WO2022249674A1 - 積層体およびその製造方法、ならびに画像表示装置 - Google Patents

積層体およびその製造方法、ならびに画像表示装置 Download PDF

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WO2022249674A1
WO2022249674A1 PCT/JP2022/012199 JP2022012199W WO2022249674A1 WO 2022249674 A1 WO2022249674 A1 WO 2022249674A1 JP 2022012199 W JP2022012199 W JP 2022012199W WO 2022249674 A1 WO2022249674 A1 WO 2022249674A1
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layer
hard coat
film
primer layer
antireflection
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PCT/JP2022/012199
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English (en)
French (fr)
Japanese (ja)
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由佳 山▲崎▼
佳史 ▲高▼見
智剛 梨木
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日東電工株式会社
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Priority to KR1020237030168A priority Critical patent/KR20240011660A/ko
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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 a laminate in which an inorganic thin film is provided on a film substrate, a manufacturing method thereof, and an image display device.
  • An antireflection film is sometimes provided on the surface of image display devices such as liquid crystal displays and organic EL displays for the purpose of improving the visibility of displayed images.
  • 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.
  • a hard coat layer may be provided on the antireflection layer formation surface of the film substrate for the purpose of preventing damage due to contact from the outside.
  • the adhesion between the hard coat layer and the inorganic thin film, which are made of organic substances, is low, and delamination may occur between the hard coat layer and the inorganic thin film. is proposed.
  • a primer layer tends to improve the adhesion of inorganic thin films such as an antireflection layer, but in an environment exposed to ultraviolet rays such as outdoors, even if a primer layer is provided, the inorganic thin film may deteriorate due to light deterioration. Adhesion may decrease.
  • a primer layer made of silicon oxide (SiO x ; 0 ⁇ x ⁇ 2) in an oxygen-deficient state (non-stoichiometric composition) is formed on a hard coat layer, and an antireflection layer is formed thereon. By doing so, the antireflection layer has high adhesion even after high-intensity light irradiation (weather resistance test).
  • a primer layer made of silicon oxide with a non-stoichiometric composition is deposited by reactive sputtering using a silicon target.
  • the present inventors have found that the antireflection film provided with a silicon oxide thin film as a primer layer between the hard coat layer and the antireflection layer has unstable characteristics such as adhesion and transparency of the antireflection layer. It turns out there is.
  • an object of the present invention is to provide a laminate having excellent quality stability such as adhesion of an inorganic thin film.
  • the present invention relates to a laminate and its manufacturing method.
  • the laminate includes a hard coat film having a hard coat layer on one main surface of a film substrate, a primer layer provided in contact with the hard coat layer, and an inorganic thin film provided in contact with the primer layer.
  • the inorganic thin film formed on the primer layer is an antireflection layer comprising a laminate of a plurality of thin films having different refractive indices. Each thin film constituting the antireflection layer may be an inorganic oxide thin film.
  • the primer layer is a metal oxide thin film and contains oxides of specific metal elements.
  • the metal element of the metal oxide preferably has a metal-oxygen bond dissociation energy of 450 to 780 kJ/mol at a temperature of 298K.
  • metal elements include Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Tc, Re, Ru, Os, Al, and Sn. Among them, Ti and Sn are particularly preferred. It is preferable that the total amount of these metal elements is 50 atomic % or more based on the total amount of metal elements in the metal oxide.
  • the primer layer is deposited, for example, by sputtering using an oxide target.
  • the thickness of the primer layer is preferably about 0.5 to 30 nm.
  • the formation of the inorganic thin film on the primer layer may be performed by reactive sputtering.
  • the hard coat layer may contain a binder resin and fine particles.
  • the hard coat layer contains a binder resin and nanoparticles with a particle size of 10 to 100 nm, and the content of the nanoparticles is 20 to 100 parts by weight based on 100 parts by weight of the binder resin.
  • FIG. 3 is a cross-sectional view showing a lamination configuration of antireflection films.
