WO2022209829A1 - Corps multicouche optique et dispositif d'affichage d'image - Google Patents

Corps multicouche optique et dispositif d'affichage d'image Download PDF

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Publication number
WO2022209829A1
WO2022209829A1 PCT/JP2022/011403 JP2022011403W WO2022209829A1 WO 2022209829 A1 WO2022209829 A1 WO 2022209829A1 JP 2022011403 W JP2022011403 W JP 2022011403W WO 2022209829 A1 WO2022209829 A1 WO 2022209829A1
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Prior art keywords
hard coat
coat layer
fine particles
layer
inorganic fine
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PCT/JP2022/011403
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English (en)
Japanese (ja)
Inventor
佳史 ▲高▼見
恵梨 上田
寛也 遠藤
遼太郎 横井
Original Assignee
日東電工株式会社
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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 CN202280026381.3A priority Critical patent/CN117157560A/zh
Priority to KR1020237026941A priority patent/KR20230159817A/ko
Publication of WO2022209829A1 publication Critical patent/WO2022209829A1/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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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

Definitions

  • the present invention relates to an optical laminate comprising an inorganic thin film on a hard coat film, and an image display device comprising the optical laminate.
  • An optical film such as an antireflection film is sometimes provided on the surface of an image display device such as a liquid crystal display or an organic EL display for the purpose of improving the visibility of the displayed image.
  • An antireflection film has an antireflection layer composed of a plurality of thin films having different refractive indices on a film substrate.
  • An antireflection film using an inorganic thin film such as an inorganic oxide as the thin film forming the antireflection layer can easily adjust the refractive index and film thickness, and therefore can achieve high antireflection properties.
  • Patent Document 1 describes that the adhesion between the hard coat layer and the antireflection layer can be improved by forming the antireflection layer on the hard coat layer containing fine particles via a primer layer.
  • a transparent cover layer made of glass or a rigid plastic substrate is provided on the surface of an image display device for the purpose of protecting the display panel from external impact. From this point of view, a configuration without a rigid cover layer is also adopted. In a structure without a cover layer, the antireflection film provided on the outermost surface is required to have higher hardness. Moreover, in recent years, pen-touch type touch panels have been increasingly installed mainly in notebook computers, and antireflection films are required to have a high level of sliding resistance.
  • the thickness of the hard coat layer provided directly under the antireflection layer By increasing the thickness of the hard coat layer provided directly under the antireflection layer, it is possible to improve the hardness and sliding resistance of the antireflection film.
  • the thickness of the hard coat layer containing fine particles is increased, the flex resistance of the hard coat layer is reduced, and the hard coat layer tends to crack or break during roll transport or handling such as lamination with other members. , the handling property tends to decrease.
  • the hard coat layer does not contain fine particles, cracking and cracking of the hard coat layer tend to be suppressed, but adhesion to the inorganic thin film such as an antireflection layer provided on the hard coat layer tends to decrease. Therefore, it is not easy to achieve both adhesion and handleability of an inorganic thin film in the conventional technology.
  • an object of the present invention to provide an optical layered body having high hardness, excellent adhesion between a hard coat layer and an inorganic thin film such as an antireflection layer, and excellent handleability with little cracking.
  • the present invention relates to an optical laminate comprising a front hard coat layer and an inorganic thin film in contact thereon on one main surface of a film substrate.
  • a back hard coat layer may be provided on the other main surface of the film substrate.
  • An example of an optical laminate is an antireflection film that includes an antireflection layer composed of a plurality of inorganic thin films with different refractive indices on a hard coat layer.
  • the antireflection layer may have an inorganic primer layer on the surface in contact with the front hard coat layer.
  • Such an optical layered body is arranged, for example, on the viewing side surface of an image display device.
  • the front hard coat layer contains a binder resin and inorganic fine particles.
  • the thickness of the front hard coat layer is preferably 7 to 50 ⁇ m.
  • the arithmetic mean height Sa of the surface of the front hard coat layer in contact with the inorganic thin film is preferably 1.0 nm or more.
  • the particle size of the inorganic fine particles is relatively large compared to the entire heart coat layer, or the content of the inorganic fine particles is relatively large compared to the entire hard coat layer. big.
  • the average primary particle diameter Da of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the interface with the inorganic thin film of the front hard coat layer is 30 to 70 nm, and the average of the inorganic fine particles contained in the entire front hard coat layer A primary particle diameter D is smaller than Da.
  • the average primary particle diameter Da of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the interface with the inorganic thin film of the front hard coat layer is 30 to 70 nm, and the thickness from the interface with the inorganic thin film of the front hard coat layer
  • the weight concentration of the inorganic fine particles in the range of 1 ⁇ m in the direction is greater than the weight concentration of the inorganic fine particles in the entire front hard coat layer.
  • the average primary particle diameter Da of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the interface with the inorganic thin film of the front hard coat layer is larger than the average primary particle diameter D of the inorganic fine particles contained in the entire front hard coat layer, and
  • the weight concentration of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the interface with the inorganic thin film of the front hard coat layer may be higher than the weight concentration of the inorganic fine particles in the entire front hard coat layer.
  • the weight concentration of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the interface with the inorganic thin film of the front hard coat layer may be 20% by weight or more.
  • the front hard coat layer comprises two or more layers, including a first hard coat layer in contact with the inorganic thin film, and a second hard coat layer located closer to the film substrate than the hard coat layer. and at least the first hard coat layer contains inorganic fine particles.
  • the front hard coat layer may have a two-layer structure of a first hard coat layer and a second hard coat layer, or may have a laminated structure of three or more layers.
  • the average primary particle diameter D1 of the inorganic fine particles in the first hard coat layer is preferably 30 to 70 nm.
  • the average primary particle diameter D2 of the inorganic fine particles in the second hard coat layer is preferably smaller than D1.
  • D2 may be greater than or equal to 5 nm and less than 30 nm.
  • the weight concentration of the inorganic fine particles in the first hard coat layer may be higher than the weight concentration of the inorganic fine particles in the entire front hard coat layer.
  • the weight concentration of the inorganic fine particles in the first hard coat layer may be 20 to 80% by weight.
  • the weight concentration of the inorganic fine particles in the second hard coat layer may be lower than the weight concentration of the inorganic fine particles in the first hard coat layer.
  • the second hard coat layer may not contain fine particles.
  • the thickness of the first hard coat layer may be 1 to 15 ⁇ m.
  • the thickness of the second hard coat layer may be 5 to 30 ⁇ m.
  • the thickness of the first hard coat layer may be 50% or less of the thickness of the entire front hard coat layer.
