably 170°C or lower.
  • the glass transition temperature of the resin (b1) is at least the lower limit, the heat resistance of the laminate can be effectively improved.
  • the glass transition temperature is equal to or lower than the upper limit, moldability can be improved.
  • the surface of the protective film on the side in contact with the adhesive layer may be subjected to surface treatment such as corona treatment or plasma treatment. That is, one surface of the protective film can be surface-treated and an adhesive layer can be formed on the surface.
  • surface treatment such as corona treatment or plasma treatment. That is, one surface of the protective film can be surface-treated and an adhesive layer can be formed on the surface.
  • the thickness of the protective film in the laminate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 150 ⁇ m or less, more preferably 140 ⁇ m or less.
  • the protective film in the laminate of the present invention is a layer of a resin containing a crystalline polymer
  • the polymer constituting the protective film may be crystallized with a degree of crystallinity above a certain level.
  • a specific crystallinity range is preferably 20% or higher, more preferably 25% or higher, and particularly preferably 30% or higher.
  • the upper limit of the crystallinity is not particularly limited, it can be 95% or less.
  • Adhesive layer When the laminate of the present invention is provided with an adhesive layer, examples of adhesives constituting the adhesive layer include those using various polymers as base polymers. Examples of such base polymers include acrylic polymers, urethane polymers, polyester polymers, rubber polymers, epoxy polymers, and silicone polymers. In addition, the adhesive may contain optional components such as a polymerization initiator, a curing agent, an ultraviolet absorber, a colorant, and an antistatic agent in combination with the base polymer. Adhesives include adhesives (pressure sensitive adhesives).
  • a commercially available product can be used as the adhesive.
  • the adhesive layer can be constructed by using them.
  • the adhesive layer may have a single layer structure or a multilayer structure.
  • the thickness of the adhesive layer is not particularly limited, and can be in the range of, for example, 3 ⁇ m to 30 ⁇ m, such as 5 ⁇ m to 20 ⁇ m.
  • the laminate of the invention can be produced by any method. From the viewpoint of easily producing a laminate that satisfies the requirements defined by formulas (1) and (2), the laminate of the present invention can be produced by a production method including the following steps (1) and (2). preferable.
  • the manufacturing method will be described below as a method for manufacturing the laminate of the present invention.
  • Step (1) A step of laminating the pre-annealed base material and the pre-annealed protective film to obtain a pre-annealed laminate comprising the pre-annealed base material and the pre-annealed protective film.
  • Step (2) A step of annealing the pre-annealed laminate.
  • Examples of the material of the pre-annealing base material used in step (1) are the same as those listed above as examples of the resin (a1), which is the material constituting the base material of the laminate of the present invention.
  • the pre-annealed substrate and pre-annealed protective film may have different storage modulus and thermal shrinkage than the substrate and protective film in the laminate, they are at this point represented by formulas (1)-(2) above. does not have to be satisfied.
  • the method for preparing the base material before annealing is not particularly limited, and it can be prepared by any film manufacturing method.
  • the substrate before annealing can be prepared by employing a known molding method such as a melt extrusion method and molding the resin (a1) into a long film shape.
  • a commercially available product may be used as the base material before annealing.
  • a film obtained by molding the resin (a1) by a molding method such as a melt extrusion method, or a commercially available film of the resin (a1) can be used as it is as a base material before annealing.
  • these films may be used as raw films, optionally subjected to any treatment, and then used as the base material before annealing.
  • a raw film may be subjected to a process of stretching to obtain a film having desired retardation, dimensions and other properties, which may be used as a pre-annealing substrate.
  • the stretching may be followed by a step of promoting crystallization of the resin (a1).
  • the stretching direction there are no restrictions on the stretching direction, and examples include the longitudinal direction, width direction, and oblique direction.
  • the oblique direction means a direction perpendicular to the thickness direction and neither parallel nor perpendicular to the width direction.
  • the stretching direction may be one direction or two or more directions. Therefore, as the stretching method, for example, a method of uniaxially stretching the original film in the longitudinal direction (longitudinal uniaxial stretching method), a method of uniaxially stretching the original film in the width direction (horizontal uniaxial stretching method), etc. Uniaxial stretching method.