  • the laminate of the present invention comprises a primer layer on the hard coat layer of the hard coat film, and an inorganic thin film thereon.
  • Such laminates include films for image display devices such as antireflection films and transparent electrode films, solar radiation control films, heat shielding/insulating films, light control films, electromagnetic wave shielding films, and the like, which are provided on window glasses and show windows. film, gas barrier film, and the like.
  • FIG. 1 is a cross-sectional view showing a laminated configuration example of an antireflection film as an embodiment of the laminate.
  • the antireflection film 100 includes a hard coat film 1 having a hard coat layer 11 provided on one main surface of a film substrate 10, a primer layer 3 in contact with the hard coat layer 11, and an antireflection layer 5 in contact with the primer layer.
  • the antireflection layer 5 is a laminate of two or more inorganic thin films having different refractive indices.
  • the antireflection layer 5 has a configuration in which high refractive index layers 51 and 53 and low refractive index layers 52 and 54 are alternately laminated.
  • the film substrate 10 of the hard coat film for example, a transparent film is used.
  • 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 for example, 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 10 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 hard coat layer is a cured resin layer, and is formed by applying a composition containing a curable resin onto the film substrate and curing the resin component.
  • the hard coat layer may contain fine particles in addition to the cured resin.
  • curable resin As the curable resin (binder resin) of the hard coat layer 11, curable resins such as thermosetting resins, photo-curable 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. Among these resins, acrylic resins, acrylic urethane resins, and epoxy resins are preferable because they have high hardness and can be photocured, and acrylic urethane resins are particularly preferable.
  • the photocurable resin composition 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.
  • polyfunctional compounds having two or more (meth)acryloyl groups in one molecule include tricyclodecanedimethanol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylol.
  • propane triacrylate pentaerythritol tetra(meth)acrylate, dimethylolpropane tetraacrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol (meth)acrylate, 1,9-nonanediol diacrylate, 1, 10-decanediol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, dipropylene glycol diacrylate, isocyanuric acid tri(meth)acrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetra Examples include acrylates and oligomers or prepolymers thereof.
  • (meth)acryl means acryl and/or methacryl.
  • a polyfunctional compound having two or more (meth)acryloyl groups in one molecule may have a hydroxyl group.
  • the use of a polyfunctional compound containing a hydroxyl group tends to improve the adhesion between the film substrate and the hard coat layer.
  • Compounds having a hydroxyl group and two or more (meth)acryloyl groups in one molecule include pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate.
  • Acrylic urethane resins contain urethane (meth)acrylate monomers or oligomers as polyfunctional compounds.
  • the number of (meth)acryloyl groups in the urethane (meth)acrylate is preferably 3 or more, more preferably 4-15, and even more preferably 6-12.
  • the molecular weight of the urethane (meth)acrylate oligomer is, for example, 3000 or less, preferably 500-2500, more preferably 800-2000.
  • Urethane (meth)acrylate is obtained, for example, by reacting hydroxy (meth)acrylate obtained from (meth)acrylic acid or (meth)acrylic acid ester and polyol with diisocyanate.
  • the content of the polyfunctional compound in the composition for forming a hard coat layer is preferably 50 parts by weight or more with respect to a total of 100 parts by weight of the resin components (monomers, oligomers and prepolymers that form a binder resin upon curing). 60 parts by weight or more is more preferable, and 70 parts by weight or more is even more preferable.
  • the content of the polyfunctional monomer is within the above range, the hardness of the hard coat layer tends to be increased.
  • fine particles By including fine particles in the hard coat layer 11, it is possible to adjust the surface shape, impart optical properties such as antiglare properties, and improve the adhesion of the antireflection layer.
  • Fine particles include inorganic oxide fine particles such as silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide, glass fine particles, polymethyl methacrylate, polystyrene, polyurethane, and acrylic-styrene copolymer. , benzoguanamine, melamine, polycarbonate, and other crosslinked or uncrosslinked organic microparticles can be used without particular limitation.