  • the thickness of the first hard coat layer may be smaller than the thickness of the second hard coat layer.
  • the thickness of the front hard coat layer is 7 ⁇ m or more, and the inorganic fine particles having the above particle diameter are present in the vicinity of the interface with the inorganic thin film. Excellent adhesion.
  • the inorganic fine particles when looking at the entire hard coat layer in bulk, the inorganic fine particles have a smaller average particle diameter and/or a smaller content ratio of the inorganic fine particles than the vicinity of the interface with the inorganic thin film, so the hard coat layer is resistant to bending. It can suppress deterioration of handleability due to cracks.
  • FIG. 3 is a cross-sectional view showing the lamination form of the optical laminate of one embodiment.
  • FIG. 3 is a cross-sectional view showing the lamination form of the optical laminate of one embodiment.
  • the optical laminate of the present invention has an inorganic thin film in contact with the hard coat layer of the hard coat film.
  • Such optical laminates include films for image display devices such as antireflection films and transparent electrode films, solar control films, heat shielding/heat insulating films, light control films and electromagnetic wave shielding films for window glasses and show windows.
  • films for image display devices such as antireflection films and transparent electrode films, solar control films, heat shielding/heat insulating films, light control films and electromagnetic wave shielding films for window glasses and show windows.
  • a film, a gas barrier film, etc. which are provided are mentioned.
  • FIG. 1 is a cross-sectional view showing a lamination configuration example of an antireflection film, which is an embodiment of an optical laminate.
  • the antireflection film 100 has an antireflection layer 5 on the hard coat layer 11 of the hard coat film 1 .
  • the antireflection layer 5 is a laminate of two or more inorganic thin films having different refractive indices.
  • the antireflection layer 5 includes an inorganic primer layer 50 on the surface in contact with the hard coat layer 11, and thereon high refractive index layers 51 and 53 and low refractive index layers 52 and 54. are stacked alternately.
  • the hard coat film 1 has a hard coat layer 11 on at least one surface of a film substrate 10, and an inorganic thin film 5 is provided on the hard coat layer 11 to form an optical laminate.
  • the hard coat film may have hard coat layers 11 and 12 on both main surfaces of the film substrate 10 .
  • the inorganic thin film 5 is provided on one hard coat layer 11 (front hard coat layer).
  • the optical laminate may have inorganic thin films on both sides of the hard coat film.
  • a transparent film is preferably used as the film substrate 10 of the hard coat film 1 .
  • the visible light transmittance of the transparent film is preferably 80% or higher, more preferably 90% or higher.
  • the resin material that constitutes the transparent film a resin material that is excellent in transparency, mechanical strength, and thermal stability is preferable.
  • resin materials include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) Examples include acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • cellulose resins such as triacetyl cellulose
  • polyester resins such as polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)
  • acrylic resins cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • the film substrate 10 does not necessarily have to be transparent.
  • a laminate of a plurality of films may also be used as the film substrate 10 .
  • a polarizing plate in which a protective film is provided on the surface of a polarizer may be used as the film substrate 10 .
  • the thickness of the film substrate is not particularly limited, it is preferably about 5 to 300 ⁇ m, more preferably 10 to 250 ⁇ m, and even more preferably 20 to 200 ⁇ m, from the viewpoint of strength, workability such as handleability, and thinness.
  • the hard coat film 1 is formed by providing the hard coat layer 11 on the main surface of the film substrate 10 .
  • the thickness of the hard coat layer 11 (total thickness in the case of a laminated structure) is preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 12 ⁇ m or more, and is 15 ⁇ m or more, 18 ⁇ m or more, or 20 ⁇ m or more. There may be.
  • the upper limit of the thickness of the hard coat layer 11 is not particularly limited. It may be 35 ⁇ m or less or 30 ⁇ m or less.
  • the hard coat layer 11 has a laminated structure of two or more hard coat layers, and the first hard coat layer 111 on the outermost surface (the surface on which the inorganic thin film 5 is formed) and the first hard coat layer 111 also includes a second hard coat layer 112 located on the side closer to the film substrate 10 .
  • a hard coat layer having a two-layer laminate structure can be obtained.
  • Hard coat layer 11 may include three or more layers. A hard coat layer having a large thickness can be easily formed by using a laminated structure of two or more layers.
  • the outermost first hard coat layer 111 contains inorganic fine particles. By including the inorganic fine particles in the first hard coat layer 111, the surface hardness of the hard coat layer 11 is increased, and irregularities are formed on the surface, thereby improving adhesion with the inorganic thin film 5 provided on the hard coat layer 11. can.
  • Materials for inorganic fine particles include silica, titanium oxide, aluminum oxide, zirconium oxide, titanium oxide, niobium oxide, zinc oxide, tin oxide, cerium oxide, magnesium oxide, calcium carbonate, calcium sulfate, barium sulfate, talc, and kaolin. mentioned.
  • silica particles are preferable because they have a low refractive index and can reduce the difference in refractive index from the binder resin.
  • Porous particles or hollow particles may be used as the inorganic fine particles.
  • a functional group such as an acrylic group or an epoxy group may be introduced into the surface of the inorganic fine particles for the purpose of enhancing adhesion and affinity with the resin.
  • the shape of the inorganic fine particles is not particularly limited, it is preferably a (substantially) spherical shape with an aspect ratio of 1.5 or less.
  • the aspect ratio of the inorganic fine particles is more preferably 1.2 or less, more preferably 1.1 or less.
  • the average primary particle diameter D1 of the inorganic fine particles contained in the first hard coat layer 111 is preferably 30 to 70 nm, preferably 35 to 65 nm. , or 40-60 nm.
  • the primary particle size of the fine particles is obtained by the Coulter method, and the median value D50 in the particle size distribution is taken as the average primary particle size.
  • the first hard coat layer 111 preferably contains a small amount of coarse particles.
  • the 90% particle diameter (D90) of the inorganic fine particles contained in the first hard coat layer 111 is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less.
  • the 10% particle diameter (D10) of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more.
  • D10 is the particle size at which the particle size is cumulatively 10% from the small particle size side
  • D90 is the particle size at which the particle size is cumulatively 90% from the small particle size side.
  • D90 is 100 nm or less
  • the amount of particles having a particle diameter of 100 nm or more is 10% or less on a weight basis.
  • the first hard coat layer 111 may contain organic fine particles in addition to inorganic fine particles. Even when organic fine particles are contained, the D90 and D10 of the entire fine particles contained in the first hard coat layer 111 are within the above ranges. Preferably. From the viewpoint of improving adhesion with the inorganic thin film 5, the first hard coat layer 111 preferably does not contain organic fine particles. Less is preferred.