  • a simultaneous biaxial stretching method in which the original film is stretched in the longitudinal direction and in the width direction at the same time a sequential biaxial stretching method in which the original film is stretched in one of the longitudinal direction and the width direction and then stretched in the other direction, etc.
  • Examples of modes of uniaxial stretching include fixed-end uniaxial stretching and free-end uniaxial stretching.
  • the fixed-end uniaxial stretching method is a stretching method in which the ends in the direction perpendicular to the stretching direction of the raw film are fixed, and the free-end uniaxial stretching method fixes the ends in the direction perpendicular to the stretching direction of the raw film. It is a drawing method performed without stretching.
  • the longitudinal uniaxial stretching method is often free-end uniaxial stretching, and the transverse uniaxial stretching method is often fixed-end uniaxial stretching.
  • the draw ratio can be adjusted as appropriate so that the substrate in the laminate has desired retardation, dimensions and other properties. Specifically, it is preferably 1-fold or more, more preferably 1.01-fold or more, preferably 15-fold or less, more preferably 11-fold or less.
  • the stretching is biaxial stretching, it is preferable that the area ratio, that is, the product of the stretching ratios in two directions is within such a range.
  • the stretching temperature is preferably "Tg + 5°C” or higher, more preferably “Tg + 10°C” or higher, preferably “Tg + 100°C” or lower, more preferably “Tg + 90°C” or lower.
  • Tg represents the glass transition temperature of the polymer being stretched.
  • the stretching temperature is equal to or higher than the lower limit of the above range, the original film can be sufficiently softened and stretched uniformly.
  • the stretching temperature is equal to or lower than the upper limit of the above range, it is possible to suppress the hardening of the original film due to the progress of crystallization of the polymer, so that the stretching can be performed smoothly, and the stretching causes a large birefringence. can be expressed.
  • usually the haze of the resulting substrate can be reduced to increase transparency.
  • the crystallization promotion step can be performed by heating the film after the stretching step. Such heating can be done while the film dimensions are controlled and maintained at the stretched dimensions, or by shrinking the stretched dimensions by a controlled fraction.
  • the ratio of dimensional change when the film is shrunk is preferably 0.90 times or more and less than 1 time.
  • the product of the area magnification that is, the magnification of the dimensional change in the two directions is preferably within such a range.
  • the reduction ratio is the ratio of the size after reduction to the size before reduction being 1.
  • the heating temperature in the crystallization promoting step is usually higher than the glass transition temperature Tg of the crystalline polymer and lower than the melting point Tm of the crystalline polymer. More specifically, the heating temperature is preferably Tg° C. or higher, more preferably Tg+10° C. or higher, and preferably Tm ⁇ 10° C. or lower, more preferably Tm ⁇ 20° C. or lower. By setting the heating temperature within this range, crystallization of the crystalline polymer can be rapidly progressed while suppressing white turbidity due to progress of crystallization.
  • the heat treatment time is preferably 1 second or longer, more preferably 5 seconds or longer, and preferably 30 minutes or shorter, more preferably 15 minutes or shorter.
  • Pre-annealing protective film and adhesive layer Examples of the material of the pre-annealing protective film used in step (1) are the same as those listed above as examples of the resin (b1), which is the material constituting the protective film of the laminate of the present invention.
  • the method for preparing the protective film before annealing is not particularly limited, and it can be prepared by any film manufacturing method.
  • a pre-annealing protective film can be prepared by employing a known molding method such as a melt extrusion method and molding the resin (b1) into a long film shape.
  • a commercially available product may be used as the pre-annealing protective film.
  • the pre-annealing protective film may be a stretched film, but may also be a film that has not been stretched.
  • an adhesive layer may be provided on the surface of the protective film before annealing to form a composite film.
  • the adhesive layer can be formed by applying an adhesive to the surface of the pre-annealing protective film.
  • the applied adhesive layer can be further subjected to a curing treatment as necessary to obtain an adhesive layer having desired physical properties.
