WO2023210436A1 - 反射防止フィルム及びその製造方法、並びに画像表示装置 - Google Patents

反射防止フィルム及びその製造方法、並びに画像表示装置 Download PDF

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WO2023210436A1
WO2023210436A1 PCT/JP2023/015426 JP2023015426W WO2023210436A1 WO 2023210436 A1 WO2023210436 A1 WO 2023210436A1 JP 2023015426 W JP2023015426 W JP 2023015426W WO 2023210436 A1 WO2023210436 A1 WO 2023210436A1
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Prior art keywords
layer
antireflection
film
antireflection film
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PCT/JP2023/015426
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English (en)
French (fr)
Japanese (ja)
Inventor
幸大 宮本
翔太 長命
翔 橋本
豊 角田
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN202380035774.5A priority Critical patent/CN119096168A/zh
Priority to JP2024517219A priority patent/JPWO2023210436A1/ja
Priority to KR1020247024955A priority patent/KR20250004616A/ko
Publication of WO2023210436A1 publication Critical patent/WO2023210436A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025028541A priority patent/JP2025087744A/ja
Ceased legal-status Critical Current

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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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • B32B7/027—Thermal 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
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to an antireflection film, a method for manufacturing the same, and an image display device.
  • An antireflection film is placed on the viewing side of an image display device such as a liquid crystal display or an organic EL display for the purpose of preventing image quality deterioration due to reflection of external light and improving contrast.
  • An antireflection film includes an antireflection layer made of a laminate of a plurality of thin films having different refractive indexes on a transparent film base material.
  • an SiO primer layer is provided on a hard coat film, and a niobium oxide (Nb 2 O 5 ) layer as a high refractive index layer and a silicon oxide (SiO 2 O 5 ) layer as a low refractive index layer are provided on the hard coat film. ) layers are disclosed.
  • foldable image display device equipped with an organic EL panel using a foldable substrate (flexible substrate) such as a resin film
  • a cover window of a foldable display for example, an antireflection film in which an antireflection layer is provided on a flexible substrate is used.
  • Foldable displays are generally stored in a folded state. In the folded state, compressive stress is applied to the inside of the folded portion (bending portion), and tensile stress is applied to the outside of the bent portion.
  • the antireflection film When the display is folded with the display surface facing inside, the antireflection film is in a folded state (bent state) with the surface on which the antireflection layer is formed inside.
  • a display When a display is stored in a bent state at high temperatures or high temperatures and high humidity, fine cracks may occur in the antireflection layer, causing a decrease in the visibility of the display.
  • the present invention provides an anti-reflective film that does not easily crack in its anti-reflective layer and has excellent bending resistance even when stored in a bent state at high temperatures or high-temperature, high-humidity conditions, a method for producing the same, and the anti-reflective film.
  • the purpose is to provide an image display device using film.
  • the present invention includes the following aspects.
  • An antireflection film comprising a transparent film base material, a hard coat layer, and an antireflection layer in this order, When a heat resistance test is performed in which the temperature is maintained at 85°C for 48 hours, the dimensional change rate in the direction of any one side before and after the heat resistance test is -0.10% or more and 0.10% or less. An anti-reflective film.
  • An antireflection film comprising a transparent film base material, a hard coat layer, and an antireflection layer in this order, When a heat-and-moisture resistance test was conducted in an environment with a temperature of 60°C and a relative humidity of 95% for 48 hours, the dimensional change rate in any one side direction before and after the heat-and-moisture test was 0.01% or more. An anti-reflection film having an anti-reflection content of 20% or less.
  • An image display device comprising an image display panel and the antireflection film according to any one of [1] to [9], which is disposed on the viewing side of the image display panel.
  • an anti-reflective film which does not easily cause cracks in the anti-reflective layer and has excellent bending resistance even when stored in a bent state at high temperatures or high-temperature, high-humidity conditions, and a method for producing the anti-reflective film.
  • An image display device using the present invention can be provided.
  • FIG. 1 is a cross-sectional view showing an example of an antireflection film according to the present invention. It is a sectional view showing other examples of the antireflection film concerning the present invention.
  • FIG. 1 is a cross-sectional view showing an example of an image display device according to the present invention.
  • FIG. 3 is a cross-sectional view showing a bent state of a test piece when evaluating the bending resistance of an antireflection film.
  • Refractive index is the refractive index for light with a wavelength of 550 nm in an atmosphere at a temperature of 23°C.
  • the "principal surface" of a layered material refers to a surface perpendicular to the thickness direction of the layered material.
  • the numerical value of the thickness (film thickness) of each layer constituting the anti-reflection film is determined by randomly selecting 10 measurement points from a cross-sectional image of the layer cut in the thickness direction, and measuring the thickness at the 10 selected measurement points. This is the arithmetic mean value of 10 measured values.
  • the direction of any one side means a direction parallel to any one of the four sides of a rectangular or square anti-reflection film.
  • the direction of any one side of the antireflection film may be referred to as a "first direction.”
  • a direction perpendicular to the first direction (specifically, a direction parallel to the side perpendicular to the first direction among the four sides) may be referred to as a "second direction.”
  • the first direction is, for example, the transport direction of the film (hereinafter sometimes referred to as "MD direction”) when forming the antireflection layer by the roll-to-roll sputtering method described later.
  • the second direction is, for example, a direction (hereinafter sometimes referred to as "TD direction”) orthogonal to the transport direction of the film when forming the antireflection layer by the roll-to-roll sputtering method described below.
  • the compound and its derivatives may be collectively referred to by adding "system” after the compound name.
  • a polymer name when expressed by adding "system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.
  • the components, functional groups, etc. illustrated in this specification may be used alone, or two or more types may be used in combination, unless otherwise specified.
  • antireflection film ARF1 and antireflection film ARF2 will be described as specific examples of the antireflection film according to the first embodiment of the present invention.
  • the antireflection film ARF1 and the antireflection film ARF2 are both antireflection films (laminates) having a transparent film base material, a hard coat layer, and an antireflection layer in this order.