  • the content (weight concentration) of the organic fine particles in the first hard coat layer is preferably 50% or less, more preferably 30% or less, still more preferably 10% or less, 5% or less, or 3% or less of the inorganic fine particle content. , 1% or less, or 0.
  • the content of inorganic fine particles in the first hard coat layer 111 is preferably 20 to 80% by weight with respect to the total solid content (total of binder and fine particles).
  • the content of the inorganic fine particles is within the above range, the fine particles are excellent in dispersibility in the binder resin, and an uneven shape in which the convex portions are uniformly distributed within the surface is easily formed.
  • the content of the inorganic fine particles in the first hard coat layer is preferably 25 to 75% by weight. , 30-70% by weight, 35-65% by weight or 40-60% by weight.
  • the first hard coat layer 111 may have a fine particle content distribution in the thickness direction, and the fine particle content in the vicinity of the surface (interface with the inorganic thin film) may be large. For example, by unevenly distributing fine particles on the surface when forming the first hard coat layer, a hard coat layer having a relatively large content of fine particles in the vicinity of the surface can be obtained. After forming the hard coat layer (after curing the binder), by selectively etching the binder in the vicinity of the surface by dry etching or wet etching such as plasma treatment, the content of fine particles in the vicinity of the surface can be relatively reduced. A large hard coat layer is obtained.
  • the content of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface (interface with the inorganic thin film) is preferably 20% by weight or more, more preferably 30% by weight or more, and 40% by weight.
  • the above is more preferable, and it may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight or more.
  • the content of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface of the hard coat layer 11 is preferably 97% by weight or less, more preferably 95% by weight or less, and 93% by weight or less or 90% by weight or less. good too.
  • the ratio is preferably 20 to 97%, more preferably 30 to 95%, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, or 80% or more, and may be 93% or less. Alternatively, it may be 90% or less.
  • the area ratio occupied by the inorganic fine particles in the cross section of the hard coat layer is calculated by binarizing the observation image (cross-sectional image) obtained by observing the cross section with an electron microscope, specifying the area occupied by the fine particles, and calculating the area ratio. is obtained by
  • the arithmetic mean height Sa of the surface (inorganic thin film forming surface) of the hard coat layer 11 is preferably 1.0 nm or more, more preferably 1.5 nm or more, and 2.0 nm or more. is more preferable, and may be 2.5 nm or more, 3.0 nm or more, 3.5 nm or more, 4.0 nm or more, or 4.5 nm or more.
  • the surface unevenness of the hard coat layer becomes coarse sufficient adhesion may not be achieved.
  • the arithmetic mean height Sa of the surface of the hard coat layer 11 is preferably 8 nm or less, more preferably 7.5 nm or less, even more preferably 7 nm or less, and may be 6 nm or less or 5.5 nm or less.
  • the arithmetic mean height Sa is calculated according to ISO 25178 from an observation image of 1 ⁇ m square using an atomic force microscope (AFM).
  • the surface unevenness is formed.
  • the hard coat layer 11 having Sa described above can be obtained.
  • the arithmetic mean height Sa of the hard coat layer 11 can also be increased by dry etching or wet etching the hard coat layer containing fine particles to expose the fine particles on the surface.
  • the hard coat layer 11 has a second hard coat layer 112 arranged closer to the film substrate 10 than the first hard coat layer 111 .
  • the first hard coat layer on the outermost surface of hard coat layer 11 contains inorganic fine particles having an average primary particle diameter D1 of 30 to 70 nm, thereby forming inorganic thin film 5 on hard coat layer 11. Adhesion with is enhanced.
  • the thickness of the hard coat layer containing fine particles having an average primary particle diameter of 30 nm or more is increased for the purpose of improving the hardness of the hard coat layer, the flex resistance of the hard coat layer decreases, and during roll conveyance and other The hard coat layer is likely to be broken or cracked during handling such as bonding to a member, and the handleability tends to deteriorate.
  • the side closer to the film substrate 10 than the first hard coat layer 111 contains inorganic particles having a smaller particle diameter than the fine particles of the first hard coat layer, or the content of the inorganic fine particles is higher than that of the first hard coat layer.
  • the second hard coat layer 112 contains inorganic fine particles and has an average primary particle diameter D2 smaller than the average primary particle diameter D1 of the inorganic fine particles in the first hard coat layer 111 .
  • D2 is smaller than D1
  • the average primary particle diameter D of the inorganic fine particles contained in the entire hard coat layer 11 is smaller than D1, so that the hard coat layer 11 tends to have improved flex resistance.
  • the average primary particle diameter D1 of the inorganic fine particles in the first hard coat layer 111 is larger than the average primary particle diameter D of the inorganic fine particles contained in the entire hard coat layer, the flexibility of the hard coat layer 11 is improved. Adhesion to the inorganic thin film 5 can be improved without deteriorating.
  • the average primary particle diameter D2 of the inorganic fine particles contained in the second hard coat layer 112 is preferably less than 30 nm, and preferably 28 nm or less. More preferably, it may be 25 nm or less or 20 nm or less. From the viewpoint of ensuring the dispersibility of the inorganic fine particles, D2 is preferably 5 nm or more, and may be 10 nm or more.
  • the average primary particle diameter D of the inorganic fine particles contained in the entire hard coat layer 11 is preferably 10 to 70 nm, more preferably 15 to 60 nm, and may be 20 to 55 nm or 23 to 50 nm.
  • the content of coarse particles in the second hard coat layer 112 is preferably small.
  • the 90% particle diameter (D90) of the inorganic fine particles contained in the second hard coat layer 112 is preferably 60 nm or less, more preferably 40 nm or less, and even more preferably 30 nm or less.
  • the 10% particle diameter (D10) of the inorganic fine particles is preferably 3 nm or more, more preferably 5 nm or more.
  • Second hard coat layer 112 may contain organic fine particles in addition to inorganic fine particles. Preferably. From the viewpoint of improving adhesion with the inorganic thin film 5, the second hard coat layer 112 preferably does not contain organic fine particles. Less is preferred.
  • the content (weight concentration) of the organic fine particles in the second hard coat layer is preferably 50% or less, more preferably 30% or less, further preferably 10% or less, 5% or less, or 3% or less of the inorganic fine particle content. , 1% or less, or 0.
  • the preferred form of the material and shape of the inorganic fine particles contained in the second hard coat layer are the same as those described above for the inorganic fine particles in the first hard coat layer.
