WO2021106788A1 - Antireflection film, method for producing same, and image display device - Google Patents
Antireflection film, method for producing same, and image display device Download PDFInfo
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- WO2021106788A1 WO2021106788A1 PCT/JP2020/043414 JP2020043414W WO2021106788A1 WO 2021106788 A1 WO2021106788 A1 WO 2021106788A1 JP 2020043414 W JP2020043414 W JP 2020043414W WO 2021106788 A1 WO2021106788 A1 WO 2021106788A1
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- Prior art keywords
- layer
- film
- antireflection
- hard coat
- oxide
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- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to an antireflection film, a method for producing the same, and an image display device including the antireflection film.
- An antireflection film may be 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.
- the antireflection film includes an antireflection layer composed of a plurality of thin films having different refractive indexes on a film base material.
- 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 the film thickness, so that high antireflection characteristics can be realized.
- a hard coat layer may be provided on the antireflection layer forming surface of the film base material for the purpose of preventing damage due to external contact.
- the hard coat layer formed of an organic substance and the inorganic thin film have a small adhesion between the layers, and delamination may occur. In particular, in an environment exposed to ultraviolet rays such as outdoors, the problem of delamination tends to become noticeable.
- Patent Document 1 a primer layer made of silicon oxide (SiO x ; 0 ⁇ x ⁇ 2) in an oxygen-deficient state (non-stoichiometric composition) is formed on the hard coat layer, and an antireflection layer is formed on the primer layer. It is described that the adhesion of the antireflection layer is improved by doing so.
- a primer layer made of silicon oxide having a non-stoichiometric composition is formed by reactive sputtering using a silicon target.
- the antireflection film in which a silicon oxide thin film is provided 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 turned out to be.
- an object of the present invention is to provide an antireflection film having excellent quality stability such as adhesion and transparency.
- the present invention relates to an antireflection film and a method for producing the same.
- the antireflection film is used, for example, by arranging it on the surface of the image display device on the visual side.
- the antireflection film includes a hard coat film having a hard coat layer on one main surface of a film base material, a primer layer provided in contact with the hard coat layer, and an antireflection layer provided in contact with the primer layer. And.
- the hard coat layer may contain fine particles in addition to the binder resin.
- the primer layer arranged between the hard coat layer and the antireflection layer is a metal oxide layer containing metal oxides such as In and Sn.
- metal oxide an indium-based oxide containing indium oxide as a main oxide is preferable, and indium tin oxide (ITO) is particularly preferable.
- the primer layer is formed by a sputtering method using, for example, an oxide target.
- the thickness of the primer layer is preferably about 0.5 to 30 nm.
- the antireflection layer is a laminate of a plurality of thin films having different refractive indexes, and each thin film may be an inorganic oxide thin film.
- the antireflection layer is formed by, for example, a sputtering method.
- the antireflection layer can also be formed by reactive sputtering.
- the primer layer placed between the hard coat layer and the antireflection layer is a metal oxide layer, there is little fluctuation or variation in the oxidation state, and the antireflection film with excellent quality such as adhesion and transparency is stable. Can be provided.
- FIG. 1 is a cross-sectional view showing an example of a laminated configuration of antireflection films.
- the antireflection film 100 includes a hard coat film 1 having a hard coat layer 11 provided on one main surface of the film base material 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 layers of inorganic thin films having different refractive indexes.
- the antireflection layer 5 has a structure in which high refractive index layers 51 and 53 and low refractive index layers 52 and 54 are alternately laminated.
- the film base material 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 more, more preferably 90% or more.
- the resin material constituting the transparent film for example, a resin material having excellent transparency, mechanical strength, and thermal stability is preferable.
- the resin material include cellulose-based resins such as triacetyl cellulose, polyester-based resins, polyether sulfone-based resins, polysulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyolefin-based resins, (meth).
- examples thereof include acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
- the film base material 10 does not necessarily have to be transparent. Further, as the film base material 10, a laminate of a plurality of films may be used. For example, as will be described later, a polarizing plate provided with a protective film on the surface of the polarizer may be used as the film base material 10.
- the thickness of the film base material 10 is not particularly limited, but 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 workability such as strength and handleability, and thin layer property.
- the hard coat film 1 is formed by providing the hard coat layer 11 on the main surface of the film base material 10.
- the hard coat layer is a curable resin layer, and is formed by applying a composition containing a curable resin onto a film substrate and curing the resin component.
- the hard coat layer may contain fine particles in addition to the cured resin.
- a curable resin such as a thermosetting resin, a photocurable resin, or an electron beam curable resin is preferably used.
- the curable resin include polyester-based, acrylic-based, urethane-based, acrylic-urethane-based, amide-based, silicone-based, silicate-based, epoxy-based, melamine-based, oxetane-based, and acrylic urethane-based.
- acrylic resins, acrylic urethane resins, and epoxy resins are preferable, and acrylic urethane resins are particularly preferable because they have high hardness and can be photocured.
- the photocurable resin composition contains a polyfunctional compound having two or more photopolymerizable (preferably ultraviolet-polymerizable) functional groups.
- the polyfunctional compound may be a monomer or an oligomer.
- As the photopolymerizable polyfunctional compound a compound containing two or more (meth) acryloyl groups in one molecule is preferably used.
