WO2004031813A1 - 反射防止フィルム - Google Patents
反射防止フィルム Download PDFInfo
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- WO2004031813A1 WO2004031813A1 PCT/JP2003/011969 JP0311969W WO2004031813A1 WO 2004031813 A1 WO2004031813 A1 WO 2004031813A1 JP 0311969 W JP0311969 W JP 0311969W WO 2004031813 A1 WO2004031813 A1 WO 2004031813A1
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- WIPO (PCT)
- Prior art keywords
- layer
- film
- light
- fine particles
- antireflection
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J5/00—Details relating to vessels or to leading-in conductors common to two or more basic types of discharge tubes or lamps
- H01J5/02—Vessels; Containers; Shields associated therewith; Vacuum locks
- H01J5/16—Optical or photographic arrangements structurally combined with the vessel
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- 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
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/86—Vessels; Containers; Vacuum locks
- H01J29/89—Optical or photographic arrangements structurally combined or co-operating with the vessel
- H01J29/896—Anti-reflection means, e.g. eliminating glare due to ambient light
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
- H01J2211/20—Constructional details
- H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
- H01J2211/44—Optical arrangements or shielding arrangements, e.g. filters or lenses
- H01J2211/442—Light reflecting means; Anti-reflection means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2329/00—Electron emission display panels, e.g. field emission display panels
- H01J2329/86—Vessels
- H01J2329/89—Optical components structurally combined with the vessel
- H01J2329/892—Anti-reflection, anti-glare, viewing angle and contrast improving means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/261—In terms of molecular thickness or light wave length
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to a coating type antireflection film used in a display field such as a CRT (cathode ray tube) screen, a PDP (plasma display panel) screen and an LCD (liquid crystal) screen.
- a display field such as a CRT (cathode ray tube) screen, a PDP (plasma display panel) screen and an LCD (liquid crystal) screen.
- the display surface On a surface such as CRT, external light, illumination light, or bright surrounding scenery is reflected on the surface to form an image, resulting in reduced visibility. Therefore, in order to reduce such reflections, the display surface is subjected to anti-glare processing for fine unevenness processing or coating with a thin film, so that anti-reflection processing for reducing reflection by light interference is performed. May be done. Applying these anti-reflection treatments directly to the display surface will increase the cost, and in recent years, a method of attaching a film subjected to the anti-reflection treatment to the display surface has been widely adopted.
- Conventional coating-type antireflection films are mainly formed by laminating a hard coat layer, a high-refractive-index layer, and a low-refractive-index layer sequentially from the lower layer side on the surface of a transparent base film made of a synthetic resin. Used.
- a hard coat layer as a hard protective layer made of an acrylic resin or siloxane is formed on a base film made of an organic film, and an antireflection layer is further formed thereon. Structure.
- This anti-reflection film is attached to the display surface with an adhesive or an adhesive.
- the refractive index of the low refractive index layer is about 1.37.
- a large amount of low-refractive-index fluororesin must be compounded in the outermost low-refractive-index layer.
- the scratch resistance of the antireflection film is greatly reduced due to the softness of the fluororesin.
- the low refractive index layer can be easily removed simply by rubbing with a plastic eraser.
- Silicone resin may be used to increase the abrasion resistance of the outermost layer. In this case, however, it is difficult to reduce the refractive index to 1.47 or less, which not only deteriorates the antireflection performance but also reduces chemical resistance. Properties, especially alkali resistance, become very weak.
- the anti-reflection film for CRT is required to have an anti-reflection performance not only because of its excellent anti-reflection performance but also because of its anti-static function against static electricity due to display surface charging and weak electromagnetic waves radiated from the display surface. It is required 1 is 0 8 ⁇ port following a low resistance value. In addition, low cost is always desired for industrial products.
- the coating type anti-reflection film is preferable in terms of cost, but if a material that does not absorb visible light is used in the coating type anti-reflection film, the anti-reflection properties such as the minimum reflectance and luminous reflectance will be reduced. Since the performance is reduced, it is necessary to form a light absorbing layer. However, if the light absorbing layer is formed thick, the light transmittance becomes extremely low. Therefore, the light absorbing layer needs to be an ultrathin film having a thickness of 100 nm or less.
- the light-absorbing layer for example, carbon
- the surface resistance of the antireflection film obtained becomes 1 X 1 0 9 ⁇ port above, CRT applications As unusable. Disclosure of the invention
- a first object of the present invention is to provide an antireflection film having low reflectance and excellent scratch resistance.
- the second object of the present invention is to provide a low-cost coated antireflection film having excellent antireflection performance and having a good surface resistance suitable for CRT applications. I do.