  • the content of the inorganic fine particles in the second hard coat layer 112 is preferably 80% by weight or less, more preferably 70% by weight, based on the total solid content (total of binder and fine particles).
  • the following is more preferable, 60% by weight or less is more preferable, and it may be 50% by weight or less or 40% by weight or less.
  • the second hard coat layer 112 may not contain inorganic fine particles.
  • the second hard coat layer 112 preferably contains inorganic fine particles, and the content of the inorganic fine particles in the second hard coat layer 112 is 5% by weight based on the total solid content. 10% by weight or more is more preferable, and it may be 15% by weight or more, 20% by weight or more, or 25% by weight or more.
  • the weight concentration of the inorganic fine particles in the second hard coat layer 112 may be the same as the weight concentration of the inorganic fine particles in the first hard coat layer 111, or may be higher than the weight concentration of the inorganic fine particles in the first hard coat layer 111. It may be smaller than the weight concentration of the inorganic fine particles in the first hard coat layer 111 .
  • the weight concentration of the inorganic fine particles in the second hard coat layer 112 is lower than the weight concentration of the inorganic fine particles in the first hard coat layer 111, and the second hard coat layer 112 does not contain fine particles. may Since the concentration of fine particles in the second hard coat layer is low, the concentration of fine particles in the whole hard coat layer (bulk) becomes lower than the concentration of fine particles in the first hard coat layer, and the bending resistance of the hard coat layer is improved. Sometimes.
  • the inorganic thin film can be formed without reducing the bending resistance of the hard coat layer 11. 5 can be improved.
  • the weight concentration of the inorganic fine particles in the second hard coat layer 112 is 0.9 times or less, 0.8 times or less, 0.7 times or less, or 0.6 times or less than the weight concentration of the inorganic fine particles in the first hard coat layer 111. , 0.5 times or less, 0.4 times or less, 0.3 times or less, or 0.2 times or less, and the second hard coat layer 112 may not contain inorganic fine particles.
  • the average primary particle diameter D2 thereof may be the same as the average primary particle diameter D1 of the inorganic fine particles in the first hard coat layer 111, or may be larger than D1. may be smaller.
  • D2 is preferably smaller than D1, preferably less than 30 nm, more preferably 28 nm or less, and 25 nm or less or 20 nm or less, as in the first embodiment. may be From the viewpoint of ensuring the dispersibility of the inorganic fine particles, D2 is preferably 5 nm or more, and may be 10 nm or more.
  • the types of inorganic fine particles, the distribution of particle diameters, and the preferred range of the content (weight concentration) of the second hard coat layer 112 are the same as those described above for the first embodiment.
  • a hard coat layer-forming composition containing a binder resin component (a curable resin component for forming the binder resin) and inorganic fine particles is applied onto a film substrate, and the binder resin component is cured to form a hard coat layer 11. is formed.
  • the first hard coat layer 111 is formed on the second hard coat layer 112, thereby forming the second hard coat layer on the film substrate 10.
  • a hard coat film 1 comprising 112 and first hard coat layer 111 in order is obtained.
  • Two or more hard coat layers may be formed at the same time using a multi-layer die or the like.
  • another hard coat layer is formed to form a hard coat having a laminated structure of three or more layers. Layers may be formed.
  • curable resins such as thermosetting resins, photocurable resins, and electron beam curable resins are preferably used.
  • Types of curable resins include polyester, acrylic, urethane, acrylic urethane, amide, silicone, silicate, epoxy, melamine, oxetane, and acrylic urethane.
  • acrylic resins, acrylic urethane resins, and epoxy resins are preferable because they have high hardness and can be photocured.
  • the photocurable binder resin component contains a polyfunctional compound having two or more photopolymerizable (preferably ultraviolet polymerizable) functional groups.
  • Polyfunctional compounds may be monomeric or oligomeric.
  • As the photopolymerizable polyfunctional compound a compound containing two or more (meth)acryloyl groups in one molecule is preferably used.
  • composition of the binder resin in the first hard coat layer and the composition of the binder resin in the second hard coat layer may be the same or different.
  • the composition for forming a hard coat layer contains the above binder resin component and inorganic fine particles, and optionally contains a solvent capable of dissolving the binder resin component.
  • the composition for forming the second hard coat layer need not contain inorganic fine particles.
  • the composition preferably contains an appropriate polymerization initiator.
  • the binder resin component is a photocurable resin
  • the composition preferably contains a photopolymerization initiator.
  • the composition for forming a hard coat layer contains a leveling agent, a thixotropic agent, an antistatic agent, an antiblocking agent, a dispersant, a dispersion stabilizer, an antioxidant, an ultraviolet absorber, an antifoaming agent, and a thickener. , surfactants, and lubricants.
  • the hard coat layer is formed by applying the composition for forming the hard coat layer onto the film substrate, and removing the solvent and curing the resin as necessary.
  • the hard coat layer-forming composition may be applied by any appropriate method such as bar coating, roll coating, gravure coating, rod coating, slot orifice coating, curtain coating, fountain coating, and comma coating. method can be adopted. As described above, two or more layers may be simultaneously coated onto the film substrate using a multi-layer die or the like.
  • the heating temperature 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, about 50°C to 150°C.
  • photocuring is performed by irradiating active energy rays such as ultraviolet rays.
  • the integrated light quantity of the irradiation light is preferably about 100 to 500 mJ/cm 2 .
  • the first hard coat layer may be applied before curing the second hard coat layer, or the first hard coat layer may be applied after curing the second hard coat layer.
  • a hard coat layer may be applied. After the second hard coat layer is applied and the solvent is removed, the first hard coat layer is applied and the solvent is removed, and the second hard coat layer and the first hard coat layer are cured at the same time.
  • the surface of the hard coat layer 11 (the surface of the first hard coat layer 111) may be surface-treated.
  • Examples of surface treatment include surface modification treatments such as corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, alkali treatment, acid treatment, and treatment with a coupling agent.
  • a vacuum plasma treatment may be performed as the surface treatment.
  • the surface roughness of the hard coat layer 11 can also be adjusted by etching the hard coat layer by surface treatment. For example, if a vacuum plasma treatment is performed at high discharge power, the resin component on the surface of the hard coat layer is likely to be selectively etched, and the inorganic fine particles remain almost unetched. , and the arithmetic mean height Sa of the surface of the hard coat layer tends to increase.
  • Inert gases such as helium, neon, argon, krypton, xenon, and radon are preferable as the atmosphere gas in the vacuum plasma treatment, and argon is particularly preferable.