- polyfunctional compound having two or more (meth) acryloyl groups in one molecule include tricyclodecanedimethanol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylol.
- (meth) acrylic means acrylic and / or methacryl.
- a polyfunctional compound having two or more (meth) acryloyl groups in one molecule may have a hydroxyl group.
- a polyfunctional compound containing a hydroxyl group By using a polyfunctional compound containing a hydroxyl group, the adhesion between the film substrate and the hard coat layer tends to be improved.
- the compound 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 resin contains a monomer or oligomer of urethane (meth) acrylate as a polyfunctional compound.
- the number of (meth) acryloyl groups contained in the urethane (meth) acrylate is preferably 3 or more, more preferably 4 to 15, and even more preferably 6 to 12.
- the molecular weight of the urethane (meth) acrylate oligomer is, for example, 3000 or less, preferably 500 to 2500, and more preferably 800 to 2000.
- Urethane (meth) acrylate is obtained, for example, by reacting hydroxy (meth) acrylate obtained from (meth) acrylic acid or (meth) acrylic acid ester with a 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 100 parts by weight in total of the resin components (monomers, oligomers and prepolymers forming a binder resin by curing). 60 parts by weight or more is more preferable, and 70 parts by weight or more is further preferable. When the content of the polyfunctional monomer is within the above range, the hardness of the hard coat layer tends to be increased.
- the hard coat layer 11 contains fine particles, it is possible to adjust the surface shape, impart optical characteristics such as antiglare, and improve the adhesion of the antireflection layer.
- the 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, polymethylmethacrylate, polystyrene, polyurethane, and acrylic-styrene copolymer.
- inorganic oxide fine particles such as silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide
- glass fine particles polymethylmethacrylate, polystyrene, polyurethane, and acrylic-styrene copolymer.
- Crosslinked or uncrosslinked organic fine particles made of transparent polymers such as benzoguanamine, melamine and polystyrene can be used without particular limitation.
- the average particle size (average primary particle size) of the fine particles is preferably about 10 nm to 10 ⁇ m.
- the fine particles have an average particle size of about 0.5 ⁇ m to 10 ⁇ m or an average particle size on the order of ⁇ m (hereinafter, may be referred to as “microparticles”) depending on the particle size, and have an average particle size of about 10 nm to 100 nm. It can be roughly divided into fine particles having a particle size (hereinafter sometimes referred to as “nanoparticles”) and fine particles having a particle size intermediate between microparticles and nanoparticles.
- the hard coat layer 11 contains nanoparticles, fine irregularities are formed on the surface, and the adhesion between the hard coat layer 11 and the primer layer 3 and the antireflection layer 5 tends to be improved.
- nanoparticles 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 30 to 60 nm. More preferred. Further, from the viewpoint of suppressing the coloring of the 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, still more preferably 45 nm or less. The average primary particle size is the weight average particle size measured by the Coulter counter 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 having excellent adhesion to the inorganic thin film on the surface of the hard coat layer 11, the content of nanoparticles in the hard coat layer 11 is 20 to 100 weight by weight with respect to 100 parts by weight of the binder resin. Parts are preferable, 25 to 90 parts by weight are more preferable, and 30 to 80 parts by weight are further preferable.
- the hard coat layer 11 contains microparticles, protrusions having a diameter on the order of submicron or ⁇ m are formed on the surface of the hard coat layer 11 and the surface of the thin film formed on the hard coat layer 11, and antiglare is imparted. ..
- the microparticles preferably have a small difference in refractive index from the binder resin of the hard coat layer, and 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, still more preferably 3 to 8 parts by weight, based on 100 parts by weight of the binder resin.
- the hard coat layer 11 may contain only one of nanoparticles and microparticles, or may contain both. Further, it may contain fine particles having a particle size intermediate between nanoparticles and microparticles.
- the composition for forming a hard coat layer contains the above-mentioned binder resin component, and if necessary, contains a solvent capable of dissolving the binder resin component.
- the composition for forming a hard coat layer may contain fine particles.
- the binder resin component is a photocurable resin
- the composition contains a photopolymerization initiator.
- the composition for forming a hard coat layer includes a leveling agent, a thixotropy agent, an antistatic agent, an antiblocking agent, a dispersant, a dispersion stabilizer, an antioxidant, an ultraviolet absorber, an antifoaming agent, and a thickener.
- Surfactants, lubricants and other additives may be included.
- a hard coat layer is formed by applying a composition for forming a hard coat layer on a film substrate, removing a solvent and curing the resin as necessary.
- a method for applying the composition for forming a hard coat layer any appropriate method such as a bar coat method, a roll coat method, a gravure coat method, a rod coat method, a slot orifice coat method, a curtain coat method, a fountain coat method, and a comma coat method is appropriate. Method can be adopted.
- the heating temperature after coating may be set to an appropriate temperature according to the composition of the hard coat layer forming composition and the like, and is, for example, about 50 ° C. to 150 ° C.
- the binder resin component is a photocurable resin
- photocuring is performed by irradiating with active energy rays such as ultraviolet rays.
- active energy rays such as ultraviolet rays.
- the integrated light amount 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, but 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 Before forming the primer layer 3 and the antireflection layer 5 on the hard coat layer 11, the hard coat layer 11 has an object of further improving the adhesion between the hard coat layer 11 and the primer layer 3 and the antireflection layer 5.