  • the average particle size (average primary particle size) of fine particles is preferably about 10 nm to 10 ⁇ m.
  • Fine particles have a particle diameter of about 0.5 ⁇ m to 10 ⁇ m, submicrons or ⁇ m order (hereinafter sometimes referred to as “microparticles”), and have a particle diameter of about 10 nm to 100 nm. They can be roughly classified into microparticles (hereinafter sometimes referred to as “nanoparticles”) and microparticles having a particle size intermediate between microparticles and nanoparticles.
  • nanoparticles in the hard coat layer 11 tends to form fine irregularities on the surface and improve the adhesion between the hard coat layer 11 and the primer layer 3 and the antireflection layer 5 .
  • inorganic fine particles are preferable, and inorganic oxide fine particles are particularly preferable.
  • silica particles are preferable because they have a low refractive index and can reduce the difference in refractive index from the binder resin.
  • the average primary particle diameter of the nanoparticles is preferably 20 to 80 nm, more preferably 25 to 70 nm, and more preferably 30 to 60 nm. More preferred. From the viewpoint of suppressing coloring of reflected light on the surface of the hard coat layer, the average primary particle size of the nanoparticles is preferably 55 nm or less, more preferably 50 nm or less, and even more preferably 45 nm or less.
  • the average primary particle size is the weight average particle size measured by the Coulter count method.
  • the amount of nanoparticles in the hard coat layer 11 may be about 1 to 150 parts by weight with respect to 100 parts by weight of the binder resin. From the viewpoint of forming a surface shape with excellent adhesion to the inorganic thin film on the surface of the hard coat layer 11, the content of the nanoparticles in the hard coat layer 11 is 20 to 100 parts by weight with respect to 100 parts by weight of the binder resin. parts, more preferably 25 to 90 parts by weight, even more preferably 30 to 80 parts by weight.
  • microparticles in the hard coat layer 11 projections with a diameter of submicron or ⁇ m order are formed on the surface of the hard coat layer 11 and the surface of the thin film formed thereon, thereby imparting antiglare properties.
  • the microparticles preferably have a small refractive index difference from the binder resin of the hard coat layer, and are preferably low refractive index inorganic oxide particles such as silica or polymer fine particles.
  • the average primary particle size of the microparticles is preferably 1 to 8 ⁇ m, more preferably 2 to 5 ⁇ m.
  • the content of the microparticles in the hard coat layer 11 is not particularly limited, but is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, and even more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.
  • the hard coat layer 11 may contain either one of nanoparticles and microparticles, or may contain both. It may also contain fine particles having a particle size intermediate between nanoparticles and microparticles.
  • the composition for forming a hard coat layer contains the binder resin component described above and, if necessary, a solvent capable of dissolving the binder resin component. As described above, the composition for forming a hard coat layer may contain fine particles. When the binder resin component is a photocurable resin, the composition preferably contains a photopolymerization initiator. In addition to the above, 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.
  • a hard coat layer is formed by applying the composition for forming a hard coat layer onto a film substrate, and optionally removing the solvent and curing the resin.
  • 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.
  • 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.
  • the binder resin component is a photocurable resin
  • 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 thickness of the hard coat layer 11 is not particularly limited, it is preferably about 1 to 10 ⁇ m, more preferably 2 to 9 ⁇ m, and even more preferably 3 to 8 ⁇ m from the viewpoint of achieving high hardness and appropriately controlling the surface shape.
  • the hard coat layer 11 is formed.
  • a surface treatment may be performed. 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 can also be adjusted by vacuum plasma treatment. For example, if vacuum plasma treatment is performed at high discharge power, the surface unevenness of the hard coat layer tends to increase and the adhesion to the inorganic thin film tends to improve.
  • Primer layer 3 is formed on the hard coat layer 11, and an antireflection layer 5 is formed thereon.
