WO2022260152A1 - Film de revêtement dur, élément optique et dispositif d'affichage d'image - Google Patents

Film de revêtement dur, élément optique et dispositif d'affichage d'image Download PDF

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Publication number
WO2022260152A1
WO2022260152A1 PCT/JP2022/023388 JP2022023388W WO2022260152A1 WO 2022260152 A1 WO2022260152 A1 WO 2022260152A1 JP 2022023388 W JP2022023388 W JP 2022023388W WO 2022260152 A1 WO2022260152 A1 WO 2022260152A1
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WIPO (PCT)
Prior art keywords
layer
hard coat
average thickness
coat film
light
Prior art date
Application number
PCT/JP2022/023388
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English (en)
Japanese (ja)
Inventor
尚樹 橋本
幸大 宮本
岳仁 淵田
裕貴 水川
豊 角田
豪彦 安藤
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202280041594.3A priority Critical patent/CN117480412A/zh
Priority to KR1020237044520A priority patent/KR20240011799A/ko
Publication of WO2022260152A1 publication Critical patent/WO2022260152A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • 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
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness

Definitions

  • the present invention relates to hard coat films, optical members, and image display devices.
  • a hard coat film is a film in which a hard coat layer is provided on the film surface to increase the surface strength, etc., and is widely used in image display devices (Patent Document 1, etc.).
  • an object of the present invention is to provide a hard coat film, an optical member, and an image display device that achieve both surface abrasion resistance and bending resistance.
  • the hard coat film of the present invention is A hard coat layer (B), an optical functional layer (C) and an antifouling layer (D) are laminated in the order described above on at least one surface of the light transmissive substrate (A),
  • the antifouling layer (D) contains fluorine as an element
  • the average thicknesses of the light-transmitting substrate (A), the hard coat layer (B) and the optical function layer (C) are characterized by satisfying the following formulas (1) and (2).
  • dS is the average thickness [ ⁇ m] of the light transmissive substrate (A)
  • dH is the average thickness [ ⁇ m] of the hard coat layer (B)
  • dI is the average thickness [ ⁇ m] of the optical function layer (C).
  • the optical member of the present invention is an optical member containing the hard coat film of the present invention.
  • the image display device of the present invention is an image display device containing the hard coat film of the present invention or the optical member of the present invention.
  • a hard coat film, an optical member, and an image display device that have both surface abrasion resistance and bending resistance.
  • FIG. 1 is a cross-sectional view illustrating the configuration of the hard coat film of the present invention.
  • FIG. 2 is a cross-sectional view showing another example of the hard coat film of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing the bending resistance test method of the example.
  • the antifouling layer (D) may have a surface roughness in the range of 1 to 10 nm on the side opposite to the substrate (A).
  • the average thickness of the hard coat layer (B) may be in the range of 2 to 12 ⁇ m.
  • the light-transmitting substrate (A) may have an average thickness of 100 ⁇ m or less.
  • the antifouling layer (D) may have an average thickness in the range of 1 to 30 nm.
  • the hard coat layer (B) may contain at least one selected from the group consisting of organic resin, silicon oxide, titanium oxide and zirconium oxide.
  • the optical member of the present invention may be, for example, a polarizing plate.
  • the hard coat layer (B), the optical function layer (C) and the antifouling layer (D) are arranged in the order described above on only one side of the light-transmitting substrate (A). laminated, An adhesive layer is laminated on the other surface of the light-transmitting substrate (A),
  • the hard coat film may be attached to a member containing glass or a plastic film via the adhesive layer.
  • weight and “mass” may be read interchangeably unless otherwise specified.
  • parts by weight may be read as “parts by weight”
  • parts by weight may be read as “parts by weight”
  • mass% may be read as “% by weight”
  • % by weight may be read as “% by mass”.
  • the hard coat film of the present invention as described above, A hard coat layer (B), an optical functional layer (C) and an antifouling layer (D) are laminated in the order described above on at least one surface of the light transmissive substrate (A), The antifouling layer (D) contains fluorine as an element,
  • the average thicknesses of the light-transmitting substrate (A), the hard coat layer (B) and the optical function layer (C) are characterized by satisfying the following formulas (1) and (2).
  • dS is the average thickness [ ⁇ m] of the light transmissive substrate (A)
  • dH is the average thickness [ ⁇ m] of the hard coat layer (B)
  • dI is the average thickness [ ⁇ m] of the optical function layer (C).
  • FIG. 1 schematically shows an example of the configuration of the hard coat film of the present invention.
  • the hard coat film 10 includes a hard coat layer (B) 12, an optical function layer (C) 13 and an antifouling layer (D) on at least one surface of a light transmissive substrate (A) 11. 14 are stacked in the above order.
  • the antifouling layer (D) 14 contains fluorine as an element.
  • dS is the average thickness [ ⁇ m] of the light transmissive substrate (A) 11 .
  • dH is the average thickness [ ⁇ m] of the hard coat layer (B) 12 .
  • dI is the average thickness [ ⁇ m] of the optical function layer (C) 13 .
  • dF is the average thickness [ ⁇ m] of the antifouling layer (D) 14 .
  • the average thickness dS [ ⁇ m] of the light-transmitting substrate (A) 11, the average thickness dH [ ⁇ m] of the hard coat layer (B) 12, and the average thickness dI [ ⁇ m] of the optical function layer (C) 13 are calculated according to the above formula It satisfies the relationships (1) and (2).
  • “on” or “on the surface” may be in a state of being in direct contact with the surface, or may be in a state of intervening another layer or the like.
  • the hard coat film 10A comprises a hard coat layer (B) 12, an optical functional layer (C) 13 and an antifouling layer (D) on at least one surface of a light transmissive substrate (A) 11. 14 are stacked in the above order.
  • the antifouling layer (D) 14 contains fluorine as an element.
  • the surfaces of the optical functional layer (C) 13 and the antifouling layer (D) 14 formed on the hard coat layer (B) 12 also have the same uneven shape as the surface of the hard coat layer (B) 12. .
  • the hard coat layer (B) 12 contains particles. As illustrated, the hard coat layer (B) 12 is formed by containing particles 12b in a resin layer 12a.
  • “on” or “on the surface” may be in a state of being in direct contact with the surface, or may be in a state of intervening another layer or the like.
  • the light transmissive substrate (A) 11, the hard coat layer (B) 12, the optical function layer (C) 13 and the antifouling layer (D) 14 are directly laminated, which will be described later. It may be laminated via other layers so as to be carried out.
  • each of the layers (A) to (D) may be flat as shown in FIG. 1, or may be uneven as shown in FIG.