  • the anti-reflection film ARF1 was subjected to a heat resistance test held for 48 hours in an environment with a temperature of 85°C, the dimensional change rate in the first direction before and after the heat resistance test was -0.10% or more and 0.10% or less. It is.
  • the dimensional change rate in the first direction before and after the heat-and-moisture test was 0.01% or more. .20% or less.
  • the antireflection film ARF1 is suppressed from shrinking in the first direction at high temperatures, the antireflection layer is unlikely to crack even if stored in a bent state at high temperatures, and has excellent bending resistance.
  • the anti-reflection film ARF2 is suppressed from shrinking in the first direction under high temperature and high humidity conditions, the anti-reflection layer is unlikely to crack even when stored in a bent state under high temperature and high humidity conditions, and has excellent bending resistance. .
  • each of the antireflection film ARF1 and the antireflection film ARF2 will be referred to as "antireflection film ARF" unless it is necessary to distinguish between them.
  • the property that the antireflection layer is difficult to crack even when stored in a bent state at high temperatures is sometimes simply referred to as "bending resistance at high temperatures.”
  • the property that the antireflection layer is difficult to crack even when stored in a bent state under high temperature and high humidity is sometimes simply referred to as "bending resistance under high temperature and high humidity.”
  • a high temperature environment or a high temperature, high humidity environment may be referred to as a "harsh environment”.
  • the property that the antireflection layer is difficult to crack even when stored in a bent state in a harsh environment is sometimes simply referred to as "bending resistance under a harsh environment.”
  • a heat resistance test in which an antireflection film is held for 48 hours in an environment at a temperature of 85° C. may be simply referred to as a “heat resistance test.”
  • a heat-and-moisture resistance test in which an antireflection film is held for 48 hours in an environment with a temperature of 60° C.
  • a heat-and-moisture resistance test may be simply referred to as a "heat-and-moisture resistance test.”
  • a heat resistance test or a heat and humidity resistance test may be referred to as a "severe environment test.”
  • the "severe environment test” is a test for antireflection films.
  • the relative humidity of the atmosphere in the heat resistance test is, for example, 1% or less, and may be 0.5% or less or 0.1% or less.
  • the dimensional change rate in the first direction or the second direction is ⁇ 0%, it means that the length in the first direction or the second direction becomes smaller due to the severe environment test.
  • the dimensional change rate in the first direction or the second direction is >0%, it means that the length in the first direction or the second direction increases due to the severe environment test.
  • the method for measuring the dimensional change rate is the same method as in the examples described later or a method similar thereto.
  • the dimensional change rate in the second direction before and after the heat resistance test is preferably -0.10% or more and 0.10% or less.
  • the dimensional change rate in the first direction and the second direction before and after the heat resistance test is -0.09% or more. , more preferably -0.08% or more, and may be -0.07% or more, -0.06% or more, or -0.05% or more.
  • the dimensional change rate in the first direction and the second direction before and after the heat resistance test must be 0.09% or less. It is preferably 0.05% or less, more preferably 0.04% or less, 0.03% or less, 0.02% or less, or 0.01% or less.
  • At least one of the dimensional change rates in the first direction and the second direction before and after the heat resistance test is 0.00% or more and 0.10% or less. It is preferably 0.00% or more and 0.04% or less, even more preferably 0.00% or more and 0.03% or less, and 0.00% or more and 0.02% or less. It is even more preferable that it is, and it is especially preferable that it is 0.00% or more and 0.01% or less.
  • the dimensional change rate in the first direction before and after the heat resistance test must be 0.00% or more and 0.10% or less, and the It is preferable that the dimensional change rate in the second direction is -0.07% or more and 0.00% or less, and the dimensional change rate in the first direction before and after the heat resistance test is 0.00% or more and 0.04% or less. It is more preferable that the dimensional change rate in the second direction before and after the heat resistance test is -0.07% or more and 0.00% or less, and the dimensional change rate in the first direction before and after the heat resistance test is 0.00%.
  • the dimensional change rate in the second direction before and after the heat resistance test is -0.06% or more and 0.00% or less
  • the dimensional change rate in the first direction before and after the heat resistance test is It is even more preferable that the dimensional change rate is 0.00% or more and 0.02% or less, and the dimensional change rate in the second direction before and after the heat resistance test is -0.05% or more and 0.00% or less.
  • the dimensional change rate in the first direction before and after the heat resistance test is 0.00% or more and 0.01% or less
  • the dimensional change rate in the second direction before and after the heat resistance test is -0.05% or more and 0.00 % or less is particularly preferable.
  • an antireflection film should be used. It is preferable to store the ARF 1 in a state bent in the first direction.
  • the dimensional change rate in the second direction before and after the heat and humidity resistance test is preferably 0.01% or more and 0.20% or less.
  • the dimensional change rate in the first direction and the second direction before and after the heat and humidity resistance test must both be 0.02% or more.
  • it is 0.03% or more, more preferably 0.04% or more, 0.05% or more, 0.06% or more, 0.07% or more, 0.08% or more, or 0.09% or more.
  • the dimensional change rate in the first direction and the second direction before and after the heat and humidity resistance test must both be 0.15% or less.
  • the dimensional change rate in the first direction and the second direction before and after the heat and humidity resistance test must be 0.05% or more and 0.13%. % or less, more preferably 0.06% or more and 0.13% or less, even more preferably 0.07% or more and 0.13% or less, and 0.08% or more and 0.13%. % or less, and particularly preferably 0.09% or more and 0.13% or less.
  • the dimensional change rate in the first direction before and after the heat and humidity test must be 0.05% to 0.11%, and the film must be resistant to heat and humidity. It is preferable that the dimensional change rate in the second direction before and after the test is 0.10% or more and 0.13% or less, and the dimensional change rate in the first direction before and after the moist heat resistance test is 0.06% or more and 0.11% or less.