  • the discharge power in vacuum plasma processing is, for example, about 0.08 to 4 kW. If the discharge power is excessively high, the etching of the binder resin proceeds excessively, making the surface of the hard coat layer coarser and causing the inorganic fine particles to fall off, which may lead to a decrease in adhesion. If the discharge power is too low, the discharge becomes unstable, which may lead to deterioration of the uniformity of the treated surface. Therefore, the discharge power in the vacuum plasma treatment is preferably 1 kW or less, more preferably 0.5 kW or less.
  • the treatment time is preferably about 0.05 to 1.0 seconds, more preferably 0.1 to 0.6 seconds.
  • the energy density during discharge is preferably about 0.1 to 5.0 kW/m 2 , more preferably 0.15 to 2.0 kW/m 2 .
  • the thickness of hard coat layer 11 is preferably 7 to 50 ⁇ m.
  • the sum of the thickness of the first hard coat layer 111 and the thickness of the second hard coat layer 112 is within the above range. is preferred.
  • the hardness of the optical layered body having the inorganic thin film 5 on the hard coat layer 11 is greatly affected by the first hard coat layer 111 which is the outermost layer of the hard coat layer 11 and the base of the inorganic thin film 5 .
  • Hardness tends to increase as the thickness of the first hard coat layer 111 containing inorganic fine particles with an average primary particle diameter D1 of 30 to 70 nm increases. Therefore, the thickness of the first hard coat layer 111 is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and may be 2.5 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, or 5 ⁇ m or more.
  • the thickness of the first hard coat layer 111 is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, and may be 10 ⁇ m or less or 8 ⁇ m or less.
  • the thickness of the first hard coat layer 111 is preferably as small as possible within the range where adhesion to the inorganic thin film and surface hardness can be ensured.
  • the thickness of the first hard coat layer 111 is preferably 50% or less of the total thickness of the hard coat layer 11, and may be 40% or less, 30% or less, or 25% or less. From the viewpoint of improving hardness, the thickness of the first hard coat layer 111 is preferably 5% or more of the total thickness of the hard coat layer 11, more preferably 10% or more, and may be 15% or more or 20% or more. .
  • the thickness of the second hard coat layer 112 is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and is 10 ⁇ m or more, 12 ⁇ m or more, or 14 ⁇ m or more.
  • the thickness of the second hard coat layer 112 is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and may be 22 ⁇ m or less or 20 ⁇ m or less.
  • the thickness of the first hard coat layer 111 is preferably smaller than the thickness of the second hard coat layer 112 in order to increase the bending resistance of the hard coat layer.
  • the thickness of the first hard coat layer 111 is 0.9 times or less, 0.8 times or less, 0.7 times or less, 0.6 times or less, 0.5 times or less, or 0 times the thickness of the second hard coat layer 112 . 0.4 times or less, or 0.3 times or less. From the viewpoint of improving hardness, the thickness of the first hard coat layer 111 is preferably 0.1 times or more, 0.15 times or more, 0.2 times or more, or 0.25 times or more the thickness of the second hard coat layer 112. may be
  • the hard coat layer 11 has a laminated structure of two or more layers.
  • the average particle diameter of the inorganic fine particles should be relatively large, or the content (content ratio) of the inorganic fine particles should be relatively large, as compared with the bulk. That is, since a relatively large amount of inorganic fine particles having a particle diameter of about 30 to 70 nm are present in the vicinity of the interface between the hard coat layer 11 and the inorganic thin film 5, the hard coat layer 11 maintains its flex resistance. Surface hardness and adhesion to inorganic thin films can be improved.
  • the average primary particle diameter Da of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface of the hard coat layer 11 (interface with the inorganic thin film 5) is preferably 30 to 70 nm, 35 to 65 nm, or even 40 to 60 nm. good.
  • the average primary particle diameter D of the inorganic fine particles contained in the hard coat layer 11 as a whole is preferably smaller than Da.
  • the content (weight concentration) of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface of the hard coat layer 11 is preferably 20% by weight or more, more preferably 30 to 97% by weight, and more preferably 40% to 96% by weight. % is more preferable, and may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight or more, and 95% by weight or less, 93% by weight or less, or 90% by weight or less. There may be.
  • the weight concentration of the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface of the hard coat layer 11 may be higher than the weight concentration of the inorganic fine particles in the entire hard coat layer 11 . In the hard coat layer 11, the inorganic fine particles may be unevenly distributed near the surface (the interface with the inorganic thin film 5).
  • the area ratio occupied by the inorganic fine particles in the range of 1 ⁇ m in the thickness direction from the surface is preferably 20 to 97%, more preferably 30 to 95%, 40% or more, 50% or more, 60%. 70% or more, 75% or more, or 80% or more, or 93% or less, or 90% or less.
  • the hard coat film includes the front hard coat layer 11 on one main surface of the film substrate 10 (the surface on which the inorganic thin film 5 is formed), and the back hard coat layer 12 on the other surface of the film substrate 10. may be provided.
  • the back hard coat layer 12 By providing the back hard coat layer 12, the hardness of the entire optical layered body may be increased, and the surface hardness of the inorganic thin film 5 side may be improved.
  • the composition of the back hard coat layer 12 is not particularly limited, and may or may not contain fine particles.
  • the back hard coat layer 12 may be a single layer or may have a laminated structure of two or more layers. From the viewpoint of improving hardness, the thickness of the back hard coat layer 12 is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and may be 3 ⁇ m or more, 4 ⁇ m or more, or 5 ⁇ m or more.
  • the thickness of the back hard coat layer 12 may be 40 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less.
  • the thickness of the back hard coat layer 12 may be smaller than the thickness of the front hard coat layer 11 .
  • the thickness of the back hard coat layer is 0.9 times or less, 0.8 times or less, 0.7 times or less, 0.6 times or less, 0.5 times or less, or 0.4 times the thickness of the front hard coat layer 11. or less, or 0.3 times or less. From the viewpoint of improving the surface hardness, when the rear hard coat layer 12 is provided, its thickness is preferably 0.1 times or more, more preferably 0.2 times or more, or 0.25 times or more than the thickness of the front hard coat layer 11. may
  • An optical laminate is obtained by forming the inorganic thin film 5 on the hard coat layer 11 of the hard coat film 1 .
  • materials for the inorganic thin film include metals and metal compounds (metal or metalloid oxides, nitrides, carbides, sulfides, fluorides, etc.).
  • the inorganic thin film may be conductive, insulating, or semiconducting.
  • Various functions are imparted by providing the inorganic thin film on the hard coat layer. For example, as shown in FIG. 1, by laminating a plurality of thin films having different refractive indices as inorganic thin films, an antireflection layer is formed to obtain a hard-coated antireflection film.