- Surface treatment may be performed. Examples of the surface treatment include surface modification treatments such as corona treatment, plasma treatment, frame treatment, ozone treatment, primer treatment, glow treatment, alkali treatment, acid treatment, and treatment with a coupling agent. 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, when vacuum plasma treatment is performed with high discharge power, the surface unevenness of the surface of the hard coat layer becomes large, and the adhesion to the inorganic thin film tends to be improved.
- Primer layer 3 is formed on the hard coat layer 11, and an antireflection layer 5 is formed on the primer layer 3.
- 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.
- An antireflection film that does not easily peel off the preventive layer can be obtained.
- the primer layer 3 is a metal oxide thin film.
- metal here is a concept that does not include metalloids such as silicon. Metals include Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Examples thereof include Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb and the like.
- the metal oxide layer may be a composite oxide, and may contain a metalloid such as B, C, Ge, P, As, Sb, Be, Se, Te, Po, At as a dopant element. Specific examples of metal oxides containing Sb, which is a semimetal as a dopant, include antimony-doped tin oxide (ATO).
- ATO antimony-doped tin oxide
- the primer layer preferably contains an oxide of one or more metals selected from the group consisting of In and Sn because of its high transparency, and one of In and Sn is used as the main metal element.
- Metal oxides are preferred.
- indium-based oxides containing indium oxide as a main component are preferable because they have high transparency and excellent optical stability.
- the indium-based oxide preferably contains 60% by weight or more of indium oxide.
- indium oxides include indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Of these, ITO is preferable because it is highly transparent and has excellent adhesion to the hard coat layer.
- the amount of indium oxide in ITO is preferably about 80 to 98%.
- 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 film thickness of the primer layer is within the above range, the adhesion to the hard coat layer 11 can be improved, and the light transmission of the antireflection film can be improved.
- the primer layer of the antireflection film may be a dielectric or a conductor. Even when the metal oxide of the primer layer 3 is a conductive oxide such as ITO, the primer layer does not require conductivity, so that a large thickness unlike a transparent electrode is not required. From the viewpoint of increasing the light transmittance, it is preferable that the primer layer 3 has a small thickness within a range in which adhesion with the hard coat layer 11 and the antireflection layer 5 can be ensured.
- 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 indexes.
- the optical film thickness (product of refractive index and thickness) of the thin film is adjusted so that the inverted phases of the incident light and the reflected light cancel each other out. Due to the multi-layered laminate of a plurality of thin films having different refractive indexes, the reflectance can be reduced in a wide wavelength range of visible light.
- an inorganic material is preferable, and a ceramic material composed of a metal or metalloid oxide, a nitride, a fluoride or the like is preferable, and among them, a metal or metalloid oxide (inorganic oxide) is preferable. Is preferable.
- the antireflection layer 5 is preferably an alternating laminate of a high refractive index layer and a low refractive index layer.
- the thin film 54 provided as the outermost layer 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.
- the high refractive index material include titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO) and the like. Of these, 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.
- the low refractive index material examples include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, hafnium fluoride, lanthanum fluoride and the like. Of these, silicon oxide is preferable. In particular, it is preferable that niobium oxide (Nb 2 O 5 ) thin films 51 and 53 as a high refractive index layer and silicon oxide (SiO 2 ) thin films 52 and 54 as a low refractive index layer are alternately laminated. In addition to the low refractive index layer and the high refractive index layer, a medium refractive index layer having a refractive index of about 1.6 to 1.9 may be provided.
- the film thickness of the high refractive index layer and the low refractive index layer is about 5 to 200 nm, respectively, and is preferably about 15 to 150 ⁇ m.
- the film thickness of each layer may be designed so that the reflectance of visible light becomes small according to the refractive index, the laminated structure, and the like.
- a high refractive index layer 51 having an optical film thickness of about 25 nm to 55 nm and a low refractive index layer having an optical film thickness of about 35 nm to 55 nm are formed from the hard coat film 1 side.
- the antireflection layer is not limited to the four-layer structure, and may be a two-layer structure, a three-layer structure, a five-layer structure, or a laminated structure of six or more layers.
- the method for forming the thin film forming the primer layer 3 and the antireflection layer 5 is not particularly limited, and either a wet coating method or a dry coating method may be used. Since a thin film having a uniform film thickness can be formed, a dry coating method such as vacuum deposition, CVD, sputtering, or electron beam steaming is preferable. Of these, the sputtering method is preferable because it has excellent film thickness uniformity and easily forms a dense film.
- the roll-to-roll method enables continuous film formation of thin films while transporting the film substrate in one direction (longitudinal direction). 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 film is formed 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 formation of the oxide layer by the sputtering method can be carried out by either a method using an oxide target or a reactive sputtering using a (semi-) metal target.
- the thin film constituting the antireflection layer 5 is preferably formed by reactive sputtering using a metal or metalloid target.
- a metal or metalloid target As the sputtering power source used for reactive sputtering, DC or MF-AC is preferable.
- the film is formed 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 small compared to the stoichiometric composition, resulting in an oxygen deficiency state, and the antireflection layer tends to have a metallic luster and the transparency tends to decrease. Further, in the oxide region where the amount of oxygen is large, the film formation rate tends to be extremely lowered.