  • the adhesive layer can be provided by transferring a layer of an adhesive film to the surface of the protective film before annealing.
  • Examples of coating methods for coating the adhesive include wire bar coating, spray coating, roll coating, gravure coating, die coating, curtain coating, slide coating, and extrusion coating. be done.
  • Examples of adhesive curing treatments include drying treatments, examples of which include vacuum drying, heat drying, and combinations thereof.
  • the pre-annealing base material is a resin layer containing a crystalline alicyclic structure-containing polymer
  • the polymer constituting the pre-annealing base material can be crystallized with a degree of crystallinity above a certain level.
  • a specific crystallinity range is preferably 20% or higher, more preferably 25% or higher, and particularly preferably 30% or higher.
  • the upper limit of the crystallinity is not particularly limited, it can be 95% or less.
  • the pre-annealing protective film is a layer of a resin containing a crystalline polymer
  • the polymer constituting the pre-annealing protective film can be crystallized with a degree of crystallinity above a certain level.
  • a specific crystallinity range is preferably 20% or higher, more preferably 25% or higher, and particularly preferably 30% or higher.
  • the upper limit of the crystallinity is not particularly limited, it can be 95% or less.
  • the storage elastic modulus and thermal shrinkage of the pre-annealed base material and pre-annealed protective film are such that the storage elastic modulus and thermal shrinkage of the base material and protective film in the product laminate are the desired values described above. and preparation conditions can be adjusted accordingly.
  • the storage elastic modulus and thermal shrinkage of the pre-annealed base material and the pre-annealed protective film and their ratios themselves are not particularly limited, but values within the following ranges are preferred.
  • the storage elastic modulus pE's at 180°C of the base material before annealing and the storage elastic modulus pE'p at 180°C of the protective film before annealing are in a specific range of their ratio pE's/pE'p. is preferred.
  • the value of pE's/pE'p is preferably less than 1, more preferably 0.95 or less, even more preferably 0.90 or less.
  • the lower limit of pE's/pE'p is not particularly limited, it can be 0.1 or more.
  • Each value of pE's and pE'p is not particularly limited, but can be, for example, 1.0 ⁇ 10 7 Pa or more and 1.0 ⁇ 10 9 Pa or less.
  • the thermal shrinkage rate pFs (%) of the base material before annealing in the longitudinal direction of the laminate at 180 ° C. 2 minutes and the thermal shrinkage rate pFp (%) of the protective film in the longitudinal direction of the laminate at 180 ° C. 2 minutes before annealing are
  • the difference pFs-pFp is preferably a value within a specific range.
  • the value of pFs ⁇ pFp is preferably ⁇ 1.0% or more, more preferably ⁇ 0.8% or more, while preferably 1.0% or less, more preferably 0.8% or less. be.
  • Each value of pFs and pFp is not particularly limited, but can be, for example, -0.3% or more and 1.0% or less.
  • the laminate of the present invention comprising a substrate and a protective film that satisfy the above formulas (1) and (2) can be easily manufactured. can be manufactured to
  • Step (1) can be carried out by stacking a long pre-annealed base material and a pre-annealed protective film on top of each other with their longitudinal directions aligned, and pressurizing them. Pressurization can be performed continuously by a device such as a nip roll that presses a long film.
  • the protective film before annealing constitutes a composite film with an adhesive layer
  • the surface of the composite film on the side of the adhesive layer is laminated to the surface of the substrate before annealing, thereby providing the substrate before annealing and the protection before annealing.
  • a pre-annealed laminate in which the film is bonded via an adhesive layer can be obtained.
  • Step (2) The annealing treatment in step (2) can be performed by heating the pre-annealed laminate while restraining it in at least one of its in-plane directions.
  • the pre-annealed laminate can be constrained, for example, by constraining the pre-annealed laminate in its longitudinal direction, width direction, or both directions.
  • Annealing treatment involving restraint in the longitudinal direction of the pre-annealed laminate can be performed using, for example, a roll support type film dryer.