  • the method for measuring the "average thickness" of each layer (A) to (D) is not particularly limited, but for example, linear gauge, TEM (transmission electron microscope), fluorescent X-ray, etc. Specifically, for example, it can be measured by the method described in Examples below. Further, for example, even if the surface of each layer (for example, the hard coat layer (B)) has unevenness and the thickness of each part varies, for example, any three points can be detected by imaging in a 1 ⁇ m square field of view. The thickness is measured, and the thickness is measured at 5 points in a 1 ⁇ m square visual field in the same manner, and the average value of the thickness measurement results at 15 points in total is taken as the average thickness, whereby the average thickness can be measured.
  • the hard coat film of the present invention satisfies the following formula (1). That is, the product of the average thickness dH [ ⁇ m] of the hard coat layer (B) and the average thickness dI [ ⁇ m] of the optical function layer (C) is in the range of 0.2-4. 0.2 ⁇ dH ⁇ dI ⁇ 4 (1)
  • dH [ ⁇ m] ⁇ dI [ ⁇ m] may be, for example, 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more, for example, 4.0 or less, 3.5 or less , 3.0 or less, or 2.5 or less, for example, 0.2 to 4.0, 0.3 to 3.5, 0.4 to 3.0, or 0.5 to 2.0. 5 may be used.
  • the hard coat film of the present invention satisfies the following formula (2). That is, the average thickness dH [ ⁇ m] of the hard coat layer (B) and the average thickness dH [ ⁇ m] of the hard coat layer (B) are added to the average thickness dS [ ⁇ m] of the light-transmitting substrate (A). ] is in the range of 0.02 to 0.62. 0.02 ⁇ (dH+dI)/dS ⁇ 0.62 (2)
  • (dH [ ⁇ m] + dI [ ⁇ m])/dS [ ⁇ m] may be, for example, 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more, for example, 0.6 0.5 or less, 0.4 or less, or 0.3 or less, for example, 0.02 to 0.6, 0.03 to 0.5, 0.04 to 0.4, or It may be from 0.05 to 0.3.
  • the hard coat film of the present invention contains layers other than the light transmissive substrate (A), the hard coat layer (B), the optical function layer (C) and the antifouling layer (D). It may or may not contain
  • the light-transmitting substrate (A), the hard coat layer (B), the optical function layer (C), and the antifouling layer (D) may be directly laminated. You may laminate
  • adheresive layer means “adhesive layer or adhesive layer”.
  • Adhesive layer means “a layer formed by an adhesive”.
  • Adhesive layer means “a layer formed by an adhesive”.
  • an adhesive that has a relatively small adhesive force (adhesive force) and can be removed from the adherend is called an "adhesive”, and has a relatively large adhesive force (adhesive force) that makes it impossible to remove the adherend. Difficult things are sometimes called “adhesives” to distinguish them.
  • a substance with a relatively small adhesive force is called an "adhesive”
  • a substance with a relatively large adhesive force is called an “adhesive”
  • the adhesive layer may be, for example, an adhesive layer formed of an adhesive (adhesive composition).
  • the thickness of the adhesive layer is not particularly limited. may be Although the adhesive is not particularly limited, examples thereof include (meth)acrylic polymers. For example, these may be dissolved or dispersed in a solvent to form a solution or dispersion, which may be used as the pressure-sensitive adhesive (pressure-sensitive adhesive composition). Examples of the solvent include ethyl acetate and the like, and one type thereof may be used alone, or a plurality of types may be used in combination.
  • the concentration of the solute or dispersoid (e.g., the acrylic polymer) in the solution or dispersion may be, for example, 10% by mass or more, or 15% by mass or more, for example, 60% by mass or less, or 50% by mass. % or less, 40 mass % or less, or 25 mass % or less.
  • (meth)acrylic polymer refers to a polymer or copolymer of at least one monomer selected from (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide.
  • (meth)acrylic acid means “at least one of acrylic acid and methacrylic acid”
  • (meth)acrylic acid ester means “at least one of acrylic acid ester and methacrylic acid ester”.
  • examples of the (meth)acrylic acid ester include linear or branched alkyl esters of (meth)acrylic acid.
  • the number of carbon atoms in the alkyl group may be, for example, 1 or more, 2 or more, 3 or more, or 4 or more, for example, 18 or less, 16 or less. , 14 or less, 12 or less, 10 or less, or 8 or less.
  • Said alkyl groups may be substituted or unsubstituted, for example with one or more substituents.
  • substituents include hydroxyl groups and the like, and in the case of a plurality of substituents, they may be the same or different.
  • Specific examples of the (meth)acrylic acid ester include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and the like.
  • the said adhesive may use only one type, and may use multiple types together.
  • the light-transmitting substrate (A) is not particularly limited. A base material etc. are mentioned.
  • the transparent plastic film substrate is not particularly limited, but preferably has excellent visible light transmittance (preferably light transmittance of 90% or more) and excellent transparency (preferably haze value of 1% or less).
  • a transparent plastic film substrate described in JP-A-2008-90263 As the transparent plastic film substrate, one having optically low birefringence is preferably used.
  • the hard coat film of the present invention can also be used for a polarizing plate as a protective film, for example.
  • a film formed of polyolefin or the like having a or norbornene structure is preferable.
  • the transparent plastic film substrate may be the polarizer itself.
  • Such a structure eliminates the need for a protective layer made of TAC or the like and simplifies the structure of the polarizing plate, thereby reducing the number of steps for manufacturing the polarizing plate or the image display device and improving the production efficiency.
  • the polarizing plate can be made thinner.
  • the transparent plastic film substrate is a polarizer, for example, the non-transparent layer functions as a protective layer.
  • the hard coat film of the present invention also functions as a cover plate, for example, when attached to the surface of a liquid crystal cell.
  • the average thickness of the light-transmitting substrate (A) is not particularly limited. 100 ⁇ m or less, such as 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 60 ⁇ m or less, for example, 10-100 ⁇ m, 20-90 ⁇ m, 30-80 ⁇ m, 40-70 ⁇ m, or 50 ⁇ m or less. It may be 60 ⁇ m. From the viewpoints of ensuring workability and bending resistance, it is preferable that the average thickness of the light-transmitting substrate (A) is not too large. From the viewpoint of insufficient strength, it is preferable that the average thickness of the light-transmitting substrate (A) is not too small.
  • the method for measuring the average thickness of the light-transmitting substrate (A) is not particularly limited, but for example, it can be measured using a linear gauge as in Examples described later.
  • the refractive index of the light transmissive substrate (A) is not particularly limited.
  • the refractive index ranges, for example, from 1.30 to 1.80 or from 1.40 to 1.70.
  • refractive index refers to the refractive index at a wavelength of 550 nm unless otherwise specified.
  • the method for measuring the refractive index is not particularly limited, but in the case of the refractive index of fine substances such as particles, for example, the Becke method can be used. In the Becke method, a sample to be measured is dispersed in a standard refractive liquid on a slide glass, and the refractive index of the standard refractive liquid when the outline of the sample disappears or becomes blurred when observed with a microscope is used as the refractive index of the sample.