  • the dimensional change rate in the second direction before and after the heat-and-moisture test is 0.11% or more and 0.13% or less, and the dimensional change rate in the first direction before and after the heat-and-moisture test is 0.07 % or more and 0.11% or less, and it is more preferable that the dimensional change rate in the second direction before and after the heat-and-moisture test is 0.11% or more and less than 0.13%, and the dimensional change rate in the first direction before and after the heat-and-moisture test is more preferably It is even more preferable that the dimensional change rate is 0.08% or more and 0.11% or less, and the dimensional change rate in the second direction before and after the moisture and heat resistance test is 0.11% or more and 0.13% or less.
  • the dimensional change rate in the first direction before and after the thermal test is 0.09% or more and 0.11% or less
  • the dimensional change rate in the second direction before and after the moist heat resistance test is 0.12% or more and 0.13% or less. It is particularly preferable that there be. If the dimensional change rates in the first and second directions before and after the heat-and-moisture test are within the above ranges, it is necessary to It is preferable to store the prevention film ARF2 in a state bent in the first direction.
  • FIG. 1 is a cross-sectional view showing an example of an antireflection film ARF.
  • the antireflection film 10 shown in FIG. 1 has a transparent film base material 11, a hard coat layer 12, and an antireflection layer 13 in this order.
  • the dimensional change rate of the antireflection film 10 in the first direction before and after the heat resistance test is ⁇ 0.10% or more and 0.10% or less.
  • the dimensional change rate of the antireflection film 10 in the first direction before and after the heat and humidity resistance test is 0.01% or more and 0.20% or less.
  • the antireflection film 10 also includes a primer layer 18 disposed between the hard coat layer 12 and the antireflection layer 13, and an antifouling layer disposed on the opposite side of the antireflection layer 13 from the hard coat layer 12 side. 19. That is, the antireflection film 10 has a transparent film base material 11, a hard coat layer 12, a primer layer 18, an antireflection layer 13, and an antifouling layer 19 in this order.
  • the antireflection layer 13 has four layers in this order: a high refractive index layer 14, a low refractive index layer 15, a high refractive index layer 16, and a low refractive index layer 17 from the hard coat layer 12 side (primer layer 18 side). Details of the high refractive index layer and the low refractive index layer will be described later.
  • the antireflection layer of the antireflection film ARF is not limited to a four-layer structure like the antireflection layer 13, but may have a two-layer structure, a three-layer structure, a five-layer structure, or a laminated structure of six or more layers. good.
  • the antireflection layer of the antireflection film ARF is preferably an alternate laminate of two or more high refractive index layers and two or more low refractive index layers.
  • the outermost layer (the layer farthest from the hard coat layer 12) of the antireflection layer of the antireflection film ARF is preferably a low refractive index layer.
  • the antireflection film ARF may have a layer structure different from that of the antireflection film 10 shown in FIG.
  • the antireflection film ARF may be an antireflection film 20 that further includes an adhesive layer 21 disposed on the side opposite to the hard coat layer 12 side of the transparent film base material 11. good.
  • the adhesive constituting the adhesive layer 21 is not particularly limited, and includes, for example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate-vinyl chloride copolymer, modified polyolefin, and epoxy resin. , a transparent adhesive having a base polymer such as fluororesin, natural rubber, or synthetic rubber can be appropriately selected and used.
  • the thickness of the adhesive layer 21 is not particularly limited, but from the viewpoint of achieving both thin layer property and adhesive property, it is preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • a release liner may be temporarily attached to the main surface of the adhesive layer 21 on the side opposite to the transparent film base material 11 side.
  • the release liner protects the surface of the adhesive layer 21, for example, until the antireflection film 20 is bonded to an image display panel 101 (see FIG. 3), which will be described later.
  • a plastic film made of acrylic, polyolefin, cyclic polyolefin, polyester, etc. is suitably used as the constituent material of the release liner.
  • the thickness of the release liner is, for example, 5 ⁇ m or more and 200 ⁇ m or less.
  • the surface of the release liner is preferably subjected to a release treatment.
  • Materials for the mold release agent used in the mold release treatment include silicone materials, fluorine materials, long chain alkyl materials, fatty acid amide materials, and the like.
  • the anti-reflection film according to the present invention is not limited to the above-described structure.
  • the antireflection film according to the present invention has a dimensional change rate in the first direction before and after the heat resistance test of -0.10% or more and 0.10% or less, and a dimensional change in the first direction before and after the heat and humidity resistance test.
  • the ratio may be 0.01% or more and 0.20% or less.
  • an antireflection film can be obtained that has excellent bending resistance under high temperature conditions and also has excellent bending resistance under high temperature and high humidity conditions.
  • the antireflection film according to the present invention may be an antireflection film that does not include a primer layer and an antifouling layer. Further, the antireflection film according to the present invention may include an optical functional layer different from the layers included in the above-mentioned structure (transparent film base material, hard coat layer, primer layer, antireflection layer, and antifouling layer). good.
  • antireflection film More specifically, antireflection film ARF
  • antireflection film ARF antireflection film ARF
  • the transparent film base material is, for example, a flexible transparent resin film.
  • materials constituting the transparent film base material include polyester resin, polyolefin resin, polystyrene resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polysulfone resin, polyamide resin, polyimide resin, cellulose resin, norbornene resin, and polyarylate. resin, and polyvinyl alcohol resin.
  • polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
  • polyolefin resins include polyethylene, polypropylene, and cycloolefin polymer (COP).
  • the cellulose resin examples include triacetyl cellulose (TAC). These materials may be used alone or in combination of two or more.
  • the material for the transparent film base material is preferably one selected from the group consisting of polyester resin, polyolefin resin, and cellulose resin, and selected from the group consisting of PET, COP, and TAC. One type is more preferable, and PET is even more preferable. That is, the transparent film base material is preferably a type of film selected from the group consisting of polyester resin film, polyolefin resin film, and cellulose resin film, and preferably selected from the group consisting of PET film, COP film, and TAC film. One type of film is more preferred, and a PET film is even more preferred.
  • the thickness of the transparent film base material is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 20 ⁇ m or more.
  • the thickness of the transparent film base material is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less from the viewpoint of handleability.
  • One or both main surfaces of the transparent film base material may be subjected to surface modification treatment.
  • surface modification treatments include corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • the total light transmittance (JIS K 7375-2008) of the transparent film base material is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. % or less.