  • the roll support type dryer is equipped with an upstream nip roll, a downstream nip roll, and an oven provided between them, and by adjusting the peripheral speed ratio between the upstream nip roll and the downstream nip roll, A long film is transported under tension, passed through the oven in between, and guided by only unconstrained rolls that support the film from below in the oven. It is an apparatus capable of heating the film without restraint in the width direction of the film.
  • Annealing treatment can be performed by conveying the pre-annealed laminate in a direction along its longitudinal direction, continuously introducing it into a dryer, and heating it.
  • the tension applied to the film is preferably 3 N/m or more and 25 N/m or less.
  • Annealing treatment involving restraint in the longitudinal direction of the pre-annealed laminate can be performed, for example, using an apparatus having the same structure as the apparatus used for stretching. More specifically, a device such as a tenter-type stretching machine that can control both the longitudinal and width dimensions of a long film and continuously heat the film is used, and the film is stretched in the stretching machine. Annealing can be performed by conveying and heating the film while it is gripped and the dimensions in the longitudinal and width directions of the film are maintained unchanged.
  • the heating temperature in the annealing treatment is usually higher than the glass transition temperature Tg of the crystalline polymer and lower than the melting point Tm of the crystalline polymer. More specifically, the heating temperature is preferably Tg+20° C. or higher, more preferably Tg+40° C. or higher, and preferably Tm ⁇ 20° C. or lower, more preferably Tm ⁇ 40° C. or lower.
  • the heating time is preferably 5 seconds or longer, more preferably 10 seconds or longer, while preferably 30 minutes or shorter, more preferably 15 minutes or shorter.
  • the pre-annealed base material which is a resin film containing a crystalline alicyclic structure-containing polymer
  • the flatness is likely to be impaired, and such a phenomenon is , especially when the pre-annealed substrate is stretched at a high areal ratio prior to annealing.
  • simply providing the protective film does not reduce the damage to the flatness, and the resulting substrate may not exhibit sufficient heat resistance due to the annealing treatment.
  • the materials of the pre-annealed base material and the pre-annealed protective film and the treatment conditions prior to the annealing treatment are changed to the above formulas (1) and ( A laminated body having good flatness and heat resistance can be easily produced by preparing a laminated body before annealing in a state appropriately adjusted so as to satisfy 2) and subjecting this to an annealing treatment.
  • the method for producing a laminate of the present invention may further include optional steps in addition to the steps (1) and (2).
  • optional steps include a step of forming an additional layer such as a conductive layer on the surface of the substrate included in the laminate, and a step of winding the laminate to obtain a roll.
  • the laminate of the present invention can be used as it is as a constituent element of an optical device, or a constituent element of other electronic and electrical parts that are not limited to optical devices.
  • the protective film can be peeled off from the laminate of the present invention, and the remaining substrate can be used as a component of optical devices or other electronic and electrical components.
  • components of optical devices include substrate films, retardation films, polarizing films, and light diffusion sheets in display devices such as liquid crystal display devices and organic electroluminescence display devices and other devices.
  • the substrate film can be used particularly effectively as a touch panel substrate film and a flexible display substrate film by taking advantage of its flexibility.
  • it is preferably used as a constituent element of light-condensing sheets, optical cards, and the like.
  • Examples of other electronic components and components of electrical components include films for flexible printed circuit boards, film capacitors, high frequency circuit board films, antenna substrate films, battery separator films, and release films.
  • the laminate can maintain good flatness, undergo little change in shape due to heat load, and curl less in a high-temperature environment. Therefore, it can be used particularly useful as a base material for manufacturing an optical element (for example, a conductive layer included in a touch panel) whose formation process is performed at high temperature.
  • an optical element for example, a conductive layer included in a touch panel
  • the substrate in the laminate of the present invention can also be used particularly effectively as a retardation layer after peeling from the laminate.
  • the substrate in the laminate of the present invention can further be used as a protective film for protecting a polarizer, taking advantage of its high flatness and heat resistance.