  • the method for measuring the refractive index of a measurement object whose refractive index cannot be measured by the Becke method is not particularly limited, but for example, It can be measured using a general refractometer (instrument for measuring refractive index).
  • the refractometer is also not particularly limited, and examples thereof include an Abbe refractometer. Examples of the Abbe refractometer include a multi-wavelength Abbe refractometer DR-M2/1550 (trade name) manufactured by Atago Co., Ltd.
  • the hard coat layer (B) is not particularly limited, and may be, for example, similar to or similar to a hard coat layer of a general hard coat film.
  • the hard coat layer (B) may be formed of a resin layer.
  • the hard coat layer (B) may or may not contain fillers, thixotropy-imparting agents, surface control agents, pigments, dyes, and the like.
  • the filler is not particularly limited, it may be, for example, particles.
  • the particles are not particularly limited, and may be, for example, organic particles or inorganic particles, and may be amorphous particles or spherical particles. The material for forming the hard coat layer (B) will be described later in detail.
  • the average thickness of the hard coat layer (B) is not particularly limited. for example, 30 ⁇ m or less, 25 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, or 10 ⁇ m or less, for example, 0.5-30 ⁇ m, 1.0-25 ⁇ m, 101.5-20 ⁇ m, 2.0 ⁇ m or less. ⁇ 15 ⁇ m, or 2.5-10 ⁇ m. From the viewpoint of preventing curling and processing defects, it is preferable that the average thickness of the hard coat layer (B) is not too large. From the viewpoint of preventing a decrease in pencil hardness and insufficient hardness, it is preferable that the average thickness of the hard coat layer (B) is not too small.
  • the method for measuring the average thickness of the hard coat layer (B) is not particularly limited, but for example, it can be measured using a linear gauge as in Examples described later.
  • the surface roughness of the surface of the hard coat layer (B) opposite to the substrate (A) is not particularly limited, but is, for example, 1 nm or more, 1.5 nm or more, or 2.0 nm or more. , 2.5 nm or more, or 3.0 nm or more, for example, 10 nm or less, 9.5 nm or less, 9.0 nm or less, 8.5 nm or less, or 8.0 nm or less, for example, It may be 1-10 nm, 1.5-9.5 nm, 2.0-9.0 nm, 2.5-8.5 nm, or 3.0-8.0 nm.
  • the "surface roughness" of each layer of the hard coat film of the present invention refers to the surface roughness on the side opposite to the substrate (A).
  • the surface roughness of the hard coat layer (B) affects, for example, the adhesion between the hard coat layer (B) and the optical function layer (C). From the viewpoint of preventing haze and scratching of the surface, it is preferable that the surface roughness of the hard coat layer (B) is not too large. From the viewpoint of preventing poor adhesion with the optical function layer (C) and preventing deterioration of antiblocking properties, it is preferable that the surface roughness of the hard coat layer (B) is not too small.
  • the method for measuring the surface roughness Ra of each layer of the hard coat film is not particularly limited, but it can be measured, for example, by the following measuring method.
  • the surface roughness of the outermost layer when the surface roughness of the outermost layer is measured, the surface roughness of the layer below it can be generally estimated to be approximately equal to the surface roughness of the outermost layer.
  • the antifouling layer (D) is the outermost layer.
  • the antifouling layer (D) is the outermost layer
  • the optical functional layer (C) and the hard coat layer (B) can be estimated to be approximately equal to the measured value of the surface roughness of the antifouling layer (D).
  • the optical function layer (C) may be, for example, an antireflection layer having an antireflection function.
  • the optical function layer (C) may be an inorganic layer formed of an inorganic substance, for example.
  • the “inorganic substance” includes, for example, an organic-inorganic hybrid material described later.
  • the inorganic substance that is the material for forming the optical function layer (C) is not particularly limited, but may contain, for example, at least one selected from the group consisting of metals, metal oxides, silicon and silicon oxides. .
  • the optical functional layer (C) will be described below with reference to examples.
  • the metal is not particularly limited, but examples thereof include aluminum, zinc, tin, indium, gallium, zirconium, lead and the like.
  • the metal oxide is not particularly limited, but for example, aluminum oxide (eg, Al 2 O 3 ), zinc-tin composite oxide (ZTO), indium-tin composite oxide (ITO), indium-zinc composite oxide (IZO), Gallium-zinc composite oxide (GZO), zirconium oxide (ZrO 2 ), and the like are included.
  • the silicon oxide is, for example, a compound represented by SiOx (0 ⁇ x ⁇ 2). Examples of the silicon oxide include, but are not limited to, silicon dioxide (SiO 2 ).
  • the material for forming the optical functional layer (C) is not particularly limited, and may be the same as the optical functional layer in a general optical film (eg, hard coat film).
  • a general optical film eg, hard coat film
  • the material for forming it may be the same as that of a general antireflection layer.
  • the material for forming the layer may be the same as for general inorganic layers.
  • the optical function layer (C) may consist of only one layer, or may consist of a plurality of layers. Each layer of the optical function layer (C) may be made of only one type of forming material, or may be made of a plurality of types of forming materials.
  • the optical function layer (C) may be a laminate of an adhesion layer and another layer.
  • the adhesion layer is formed on the hard coat layer (B), and then The other layers may be formed.
  • the adhesion layer may be, for example, an ITO layer. ITO has a high refractive index and absorbs light easily, so if the thickness of the ITO layer is too large, for example, antireflection performance may decrease. Therefore, when the optical function layer (C) is an antireflection layer, it is preferable not to increase the thickness of the ITO layer too much.
  • the optical function layer (C) may contain, for example, an organic-inorganic hybrid material.
  • the organic-inorganic hybrid material is not particularly limited, but examples thereof include polysiloxane resins and silsesquioxane resins.
  • the optical function layer (C) may or may not contain, for example, components other than the inorganic substance. Said other component may be, for example, an organic compound.
  • the organic compound is not particularly limited, but may be, for example, various resins.
  • the resin is not particularly limited, for example, it may be the same as the resin that can be used as the material for forming the light-transmitting base material (A), and one type of resin may be used alone or a plurality of types may be used in combination.
  • the resin may be, for example, an acrylic resin or the like.
  • the optical function layer (C) may be formed of a mixture of acrylic resin and zirconium oxide, a mixture of acrylic resin and silicon oxide (silica), or the like.
  • the content is not particularly limited, but may be, for example, 10% by mass or less, 5% by mass or less, or 1% by mass or less. is not particularly limited, but is, for example, a numerical value exceeding 0% by mass.
  • a method for forming the optical function layer (C) is not particularly limited, but a so-called dry process (a forming method that does not use a solvent) is preferable. Specifically, for example, it may be formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD). Specific methods for vacuum deposition, sputtering, and chemical vapor deposition (CVD) are also not particularly limited, and may be, for example, the same or similar to general methods.
  • the method for forming the optical function layer (C) of the present invention is not particularly limited.
  • the optical function layer (C) having a certain thickness or more is formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • the optical function layer (C) of the present invention can be formed.