  • the hard coat layer is a layer that increases mechanical properties such as hardness and elastic modulus of the antireflection film.
  • the hard coat layer is made of, for example, a cured product of a curable resin composition (composition for forming a hard coat layer).
  • a curable resin composition composition for forming a hard coat layer.
  • the curable resin contained in the curable resin composition include polyester resin, acrylic resin, urethane resin, acrylic urethane resin, amide resin, silicone resin, epoxy resin, and melamine resin. These curable resins may be used alone or in combination of two or more. From the viewpoint of increasing the hardness of the hard coat layer, the curable resin is preferably one or more selected from the group consisting of acrylic resins and acrylic urethane resins, and acrylic resins are more preferred.
  • examples of the curable resin composition include an ultraviolet curable resin composition and a thermosetting resin composition. From the viewpoint of improving productivity of the antireflection film, the curable resin composition is preferably an ultraviolet curable resin composition.
  • the ultraviolet curable resin composition contains one or more types selected from the group consisting of ultraviolet curable monomers, ultraviolet curable oligomers, and ultraviolet curable polymers. Specific examples of ultraviolet curable resin compositions include the hard coat layer forming composition described in JP-A No. 2016-179686.
  • the curable resin composition may contain fine particles.
  • fine particles include metal oxide particles, glass particles, and organic particles.
  • materials for the metal oxide particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
  • materials for the organic particles include polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate.
  • the thickness of the hard coat layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more. From the viewpoint of ensuring flexibility of the antireflection film, the thickness of the hard coat layer is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 35 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the main surface of the hard coat layer opposite to the transparent film substrate side may be subjected to surface modification treatment.
  • surface modification treatments include plasma treatment, corona treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • plasma treatment corona treatment
  • ozone treatment primer treatment
  • glow treatment glow treatment
  • coupling agent treatment coupling agent treatment.
  • the main surface on the opposite side is preferably plasma-treated.
  • Primer layer In order to improve the adhesion between the hard coat layer and the antireflection layer, it is preferable to provide a primer layer between the hard coat layer and the antireflection layer.
  • Materials for the primer layer include metals (or metalloids) such as silicon, nickel, chromium, tin, gold, silver, platinum, zinc, titanium, indium, tungsten, aluminum, zirconium, and palladium; ); oxides, fluorides, sulfides, nitrides, etc. of these metals (or semimetals).
  • the oxide constituting the primer layer may be a composite oxide such as indium tin oxide (ITO).
  • ITO indium tin oxide
  • inorganic oxides are preferred, and silicon oxide, indium oxide, or ITO are particularly preferred.
  • the thickness of the primer layer is preferably 0.5 nm or more and 20 nm or less, and 0.5 nm or more. It is more preferably 10 nm or less, and even more preferably 1.0 nm or more and 10 nm or less.
  • the antireflection layer is composed of two or more thin films having different refractive indexes. Generally, the optical thickness (product of refractive index and thickness) of the thin film of the antireflection layer is adjusted so that the reversed phases of incident light and reflected light cancel each other out.
  • the antireflection layer a multilayer laminate of two or more thin films with different refractive indexes, the reflectance can be reduced in a wide wavelength range of visible light.
  • the antireflection layer examples include metal (or metalloid) oxides, nitrides, and fluorides.
  • the antireflection layer is preferably an alternating laminate of high refractive index layers and low refractive index layers.
  • the high refractive index layer has a refractive index of, for example, 1.9 or more, preferably 2.0 or more.
  • the material for the high refractive index layer include titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, ITO, and antimony-doped tin oxide (ATO). Among these, one or more selected from the group consisting of titanium oxide and niobium oxide are preferred.
  • the low refractive index layer has a refractive index of, for example, 1.6 or less, preferably 1.5 or less.
  • Examples of the material for the low refractive index layer include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, hafnium fluoride, and lanthanum fluoride. Among them, silicon oxide is preferred. In particular, it is preferable to alternately laminate niobium oxide (Nb 2 O 5 ) thin films as high refractive index layers and silicon oxide (SiO 2 ) thin films as low refractive index layers. In addition to the low refractive index layer and the high refractive index layer, a medium refractive index layer having a refractive index of more than 1.6 and less than 1.9 may be provided.
  • the film thickness of the high refractive index layer and the low refractive index layer is preferably 5 nm or more and 200 nm or less, and more preferably 10 nm or more and 150 nm or less.
  • the film thickness of each layer may be designed in accordance with the refractive index, laminated structure, etc. so that the reflectance of visible light is small.
  • a laminated structure of a high refractive index layer and a low refractive index layer includes, from the hard coat layer side, a high refractive index layer with an optical thickness of 20 nm or more and 55 nm or less, a low refractive index layer with an optical thickness of 35 nm or more and 55 nm or less, and an optical A four-layer structure consisting of a high refractive index layer with a film thickness of 80 nm or more and 250 nm or less, and a low refractive index layer with an optical film thickness of 100 nm or more and 150 nm or less is exemplified.
  • the antireflection layer is a four-layer alternating laminate in which niobium oxide (Nb 2 O 5 ) thin films as high refractive index layers and silicon oxide (SiO 2 ) thin films as low refractive index layers are alternately laminated.
  • the structure of the antireflection layer includes, from the hard coat layer side, a niobium oxide thin film with a thickness of 5 nm or more and 20 nm or less, a silicon oxide thin film with a thickness of 20 nm or more and 40 nm or less, a niobium oxide thin film with a thickness of 65 nm or more and 120 nm or less, and a niobium oxide thin film with a thickness of 60 nm or more.
  • An example is a structure in which silicon oxide thin films with a thickness of 100 nm or less are provided in this order.
  • the thickness of the antireflection layer is preferably 150 nm or more and 280 nm or less, more preferably 180 nm or more and 280 nm or less, and 190 nm or more and 260 nm or less. It is more preferably 200 nm or more and 250 nm or less.
  • the thickness of an antireflection layer is the sum total (total thickness) of the thickness of each layer which comprises an antireflection layer.