- the oxide film can be formed at a high rate.
- a plasma emission monitoring method PEM method
- PEM plasma emission monitoring method
- control is performed by detecting the plasma emission intensity and feeding it back to the amount of oxygen introduced.
- the film formation in the transition region can be maintained by setting the control value (set point) of the emission intensity within a predetermined range, performing PEM control, and adjusting the amount of oxygen introduced.
- Control may be performed by an impedance method that controls the amount of oxygen introduced so that the plasma impedance becomes constant, that is, the discharge voltage becomes 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 high film formation rate, but the film quality may change due to a slight change in the amount of reactive gas introduced such as oxygen. On the other hand, when the 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 forming conditions such as the amount of oxygen introduced change. Further, if a conductive oxide target such as ITO is used, it is possible to form a film at a high rate by DC sputtering.
- the substrate temperature when the primer layer is sputter-deposited 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 when the primer layer is sputter-deposited can be appropriately set according to the type of target and the film thickness of the primer layer.
- the primer layer 3 is formed by sputtering using an oxide target
- an oxidizing gas such as oxygen
- an inert gas such as argon
- oxygen oxygen desorbed from the target during sputtering is supplemented, so that an oxide thin film having a stoichiometric composition is likely to be formed, and the transparency tends to be improved.
- the adhesion of the antireflection layer tends to improve.
- the amount of oxygen introduced during sputter film formation is, for example, about 0.1 to 100 parts by volume, preferably 0.3 parts by volume or more, and 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 sputter 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, 20 parts by volume or more, or 25 parts by volume or more.
- the amount of oxygen introduced during sputter film formation 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 deficiency is slight even when no introduction is made, and a significant decrease in transparency can be avoided.
- the conductivity tends to decrease if the amount of oxygen introduced is excessively large.
- the primer layer is not required to have conductivity, so that even if the amount of oxygen introduced is large, the conductivity is particularly high. No problem arises.
- the adhesion of the antireflection layer tends to improve, so that the amount of oxygen introduced is larger than the general conditions for forming a conductive film such as a transparent electrode. It is preferable to form a primer layer.
- An antireflection film in which silicon oxide is provided as a primer layer between the hard coat layer and the antireflection layer has a large variation in the film quality of the primer layer, and tends to cause a decrease in adhesion and a decrease in transparency.
- One of the factors that change the film quality of the silicon oxide primer layer 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 formed by reactive sputtering using a Si target, but the composition changes due to a slight difference in film forming conditions.
- the amount of oxygen is small, the transparency tends to decrease, and when the amount of oxygen is large, SiO 2 having no oxygen deficiency (stoichiometric composition) is generated, and the adhesion of the antireflection layer decreases.
- 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, but in the film formation of an oxide having a non-chemical composition, it is incorporated into a thin film. It is not easy to control the amount of oxygen to be generated to be constant, and the characteristics are likely to vary.
- the metal oxide primer layer such as ITO
- the characteristic change due to the deviation of the oxygen amount is unlikely to occur, and the fine adjustment of the oxygen amount is not required. Therefore, it is possible to provide an antireflection film having stable quality such as transparency and adhesion of the antireflection layer. Further, by increasing the amount of oxygen introduced during the formation of the primer layer, it is possible to realize better adhesion than the SiO x primer layer.
- the antireflection film may have an additional functional layer on the antireflection layer 5.
- the silicon oxide layer is arranged as the low refractive index layer 54 on the outermost surface of the antireflection layer 5, the silicon oxide has high wettability, and contaminants such as fingerprints and hand stains easily adhere to it. 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 the 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 is 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.
- a fluorine group-containing silane compound, a fluorine group-containing organic compound, 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, a gravure coating method, a dry method such as a CVD method, or the like.
- the thickness of the antifouling layer is usually about 1 to 100 nm, preferably 2 to 50 nm, and more preferably 3 to 30 nm.
- the antireflection film is used by arranging it on the surface of an image display device such as a liquid crystal display or an organic EL display. For example, by arranging the antireflection film on the viewing side surface of the panel including the 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 another film.
- a polarizing plate with an antireflection layer can be formed by attaching a polarizing element to the non-formed surface of the hard coat layer of the film base material 10.
- a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymerization system partially saponified film, and a bicolor substance such as iodine or a dichroic dye are used.
- a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymerization system partially saponified film, and a bicolor substance such as iodine or a dichroic dye are used.
- examples thereof include those obtained by adsorbing and uniaxially stretching the film, and polyene-based oriented films such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride.
- polyvinyl alcohol or a polyvinyl alcohol-based film such as partially formalized polyvinyl alcohol is adsorbed with a dichroic substance such as iodine or a dichroic dye and oriented in a predetermined direction.
- 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 or the like.
- the transparent protective film may be bonded to only one surface of the polarizer, or may be bonded to both sides.
- a transparent protective film is provided on the surface of the polarizer opposite to the surface on which the antireflection film is attached.
- the antireflection film since the antireflection film also functions as a transparent protective film, it is not necessary to provide a transparent protective film, but a transparent protective film is provided between the polarizer and the antireflection film. It may have been.
- the same material as the above-mentioned material is preferably used as the material of the transparent film base material. It is preferable to use an adhesive for bonding the polarizer and the transparent film.