  • Glass transition temperature Tg and melting point Tm Glass transition temperature Tg and melting point Tm
  • DSC differential scanning calorimeter
  • the thickness of the film was measured using a contact thickness gauge (Code No. 543-390, manufactured by MITUTOYO).
  • Thermal shrinkage rate In the measurement of the thermal shrinkage rate (pFs and pFp) of the pre-annealed base material and the pre-annealed protective film, each film was cut out in an environment of 23 ° C. (room temperature) to obtain a square sample film with a size of 120 mm ⁇ 120 mm. .
  • the thermal shrinkage rate of the protective film was measured in the state of the composite film with the adhesive layer.
  • Each side of the square of the sample film was oriented parallel to the longitudinal direction or width direction of the film.
  • This sample film was heated under predetermined heating conditions, then cooled to 23°C (room temperature), and then the lengths of the four sides of the sample film were measured.
  • Two heating conditions 145° C. for 60 minutes and 200° C. for 10 minutes, were used for the measurement of the base material before annealing and the protective film before annealing.
  • the heating conditions were 180° C. for 2 minutes. Further measurements on the substrate after annealing were performed at 145° C. for 60 minutes and 200° C. for 10 minutes.
  • the thermal shrinkage rate of the sample film was calculated based on the following formula (I).
  • LB indicates the side length of the sample film before heating
  • LB is 120 mm in this measurement
  • LA indicates the side length of the sample film after heating.
  • Thermal shrinkage rate (%) [(L B -L A )/L B ] ⁇ 100 (I)
  • a positive value for the thermal shrinkage ratio indicates that the film shrinks due to heating, and a negative value indicates that the film elongates due to heating.
  • the average value of the shrinkage rate of the two sides along the transport direction of the film (that is, the longitudinal direction of the long film) is taken as the heat shrinkage rate in the transport direction of the film, that is, the heat shrinkage rate in the longitudinal direction of the long film. adopted. Also, the average value of the heat shrinkage rates of the two sides along the width direction of the film was adopted as the heat shrinkage rate in the width direction of the long film. Furthermore, for the base material and protective film after annealing, the value of Fs - Fp was obtained from the heat shrinkage rate Fs (%) in the longitudinal direction of the base material and the heat shrinkage rate Fp (%) in the longitudinal direction of the protective film. .
  • the annealed laminate was cut into a square piece of 300 mm ⁇ 300 mm, and the substrate and the protective film were peeled off.
  • the base material was spread on a horizontal and flat desk, and the smoothness of the surface of the base material was visually evaluated according to the following criteria.
  • Good No corrugated sheet-like wrinkles with streaks along the conveying direction, practically no problem.
  • Acceptable Slight corrugated sheet-like wrinkles having streaks along the conveying direction, but no problem in practical use.
  • Poor There are corrugated sheet-like wrinkles with streaks along the conveying direction, which poses a practical problem.
  • crystallinity The crystallinity of the base material before annealing and the protective film before annealing was measured by the following method, using these as sample films cut into appropriate sizes.
  • the density of the sample film was measured using a helium gas replacement type dry automatic density meter "AccuPyc 1340" (manufactured by Micromeritics). About 3 g of the sample film was cut into strips having a width of 30 mm or less, rolled into a container of 10 cm 3 , and measured while maintaining the temperature at 25°C. Density was determined from 10 replicate measurements.
  • D (g/cm 3 ) represents the determined density of the sample film. Da indicates the complete amorphous density (g/cm 3 ) of the polymer forming the sample film. Db indicates the full crystal density (g/cm 3 ) of the polymer forming the sample film.
  • 53 J/g was used as the melting enthalpy (J/g) when the degree of crystallinity was 100%.
  • Crystallinity of polyamide film The crystallinity of the sample film, which is a polyamide film, was measured by the X-ray diffraction method.