  • the inorganic substance is not particularly limited, but may contain, for example, at least one material selected from the group consisting of metals, metal oxides, silicon and silicon oxides, as described above.
  • the average thickness of the optical function layer (C) is not particularly limited. For example, it may be 0.5 ⁇ m or less, 0.4 ⁇ m or less, 0.3 ⁇ m or less, 0.2 ⁇ m or less, or 0.1 ⁇ m or less, such as 0.05 to 0.5 ⁇ m, 0.06 to 0.4 ⁇ m. , 0.07-0.3 ⁇ m, 0.08-0.2 ⁇ m, or 0.09-0.1 ⁇ m. From the viewpoint of preventing deterioration of bending resistance, it is preferable that the average thickness of the optical function layer (C) is not too large. From the viewpoint of preventing deterioration of sliding resistance, it is preferable that the average thickness of the optical function layer (C) is not too small. Although the method for measuring the average thickness of the optical function layer (C) is not particularly limited, for example, it can be measured using a TEM (transmission electron microscope) as in Examples described later.
  • the surface roughness of the optical function layer (C) is not particularly limited, but is, for example, the same as the surface roughness of the hard coat layer (B). Moreover, from the viewpoint of preventing haze and scratching of the surface, it is preferable that the surface roughness of the optical function layer (C) is not too large. From the viewpoint of preventing poor adhesion with the antifouling layer (D) and preventing deterioration of antiblocking properties, it is preferable that the surface roughness of the optical function layer (C) is not too small.
  • the antifouling layer (D) is not particularly limited, but may be, for example, similar to or conforming to an antifouling layer used in general optical members and the like.
  • the antifouling layer (D) contains fluorine as an element as described above.
  • the antifouling layer (D) may contain at least one of elemental fluorine and a fluorine compound as an antifouling component.
  • the antifouling component include, but are not particularly limited to, an organic silane compound having a perfluoropolyether group.
  • the antifouling layer (D) may or may not contain components other than the antifouling component.
  • the content is not particularly limited, but is, for example, 50% by mass or less, 25% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass. % or less, or 1% by mass or less, and the lower limit is not particularly limited, but it is, for example, a numerical value exceeding 0% by mass.
  • the antifouling layer (D) can exhibit high antifouling properties even with a small film thickness, for example, so that the optical function of the optical function layer (C) is less likely to be impaired.
  • the optical function of the optical function layer (C) includes, for example, an antireflection function.
  • the antifouling layer (D) contains fluorine as an element, for example, a low refractive index can be realized, and the refractive index difference with the optical function layer (C) is reduced. Accordingly, for example, the antifouling layer (D) is less likely to change the reflection spectrum of the optical function layer (C), and less likely to impede the optical function (for example, antireflection function) of the optical function layer (C).
  • the antifouling layer (D) in the present invention can achieve, for example, a low refractive index as described above.
  • the antifouling layer (D) in the present invention can be formed (formed) by various methods such as wet coating and vapor deposition, depending on the material used to form the layer. The forming method is not limited.
  • the method for forming the antifouling layer (D) is not particularly limited as described above, but a so-called dry process (a forming method that does not use a solvent) is preferred. Specifically, for example, it may be formed by at least one method selected from the group consisting of vacuum deposition, sputtering, and chemical vapor deposition (CVD). Specific methods for vacuum deposition, sputtering, and chemical vapor deposition (CVD) are also not particularly limited, and may be, for example, the same or similar to general methods.
  • the average thickness of the antifouling layer (D) is not particularly limited, but may be, for example, 1 nm or more, 2 nm or more, 3 nm or more, 4 nm or more, or 5 nm or more. , 24 nm or less, or 22 nm or less, for example, 1-30 nm, 2-28 nm, 3-26 nm, 4-24 nm, or 5-22 nm. From the viewpoint of preventing film detachment (peeling of the antifouling layer (D)), it is preferable that the average thickness of the antifouling layer (D) is not too large.
  • the average thickness of the antifouling layer (D) is not too small.
  • the method for measuring the average thickness of the antifouling layer (D) is not particularly limited, for example, it can be measured using fluorescent X-rays as in Examples described later.
  • the surface roughness of the antifouling layer (D) is not particularly limited. for example, 10 nm or less, 9.5 nm or less, 9.0 nm or less, 8.5 nm or less, or 8.0 nm or less, for example, 1 to 10 nm, 1.5 to 9.5 nm , 2.0-9.0 nm, 2.5-8.5 nm, or 3.0-8.0 nm.
  • a method for measuring the surface roughness is not particularly limited, and is, for example, as described above. From the viewpoints of preventing haze and susceptibility to scratches, it is preferable that the surface roughness of the antifouling layer (D) is not too large. From the viewpoint of antiblocking properties, it is preferable that the surface roughness of the antifouling layer (D) is not too small.
  • the water contact angle of the antifouling layer (D) surface is not particularly limited. ° or more, 110° or more, or 115° or more. From the viewpoint of antifouling performance, it is preferable that the water contact angle of the antifouling layer (D) is not too large.
  • the hard coat film of the present invention can be used, for example, as a clear film or an antiglare film (also called AG film).
  • an antiglare film also called AG film
  • the hard coat layer (B) may be provided with antiglare properties (AG properties).
  • the hard coat film of the present invention may have, for example, a light transmittance of 90% or more at a wavelength of 550 nm for the entire hard coat film.
  • the light transmittance of the entire hard coat film at a wavelength of 550 nm is, for example, 90% or more, 92% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.
  • the method for measuring the light transmittance is not particularly limited, but it can be measured, for example, by the following measuring method.
  • the method for producing the hard coat film of the present invention is not particularly limited, and for example, it can be carried out in the same manner as or according to a general method for producing a hard coat film.
  • the method for producing the hard coat film of the present invention will be described below with reference to examples.
  • a light-transmitting substrate (A) is prepared.
  • the material, thickness, etc. of the light-transmitting substrate (A) are, for example, as described above.
  • a hard coat layer (B) is formed on the light transmissive substrate (A).
  • the method for forming the hard coat layer (B) on the light-transmitting substrate (A) is not particularly limited, but is, for example, as follows.
  • the step of forming this hard coat layer (B) may be referred to as a "hard coat layer forming step".
  • a coating solution for forming a hard coat layer hereinafter sometimes simply referred to as “coating solution” or "hard coat layer forming material" is applied onto the light-transmitting substrate (A).
  • a coating film forming step of drying the applied coating liquid to form a coating film is applied onto the light-transmitting substrate (A).
  • the hard coat layer forming step may further include a curing step of curing the coating film.
  • the curing can be performed after the drying, for example, but not limited thereto.
  • the curing can be performed, for example, by heating, light irradiation, or the like.
  • the light is not particularly limited, it may be, for example, ultraviolet light.
  • the light source for the light irradiation is also not particularly limited, and may be, for example, a high-pressure mercury lamp.