- Adhesives are based on acrylic polymers, silicon polymers, polyesters, polyurethanes, polyamides, polyvinyl alcohols, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy polymers, fluoropolymers, rubber polymers, etc.
- a polymer can be appropriately selected and used.
- a polyvinyl alcohol-based adhesive is preferably used for bonding the PVA-based polarizer.
- the amount of silica particles in the ultraviolet curable acrylic resin composition (manufactured by DIC, trade name "GRANDIC PC-1070", refractive index at a wavelength of 405 nm: 1.55) is 25 parts by weight with respect to 100 parts by weight of the resin component.
- Organo silica sol (“MEK-ST-L” manufactured by Nissan Chemical Co., Ltd., average primary particle size of silica particles (inorganic filler): 50 nm, particle size distribution of silica particles: 30 nm to 130 nm, solid content 30% by weight) is added to the mixture. And mixed to prepare a composition for forming a hard coat layer.
- the above composition was applied to one side of a triacetyl cellulose film having a thickness of 40 ⁇ m so as to have a thickness of 6 ⁇ m after drying, and dried at 80 ° C. for 3 minutes. Then, using a high-pressure mercury lamp , ultraviolet rays having an integrated light intensity of 200 mJ / cm 2 were irradiated to cure the coating layer to form a hard coat layer.
- the hard coat film after plasma treatment is introduced into a roll-to-roll type sputter film forming apparatus, the inside of the tank is depressurized to 1 ⁇ 10 -4 Pa, and then the film is run at a substrate temperature of -8 ° C. at 4 nm.
- a SiO x 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 formed in this order on the hard coat layer forming surface.
- a Si target was used to form the SiO x primer layer, and DC sputtering was performed under the conditions of a pressure of 0.2 Pa and a power density of 0.5 W / cm 2 while introducing 3 parts by volume of oxygen with respect to 100 parts by volume of argon.
- the membrane was made.
- a Si target was used to form the SiO 2 layer (low refractive index layer), and an Nb target was used to form the Nb 2 O 5 layer (high refractive index layer), and the film was formed at an argon flow rate of 400 sccm and a pressure of 0.25 Pa. It was.
- the amount of oxygen introduced so that the film formation mode maintains the transition region was adjusted by plasma emission monitoring (PEM) control.
- Anti-reflective film 1B-1F The amount of oxygen introduced during the formation of the SiO x primer layer was changed as shown in Table 1.
- the power density was doubled and the film thickness of the SiO x primer layer was set to 8 nm. Except for these changes, an antireflection film having an antireflection layer on the hard coat layer via a SiO x primer layer was produced under the same conditions as the production of the antireflection film 1A.
- Anti-reflective film 2A Similar to the preparation of the antireflection film 1A, the hard coat film was prepared and the surface was treated with argon plasma. The hard coat film after plasma treatment is introduced into a roll-to-roll type sputter film forming apparatus, the inside of the tank is depressurized to 1 ⁇ 10 -4 Pa, and then the film is run at a substrate temperature of -8 ° C. at 4 nm. An 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 were formed on the hard coat layer forming surface in this order.
- an oxide target containing indium oxide and tin oxide in a weight ratio of 90:10 was used, and while introducing 3 parts by volume of oxygen with respect to 100 parts by volume of argon, the pressure was 0.2 Pa.
- DC sputter film formation was performed under the condition of a power density of 0.5 W / cm 2.
- the SiO 2 layer and the Nb 2 O 5 layer were formed under the same conditions as the antireflection film 1A.
- Anti-reflective film 2B-2H The amount of oxygen introduced during the formation of the ITO primer layer was changed as shown in Table 1, and the power density was further changed to form the ITO primer layer having the film thickness shown in Table 1. Except for these changes, an antireflection film having an antireflection layer on the hard coat layer via an ITO primer layer was produced under the same conditions as the production of the antireflection film 2A.
- the surface of the antireflection layer of the sample after the accelerated durability test was cut at 1 mm intervals to form a grid of 100 squares.
- 2 mL of isopropyl alcohol was continuously dropped so that the surface of the antireflection layer would not dry, and a polyester wiper (“Anticon Gold” manufactured by Sampler Tech) fixed to a 20 mm square SUS jig was rubbed on a grid. It was moved (load: 1.5 kg, 1000 reciprocations).
- the number of grids 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.
- ⁇ Transmittance> The transmission spectrum of the antireflection film is measured with an integrating sphere spectrophotometer (“DOT-3” manufactured by Murakami Color Technology Laboratory), and the transmittance (Y value, which is the visual transmittance of the XYZ color system of transmitted light). Asked.
- DOT-3 integrating sphere spectrophotometer
- the antireflection film 1C provided with the SiO x primer layer had a high transmittance of 96.5% and excellent adhesion, but the antireflection film 1D having a large primer layer had a reduced transmittance. Was there. Further, the transmittance was also lowered in the antireflection films 1A and 1B in which the amount of oxygen introduced during the film formation of the SiO x primer layer was small. On the other hand, in the antireflection films 1E and 1F in which the amount of oxygen introduced during the formation of the primer layer was large, a decrease in adhesion was observed.