  • the antireflection film preferably includes an antifouling layer on the side opposite to the hard coat layer side of the antireflection layer, and more preferably includes the antifouling layer as the outermost layer of the antireflection film.
  • the antifouling layer for example, the influence of contamination from the external environment (fingerprints, hand marks, dust, etc.) can be reduced, and contaminants attached to the surface of the antireflection film can be easily removed.
  • the antifouling layer has a small refractive index difference with the outermost layer (for example, a low refractive index layer) of the antireflection layer.
  • the refractive index of the antifouling layer is preferably 1.6 or less, more preferably 1.55 or less.
  • fluorine-containing compounds are preferred as the material for the antifouling layer.
  • the fluorine-containing compound has excellent antifouling properties and can contribute to lowering the refractive index.
  • alkoxysilane compounds containing a perfluoropolyether skeleton are preferred because they have excellent water repellency and can exhibit high antifouling properties.
  • alkoxysilane compound containing a perfluoropolyether skeleton include alkoxysilane compounds having a plurality of linear or branched perfluoroalkylene oxide units having 1 to 4 carbon atoms.
  • linear or branched perfluoroalkylene oxide units having 1 to 4 carbon atoms examples include perfluoromethylene oxide units (-CF 2 O-) and perfluoroethylene oxide units (-CF 2 CF 2 O-), perfluoropropylene oxide unit (-CF 2 CF 2 CF 2 O-), perfluoroisopropylene oxide unit (-CF(CF 3 )CF 2 O-), and the like.
  • the thickness of the antifouling layer is, for example, 2 nm or more and 50 nm or less. The greater the thickness of the antifouling layer, the more the antifouling property tends to improve.
  • the thickness of the antifouling layer is preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 8 nm or more.
  • the thickness of the antifouling layer is preferably 30 nm or less, more preferably 20 nm or less.
  • the antireflection film according to the first embodiment preferably satisfies the following condition 1, more preferably satisfies the following condition 2, and satisfies the following condition. It is more preferable that condition 3 is satisfied, and even more preferable that condition 4 below is satisfied.
  • Condition 1 At least one of the dimensional change rates in the first direction and the second direction before and after the heat resistance test is 0.00% or more and 0.04% or less.
  • Condition 2 Condition 1 above is satisfied, and the thickness of the antireflection layer is 150 nm or more and 280 nm or less.
  • Condition 3 The dimensional change rate in the first direction before and after the heat resistance test is 0.00% or more and 0.04% or less, and the dimensional change rate in the second direction before and after the heat resistance test is -0.07% or more and 0. .00% or less.
  • Condition 4 Condition 3 above is satisfied, and the thickness of the antireflection layer is 150 nm or more and 280 nm or less.
  • the antireflection film according to the first embodiment preferably satisfies the following condition i, and more preferably satisfies the following condition ii. It is preferable that the following condition iii is satisfied, and it is even more preferable that the following condition iv is satisfied.
  • Condition i The dimensional change rates in the first direction and the second direction before and after the heat and humidity resistance test are both 0.05% or more and 0.13% or less.
  • Condition ii The above condition i is satisfied, and the thickness of the antireflection layer is 150 nm or more and 280 nm or less.
  • Condition iii The dimensional change rate in the first direction before and after the heat-and-moisture test is 0.05% to 0.11%, and the dimensional change rate in the second direction before and after the heat-and-moisture test is 0.10% to 0. It is 13% or less.
  • Condition iv Condition iii above is satisfied, and the thickness of the antireflection layer is 150 nm or more and 280 nm or less.
  • the antireflection film according to the first embodiment must satisfy the above conditions 1 and i. It is preferable that conditions 2 and ii are satisfied, it is more preferable that conditions 3 and iii are satisfied, and it is even more preferable that conditions 4 and iv are satisfied.
  • the image display device includes an image display panel and the antireflection film according to the first embodiment, which is disposed on the viewing side of the image display panel.
  • the image display device includes an image display panel and the antireflection film according to the first embodiment, which is disposed on the viewing side of the image display panel.
  • FIG. 3 is a cross-sectional view showing an example of an image display device according to the second embodiment.
  • the image display device 100 shown in FIG. 3 includes an image display panel 101 and a reflective film, which is an example of an antireflection film according to the first embodiment, disposed on the viewing side (upper side in FIG. 3) of the image display panel 101.
  • a prevention film 10 is provided.
  • the transparent film base material 11 of the antireflection film 10 and the image display panel 101 are bonded together with an adhesive layer 21 interposed therebetween.
  • Examples of the image display panel 101 include image display panels including image display cells such as liquid crystal cells and organic EL cells.
  • the image display device according to the second embodiment has an antireflection film disposed on the viewing side of the image display panel, so reflection of external light is reduced and visibility is excellent. Furthermore, since the image display device according to the second embodiment includes the antireflection film according to the first embodiment (an antireflection film with excellent bending resistance under harsh environments), the image display device can be bent with the antireflection layer forming side facing inside. Even when stored in a bent state, the anti-reflection layer is unlikely to crack at the bends. Therefore, the image display device according to the second embodiment can also be used as a foldable display, for example.
  • the bending point of the foldable display is a bending point where the antireflection film can be bent in the first direction.
  • the method for manufacturing the antireflection film according to the third embodiment is a preferred method for manufacturing the antireflection film according to the first embodiment.
  • descriptions of contents that overlap with those of the first embodiment will be omitted.
  • the method for manufacturing an antireflection film according to the third embodiment includes a step Sa of forming an antireflection layer on the side opposite to the transparent film substrate side of the hard coat layer using a roll-to-roll sputtering film forming apparatus; After the step Sa, a step Sb is provided in which the laminate on which the antireflection layer is formed is heated. Since the method for manufacturing the antireflection film according to the third embodiment includes the step Sa and the step Sb, the antireflection film according to the first embodiment can be easily manufactured.
  • step Sa will be referred to as "antireflection layer forming step.”
  • step Sb will be referred to as "antireflection layer heating step.”
  • the method for manufacturing an antireflection film according to the third embodiment may include steps (other steps) other than the antireflection layer forming step and the antireflection layer heating step.