  • the coating liquid may be, for example, a coating liquid containing a resin material and a diluent solvent (hereinafter sometimes simply referred to as "solvent").
  • the coating liquid may or may not contain components other than these.
  • the other components include, but are not limited to, thixotropy-imparting agents and fillers.
  • the filler include particles.
  • the particles are not particularly limited, and may be, for example, organic particles or inorganic particles, and may be amorphous particles or spherical particles.
  • the thixotropic agent, the particles, and the like are not particularly limited, but may be, for example, the same as or similar to the thixotropic agent, particles, and the like contained in a general hard coat layer.
  • the particles include acrylic-styrene copolymers, silicone resins, and silica.
  • the resin material contained in the coating liquid may be, for example, the resin itself that forms the hard coat layer (B), or may be a resin material that forms the resin through polymerization, curing, or the like.
  • the resin is not particularly limited, but may be, for example, a thermosetting resin, an ionizing radiation curable resin, or the like.
  • the resin may contain, for example, an acrylate resin (also referred to as acrylic resin), and may contain, for example, a urethane acrylate resin.
  • the resin may be, for example, a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate.
  • the resin material may contain, for example, an oligomer having a functional group and a monomer.
  • the resin forming the hard coat layer (B) may be a copolymer of the oligomer having the functional group and the monomer.
  • the oligomer having the functional group include, but are not particularly limited to, curable urethane acrylate resins.
  • the curable urethane acrylate resin include "UV-1700TL" (trade name) manufactured by Mitsubishi Chemical Corporation, "UT-7314" (trade name) manufactured by Mitsubishi Chemical Corporation, and the like.
  • the monomer include, but are not limited to, polyfunctional acrylates.
  • Examples of the polyfunctional acrylate include trade name "M-920" manufactured by Toagosei Co., Ltd., and the like.
  • the solvent is not particularly limited, and various solvents can be used. One type may be used alone, or two or more types may be used in combination. For example, the optimum solvent type and solvent ratio may be appropriately selected according to the composition of the resin, the types and contents of the nanosilica particles and the thixotropy-imparting agent.
  • the solvent examples include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, t-butyl alcohol (TBA), 2-methoxyethanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclo ketones such as pentanone; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve ; aliphatic hydrocarbons such as hexane, heptane and octane; and aromatic hydrocarbons such as benzene, toluene and xylene.
  • alcohols such as methanol, ethanol, isopropyl alcohol (
  • the solvent may contain a hydrocarbon solvent and a ketone solvent.
  • Said hydrocarbon solvent may be, for example, an aromatic hydrocarbon.
  • the aromatic hydrocarbon may be, for example, at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene.
  • the ketone solvent may be, for example, cyclopentanone and at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone.
  • the solvent preferably contains the hydrocarbon solvent (eg, toluene), for example, in order to dissolve the thixotropic agent (eg, thickener).
  • the solvent may be, for example, a solvent obtained by mixing the hydrocarbon solvent and the ketone solvent at a mass ratio of 90:10 to 10:90.
  • the mass ratio of the hydrocarbon solvent and the ketone solvent may be, for example, 80:20-20:80, 70:30-30:70, or 40:60-60:40.
  • the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone.
  • the solvent may contain, for example, toluene, and may further contain at least one selected from the group consisting of ethyl acetate, butyl acetate, IPA, methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, and TBA. good.
  • a good solvent for the acrylic film (acrylic resin) can be suitably used.
  • the solvent may be, for example, a solvent containing a hydrocarbon solvent and a ketone solvent, as described above.
  • Said hydrocarbon solvent may be, for example, an aromatic hydrocarbon.
  • the aromatic hydrocarbon may be, for example, at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene.
  • the ketone solvent may be, for example, at least one selected from the group consisting of cyclopentanone, acetone, methylethylketone, methylisobutylketone, diethylketone, cyclohexanone, isophorone, and acetophenone.
  • the solvent may be, for example, a solvent obtained by mixing the hydrocarbon solvent and the ketone solvent at a mass ratio of 90:10 to 10:90.
  • the mass ratio of the hydrocarbon solvent and the ketone solvent may be, for example, 80:20-20:80, 70:30-30:70, or 40:60-60:40.
  • the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone.
  • the solvent is not particularly limited, but examples include ethyl acetate, methyl ethyl ketone, MIBK (methyl isobutyl ketone), and cyclopentanone. etc., and one type may be used alone or a plurality of types may be used in combination.
  • the solvent may be, for example, a mixed solvent of MIBK and cyclopentanone.
  • the mixing ratio of MIBK and cyclopentanone is not particularly limited, but may be, for example, 90:10 to 10:90, 80:20 to 20:80, 70:30 to 30:70 in mass ratio.
  • the solvent it is possible to exhibit good thixotropic properties in the antiglare hard coat layer-forming material (coating liquid) when the thixotropy-imparting agent is contained.
  • organoclays toluene and xylene can be suitably used alone or in combination. They can be used or used in combination.
  • modified urea butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.
  • leveling agents can be added to the hard coat layer forming material.
  • a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing coating unevenness (uniformizing the coated surface).
  • a suitable leveling agent can be selected according to the requirements.
  • the amount of the leveling agent compounded is, for example, 5 parts by weight or less, preferably in the range of 0.01 to 5 parts by weight, per 100 parts by weight of the resin.
  • Pigments, fillers, dispersants, plasticizers, UV absorbers, surfactants, antifouling agents, antioxidants, and the like are added to the hard coat layer-forming material as necessary within a range that does not impair the performance. may be These additives may be used singly or in combination of two or more.
  • photopolymerization initiators such as those described in JP-A-2008-88309, can be used for the hard coat layer-forming material.
  • Examples of the method for forming a coating film by coating the hard coat layer-forming material (coating solution) on the light-transmitting substrate (A) include a fountain coating method, a die coating method, a spray coating method, and a gravure coating method.
  • a coating method such as a coating method, a roll coating method, or a bar coating method can be used.
  • the coating film is dried and cured to form a hard coat layer (B).
  • the drying may be, for example, natural drying, air drying by blowing air, heat drying, or a combination thereof.
  • the drying temperature of the hard coat layer forming material (coating liquid) may be, for example, in the range of 30 to 200°C.
  • the drying temperature may be, for example, 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, 80° C. or higher, 90° C. or higher, or 100° C. or higher, 190° C. or lower, 180° C. or lower, 170° C. °C or lower, 160 °C or lower, 150 °C or lower, 140 °C or lower, 135 °C or lower, 130 °C or lower, 120 °C or lower, or 110 °C or lower.
  • the drying time is not particularly limited. may
  • the means for curing the coating film is not particularly limited, but ultraviolet curing is preferable.
  • the irradiation amount of the energy beam source is preferably 50 to 500 mJ/cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
  • the irradiation dose is 50 mJ/cm 2 or more, curing proceeds sufficiently and the hardness of the formed hard coat layer tends to increase. Moreover, if it is 500 mJ/cm 2 or less, coloring of the formed hard coat layer can be prevented.