  • the film thickness of the inorganic thin film 5 (the total film thickness when a plurality of thin films are included) is, for example, about 1 nm to 1 ⁇ m, and may be appropriately adjusted according to the type of thin film, the function of the optical laminate, and the like.
  • Antireflection layer An embodiment in which an antireflection layer composed of a plurality of thin films having different refractive indices is formed as the inorganic thin film will be described below.
  • the antireflection layer has an optical film thickness (product of refractive index and thickness) adjusted so that the reversed phases of incident light and reflected light cancel each other out.
  • a multi-layer stack of thin films having different refractive indices can reduce the reflectance in a wide wavelength range of visible light.
  • Materials for the thin film forming the antireflection layer 5 include inorganic materials such as metal oxides, nitrides, and fluorides.
  • the antireflection layer 5 is preferably an alternate laminate of high refractive index layers and low refractive index layers.
  • the thin film 54 provided as the outermost layer (layer farthest from the hard coat film 1) of the antireflection layer 5 is preferably a low refractive index layer.
  • the high refractive index layers 51 and 53 have, for example, a refractive index of 1.9 or more, preferably 2.0 or more.
  • high refractive index materials include titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and antimony-doped tin oxide (ATO). Among them, titanium oxide or niobium oxide is preferable.
  • the low refractive index layers 52 and 54 have, for example, a refractive index of 1.6 or less, preferably 1.5 or less.
  • low refractive index materials include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, hafnium fluoride, and lanthanum fluoride.
  • silicon oxide is preferred.
  • a medium refractive index layer having a refractive index of about 1.6 to 1.9 may be provided in addition to the low refractive index layer and the high refractive index layer.
  • the film thicknesses of the high refractive index layer and the low refractive index layer are each about 5 to 200 nm, preferably about 15 to 150 nm.
  • the film thickness of each layer may be designed so that the reflectance of visible light is reduced according to the refractive index, lamination structure, and the like.
  • a high refractive index layer 51 having an optical thickness of about 25 nm to 55 nm and a low refractive index layer having an optical thickness of about 35 nm to 55 nm 52
  • a high refractive index layer 53 with an optical thickness of about 80 nm to 240 nm
  • a low refractive index layer 54 with an optical thickness of about 120 nm to 150 nm.
  • the antireflection layer 5 preferably has an inorganic primer layer 50 on the surface of the hard coat film 1 in contact with the hard coat layer 11, and has a high refractive index layer and a low refractive index layer thereon.
  • an inorganic primer layer 50 in contact with the hard coat layer 11 having surface irregularities formed by inorganic fine particles, and providing an inorganic thin film such as a high refractive index layer or a low refractive index layer in contact with the inorganic primer layer 50, the interlayer It is possible to obtain an optical layered body (antireflection film) which has excellent adhesion and the inorganic thin film is not easily peeled off even when exposed to light such as ultraviolet rays for a long time.
  • Examples of inorganic materials constituting the primer layer 50 include metals such as silicon, nickel, chromium, tin, indium, gold, silver, platinum, zinc, titanium, tungsten, aluminum, zirconium, and palladium; alloys of these metals; inorganic materials such as oxides, fluorides, sulfides or nitrides of these metals; Among them, the inorganic material of the primer layer is preferably an oxide, and more preferably one containing a metal such as Si, In, Sn, Zn or Ti.
  • the primer layer 50 may be an inorganic oxide layer with less oxygen content than the stoichiometric composition.
  • the thickness of the inorganic primer layer 50 is, for example, about 1 to 20 nm, preferably 2 to 15 nm, more preferably 3 to 10 nm. If the film thickness of the inorganic primer layer is within the above range, both adhesion to the hard coat layer 11 and high light transmittance can be achieved.
  • the method of forming the thin film that constitutes the antireflection layer 5 is not particularly limited, and either a wet coating method or a dry coating method may be used.
  • a dry coating method such as vacuum deposition, CVD, sputtering, or electron beam deposition is preferred because it can form a thin film with a uniform thickness.
  • the sputtering method is preferable because it is excellent in the uniformity of the film thickness and can easily form a dense film.
  • a thin film can be formed continuously while transporting a long hard coat film in one direction (longitudinal direction) by a roll-to-roll method. Therefore, the productivity of the optical laminate inorganic thin film having the inorganic thin film on the hard coat film can be improved.
  • the productivity of the optical laminate inorganic thin film having the inorganic thin film on the hard coat film can be improved.
  • the inorganic thin film is preferably formed by two-roll sputtering. In order to improve the productivity of the antireflection film, it is preferable to deposit all the thin films constituting the antireflection layer 5 by sputtering.
  • the sputtering method film formation is performed while introducing an inert gas such as argon and, if necessary, a reactive gas such as oxygen into the chamber.
  • the deposition of the oxide layer by the sputtering method can be carried out by either a method using an oxide target or reactive sputtering using a metal target. Reactive sputtering using a metal target is preferable for forming a metal oxide film at a high rate.
  • the arithmetic mean height Sa of the surface of the inorganic thin film 5 is preferably 1.0 nm or more, more preferably 1.5 nm or more, even more preferably 2.0 nm or more, and 2.5 nm. Above, it may be 3.0 nm or more, 3.5 nm or more, 4.0 nm or more, or 4.5 nm or more.
  • the inorganic thin film 5 is formed by a dry process such as a sputtering method, the surface of the inorganic thin film 5 tends to have an uneven shape reflecting the surface shape of the underlying hard coat layer 11 .
  • the inorganic thin film 5 also reflects the uneven shape of the inorganic fine particles of the hard coat layer 11. It is easy to form a smooth surface shape.
  • the arithmetic mean height Sa of the surface of the inorganic thin film 5 is preferably 8 nm or less, more preferably 7.5 nm or less, even more preferably 7 nm or less, and may be 6 nm or less or 5.5 nm or less.
  • the optical stack may comprise additional functional layers on the inorganic thin film 5 .
  • the antireflection film placed on the outermost surface of the image display device and the solar control film pasted on the window glass and show window are susceptible to contamination from the external environment (fingerprints, finger marks, dust, etc.).
  • the wettability of the silicon oxide is high, and contaminants such as fingerprints and finger marks are likely to adhere. Therefore, an antifouling layer (not shown) may be provided on the antireflection layer 5 for the purpose of preventing contamination from the external environment and facilitating removal of adhering contaminants.
  • the difference in refractive index between the low refractive index layer 54 on the outermost surface of the antireflection layer 5 and the antifouling layer should be small from the viewpoint of reducing reflection at the interface.