  • Other steps include, for example, a hard coat layer forming step, a hard coat layer surface treatment step, a hard coat layer heating step, a primer layer forming step, and an antifouling layer forming step, which will be described later.
  • the hard coat layer forming step is a step of forming a hard coat layer on the transparent film base material.
  • a hard coat layer is formed by applying a curable resin composition (composition for forming a hard coat layer) onto a transparent film base material, and removing the solvent and curing the resin as necessary.
  • the composition for forming a hard coat layer contains, for example, the above-mentioned curable resin and a polymerization initiator (for example, a photopolymerization initiator), and optionally a solvent capable of dissolving or dispersing these components.
  • the composition for forming a hard coat layer contains fine particles, a leveling agent, a viscosity modifier (thixotropic agent, thickener, etc.), an antistatic agent, an antiblocking agent, a dispersant, a dispersion stabilizer, and an antioxidant. It may also contain additives such as UV absorbers, antifoaming agents, surfactants, and lubricants.
  • the hard coat layer forming composition can be applied by any suitable method such as bar coating, roll coating, gravure coating, rod coating, slot orifice coating, curtain coating, fountain coating, comma coating, etc. method can be adopted.
  • the drying temperature of the coating film after application may be set to an appropriate temperature depending on the composition of the composition for forming a hard coat layer, and is, for example, 50° C. or higher and 150° C. or lower.
  • the resin component in the composition for forming a hard coat layer is a thermosetting resin
  • the coating film is cured by heating.
  • the resin component in the composition for forming a hard coat layer is a photocurable resin
  • the coating film is cured by irradiation with active energy rays such as ultraviolet rays.
  • the cumulative amount of irradiation light is preferably 100 mJ/cm 2 or more and 500 mJ/cm 2 or less.
  • the main surface of the hard coat layer opposite to the transparent film substrate side is subjected to a surface modification treatment.
  • surface modification treatments include plasma treatment, corona treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment.
  • plasma treatment for example, argon gas is used as the inert gas.
  • the discharge power in the plasma treatment is, for example, 10 W or more and 10,000 W or less.
  • the hard coat layer heating step is performed to heat a laminate including a hard coat layer (for example, a transparent film base material and a hard coat layer) before forming other layers (for example, a primer layer, an antireflection layer, etc.) on the hard coat layer.
  • This is a step of heating a film-like laminate (having a film-like laminate).
  • a roll-to-roll type sputtering film forming apparatus is used in the anti-reflection layer forming process, so from the viewpoint of increasing productivity, the above-mentioned laminate is transported in a roll-to-roll type in the hard coat layer heating process. It is preferable to heat the mixture while heating.
  • the heating device for heating include a hot air oven, an infrared heater, and the like.
  • the heating temperature of the laminate in the hard coat layer heating step is, for example, 100°C or more and 200°C or less.
  • the heating time of the laminate in the hard coat layer heating step is, for example, 30 seconds or more and 30 minutes or less.
  • the hard coat layer heating step may be performed before or after the hard coat layer surface treatment step.
  • the primer layer forming step is a step of forming (filming) a primer layer on the hard coat layer.
  • the method for forming the primer layer is not particularly limited, and may be either a wet coating method or a dry coating method.
  • a dry coating method such as a vacuum evaporation method, a CVD method, or a sputtering method is preferable because a thin film with a uniform thickness can be formed.
  • the roll-to-roll type sputtering film forming method is used as the method for forming the primer layer.
  • a method of forming a film using a film forming apparatus is preferable.
  • a long film for example, a transparent film base material on which a hard coat layer is formed
  • a primer layer and an antireflection layer are continuously applied.
  • film formation is performed while introducing an inert gas such as argon and, if necessary, a reactive gas such as oxygen into a film forming chamber.
  • an oxide layer can be formed by sputtering by either a method using an oxide target or a reactive sputtering method using a metal (or semimetal) target.
  • Examples of power sources for carrying out the sputtering method include DC power sources, AC power sources, RF power sources, and MFAC power sources (AC power sources with a frequency band of several kHz to several MHz).
  • the discharge power in the sputtering method is, for example, 1 kW or more and 100 kW or less, preferably 1 kW or more and 50 kW or less.
  • the surface temperature of the film forming roll when performing the sputtering method is, for example, -25°C or more and 25°C or less, preferably -20°C or more and 0°C or less.
  • the pressure in the film forming chamber when performing the sputtering method is preferably 0.01 Pa or more and 10 Pa or less, more preferably 0.05 Pa or more and 5 Pa or less, and still more preferably 0.1 Pa or more and 1 Pa or less.
  • an anti-reflection layer is formed on the side of the hard coat layer opposite to the transparent film substrate side (for example, on the surface of the hard coat layer or the surface of the primer layer) using a roll-to-roll sputtering film forming apparatus. do. That is, in the third embodiment, each layer of the antireflection layer is formed by a roll-to-roll sputtering method.
  • the film forming conditions can be appropriately set, for example, among the conditions described in the above-mentioned [primer layer forming step].
  • the inventors' studies have revealed that when each layer of the antireflection layer is formed by a roll-to-roll sputtering method, the antireflection film tends to shrink in harsh environments. In particular, when a stretched film such as a PET film is used as the transparent film base material, the shrinkage of the antireflection film becomes noticeable.
  • a laminate forming an antireflection layer for example, a film-like laminate having at least a transparent film base material and a hard coat layer
  • tension is applied to the laminate in the transport direction. It is presumed that this causes residual stress to occur in the laminate, making the antireflection film more likely to shrink in harsh environments.
  • the antifouling layer forming step is a step of forming an antifouling layer on the opposite side of the antireflection layer from the hard coat layer side.
  • a fluorine-containing compound is used as a material and the antifouling layer is formed by a dry coating method.
  • the dry coating method include vacuum evaporation, sputtering, and CVD, with vacuum evaporation being preferred.
  • the antireflection layer heating step is a step of heating a laminate on which an antireflection layer is formed (hereinafter sometimes referred to as a "film with an antireflection layer").