  • a solution was prepared by dissolving 0.014 parts of a tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 parts of toluene. To this solution, 0.061 part of a 19% diethylaluminum ethoxide/n-hexane solution was added and stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was placed in a pressure-resistant reactor to initiate ring-opening polymerization reaction. Thereafter, the mixture was allowed to react for 4 hours while maintaining the temperature at 53° C. to obtain a solution of a ring-opening polymer of dicyclopentadiene. The obtained ring-opening polymer of dicyclopentadiene had a number average molecular weight (Mn) and a weight average molecular weight (Mw) of 8,750 and 28,100, respectively. was 3.21.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • a filter aid ("Radiolite (registered trademark) #1500” manufactured by Showa Kagaku Kogyo Co., Ltd.) is added, and a PP pleated cartridge filter (“TCP-HX” manufactured by ADVANTEC Toyo Co., Ltd.) is used as an adsorbent.
  • TCP-HX PP pleated cartridge filter
  • the hydride contained in the reaction solution and the solution were separated using a centrifugal separator and dried under reduced pressure at 60° C. for 24 hours to obtain a crystalline hydride of a ring-opening polymer of dicyclopentadiene 28. 5 copies were obtained.
  • This hydride had a hydrogenation rate of 99% or more, a glass transition temperature Tg of 93° C., a melting point (Tm) of 267° C., and a ratio of racemo diad of 89%.
  • An antioxidant tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane was added to 100 parts of the hydride of the resulting ring-opening polymer of dicyclopentadiene. ; After mixing 1.1 parts of "Irganox (registered trademark) 1010" manufactured by BASF Japan Co., Ltd., a twin-screw extruder equipped with four die holes with an inner diameter of 3 mm ⁇ (product name "TEM-37B", manufactured by Toshiba Machine Co., Ltd. ).
  • a mixture of a hydride of a ring-opening polymer of dicyclopentadiene and an antioxidant is formed into strands by hot-melt extrusion molding, and then chopped with a strand cutter to form a pellet-shaped crystalline resin (resin A). got
  • the operating conditions of the twin-screw extruder were as follows.
  • the extruded film was supplied to a simultaneous biaxial stretching machine and subjected to a simultaneous biaxial stretching process.
  • the stretching ratio was 3.5 times in the longitudinal direction and 2.9 times in the width direction, and the stretching temperature was 115°C.
  • the film was subjected to a crystallization promotion step. To promote crystallization, the film is held in a stretching machine and heated to a temperature of 240°C for 15 seconds to reduce the film dimensions to 0.94 times in the longitudinal direction and 0.96 times in the width direction. It was done by After completion of the crystallization promoting step, the film was cooled to a temperature of 100° C.
  • a commercially available SPS (syndiotactic polystyrene) film having a thickness of 35 ⁇ m (manufactured by Kurashiki Boseki Co., Ltd., product name “Oidys (registered trademark) HNL”) was pulled out from a film roll, and one side was subjected to discharge treatment (corona treatment).
  • a corona treatment apparatus (manufactured by Kasuga Denki Co., Ltd.) was used for the discharge treatment, and the discharge conditions were an output of 500 W, an electrode length of 1.35 m, and a conveying speed of 10 m/min.
  • an acrylic pressure-sensitive adhesive (Fujimori Kogyo "Mastak series") as an adhesive was applied using a die coater so that the dry film thickness was 10 ⁇ m, The adhesive was dried by passing through a drying oven at 100°C.
  • a composite film having a protective film, which is an SPS film, and an adhesive layer formed on one surface thereof was obtained as a long film with a width of 1100 mm.
  • the heat shrinkage rate and crystallinity of the pre-annealed protective film were measured.
  • the pre-annealed laminate obtained in (1-3) was conveyed in the direction along its longitudinal direction, continuously introduced into a dryer, and subjected to annealing by heating.
  • a dryer a roll support type dryer was used. This dryer includes an upstream nip roll, a downstream nip roll, and an oven provided between them.
  • tension is applied to the film between the nip rolls.
  • the oven the film is conveyed in a state in which the film It is a device that can heat a film without restraint in the width direction.
  • the heating temperature in the annealing treatment was 200° C.
  • the heating time was 2 minutes
  • the transfer tension was 13N.