- Hard coat film 10 Film base material 11 Hard coat layer 3 Primer layer 5 Antireflection layer 51,53 Low refractive index layer 52,54 High refractive index layer 100 Antireflection film
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Abstract
Description
<フィルム基材>
ハードコートフィルム1のフィルム基材10としては、例えば、透明フィルムが用いられる。透明フィルムの可視光透過率は、好ましくは80%以上、より好ましくは90%以上である。透明フィルムを構成する樹脂材料としては、例えば、透明性、機械強度、および熱安定性に優れる樹脂材料が好ましい。樹脂材料の具体例としては、トリアセチルセルロース等のセルロース系樹脂、ポリエステル系樹脂、ポリエーテルスルホン系樹脂、ポリスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、(メタ)アクリル系樹脂、環状ポリオレフィン系樹脂(ノルボルネン系樹脂)、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、およびこれらの混合物が挙げられる。 [Hard coat film]
<Film base material>
As the
フィルム基材10の主面上にハードコート層11を設けることによりハードコートフィルム1が形成される。ハードコート層は硬化樹脂層であり、硬化性樹脂を含む組成物をフィルム基材上に塗布し、樹脂成分を硬化することにより形成される。ハードコート層は、硬化樹脂に加えて微粒子を含んでいてもよい。 <Hard coat layer>
The
ハードコート層11の硬化性樹脂(バインダー樹脂)としては、熱硬化性樹脂、光硬化性樹脂、電子線硬化性樹脂等の硬化性樹脂が好ましく用いられる。硬化性樹脂の種類としてはポリエステル系、アクリル系、ウレタン系、アクリルウレタン系、アミド系、シリコーン系、シリケート系、エポキシ系、メラミン系、オキセタン系、アクリルウレタン系等が挙げられる。これらの中でも、硬度が高く、光硬化が可能であることから、アクリル系樹脂、アクリルウレタン系樹脂、およびエポキシ系樹脂が好ましく、中でもアクリルウレタン系樹脂が好ましい。 (Curable resin)
As the curable resin (binder resin) of the
ハードコート層11が微粒子を含むことにより、表面形状を調整し、防眩性等の光学特性の付与や反射防止層の密着性向上等の作用を持たせることができる。 (Fine particles)
Since the
ハードコート層形成用組成物は、上記のバインダー樹脂成分を含み、必要に応じてバインダー樹脂成分を溶解可能な溶媒を含む。上記の通り、ハードコート層形成用組成物は微粒子を含んでいてもよい。バインダー樹脂成分が光硬化型樹脂である場合には、組成物中に光重合開始剤が含まれることが好ましい。ハードコート層形成用組成物は、上記の他に、レベリング剤、チクソトロピー剤、帯電防止剤、ブロッキング防止剤、分散剤、分散安定剤、酸化防止剤、紫外線吸収剤、消泡剤、増粘剤、界面活性剤、滑剤等の添加剤を含んでいてもよい。 (Formation of hard coat layer)
The composition for forming a hard coat layer contains the above-mentioned binder resin component, and if necessary, contains 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, it is preferable that the composition contains a photopolymerization initiator. In addition to the above, the composition for forming a hard coat layer includes a leveling agent, a thixotropy agent, an antistatic agent, an antiblocking agent, a dispersant, a dispersion stabilizer, an antioxidant, an ultraviolet absorber, an antifoaming agent, and a thickener. , Surfactants, lubricants and other additives may be included.
ハードコート層11上には、プライマー層3が形成され、その上に反射防止層5が形成される。ハードコート層11上に接してプライマー層3を設け、プライマー層3上に接して反射防止層5を設けることにより、層間の密着性に優れ、紫外線等の光に長時間晒された場合でも反射防止層の剥離が生じ難い反射防止フィルムが得られる。 <Primer layer>
A
反射防止層5は、屈折率の異なる複数の薄膜の積層体である。一般に、反射防止層は、入射光と反射光の逆転した位相が互いに打ち消し合うように、薄膜の光学膜厚(屈折率と厚みの積)が調整される。屈折率の異なる複数の薄膜の多層積層体により、可視光の広帯域の波長範囲において、反射率を小さくできる。反射防止層5を構成する薄膜としては、無機材料が好ましく、金属または半金属の酸化物、窒化物、フッ化物等からなるセラミック材料が好ましく、中でも金属または半金属の酸化物(無機酸化物)が好ましい。 <Anti-reflective layer>
The
プライマー層3および反射防止層5を構成する薄膜の成膜方法は特に限定されず、ウェットコーティング法、ドライコーティング法のいずれでもよい。膜厚が均一な薄膜を形成できることから、真空蒸着、CVD,スパッタ、電子線蒸等のドライコーティング法が好ましい。中でも、膜厚の均一性に優れ、かつ緻密な膜を形成しやすいことから、スパッタ法が好ましい。 <Film formation of primer layer and antireflection layer>
The method for forming the thin film forming the
反射防止フィルムは、反射防止層5上に、付加的な機能層を備えていてもよい。反射防止層5の最表面の低屈折率層54として酸化シリコン層が配置されている場合は、酸化シリコンの濡れ性が高く、指紋や手垢等の汚染物質が付着しやすい。そのため、外部環境からの汚染防止や、付着した汚染物質の除去を容易とする等の目的で、反射防止層5上に防汚層(不図示)を設けてもよい。 [Anti-fouling layer]
The antireflection film may have an additional functional layer on the
反射防止フィルムは、例えば液晶ディスプレイや有機ELディスプレイ等の画像表示装置の表面に配置して用いられる。例えば、液晶セルや有機ELセル等の画像表示媒体を含むパネルの視認側表面に反射防止フィルムを配置することにより、外光の反射を低減して、画像表示装置の視認性を向上できる。 [Usage pattern of antireflection film]
The antireflection film is used by arranging it on the surface of an image display device such as a liquid crystal display or an organic EL display. For example, by arranging the antireflection film on the viewing side surface of the panel including the 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.