  • the adhesion between the layers is excellent, and the reflection is reflected even when exposed to light such as ultraviolet rays for a long time. It is possible to obtain an antireflection film in which the antireflection layer is less likely to peel off.
  • the primer layer 3 is a metal oxide thin film. Note that the term “metal” here is a concept that does not include semimetals such as silicon.
  • the metal oxide of the primer layer contains, as a metal element, a metal having a metal-oxygen bond dissociation energy D 0 298 at a temperature of 298K of 450 to 780 kJ/mol.
  • the value described in Luo, Y. R., Comprehensive Handbook of Chemical Bond Energys, CRC Press, 2007 is adopted as the bond dissociation energy D 0 298 (MO) between metal and oxygen at 298 ° C. do.
  • Metals having a D 0 298 (MO) of 450 to 780 kJ/mol include Cr (461 ⁇ 8.7), Al (501.9 ⁇ 10.6), Mo (502), Sn (528), Ru(528 ⁇ 42), Tc(548), Os(575), Re(627 ⁇ 84), V(637), Ti(666.5 ⁇ 5.6), Sc(671.4 ⁇ 1.0) , Y (714.1 ⁇ 10.2), W (720 ⁇ 71), Nb (726.5 ⁇ 10.6), Zr (766.1 ⁇ 10.6), and the like.
  • the numbers in brackets are D 0 298 (MO)/kJmol ⁇ 1 .
  • D 0 298 (M ⁇ O) of the metal element M constituting the primer layer The larger the D 0 298 (M ⁇ O) of the metal element M constituting the primer layer, the more difficult it is for the antireflection layer to peel off even when exposed to light such as ultraviolet rays for a long time, and the antireflection film has better weather resistance. tend to be better.
  • D 0 298 (MO) of the metal element M constituting the primer layer is preferably 480 kJ/mol or more, more preferably 500 kJ/mol or more, and may be 520 kJ/mol or more.
  • the adhesion of the antireflection layer may be insufficient.
  • the D 0 298 (M ⁇ O) of silicon (Si), a semimetal, is about 800 kJ/mol, and a SiOx (x ⁇ 2) primer layer lacking oxygen with respect to stoichiometry reflects Adhesion to the antireflection layer is excellent, but when a stoichiometric SiO 2 primer layer is formed, adhesion to the antireflection layer tends to decrease after the weather resistance test.
  • D 0 298 (MO) of the metal element M constituting the primer layer is preferably 780 kJ/mol or less. It is not clear why the adhesion decreases when D 0 298 (M ⁇ O) is too large, but one possibility is that dangling The presence of bonds improves the adhesion with other layers, whereas in the stoichiometric composition, the metal element M has a high affinity for oxygen and high stability, so It is conceivable that the contribution to the improvement of affinity is small.
  • Examples of the metal element M having a D 0 298 (MO) of 450 to 780 kJ/mol are as described above. Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Tc, Re, Ru, Os, Al, and Sn are preferred from the viewpoint of properties. In particular, in applications requiring transparency such as antireflection films, Ti and Sn are preferred because they are excellent in oxide transparency and chemical stability.
  • the metal oxide constituting the primer layer may be a composite oxide, and as a dopant element, metal elements other than the above, and semi-metals such as B, C, Ge, P, As, Sb, Be, Se, Te, Po, At, etc. It may contain a metal element. From the viewpoint of maintaining high adhesion even after light irradiation, the ratio of the above metal to the total amount (100 atomic %) of the metal elements of the metal oxide constituting the primer layer 3 is preferably 50 atomic % or more, more preferably 60 atomic %. The above is more preferable, 70 atomic % or more is more preferable, and 80 atomic % or more, 90 atomic % or more, 95 atomic % or more, or 99 atomic % or more may be used.
  • the ratio of the metal having D 0 298 (M ⁇ O) of 450 kJ/mol or more with respect to the total amount of metal elements in the metal oxide is preferably within the above range, and D 0 298 (M It is more preferable that the ratio of the metal having —O) of 500 kJ/mol or more is within the above range.