  • a film with an antireflection layer By heating the film with an antireflection layer, for example, at least a portion of the residual stress of the film with an antireflection layer is removed, and shrinkage of the antireflection film in a harsh environment is suppressed. As a result, an antireflection film with excellent bending resistance under harsh environments can be obtained.
  • the antireflection layer heating process may be implemented before or after the antifouling layer forming process.
  • the antireflection layer heating step is preferably carried out after the antifouling layer forming step in order to obtain an antireflection film with better bending resistance under harsh environments.
  • the anti-reflection layer-coated film is coated with a roll-to-roll type in the anti-reflection layer heating process. It is preferable to heat the material while conveying it.
  • the heating device for heating include a hot air oven, an infrared heater, and the like.
  • the heating temperature of the film with an antireflection layer in the antireflection layer heating step is preferably 110°C or higher, and preferably 115°C or higher.
  • the temperature is more preferably 120°C or higher, and may be 130°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 170°C or higher, or 180°C or higher.
  • the heating time of the film with an antireflection layer in the antireflection layer heating step is preferably 30 seconds or more, and preferably 1 minute or more. It is more preferable that the heating time is 2 minutes or more, even more preferably 2 minutes or more, and may be 5 minutes or more, 10 minutes or more, or 15 minutes or more.
  • the heating temperature of the antireflection layer-equipped film in the antireflection layer heating step is preferably 200°C or lower, more preferably 190°C or lower.
  • the heating time of the antireflection layer-coated film in the antireflection layer heating step is preferably 30 minutes or less, more preferably 20 minutes or less. .
  • the dimensional change rates in the first and second directions before and after the heat resistance test, and the dimensional change rates in the first and second directions before and after the moist heat resistance test are both based on the heating conditions in the antireflection layer heating step (see details below). can be adjusted by changing the heating temperature, heating time, etc.).
  • methyl isobutyl ketone was added to the obtained mixed solution to obtain a composition for forming a hard coat layer having a solid content concentration of 40% by weight.
  • the above composition for forming a hard coat layer was applied to one main surface of a PET film ("50U48" manufactured by Toray Industries, Inc., thickness: 50 ⁇ m) as a transparent film base material to form a coating film.
  • this coating film was dried by heating at a temperature of 80° C. for 60 seconds, and then cured by ultraviolet irradiation.
  • a high-pressure mercury lamp was used as a light source, ultraviolet rays with a wavelength of 365 nm were used, and the cumulative amount of light was 300 mJ/cm 2 . Thereby, a hard coat layer with a thickness of 3 ⁇ m was formed on the PET film.
  • the optical film F1 was heated at a temperature of 140° C. for 2 minutes using a hot air oven while being transported by a roll-to-roll transport device.
  • the heated optical film F1 was introduced into a roll-to-roll type sputtering film forming apparatus, and the pressure inside the film forming chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa.
  • argon gas and oxygen gas are introduced at a volume ratio of 100:10, the surface temperature of the film forming roll is set to -8°C, and a film is formed on the hard coat layer to a thickness of 1 by sputtering.
  • a .5 nm ITO layer (primer layer) was formed.
  • an ITO target containing indium oxide and tin oxide at a weight ratio of 90:10 was used as a target material.
  • the power source was an MFAC power source
  • the discharge power was 2.5 kW
  • the pressure inside the film forming chamber was 0.2 Pa.
  • a first layer of Nb with a thickness of 12 nm is deposited on the primer layer by sputtering while transporting the optical film F1 after the primer layer has been formed using a roll-to-roll sputtering film forming apparatus.
  • 2 O 5 layer reffractive index: 2.33
  • 2nd layer 28 nm thick SiO 2 layer (refractive index: 1.46)
  • 3rd layer 100 nm thick Nb 2 O 5 layer
  • 4th layer Two SiO 2 layers with a thickness of 85 nm were deposited in this order.
  • an antireflection layer having a four-layer structure (a four-layer structure consisting of a first layer, a second layer, a third layer, and a fourth layer) was formed on the primer layer.
  • the surface temperature of the film forming roll was -8° C.
  • the MFAC power source was used as the power source
  • the pressure inside the film forming chamber was 0.7 Pa.
  • a Nb target was used, argon gas and oxygen gas were introduced at a volume ratio of 100:5, and the discharge power was set to 10.5 kW.
  • a Si target was used, argon gas and oxygen gas were introduced at a volume ratio of 100:30, and the discharge power was set at 14 kW.
  • a Nb target was used, argon gas and oxygen gas were introduced at a volume ratio of 100:13, and the discharge power was set at 22 kW.
  • a Si target was used, argon gas and oxygen gas were introduced at a volume ratio of 100:30, and the discharge power was 12 kW.
  • a dried and solidified coating agent (“SHIN-ETSU SUBELYN KY1903-1” manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient: alkoxysilane compound containing a perfluoropolyether skeleton) was used as a vapor deposition source, and the vapor deposition source was heated. At a temperature of 260° C., an antifouling layer with a thickness of 12 nm was formed on the antireflection layer by vacuum evaporation. Thereby, a laminate (hereinafter sometimes referred to as "optical film F2”) including a PET film, a hard coat layer, a primer layer, an antireflection layer, and an antifouling layer was obtained.
  • optical film F2 a laminate including a PET film, a hard coat layer, a primer layer, an antireflection layer, and an antifouling layer was obtained.
  • the optical film F2 was heated at a temperature of 120° C. for 2 minutes using a hot air oven while being transported by a roll-to-roll transport device. Thereby, the antireflection film of Example 1 was obtained.
  • Example 1 was produced using the same manufacturing method as Example 1, except that the heating conditions for optical film F1 in the hard coat layer heating step and the heating conditions for optical film F2 in the antireflection layer heating step were changed to the conditions shown in Table 1.
  • Antireflection films of Comparative Examples 2 to 9 and Comparative Examples 1 to 5 were obtained, respectively. Note that in the production of the antireflection films of Examples 6 to 9 and Comparative Example 4, the hard coat layer heating step was not performed. Further, in the production of the antireflection films of Comparative Examples 4 and 5, the antireflection layer heating step was not performed.