紫外線硬化性アクリル系樹脂組成物(DIC製、商品名「GRANDIC PC-1070」、波長405nmにおける屈折率:1.55)に、樹脂成分100重量部に対するシリカ粒子の量が25重量部となるように、オルガノシリカゾル(日産化学社製「MEK-ST-L」、シリカ粒子(無機フィラー)の平均一次粒子径:50nm、シリカ粒子の粒子径分布:30nm~130nm、固形分30重量%)を添加して混合し、ハードコート層形成用組成物を調製した。 [Making a hard coat film]
The amount of silica particles in the ultraviolet curable acrylic resin composition (manufactured by DIC, trade name "GRANDIC PC-1070", refractive index at a wavelength of 405 nm: 1.55) is 25 parts by weight with respect to 100 parts by weight of the resin component. Organo silica sol (“MEK-ST-L” manufactured by Nissan Chemical Co., Ltd., average primary particle size of silica particles (inorganic filler): 50 nm, particle size distribution of silica particles: 30 nm to 130 nm, solid content 30% by weight) is added to the mixture. And mixed to prepare a composition for forming a hard coat layer.
<表面処理>
0.5Paの真空雰囲気下でハードコートフィルムを搬送しながら、放電電力1.0kWにてハードコート層の表面にアルゴンプラズマ処理を行った。 [Anti-reflective film 1A]
<Surface treatment>
While transporting the hard coat film in a vacuum atmosphere of 0.5 Pa, the surface of the hard coat layer was subjected to argon plasma treatment with a discharge power of 1.0 kW.
プラズマ処理後のハードコートフィルムをロールトゥーロール方式のスパッタ成膜装置に導入し、槽内を1×10-4Paまで減圧した後、フィルムを走行させながら、基板温度-8℃で、4nmのSiOxプライマー層、16nmのNb2O5層、19nmのSiO2層、102nmのNb2O5層および71nmのSiO2層を、ハードコート層形成面に順に成膜した。 <Formation of primer layer and antireflection layer>
The hard coat film after plasma treatment is introduced into a roll-to-roll type sputter film forming apparatus, the inside of the tank is depressurized to 1 × 10 -4 Pa, and then the film is run at a substrate temperature of -8 ° C. at 4 nm. A SiO x 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 formed in this order on the hard coat layer forming surface.
SiOxプライマー層形成時の酸素導入量を表1に示すように変更した。反射防止フィルム1Dの作製においては、電力密度を2倍にして、SiOxプライマー層の膜厚を8nmとした。これらの変更以外は、反射防止フィルム1Aの作製と同条件にて、ハードコート層上に、SiOxプライマー層を介して反射防止層を備える反射防止フィルムを作製した。 [Anti-reflective film 1B-1F]
The amount of oxygen introduced during the formation of the SiO x primer layer was changed as shown in Table 1. In the production of the antireflection film 1D, the power density was doubled and the film thickness of the SiO x primer layer was set to 8 nm. Except for these changes, an antireflection film having an antireflection layer on the hard coat layer via a SiO x primer layer was produced under the same conditions as the production of the antireflection film 1A.
反射防止フィルム1Aの作製と同様に、ハードコートフィルムの作製およびアルゴンプラズマによる表面処理を行った。プラズマ処理後のハードコートフィルムをロールトゥーロール方式のスパッタ成膜装置に導入し、槽内を1×10-4Paまで減圧した後、フィルムを走行させながら、基板温度-8℃で、4nmのITOプライマー層、16nmのNb2O5層、19nmのSiO2層、102nmのNb2O5層および71nmのSiO2層を、ハードコート層形成面に順に成膜した。 [Anti-reflective film 2A]
Similar to the preparation of the antireflection film 1A, the hard coat film was prepared and the surface was treated with argon plasma. The hard coat film after plasma treatment is introduced into a roll-to-roll type sputter film forming apparatus, the inside of the tank is depressurized to 1 × 10 -4 Pa, and then the film is run at a substrate temperature of -8 ° C. at 4 nm. An 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 were formed on the hard coat layer forming surface in this order.
ITOプライマー層形成時の酸素導入量を表1に示すように変更し、さらに電力密度を変更して、表1に示す膜厚のITOプライマー層を形成した。これらの変更以外は、反射防止フィルム2Aの作製と同条件にて、ハードコート層上に、ITOプライマー層を介して反射防止層を備える反射防止フィルムを作製した。 [Anti-reflective film 2B-2H]
The amount of oxygen introduced during the formation of the ITO primer layer was changed as shown in Table 1, and the power density was further changed to form the ITO primer layer having the film thickness shown in Table 1. Except for these changes, an antireflection film having an antireflection layer on the hard coat layer via an ITO primer layer was produced under the same conditions as the production of the antireflection film 2A.