  • a laminate in which the hard coat layer (B) is laminated on the light-transmitting substrate (A) can be produced.
  • an optical functional layer (C) is formed on the surface of the hard coat layer (B) opposite to the light transmissive substrate (A) (optical functional layer forming step).
  • the method for forming the optical function layer (C) in this optical function layer forming step is not particularly limited, but dry processes are preferred as described above, and examples include vacuum deposition, sputtering, and chemical vapor deposition (CVD). may be formed by at least one method selected from the group consisting of Specific methods for vacuum deposition, sputtering, and chemical vapor deposition (CVD) are also not particularly limited, and may be, for example, the same or similar to general methods.
  • the material, thickness, etc. of the optical function layer (C) are, for example, as described above.
  • the hard coating layer (B) may be formed in order to increase the adhesion between the hard coating layer (B) and the optical functional layer (C).
  • the surface may be surface-treated by methods such as plasma treatment, corona treatment, water washing treatment, and solvent coating. Conditions for this surface treatment are also not particularly limited, and may be, for example, similar to or in conformity with general front surface treatment.
  • the average thickness of the light transmissive substrate (A), the hard coat layer (B) and the optical functional layer (C) is A hard coat layer (B) and an optical function layer (C) are formed so as to satisfy the relationships (1) and (2).
  • an antifouling layer (D) is further formed on the surface of the optical functional layer (C) opposite to the light-transmissive substrate (A) (antifouling layer forming step) to obtain the hard coat film of the present invention.
  • the method (manufacturing method) for forming the antifouling layer (D) in this antifouling layer forming step is not particularly limited, but may be, for example, similar to or conforming to a general antifouling layer forming method. Specifically, for example, as described above, it can be formed by a dry process, such as a vacuum deposition method, a sputtering method, a chemical vapor deposition method (CVD), or the like.
  • This method is not particularly limited, and for example, as described above, it may be similar to or based on general vacuum deposition methods, sputtering methods, and chemical vapor deposition methods (CVD).
  • the material, thickness, etc. of the antifouling layer (D) are, for example, as described above.
  • the hard coat layer (B), the optical functional layer (C) and the antifouling layer (D) are laminated in the order described above on at least one surface of the light transmissive substrate (A).
  • Inventive hardcoat films can be produced.
  • this production method is an example, and the production method of the hard coat film of the present invention is not limited to this.
  • the method for producing the hard coat film of the present invention can be, for example, a continuous production method.
  • the light-transmissive substrate (A) is elongated, and the hard coat film is conveyed while the light-transmissive substrate (A) is conveyed.
  • the manufacturing method may be such that the coating layer forming step, the optical function layer forming step, the antifouling layer forming step, and, if necessary, other steps are performed continuously.
  • the long light-transmitting substrate (A) is in the form of a roll, and the method for producing the hard coat film of the present invention while unwinding the light-transmitting substrate (A) from the roll. may be implemented.
  • the hard coat film of the present invention is not particularly limited.
  • it may be a clear film or an antiglare film (antiglare hard coat film).
  • the optical member of the present invention is not particularly limited, it may be, for example, a polarizing plate.
  • the polarizing plate is also not particularly limited, but may contain, for example, the hard coat film and polarizer of the present invention, and may further contain other constituent elements. Each constituent element of the polarizing plate may be bonded together by, for example, an adhesive or a pressure-sensitive adhesive.
  • the image display device of the present invention is also not particularly limited, and may be any image display device, such as a liquid crystal display device, an organic EL display device, an inorganic EL display device, a plasma display device, and the like.
  • the configuration of the image display device of the present invention is not particularly limited, and may have, for example, the same configuration as a general image display device.
  • an LCD can be manufactured by appropriately assembling components such as a liquid crystal cell, optical members such as a polarizing plate, and, if necessary, an illumination system (backlight, etc.) and incorporating a drive circuit.
  • the application of the image display device of the present invention is not particularly limited, and can be used for any application.
  • Applications include, for example, personal computer monitors, laptop computers, tablets, smartphones, OA equipment such as copiers, mobile phones, clocks, digital cameras, personal digital assistants (PDAs), portable equipment such as portable game machines, video cameras, Household electrical equipment such as televisions and microwave ovens, back monitors, car navigation system monitors, car audio equipment, display equipment such as information monitors for commercial stores, security equipment such as surveillance monitors, nursing care monitors , nursing and medical equipment such as medical monitors, smart glasses, and VR equipment.
  • the image display device of the present invention may be, for example, an image display device having a camera function.
  • the transparent layer in the hard coat film of the present invention may be a transparent layer for a camera hole of an image display device.
  • the present invention it is possible to provide a hard coat film without impairing the transparency of the transparent layer. Therefore, for example, it is possible to provide an image display device without impairing the image quality of camera images. be.
  • the number of parts of substances is parts by mass (parts by weight) unless otherwise specified.
  • Example 1 According to the present invention, a hard coat layer (B), an optical functional layer (C) and an antifouling layer (D) are laminated in the order described above on one surface of a light transmissive substrate (A) in the following manner. of the hard coat film was produced.
  • a polyethylene terephthalate (PET) film (thickness: 65 ⁇ m) was prepared as the light-transmitting substrate (A).
  • a hard coat layer (B) was formed on one surface of the light transmissive substrate (A) (hard coat layer forming step).
  • a mixture of UV-curable monomer and SiO 2 filler (trade name “OPSTAR Z7540”, solid content concentration 56% by mass, manufactured by Arakawa Chemical Industries, Ltd.) 100 parts by mass (solid content conversion), light A polymerization initiator (trade name “IRGACURE906”, manufactured by BASF) 5 parts by mass and a leveling agent (trade name “LE-303”, manufactured by Kyoeisha Chemical Co., Ltd.) 0.1 part by mass are mixed to obtain a mixed solution.
  • a mixed solvent of butyl acetate and MIBK (mass ratio: 50:50) was added to the mixture to adjust the solid content concentration to 40%.
  • an ultraviolet curable resin composition (varnish) was prepared.
  • the resin composition was applied to one side of the PET film (light-transmitting substrate (A)) to form a coating film.
  • This coating film was dried by heating and then cured by UV irradiation.
  • the temperature for heating the coating film was 70° C., and the heating time was 60 seconds.
  • a high-pressure mercury lamp was used as a light source, ultraviolet rays with a wavelength of 365 nm were used, and the cumulative irradiation light amount was set at 300 mJ/cm 2 .
  • a hard coat layer (B) having a thickness of 5 ⁇ m is formed on the PET film (light-transmitting substrate (A)), and the light-transmitting substrate (A) and the hard coat layer (B) are formed.
  • the hard coat layer (B) formed in this example may be simply referred to as "HC layer”.