  • Example 2 A laminate was obtained and evaluated in the same manner as in Example 1 except for the following changes. - In the preparation of the composite film containing the protective film before annealing in (1-2), instead of the 35 ⁇ m thick SPS film, a 75 ⁇ m thick SPS film (manufactured by Kurashiki Boseki Co., Ltd., product name “Oidys (registered trademark) CN”) was used.
  • Example 3 A laminate was obtained and evaluated in the same manner as in Example 1 except for the following changes. - In the preparation of the base material before annealing in (1-1), the dimensions of the T-die opening and the operating conditions of the molding machine were changed, and the thickness of the extruded film was changed to 430 ⁇ m. Further, the draw ratio was changed from 3.5 times to 2.6 times in the longitudinal direction and from 2.9 times to 3.3 times in the width direction. However, the reduction ratio in the crystallization promoting step is the same as in Example 1. The width direction dimension of the obtained pre-annealed base material is also 1100 mm, which is the same as in Example 1.
  • Example 4 A laminate was obtained and evaluated in the same manner as in Example 1 except for the following changes. - In the preparation of the base material before annealing in (1-1), the size of the T-die opening and the operating conditions of the molding machine were changed, and the thickness of the extruded film was changed to 1000 ⁇ m.
  • Example 5 (5-1. Base material before annealing) Resin A produced in Production Example 1 was molded using a hot-melt extrusion film molding machine equipped with a T-die to obtain a long extruded film (thickness: 48 ⁇ m) with a width of approximately 1,350 mm.
  • the extruded film was supplied to a transverse stretching machine using a tenter method and subjected to fixed-end uniaxial stretching.
  • the draw ratio was 1.0 times in the longitudinal direction and 1.35 times in the width direction.
  • the extruded film was preheated at a temperature of 120°C prior to stretching and then stretched at a stretching temperature of 140°C.
  • the film was subjected to a crystallization promotion step. Acceleration of crystallization was carried out by holding the film in a stretching machine, conveying the film in a state in which the film dimension was maintained without changing, and heating the film to a temperature of 160° C. for 30 seconds. After completion of the crystallization promoting step, the film was cooled to a temperature of 100° C.
  • an acrylic pressure-sensitive adhesive (Fujimori Kogyo "Mastak series") as an adhesive was applied using a die coater so that the dry film thickness was 10 ⁇ m, The adhesive was dried by passing through a drying oven at 100°C. As a result, a composite film having a protective film that is a PET film and an adhesive layer formed on one surface thereof was obtained as a long film with a width of 1100 mm. The thermal shrinkage rate and crystallinity of the obtained pre-annealed protective film were measured.
  • the pre-annealed laminate obtained in (5-3) was conveyed in the direction along its longitudinal direction, continuously introduced into a dryer, and subjected to annealing by heating.
  • a transverse stretching machine was used as the drying machine, and the film was held in the stretching machine, and the film was conveyed and heated while the dimensions in the longitudinal direction and the width direction of the film were kept unchanged.
  • the heating temperature in the annealing treatment was 170° C., and the heating time was 5 minutes. As a result of such annealing treatment, a laminate including the substrate and the protective film was obtained.
  • the laminate obtained in (5-4) was evaluated for the elastic modulus of each layer, the thermal shrinkage of each layer, the crystallinity of each layer, the smoothness of the surface, and the amount of curl.
  • Example 6 A laminate was obtained and evaluated in the same manner as in Example 5 except for the following changes. - In the preparation of the base material before annealing in (5-1), the dimensions of the T-die opening and the operating conditions of the molding machine were changed, and the thickness of the extruded film was changed to 42 ⁇ m. Furthermore, the draw ratio in the width direction was changed from 1.35 times to 1.2 times (longitudinal direction was unchanged at 1.0 times). However, the reduction ratio in the crystallization promoting step is the same as in Example 5. The width direction dimension of the obtained pre-annealed base material is also 1100 mm, which is the same as in Example 1.
  • Example 1 A laminate was obtained and evaluated in the same manner as in (1-1) and (1-3) to (1-5) of Example 1, except for the following changes. ⁇ In (1-3), the composite film containing the protective film before annealing was used instead of the one obtained in (1-2) in Example 5 (5-2).