  • the primer layer 3 is the total content of Sc, Y, Ti, Zr, V, Nb, Cr, Mo, W, Tc, Re, Ru, Os, Al, and Sn with respect to the total amount of metal elements in the metal oxide. is preferably within the above range, and more preferably, the proportion of Ti or Sn is within the above range. That is, the primer layer is particularly preferably composed mainly of titanium oxide (TiO 2 ) or tin oxide (SnO 2 ).
  • the primer layer 3 containing a specific metal oxide is formed on the hard coat layer 11, and the antireflection layer 5 is formed thereon.
  • peeling of the antireflection layer is unlikely to occur, and an antireflection film having excellent weather resistance can be obtained.
  • the primer layer 3 tends to significantly improve the adhesion of the antireflection layer 5 .
  • the thickness of the primer layer 3 is, for example, about 0.5 to 30 nm, preferably 1 to 25 nm, and may be 2 nm or more or 3 nm or more.
  • the thickness of the primer layer 3 may be 20 nm or less, 15 nm or less, 10 nm or less, or 8 nm or less.
  • the antireflection layer 5 is a laminate of a plurality of thin films having different refractive indices.
  • the antireflection layer has an optical thickness (product of refractive index and thickness) of the thin film 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.
  • the thin film constituting the antireflection layer 5 is preferably an inorganic material, preferably a ceramic material made of metal or semimetal oxide, nitride, fluoride, etc. Among them, metal or semimetal oxide (inorganic oxide). is preferred.
  • 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 ⁇ m.
  • 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, and a low refractive index layer 54 with an optical thickness of about 120 nm to 150 nm.
  • the antireflection layer is not limited to a 4-layer structure, and may have a 2-layer structure, a 3-layer structure, a 5-layer structure, or a lamination structure of 6 or more layers.
  • a method for forming the thin films constituting the primer layer 3 and the antireflection layer 5 is not particularly limited, and may be either a wet coating method or a dry coating method.
  • 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 the film substrate in one direction (longitudinal direction) by a roll-to-roll method. Therefore, the productivity of the antireflection film including the primer layer 3 and the antireflection layer 5 composed of a plurality of thin films on the hard coat film 1 can be improved.
  • 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.
  • an inert gas such as argon
  • a reactive gas such as oxygen
  • 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 (semi)metal target.
  • the thin film forming the antireflection layer 5 is preferably deposited by reactive sputtering using a metal or semimetal target.
  • DC or MF-AC is preferable as a sputtering power source used for reactive sputtering.
  • film formation is performed while introducing an inert gas such as argon and a reactive gas such as oxygen into the chamber.
  • an inert gas such as argon
  • a reactive gas such as oxygen
  • the amount of oxygen in the obtained film is smaller than the stoichiometric composition, resulting in an oxygen-deficient state, and the antireflection layer tends to have a metallic luster and decrease in transparency.
  • the film formation rate tends to be extremely low.
  • An oxide film can be deposited at a high rate by adjusting the amount of oxygen so that sputtering deposition is in the transition region.
  • a method for controlling the amount of oxygen introduced so that the deposition mode is in the transition region there is a plasma emission monitoring method (PEM method) in which the plasma emission intensity of the discharge is detected and the amount of gas introduced into the deposition chamber is controlled. mentioned.
  • PEM plasma emission monitoring method
  • control is performed by detecting the plasma emission intensity and feeding it back to the amount of oxygen introduced. For example, by setting the emission intensity control value (set point) within a predetermined range and performing PEM control to adjust the oxygen introduction amount, film formation in the transition region can be maintained.
  • An impedance method may be used to control the amount of introduced oxygen so that the plasma impedance is constant, that is, the discharge voltage is constant.
  • an oxide target for forming the primer layer 3 It is preferable to use an oxide target for forming the primer layer 3 .