  • the laminate of the light-transmitting substrate (A) and the hard coat layer (B) produced in this example may be referred to as "HC layer-attached PET film".
  • the average thickness dS of the light transmissive substrate (A) was measured with a linear gauge. Since the light-transmissive substrate (A) of this example has a uniform thickness, it can be estimated that the thickness at any point is equal to the average thickness dS.
  • the average thickness dH of the hard coat layer (B) is obtained by measuring the average thickness of the laminate (HC layer-attached PET film) of the light-transmitting substrate (A) and the hard coat layer (B) with a linear gauge. , and the value obtained by subtracting dS from the value was defined as dH.
  • the thickness of any three points of the laminate was measured by imaging in a field of view of 1 ⁇ m square, and In the same manner, measurements were taken at 5 points in a 1 ⁇ m square field of view, and the average value of the thickness measurement results at a total of 15 points was taken as the average thickness dS+dH.
  • the HC layer surface of the HC layer-attached PET film was plasma-treated under a vacuum atmosphere of 1.0 Pa using a roll-to-roll type plasma treatment apparatus.
  • argon gas was used as an inert gas, and the discharge power was 780W.
  • an adhesion layer and an inorganic oxide base layer are formed in the order described above by a sputtering film formation method (sputter film formation step), thereby achieving the adhesion.
  • An optical functional layer (C) composed of the layer and the inorganic oxide underlayer was formed (optical functional layer forming step). Specifically, first, an indium tin oxide (ITO) layer having a thickness of 2.0 nm as an adhesion layer is first formed on the HC layer of the HC layer-attached PET film by a roll-to-roll type sputtering deposition apparatus. formed.
  • ITO indium tin oxide
  • a SiO 2 layer and a Nb 2 O 5 layer were formed on the ITO layer as inorganic oxide underlayers in the above order so that the total thickness was 0.23 ⁇ m. formed.
  • the SiO 2 layer was formed to have a thickness of 0.11 ⁇ m
  • the Nb 2 O 5 layer was formed to have a thickness of 0.12 ⁇ m.
  • an optical function layer (C) composed of the adhesion layer (ITO layer) and the inorganic oxide base layer (laminated body of the SiO 2 layer and the Nb 2 O 5 layer) was formed.
  • an ITO target is used, argon gas is used as an inert gas, and 10 parts by volume of oxygen gas is used as a reactive gas with respect to 100 parts by volume of the argon gas.
  • the ITO layer was formed by MFAC sputtering at 350 V and the pressure in the film formation chamber (film formation pressure) of 0.4 Pa.
  • a Si target and an Nb target were used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used, the discharge voltage was 350 V, the film formation pressure was 0.3 Pa, and the MFAC The SiO2 layer and the Nb2O5 layer were formed by sputtering .
  • the average thickness dI of the optical function layer (C) was measured by TEM (transmission electron microscope) observation of the cross section. Specifically, first, the surface of the optical functional layer (C) in the laminate of the light transmissive substrate (A), the hard coat layer (B) and the optical functional layer (C) is protected with an FIB resin, and then Cut in the depth direction. The cross section obtained by cutting is observed with a TEM (transmission electron microscope), and in the cross-sectional image, the optical functional layer (C) and the FIB resin protection from the interface between the hard coat layer (B) and the optical functional layer (C). The distance to the interface with the film was defined as the average thickness dI of the optical function layer (C).
  • the thickness of the optical function layer (C) in this example has a substantially uniform thickness, it can be estimated that the thickness at any point is equal to the average thickness dI.
  • the thickness of the optical function layer (C) was measured at the same 15 points as the measurement points of the average thickness dS+dH of the laminate of the light-transmitting substrate (A) and the hard coat layer (B). , and the numerical value obtained by averaging the measurement results of the 15 points was defined as the average thickness dI of the optical function layer (C).
  • the average thickness dI of the optical function layer (C) was measured in the same manner in each example and comparative example described later.
  • the average thickness dI of the optical functional layer (C) can also be measured in the same manner for the hard coat film (on which the antifouling layer (D) is formed) as a finished product.
  • an antifouling layer (D) was formed on the optical function layer (C) (antifouling layer forming step). Specifically, an antifouling layer (D) having a thickness of 10 nm was formed on the inorganic oxide underlayer by a vacuum deposition method using an alkoxysilane compound containing a perfluoropolyether group as a deposition source.
  • the vapor deposition source is a solid content obtained by drying "KY1903-1" (perfluoropolyether group-containing alkoxysilane compound, solid content concentration: 20% by mass) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the heating temperature of the vapor deposition source in the vacuum vapor deposition method was set to 260.degree.
  • the average thickness dF of the antifouling layer (D) was measured in the quantitative mode of a fluorescent X-ray spectrometer (manufactured by Rigaku Corporation, trade name ZXS Primus II).
  • the thickness of the antifouling layer (D) was measured at the same 15 points as the measurement points of the average thickness dS+dH of the laminate of the light-transmitting substrate (A) and the hard coat layer (B). , and the average value of the 15 measurement results was taken as the average thickness dF of the antifouling layer (D).
  • the hard coat layer (B), the optical function layer (C) and the antifouling layer (D) are laminated in the order described above on one surface of the light-transmitting substrate (A).
  • a hard coat film of Example (Example 1) was produced.
  • Examples 2 to 5 and Comparative Examples 1 to 4 Change the average thickness of the hard coat layer (B), the optical function layer (C), and the antifouling layer (D) on one side of the light-transmitting substrate (A) as shown in Table 1 below.
  • Hard coat films of Examples 2 to 5 and Comparative Examples 1 to 4 were produced in the same manner as in Example 1 except for the above.
  • a PET film was used as the light transmissive substrate (A).
  • the SiO 2 layer was formed to have a thickness of 0.15 ⁇ m
  • the Nb 2 O 5 layer was formed to have a thickness of 0.15 ⁇ m.
  • the SiO 2 layer was formed to have a thickness of 0.20 ⁇ m, and the Nb 2 O 5 layer was formed to have a thickness of 0.20 ⁇ m.
  • the SiO 2 layer was formed to have a thickness of 0.05 ⁇ m, and the Nb 2 O 5 layer was formed to have a thickness of 0.05 ⁇ m.
  • Abrasion resistance tests and bending resistance tests were performed on the hard coat films of the examples and comparative examples produced as described above by the following measurement methods.
  • an eraser ( ⁇ 6 mm) manufactured by Minoan was used, the load of the eraser on the surface of the antifouling layer (D) was 1 kgw/6 mm ⁇ , and the moving distance of the eraser on the surface of the antifouling layer (D) (in the reciprocating motion
  • the one-way distance) was set to 20 mm, the moving speed of the eraser was set to 40 rpm, and the number of reciprocating motions of the eraser to the antifouling layer (D) surface was set to 6000 times.
  • the water contact angle ⁇ 0 before rubbing and the water contact angle ⁇ 1 after rubbing of the portion rubbed with an eraser were measured by the following methods.