  • the refractive index of the antifouling layer is preferably 1.6 or less, more preferably 1.55 or less.
  • the material for the antifouling layer fluorine group-containing silane compounds, fluorine group-containing organic compounds, and the like are preferable.
  • the antifouling layer can be formed by a wet method such as a reverse coating method, a die coating method, or a gravure coating method, or a dry method such as a CVD method.
  • the thickness of the antifouling layer is usually about 1 to 100 nm, preferably 2 to 50 nm, more preferably 3 to 30 nm.
  • An antireflection film which is one form of an optical laminate, is used by placing it on the surface of an image display device such as a liquid crystal display or an organic EL display. For example, by arranging an antireflection film on the viewing side surface of a panel including an image display medium such as a liquid crystal cell or an organic EL cell, the reflection of external light can be reduced and the visibility of the image display device can be improved.
  • An optical laminate such as an antireflection film in which an inorganic thin film is formed on the hard coat layer has high surface hardness due to the large thickness of the hard coat layer.
  • the adhesion of the inorganic thin film is excellent due to the inclusion of inorganic fine particles having a diameter. Therefore, the optical laminate has high impact resistance and sliding resistance, and is suitable for use in image display devices without a rigid cover layer such as glass, and in image display devices equipped with pen-touch type position detection means. .
  • a laminate of a plurality of films may be used as the film substrate 10, and the hard coat layer 11 and the antireflection layer 5 may be formed thereon.
  • another film may be attached to the surface of the film substrate 10 on which the hard coat layer is not formed.
  • a polarizing plate with an antireflection layer can be formed by attaching a polarizer to the surface of the film substrate 10 on which the hard coat layer is not formed.
  • dichroic substances such as iodine and dichroic dyes are added to hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified ethylene-vinyl acetate copolymer films. and a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride.
  • a polyvinyl alcohol-based film such as polyvinyl alcohol or partially formalized polyvinyl alcohol is oriented in a predetermined direction by adsorbing a dichroic substance such as iodine or a dichroic dye.
  • Alcohol (PVA) based polarizers are preferred.
  • a PVA-based polarizer can be obtained by subjecting a polyvinyl alcohol-based film to iodine dyeing and stretching.
  • a thin polarizer having a thickness of 10 ⁇ m or less can also be used as the PVA-based polarizer.
  • Thin polarizers are described, for example, in JP-A-51-069644, JP-A-2000-338329, WO2010/100917, JP 4691205, JP 4751481, etc.
  • a thin polarizing film can be mentioned.
  • Such a thin polarizer can be obtained, for example, by a manufacturing method including a step of stretching a laminate of a PVA-based resin layer and a stretching resin substrate, and a step of dyeing with iodine.
  • a transparent protective film may be provided on the surface of the polarizer for the purpose of protecting the polarizer.
  • the transparent protective film may be attached only to one surface of the polarizer, or may be attached to both surfaces.
  • a transparent protective film is provided on the surface of the polarizer opposite to the surface provided with the antireflection film.
  • the antireflection film On the side of the polarizer on which the antireflection film is attached, the antireflection film also functions as a transparent protective film, so it is not necessary to provide a transparent protective film, but a transparent protective film may be provided between the polarizer and the antireflection film. may have been
  • the same materials as those described above as the material for the transparent film substrate are preferably used.
  • An adhesive is preferably used for bonding the polarizer and the transparent film.
  • Adhesives are based on acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl alcohol, polyvinyl ether, vinyl acetate/vinyl chloride copolymer, modified polyolefin, epoxy polymer, fluorine polymer, rubber polymer, etc. Polymers can be appropriately selected and used.
  • a polyvinyl alcohol-based adhesive is preferably used for bonding the PVA-based polarizer.
  • a hard coat resin composition (Arakawa Kagaku Kogyo "OPSTAR Z7540") was applied so that the thickness after drying was 10 ⁇ m, and dried at 80° C. for 3 minutes. After that, the coating layer was cured by irradiating ultraviolet rays using a high-pressure mercury lamp to form a hard coat layer (second hard coat layer).
  • a hard coat resin composition (“NC035" manufactured by Arakawa Chemical Industries, Ltd.) containing 60% by weight of nanosilica particles with an average primary particle diameter of 45 nm based on the total solid content is applied to a thickness of 5 ⁇ m after drying. and dried at 80°C for 3 minutes. After that, ultraviolet rays are irradiated using a high-pressure mercury lamp to cure the coating layer to form a hard coat layer (first hard coat layer), and a two-layer hard coat layer (total thickness of 15 ⁇ m) is formed on the TAC film substrate. ) was obtained.
  • NC035" manufactured by Arakawa Chemical Industries, Ltd.
  • the hard coat film was introduced into a roll-to-toll type sputtering film forming apparatus, and the pressure in the tank was reduced to 1 ⁇ 10 ⁇ 4 Pa. , argon gas and oxygen gas were introduced at a volume ratio of 98:2, and an ITO primer layer having a thickness of 3 nm was formed by DC sputtering at a substrate temperature of 20°C.
  • a sintered target containing indium oxide and tin oxide at a weight ratio of 90:10 was used as the target material for forming the ITO primer layer.
  • a 16 nm Nb 2 O 5 layer, a 19 nm SiO 2 layer, a 102 nm Nb 2 O 5 layer and a 71 nm SiO 2 layer are sequentially formed as antireflection layers to form an antireflection layer.
  • a film was produced.
  • a Nb target was used for the deposition of the Nb 2 O 5 layers
  • a Si target was used for the deposition of the SiO 2 layers.
  • Argon and oxygen were used as sputtering gases for the deposition of the Nb 2 O 5 layer and the SiO 2 layer, and the amount of oxygen introduced was adjusted by plasma emission monitoring (PEM) control so that the deposition mode maintained the transition region. did.
  • Example 2 to 4 Formation of a hard coat layer, surface treatment, and formation of an ITO primer layer and an antireflection layer were carried out in the same manner as in Example 1, except that the thickness of the hard coat layer was changed as shown in Table 1.
  • Example 5 After forming a two-layered hard coat layer on one side of the TAC film in the same manner as in Example 3, a hard coat resin composition (“OPSTAR Z7540” manufactured by Arakawa Chemical Industries) was applied to the other side of the TAC film. was used to form a hard coat layer having a thickness of 10 ⁇ m. Thereafter, in the same manner as in Example 1, the two-layered hard coat layer was subjected to surface treatment, and an ITO primer layer and an antireflection layer were formed thereon.