  • Reactive sputtering using a metal target has the advantage of a high film formation rate, but on the other hand, the film quality may change due to a slight change in the introduction amount of a reactive gas such as oxygen.
  • an oxide target if an oxide target is used, the film quality of the primer layer is stabilized because the film quality does not change much even when the film formation conditions such as the amount of oxygen introduced are changed.
  • a conductive oxide target such as titanium oxide or tin oxide is used, it is possible to form a film at a high rate by DC sputtering.
  • An oxide target with a small amount of dopant added may be used to enhance conductivity.
  • the substrate temperature when the primer layer is formed by sputtering is about -30 to 150°C, and is not particularly limited as long as the hard coat film as the substrate material has durability.
  • the pressure and power density for forming the primer layer by sputtering can be appropriately set according to the type of target and the film thickness of the primer layer.
  • an oxidizing gas such as oxygen in addition to an inert gas such as argon.
  • oxygen oxygen released from the target during sputtering is supplemented, so that an oxide thin film having a stoichiometric composition tends to be easily formed, and transparency and chemical stability tend to be improved. Further, the adhesion of the antireflection layer tends to improve as the amount of oxygen introduced during sputtering film formation increases.
  • the amount of oxygen introduced during sputtering film formation is, for example, about 0.1 to 100 parts by volume, preferably 0.3 parts by volume or more, more preferably 0.5 parts by volume or more, with respect to 100 parts by volume of the inert gas. .
  • the amount of oxygen introduced during sputtering film formation is preferably 1 part by volume or more, more preferably 5 parts by volume or more, and 10 parts by volume or more with respect to 100 parts by volume of the inert gas. is more preferable, and may be 15 parts by volume or more or 20 parts by volume or more.
  • the amount of oxygen introduced during sputtering deposition is 80 parts by volume or less, 70 parts by volume or less, 60 parts by volume or less, 50 parts by volume or less, 40 parts by volume or less, or 30 parts by volume or less with respect to 100 parts by volume of the inert gas. There may be.
  • the oxide may have a non-stoichiometric composition and the transparency of the primer layer may decrease. Oxygen vacancies are slight even if they are not introduced at all.
  • the amount of oxygen introduced is excessively large, the conductivity tends to decrease.
  • the primer layer does not require conductivity, even if the amount of oxygen introduced is large, no particular problem occurs. . Rather, as the amount of oxygen introduced increases, the adhesion of the antireflection layer tends to improve. It is preferred to deposit a layer.
  • An antireflection film in which a silicon oxide layer is provided as a primer layer between a hard coat layer and an antireflection layer undergoes large fluctuations in film quality of the primer layer, and is likely to cause deterioration in adhesion and transparency.
  • One of the factors that cause the film quality of the silicon oxide primer layer to fluctuate is that it is not easy to precisely control the composition (value of x) of SiO x , which is an oxide of Si, which is a metalloid.
  • SiO x is deposited by reactive sputtering using a Si target, but the composition changes due to slight differences in deposition conditions. If the amount of oxygen is small, the transparency tends to decrease, and if the amount of oxygen is large, SiO2 (with a stoichiometric composition) having no oxygen vacancies is generated, and the adhesion of the antireflection layer is reduced. Tend. When an oxide target is used, the amount of oxygen can be appropriately controlled while monitoring the reaction by the above-mentioned PEM control or the like in the film formation of a complete oxide. It is not easy to control the amount of oxygen that is absorbed to be constant, and the characteristics tend to vary.
  • the antireflection film may comprise additional functional layers on the antireflection layer 5 .
  • 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 is used, for example, 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.
  • the antireflection film may be laminated with other films.
  • 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 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.
  • an antireflection film comprising an antireflection layer as an inorganic thin film on a hard coat layer of a film base via a primer layer
  • the primer layer comprises an inorganic thin film other than the antireflection layer.
  • it can contribute to the improvement of adhesion and weather resistance.