  • ⁇ Method for measuring water contact angle> The water contact angle of the surface of the antifouling layer (C) opposite to the light-transmitting substrate (A) was measured for each of the hard coat films of Examples and Comparative Examples. First, about 1 ⁇ L of pure water was dropped on the surface of the antifouling layer to form water droplets. Next, the angle formed by water droplets on the surface of the antifouling layer (D) and the surface of the antifouling layer (D) was measured. A contact angle meter (trade name “DMo-501”, manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement.
  • a pressure-sensitive adhesive composition A used in a bending resistance test described below was prepared by the following method.
  • the reaction solution was heated to 130° C., and the toluene, chain transfer agent and unreacted monomer were removed by drying to obtain a solid acrylic oligomer.
  • the acrylic oligomer had a weight average molecular weight of 5100 and a glass transition temperature (Tg) of 130°C.
  • the hard coat layer (B) 12, the optical functional layer (C) 13, and the antifouling layer (D) 14 in the light-transmitting substrate (A) 11 of the hard coat film are On the surface opposite to the laminated side, acrylic adhesive layer 21 (adhesive composition A, thickness 25 ⁇ m), polyimide film 22 (manufactured by KORON, thickness 50 ⁇ m), acrylic adhesive layer 23 (said Adhesive composition A, thickness 25 ⁇ m), PET film 24 (manufactured by Toray Industries, Inc., thickness 38 ⁇ m), and acrylic adhesive layer 25 (adhesive composition A, thickness 25 ⁇ m) are laminated in this order, A simulated sample 100 simulating an organic EL display device was manufactured.
  • a cylindrical core 200 made of stainless steel and having a diameter of 1 mm was brought into contact with the antifouling layer (D) 14 side of the simulated sample (D).
  • the simulated sample 100 was folded toward the cylindrical core 200 to obtain a folded state.
  • the simulated sample 100 was opened and returned to the state shown in FIG. 3(b). This opening and closing (bending and opening) was repeated 150,000 times. This opening and closing was performed using a durability tester (model number "DMLHB-FS-C", manufactured by YUASA).
  • the folded portion 101 (the contact portion between the simulated sample 100 and the cylindrical core 200) of the simulated sample 100 is irradiated with light from an LED light source (trade name LK-H766B manufactured by Twin Bird Co., Ltd.) and bent.
  • the appearance of the portion 101 was visually inspected by reflection, and the bending resistance was evaluated in the following three grades of ⁇ .
  • ⁇ No change is observed in the appearance of the bent portion 101 before and after opening and closing.
  • ⁇ The appearance of the bent portion 101 changes before and after opening and closing, but it is difficult to confirm the state of the change.
  • x The appearance of the bent portion 101 significantly changed before and after opening and closing.
  • Table 1 summarizes the test results of wear resistance and bending resistance tested as described above.
  • the hard coat film of the present invention can be used both as a clear film and as an antiglare film (antiglare hard coat film), and can be used in a wide variety of optical members and image display devices. Therefore, its industrial utility value is enormous.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un film de revêtement dur qui présente à la fois une résistance à l'usure de surface et une endurance à la flexion.　Ledit film de revêtement dur (10) comprend une couche de revêtement dur (B) (12), une couche optiquement fonctionnelle (C) (13) et une couche antisalissure (D) (14) empilées dans cet ordre sur au moins une surface d'un matériau de base transmettant la lumière (A) (11). Un élément de la couche antisalissure (D) (14) est le fluor. L'épaisseur moyenne dS [μm] du matériau de base transmettant la lumière (A) (11), l'épaisseur moyenne dH [μm] de la couche de revêtement dur (B) (12), et l'épaisseur moyenne dI [μm] de la couche optiquement fonctionnelle (C) (13) satisfont les expressions suivantes (1) et (2). (1) : 0,2 ≤ dH × dI ≤ 4 (2) : 0,02 ≤ (dH + dI)/dS ≤ 0,62
PCT/JP2022/023388 2021-06-11 2022-06-09 Film de revêtement dur, élément optique et dispositif d'affichage d'image WO2022260152A1 (fr)

Priority Applications (2)

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CN202280041594.3A CN117480412A (zh) 2021-06-11 2022-06-09 硬涂膜、光学构件及图像显示装置
KR1020237044520A KR20240011799A (ko) 2021-06-11 2022-06-09 하드 코트 필름, 광학 부재, 및 화상 표시 장치

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JP2021098260A JP2022189597A (ja) 2021-06-11 2021-06-11 ハードコートフィルム、光学部材、及び画像表示装置
JP2021-098260 2021-06-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023210368A1 (fr) * 2022-04-28 2023-11-02 日東電工株式会社 Film antireflet et dispositif d'affichage d'image

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009075325A (ja) * 2007-09-20 2009-04-09 Toppan Printing Co Ltd 反射防止フィルム
WO2012157682A1 (fr) * 2011-05-16 2012-11-22 大日本印刷株式会社 Procédé de production d'un film antireflet, film antireflet, plaque de polarisation et dispositif d'affichage d'image
WO2017217526A1 (fr) * 2016-06-17 2017-12-21 日東電工株式会社 Film anti-reflet et son procédé de fabrication, et plaque de polarisation fixée à une couche empêchant la réflexion
WO2019107036A1 (fr) * 2017-11-29 2019-06-06 日東電工株式会社 Film de revêtement dur, corps optique en couches et dispositif d'affichage d'image
WO2021106797A1 (fr) * 2019-11-25 2021-06-03 日東電工株式会社 Film antireflet et dispositif d'affichage d'image

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4859128B2 (ja) 2007-03-15 2012-01-25 日東電工株式会社 ハードコートフィルム、ハードコートフィルム積層体、及び画像表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009075325A (ja) * 2007-09-20 2009-04-09 Toppan Printing Co Ltd 反射防止フィルム
WO2012157682A1 (fr) * 2011-05-16 2012-11-22 大日本印刷株式会社 Procédé de production d'un film antireflet, film antireflet, plaque de polarisation et dispositif d'affichage d'image
WO2017217526A1 (fr) * 2016-06-17 2017-12-21 日東電工株式会社 Film anti-reflet et son procédé de fabrication, et plaque de polarisation fixée à une couche empêchant la réflexion
WO2019107036A1 (fr) * 2017-11-29 2019-06-06 日東電工株式会社 Film de revêtement dur, corps optique en couches et dispositif d'affichage d'image
WO2021106797A1 (fr) * 2019-11-25 2021-06-03 日東電工株式会社 Film antireflet et dispositif d'affichage d'image

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023210368A1 (fr) * 2022-04-28 2023-11-02 日東電工株式会社 Film antireflet et dispositif d'affichage d'image

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TW202313334A (zh) 2023-04-01
CN117480412A (zh) 2024-01-30
KR20240011799A (ko) 2024-01-26

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