  • Example 2 A laminate was obtained by the same operation as in Example 1, except for the following changes. ⁇ In the preparation of the composite film containing the protective film before annealing in (1-2), instead of the SPS film with a thickness of 35 ⁇ m, a commercially available alicyclic structure-containing polymer film (manufactured by Nippon Zeon Co., Ltd., trade name “ ZeonorFilmTM ZF16”, thickness 146 ⁇ m) was used.
  • a commercially available alicyclic structure-containing polymer film manufactured by Nippon Zeon Co., Ltd., trade name “ ZeonorFilmTM ZF16”, thickness 146 ⁇ m
  • the extruded film was heat-treated using a roll support type dryer.
  • the heating temperature was 180° C., and the heating time was 5 minutes.
  • Discharge treatment (corona treatment) was performed on one side of the heat-treated film.
  • a corona treatment apparatus manufactured by Kasuga Denki Co., Ltd. was used for the discharge treatment, and the discharge conditions were an output of 500 W, an electrode length of 1.35 m, and a conveying speed of 10 m/min.
  • an acrylic pressure-sensitive adhesive (Fujimori Kogyo "Mastak series") as an adhesive was applied using a die coater so that the dry film thickness was 10 ⁇ m, The adhesive was dried by passing through a drying oven at 100°C. As a result, a composite film having a protective film made of a polyamide film and an adhesive layer formed on one surface thereof was obtained as a long film with a width of 1100 mm. The thermal shrinkage rate and crystallinity of the obtained pre-annealed protective film were measured.
  • Example 4 A laminate was obtained and evaluated in the same manner as in Example 1 except for the following changes. - In the preparation of the composite film containing the pre-annealed protective film in (1-2), the same substrate as the pre-annealed substrate obtained in (1-1) was used in place of the SPS film having a thickness of 35 ⁇ m. That is, in (1-2), a long composite film comprising the pre-annealed substrate obtained in (1-1) and an adhesive layer formed on one surface thereof is prepared and used. (1-3) and subsequent steps were performed.
  • Laminate 110 Base material 120: Composite film 121 Protective film 122: Adhesive layer

Abstract

La présente invention concerne un stratifié qui comprend un substrat et un film protecteur disposé sur l'une des surfaces du substrat, et qui a une forme allongée. Le substrat est une couche d'une résine comprenant un polymère cristallin contenant une structure alicyclique. Le substrat et le film protecteur satisfont les relations E's/E'p < 1 et -0,4 ≤ Fs-Fp ≤ 0,4. Dans les relations susmentionnées, E's est le module de conservation du substrat à 180 °C, E'p est le module de conservation du film protecteur à 180 °C, Fs est le taux de retrait thermique (%) du substrat dans la direction longitudinale du stratifié pendant 2 minutes à 180 °C,et Fp est le taux de retrait thermique (%) du film protecteur dans la direction longitudinale du stratifié pendant 2 minutes à 180 °C. La présente invention concerne également un procédé de fabrication d'un stratifié, le procédé comprenant un processus de recuit d'un stratifié de pré-recuit.
PCT/JP2022/013674 2021-03-30 2022-03-23 Stratifié et procédé de fabrication de celui-ci WO2022210197A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017094485A1 (fr) * 2015-11-30 2017-06-08 日本ゼオン株式会社 Film multicouche, procédé de fabrication, plaque de polarisation circulaire, film antireflet, et dispositif d'affichage à diodes électroluminescentes organiques
JP2019098523A (ja) * 2017-11-28 2019-06-24 日本ゼオン株式会社 導電フィルム用多層フィルム及び導電フィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017094485A1 (fr) * 2015-11-30 2017-06-08 日本ゼオン株式会社 Film multicouche, procédé de fabrication, plaque de polarisation circulaire, film antireflet, et dispositif d'affichage à diodes électroluminescentes organiques
JP2019098523A (ja) * 2017-11-28 2019-06-24 日本ゼオン株式会社 導電フィルム用多層フィルム及び導電フィルム

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