  • OPSTAR Z7540 manufactured by Arakawa Chemical Industries
  • Example 6 An ITO primer layer and an antireflection layer were formed on a hard coat film having hard coat layers on both sides in the same manner as in Example 5, except that the thickness of the hard coat layer was changed as shown in Table 1.
  • a hard coat resin composition containing 50% by weight of nanosilica particles with an average primary particle diameter of 45 nm based on the total solid content was applied to one side of an 80 ⁇ m thick triacetyl cellulose (TAC) film ("Fuji Tac" manufactured by Fujifilm). It was applied so that the thickness afterward would be 4 ⁇ m, and dried at 80° C. for 3 minutes. Thereafter, the coating layer was cured by irradiating ultraviolet rays using a high-pressure mercury lamp to form a hard coat layer.
  • TAC triacetyl cellulose
  • Example 1 Using the above hard coat film having a hard coat layer consisting of one layer, surface treatment of the hard coat layer and formation of an ITO primer layer and an antireflection layer were performed in the same manner as in Example 1.
  • Comparative Examples 2 and 3 In Comparative Example 2, a hard coat resin composition ("OPSTAR Z7540" manufactured by Arakawa Chemical Industries, Ltd.) containing 40% by weight of nanosilica particles with an average primary particle diameter of 15 nm relative to the total solid content was used as the hard coat composition. . In Comparative Example 3, a hard coat resin composition (“NC035” manufactured by Arakawa Chemical Industries, Ltd.) containing 60% by weight of nanosilica particles with an average primary particle diameter of 45 nm based on the total solid content was used as the hard coat composition. Formation of a hard coat layer, surface treatment, and ITO primer layer and reflective A protective layer was formed.
  • OPSTAR Z7540 manufactured by Arakawa Chemical Industries, Ltd.
  • the average primary particle size D1 of the fine particles in the first hard coat layer and the average primary particle size D2 of the fine particles in the second hard coat layer are the average primary particle sizes of the fine particles contained in the composition used to form each hard coat layer. was taken as the particle diameter of the fine particles of the hard coat layer.
  • the average primary particle diameter Da of the fine particles in the range of 1 ⁇ m in the thickness direction from the surface of the hard coat layer is It was made the same as the average primary particle diameter D1 of the fine particles of the first hard coat layer.
  • the average primary particle diameter D of the fine particles in the entire hard coat layer of Examples 1 to 6 is determined by the average primary particle sizes D1 and D2 of the fine particles in the first hard coat layer and the second hard coat layer, the content of fine particles in each layer, and Calculated based on thickness ratio.
  • ⁇ Pencil hardness> The pencil hardness of the antireflection layer surface was measured under the condition of a load of 500 g according to JIS K5600-5-4 pencil hardness test.
  • ⁇ Adhesion test (accelerated light resistance test)> A glass plate is attached to the surface of the antireflection film on the film substrate side (non-formation of the antireflection layer) via a transparent acrylic adhesive. An accelerated light resistance test was performed for 500 hours and 750 hours under the conditions of 20% humidity and 500 ⁇ 50 W/m 2 radiation intensity (300 to 700 nm integrated illuminance).
  • the surface of the antireflection layer of the sample was cut at intervals of 1 mm to form a grid of 100 squares.
  • 2 mL of isopropyl alcohol was continuously dropped so that the surface of the antireflection layer did not dry, and a polyester wiper ("Anticon Gold” manufactured by Sunplatec) fixed to a 20 mm square SUS jig was rubbed on the grid. It was moved (load: 1.5 kg, 1000 reciprocations).
  • the number of grid patterns in which the antireflection layer was peeled off in a region of 1/4 or more of the area of the mass was counted, and the adhesion was evaluated according to the following criteria.
  • C The number of peeled grids is 31 or more
  • Table 1 shows the composition of the hard coat layer (the fine particle content of each layer, the average primary particle size and thickness of the fine particles) and the evaluation results of the antireflection films of the above Examples and Comparative Examples.
  • Comparative Example 1 in which the hard coat layer had a thickness of 4 ⁇ m, the pencil hardness was 3H and the surface hardness was not sufficient.
  • Comparative Example 2 in which the hard coat layer is a single layer with a thickness of 20 ⁇ m and an average primary particle diameter of 15 nm, the pencil hardness was improved compared to Comparative Example 1, but since the particle diameter of the fine particles is small, the reflection The adhesion of the prevention layer was degraded.
  • Comparative Example 3 in which the hard coat layer was a single layer with a thickness of 15 ⁇ m and an average primary particle diameter of 45 nm, the adhesion to the antireflection layer was the same as in Comparative Example 1, and the pencil hardness was improved. Flexibility was reduced.
  • Examples 1 to 5 exhibited a high pencil hardness of 5H or higher, and both flex resistance and adhesion were good.
  • Example 2 in which the thickness of the first hard coat layer was large, the surface hardness was further improved, but the adhesion of the antireflection layer was lowered.
  • Example 2 it is believed that the increase in the thickness of the first hard coat layer contributed to the decrease in surface unevenness.
  • the hardness is high, It can be seen that a laminate having excellent adhesion between the hard coat layer and the inorganic thin film and excellent flex resistance can be obtained.
  • Reference Signs List 1 2 hard coat film 10 film substrate 11, 12 hard coat layer 5 inorganic thin film (antireflection layer) 50 inorganic primer layers 51, 53 low refractive index layers 52, 54 high refractive index layers 100, 101 optical laminate (antireflection film)

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Abstract

L'invention concerne un corps multicouche optique (100) comprenant : un film de revêtement dur (1) qui comprend une couche de revêtement dure (11) recouvrant un matériau de base de film (10) ; et un film mince inorganique (5) qui est en contact avec la couche de revêtement dur (11). La couche de revêtement dur (11) contient des particules fines inorganiques ; et à proximité de l'interface avec le film mince inorganique (5), les diamètres de particule des particules fines inorganiques sont relativement grands par rapport à ceux dans la totalité de la couche de revêtement dur, ou la teneur en particules fines inorganiques est relativement élevée par rapport à celle de la totalité de la couche de revêtement dur. Ce corps multicouche optique se caractérise par une dureté élevée, une excellente adhérence du film mince inorganique et de bonnes propriétés de manipulation.
PCT/JP2022/011403 2021-03-31 2022-03-14 Corps multicouche optique et dispositif d'affichage d'image WO2022209829A1 (fr)

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JP2002036436A (ja) * 2000-07-19 2002-02-05 Fuji Photo Film Co Ltd ハードコートフイルム及び機能性薄膜付きハードコートフイルム
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