  • Inorganic thin film materials include metals and metal compounds (metal or metalloid oxides, nitrides, carbides, sulfides, fluorides, etc.).
  • the inorganic thin film may be conductive, insulating, or semiconducting.
  • the film thickness of the inorganic thin film (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 laminate, and the like.
  • the present invention will be described in more detail below by giving specific examples of an antireflection film having a primer layer provided between a hard coat layer and an antireflection layer, but the present invention is not limited to the following specific examples. do not have.
  • the above composition was applied to one side of a 40 ⁇ m-thick triacetyl cellulose film so that the thickness after drying was 6 ⁇ m, and dried at 80° C. for 3 minutes. After that, using a high-pressure mercury lamp, the coating layer was cured by irradiating ultraviolet light with an accumulated light amount of 200 mJ/cm 2 to form a hard coat layer.
  • SiO2 primer layer For the formation of the SiO2 primer layer, a Si target was used, and DC sputtering was performed under the conditions of a pressure of 0.2 Pa and a power density of 0.5 W/ cm2 while introducing 20 parts by volume of oxygen to 100 parts by volume of argon. membrane was performed.
  • a Si target was used to form the SiO 2 layer (low refractive index layer), and a Nb target was used to form the Nb 2 O 5 layer (high refractive index layer). rice field.
  • the amount of introduced oxygen was adjusted by plasma emission monitoring (PEM) control so that the deposition mode maintained the transition region.
  • Antireflection film 2 In the same manner as in the preparation of antireflection film 1, a hard coat film was prepared and the surface was treated with argon plasma. The hard coat film after the plasma treatment was introduced into a roll-to-roll type sputtering film forming apparatus, and the pressure in the tank was reduced to 1 ⁇ 10 ⁇ 4 Pa. Then, while the film was running, the substrate temperature was ⁇ 8° C., and a thickness of 6 nm was formed. A TiO 2 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 were sequentially deposited on the hard coat layer forming surface.
  • the TiO 2 primer layer was formed by DC sputtering under the conditions of a pressure of 0.2 Pa and a power density of 0.5 W/cm 2 while introducing 6 parts by volume of oxygen to 100 parts by volume of argon using a titanium oxide target. A film was formed. The SiO 2 layer and the Nb 2 O 5 layer were deposited under the same conditions as the antireflection film 1.
  • Antireflection films 3 to 7 The oxide target used for forming the primer layer was changed to tin oxide (SnO 2 ), molybdenum oxide (WO 3 ), chromium oxide (CrO 3 ), nickel oxide (NiO), and zinc oxide (ZnO), and the film was formed. The amount of oxygen introduced and the film thickness were changed as shown in Table 1. An antireflection film having an antireflection layer on a hard coat layer via a primer layer was produced in the same manner as in the production of antireflection film 2 except for these changes.
  • 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.
  • the metal type of the primer layer For each of the antireflection films 1 to 7, the metal type of the primer layer, the amount of oxygen introduced during the formation of the primer layer (volume ratio to argon) and the thickness of the primer layer, and the adhesion of the antireflection layer before and after the accelerated weathering test Table 1 shows the evaluation results.
  • the anti-reflection film 1 in which the SiO 2 primer layer was formed by reactive sputtering using a silicon target, exhibited a significant decrease in adhesion after the accelerated weathering test.
  • the SiOx (x ⁇ 2) primer layer was formed by changing the amount of oxygen introduced during the formation of the primer layer to 3 parts by volume with respect to 100 parts by volume of argon, Even after the accelerated weathering test, the antireflection layer exhibited good adhesion, but a decrease in transmittance was observed.
  • the prevention film 4 was also the same.
  • Antireflection film 5 with nickel oxide (Ni—O: D 0 298 461 kJ/mol) as a primer layer, and zinc oxide (Zn—O: D 0 298 ⁇ 250 kJ/mol) as a primer layer.
  • the antireflection film 6 showed a marked decrease in adhesion after the accelerated weathering test.

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