<密着性試験(促進耐光試験)>
反射防止フィルムのハードコートフィルム側の面(反射防止層非形成面)を、アクリル系透明粘着剤を介してガラス板上に貼り合わせ、スガ試験機製「紫外線フェードメーターU48」を用いて、温度40℃、湿度20%、放射強度(300~700nm積算照度)500±50W/m2の条件で500時間の促進耐光試験を実施した。 [Evaluation of antireflection film]
<Adhesion test (accelerated light resistance test)>
The surface of the antireflection film on the hard coat film side (antireflection layer non-formed surface) is bonded onto a glass plate via an acrylic transparent adhesive, and the temperature is 40 using the "ultraviolet fade meter U48" manufactured by Suga Testing Machine. An accelerated light resistance test was carried out for 500 hours under the conditions of ° C., humidity of 20%, and radiant intensity (300 to 700 nm integrated illuminance) of 500 ± 50 W / m 2.
S:剥離碁盤目数が0
A:剥離碁盤目数が1~10個
B:剥離碁盤目数が11~50個
C:剥離碁盤目数が51個以上 The surface of the antireflection layer of the sample after the accelerated durability test was cut at 1 mm intervals to form a grid of 100 squares. Next, 2 mL of isopropyl alcohol was continuously dropped so that the surface of the antireflection layer would not dry, and a polyester wiper (“Anticon Gold” manufactured by Sampler Tech) fixed to a 20 mm square SUS jig was rubbed on a grid. It was moved (load: 1.5 kg, 1000 reciprocations). The number of grids 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.
S: The number of peeling grids is 0
A: The number of peeling grids is 1 to 10 B: The number of peeling grids is 11 to 50 C: The number of peeling grids is 51 or more
積分球式分光光度計(村上色彩技術研究所製「DOT-3」)により反射防止フィルムの透過スペクトルを測定し、透過率(透過光のXYZ表色系の視感透過率であるY値)を求めた。 <Transmittance>
The transmission spectrum of the antireflection film is measured with an integrating sphere spectrophotometer (“DOT-3” manufactured by Murakami Color Technology Laboratory), and the transmittance (Y value, which is the visual transmittance of the XYZ color system of transmitted light). Asked.
10 フィルム基材
11 ハードコート層
3 プライマー層
5 反射防止層
51,53 低屈折率層
52,54 高屈折率層
100 反射防止フィルム
1
Claims (9)
- フィルム基材の一主面上にハードコート層を備えるハードコートフィルムと;前記ハードコート層上に接して設けられたプライマー層と;前記プライマー層上に接して設けられた反射防止層とを備える反射防止フィルムであって、
前記反射防止層は、屈折率が異なる複数の薄膜の積層体であり、
前記プライマー層は、InおよびSnからなる群から選択される1種以上の金属の酸化物を含む金属酸化物層である、
反射防止フィルム。 A hard coat film having a hard coat layer on one main surface of a film base material; a primer layer provided in contact with the hard coat layer; and an antireflection layer provided in contact with the primer layer. Anti-reflective film
The antireflection layer is a laminate of a plurality of thin films having different refractive indexes.
The primer layer is a metal oxide layer containing an oxide of one or more metals selected from the group consisting of In and Sn.
Anti-reflective film. - 前記プライマー層がインジウム系酸化物層である、請求項1に記載の反射防止フィルム。 The antireflection film according to claim 1, wherein the primer layer is an indium-based oxide layer.
- 前記プライマー層が酸化インジウムスズ層である、請求項1に記載の反射防止フィルム。 The antireflection film according to claim 1, wherein the primer layer is an indium tin oxide layer.
- 前記プライマー層の厚みが0.5~30nmである、請求項1~3のいずれか1項に記載の反射防止フィルム。 The antireflection film according to any one of claims 1 to 3, wherein the primer layer has a thickness of 0.5 to 30 nm.
- 前記ハードコート層が、バインダー樹脂および微粒子を含む、請求項1~4のいずれか1項に記載の反射防止フィルム。 The antireflection film according to any one of claims 1 to 4, wherein the hard coat layer contains a binder resin and fine particles.
- 前記反射防止層を構成する複数の薄膜がいずれも無機酸化物薄膜である、請求項1~5のいずれか1項に記載の反射防止フィルム。 The antireflection film according to any one of claims 1 to 5, wherein the plurality of thin films constituting the antireflection layer are all inorganic oxide thin films.
- 画像表示媒体の視認側表面に、請求項1~6のいずれか1項に記載の反射防止フィルムが配置されている、画像表示装置。 An image display device in which the antireflection film according to any one of claims 1 to 6 is arranged on the surface of the image display medium on the visual side.
- 請求項1~6のいずれか1項に記載の反射防止フィルムの製造方法であって、
ハードコート層上に、酸化物ターゲットを用いたスパッタ法によりプライマー層を形成する、反射防止フィルムの製造方法。 The method for producing an antireflection film according to any one of claims 1 to 6.
A method for producing an antireflection film, in which a primer layer is formed on a hard coat layer by a sputtering method using an oxide target. - 前記プライマー層上に、反応性スパッタにより反射防止層を形成する、請求項8に記載の反射防止フィルムの製造方法。
The method for producing an antireflection film according to claim 8, wherein an antireflection layer is formed on the primer layer by reactive sputtering.
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