  • Method of measuring dimensional change rate before and after heat resistance test As a test piece for measuring the dimensional change rate before and after the heat resistance test, a 100 mm x 100 mm size (length in the MD direction) was cut from each antireflection film using a laser processing machine ("LaserPro Spirit GLS" manufactured by GCC). A test piece with a diameter of 100 mm and a length in the TD direction of 100 mm was cut out. The ambient temperature and relative humidity when cutting out the test pieces were 20° C. and 50%, respectively.
  • the dimensional change rate in each direction (MD direction and TD direction) of each test piece is calculated by comparing the length L1 (100 mm) in each direction at a temperature of 20°C and a relative humidity of 50% before the heat resistance test and after the heat resistance test. It was calculated using the above-mentioned formula from the length L2 in each direction measured after being allowed to stand for 24 hours in an atmosphere with a temperature of 20° C. and a relative humidity of 50%.
  • Test piece for measuring the dimensional change rate before and after the heat and humidity resistance test As a test piece for measuring the dimensional change rate before and after the heat and humidity resistance test, a size of 100 mm x 100 mm (length in the MD direction) was cut from each antireflection film using a laser processing machine ("LaserPro Spirit GLS" manufactured by GCC). A test piece with a diameter of 100 mm and a length in the TD direction of 100 mm was cut out. The ambient temperature and relative humidity when cutting out the test pieces were 20° C. and 50%, respectively.
  • each test piece was subjected to a heat-and-moisture resistance test in which it was left standing for 48 hours in a constant temperature and humidity tester (PL-2J manufactured by Espec) at a temperature of 60°C and a relative humidity of 95%.
  • the sample was left standing in an atmosphere with relative humidity of 50% for 24 hours, and the dimensional change rate before and after the heat and humidity resistance test was determined. That is, the dimensional change rate in each direction (MD direction and TD direction) of each test piece is calculated by comparing the length L1 (100 mm) in each direction at a temperature of 20°C and a relative humidity of 50% before the heat and humidity test and after the heat and humidity test. It was calculated using the above-mentioned formula from the length L2 in each direction measured after being allowed to stand for 24 hours in an atmosphere with a temperature of 20° C. and a relative humidity of 50%.
  • ⁇ Bending resistance evaluation> [Evaluation of bending resistance under high temperature]
  • 200 test pieces with a size of 10 mm width x 100 mm length were cut from each antireflection film using a laser processing machine ("LaserPro Spirit GLS" manufactured by GCC). (Length direction: MD direction, width direction: TD direction) was cut out.
  • the test piece 200 is bent in the MD direction (X direction in FIG. 4) so that the surface on the antireflection layer (not shown) side faces inside. Both ends were bonded to a spacer 300 having a thickness of D (D: 4.0 mm or 3.8 mm). In the state shown in FIG.
  • the bending radius of the bent portion of the test piece 200 was D/2.
  • the test piece 200 in the state shown in FIG. 4 was left undisturbed for 48 hours in a drying oven ("PH-202" manufactured by Espec) at a temperature of 85° C. and a relative humidity of 1% or less, and then taken out, and the bent portion was examined using an optical microscope. The presence or absence of cracks (white turbidity in the antireflection layer) was confirmed. When no cracks were observed, it was determined to be A. On the other hand, when cracks were confirmed, it was determined to be B.
  • test piece 200 As a test piece for evaluating bending resistance under high temperature and high humidity conditions, a test piece with a size of 10 mm width x 100 mm length was prepared from each antireflection film using a laser processing machine ("LaserPro Spirit GLS" manufactured by GCC). Piece 200 (length direction: MD direction, width direction: TD direction) was cut out. Next, as shown in FIG. 4, the test piece 200 is bent in the MD direction (X direction in FIG. 4) so that the surface on the antireflection layer (not shown) side faces inside. Both ends were bonded to a spacer 300 having a thickness of D (D: 4.0 mm or 3.8 mm). In the state shown in FIG.
  • the bending radius of the bent portion of the test piece 200 was D/2.
  • the test piece 200 in the state shown in FIG. 4 was left standing for 48 hours in a constant temperature and humidity tester ("PL-2J" manufactured by ESPEC Corporation) at a temperature of 60 ° C. and a relative humidity of 95%, and then taken out and examined under an optical microscope. The presence or absence of cracks (clouding of the antireflection layer) at the bent portion was confirmed. When no cracks were observed, it was determined to be A. On the other hand, when cracks were confirmed, it was determined to be B.
  • the dimensional change rate in the MD direction before and after the heat resistance test was -0.10% or more and 0.10% or less.
  • the dimensional change rate in the MD direction before and after the heat and humidity resistance test was 0.01% or more and 0.20% or less.
  • Example 1 to 9 As shown in Table 2, in Examples 1 to 9, the evaluation result of bending resistance under high temperature when using a spacer with a thickness of 4.0 mm was A. Therefore, the antireflection films of Examples 1 to 9 had excellent bending resistance at high temperatures. In Examples 1 to 9, the bending resistance evaluation result under high temperature and high humidity when using a spacer with a thickness of 4.0 mm was A. Therefore, the antireflection films of Examples 1 to 9 had excellent bending resistance under high temperature and high humidity conditions.
  • Comparative Examples 1 to 5 As shown in Table 2, in Comparative Examples 1 to 5, the evaluation result of the bending resistance under high temperature was B when using a spacer with a thickness of 4.0 mm. Therefore, the antireflection films of Comparative Examples 1 to 5 did not have excellent bending resistance at high temperatures. In Comparative Examples 1 to 5, the evaluation result of bending resistance under high temperature and high humidity when using a spacer with a thickness of 4.0 mm was B. Therefore, the antireflection films of Comparative Examples 1 to 5 did not have excellent bending resistance under high temperature and high humidity conditions.
  • the present invention can provide an antireflection film that has excellent bending resistance under harsh environments.
  • Adhesive layer 100 Image display device 101 Image display panel

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JPH11250805A (ja) * 1998-03-02 1999-09-17 Sony Corp 表示装置へ光反射防止膜を貼着する方法
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