- the antireflection film of the first embodiment is an antireflection film obtained by coating a base film with a plurality of thin films, wherein only the outermost layer farthest from the base film has only one layer on the base film side. It is characterized by having light absorbency.
- the antireflection film of the first embodiment has low reflectance and good scratch resistance.
- the refractive index n of the outermost layer is 1.48 to It is not too low, about 1.53.
- the antireflection film of the layer on the substrate side from the outermost layer is set to k> 0.1.
- the minimum reflectance can be set to 0 by setting k> 0.39 for the layer on the substrate side from the outermost layer. It is desirable that k of one layer on the substrate side from the outermost layer is k> 0.2 or more.
- the luminous reflectance is greatly reduced.
- the k value of the layer increases and the antireflection film has antistatic properties due to the conductivity.
- the antireflection film according to the second aspect is an antireflection film in which a hard coat layer, a transparent conductive layer, a light absorbing layer, and a low refractive index layer are laminated in this order on a transparent base material film.
- the layer, the transparent conductive layer, the light absorption layer and the low refractive index layer are all formed by coating.
- a hard coat layer is coated on a transparent substrate film, and a transparent conductive layer is coated on the hard coat layer in order to maintain a very low surface resistance.
- a light-absorbing layer is applied thereon, and a low-refractive-index layer is applied on the light-absorbing layer.
- the provision of the transparent conductive layer dramatically increases the conductivity of the coated antireflection film, and the provision of the light absorbing layer dramatically reduces the minimum reflectance and the luminous reflectance. be able to. Further, the low refractive index layer can be provided with scratch resistance.
- the thickness of the first coat layer is preferably 2 to 20 m.
- the transparent conductive layer is ATO, ZnO, is hardening acrylic binder one resin comprising at least one fine particle selected from S b 2 O 5, S n0 2, I TO, and ln 2 0 3 the group consisting of
- the film thickness is 0.3 to 0.6 for light having a wavelength of 550 nm, and the refractive index for light having a wavelength of 550 nm is 1.58 to 1.75.
- the light absorbing layer is formed by curing an acrylic binder resin containing at least one kind of fine particles selected from the group consisting of metal oxides, metal nitrides, and carbon, and attenuates the light at a wavelength of 550 nm. It is preferable that the coefficient is larger than 0.25 and the film thickness is 0.25 mm or less with respect to the light having a wavelength of 55 0 11111. Such a light absorbing layer can obtain a remarkable and excellent antireflection performance. it can.
- the low-refractive-index layer has an extinction coefficient for light having a wavelength of 550 nm of approximately 0, and a refractive index for light having a wavelength of 550 nm of 1.38 to 1.55.
- the antireflection film of the second aspect preferably, the surface resistivity is not more than 1. 0 ⁇ 1 0 8 ⁇ port, luminous reflectance below 5% 0.5 excellent antireflection performance and high antistatic performance It is a low-cost antireflection film that is also used.
- FIG. 1 is a schematic sectional view showing an example of the antireflection film of the first embodiment.
- FIG. 2 is a schematic sectional view showing an example of the antireflection film of the second embodiment.
- the antireflection film of the first embodiment is formed by coating a plurality of thin films on the surface of a transparent base film, and only one layer on the base film side from the outermost layer has a light absorbing property. Having.
- the number of layers of this thin film is preferably 2 to 5, particularly preferably 3 to 5, and as shown in FIG. 1, a hard coat layer 2 is provided on a transparent base film 1 and has an absorbency thereon. It is preferable to provide a layer 3 having a relatively high refractive index and an outermost layer 4 having a relatively low refractive index thereon.
- the base film 1 includes polyester, polyethylene terephthalate ( ⁇ ⁇ ⁇ ⁇ ), polybutylene terephthalate, polymethyl methacrylate ( ⁇ ), acryl, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl Alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene monoacetate copolymer, polyurethane, cellophane, etc., preferably P ET, PC and PMMA transparent films.
- the thickness of the base film 1 is appropriately determined according to the required characteristics (for example, strength, thinness) of the antireflection film to be obtained, and the like, but is usually in the range of 1 ⁇ to 10 ⁇ . You.
- the hard coat layer 2 a synthetic resin-based resin is preferable, and a UV-curable or electron beam-curable synthetic resin, in particular, a polyfunctional acrylic resin is particularly preferable.
- the thickness of the hard coat layer 2 is preferably 2 to 20 / m.
- the layer 3 that is only one layer from the outermost layer on the substrate film side may be a layer in which fine particles are blended in a synthetic resin to impart light absorption.
- the fine particles may be one or more of carbon black, fullerene and titanium black.
- carbon black or fullerene is blended, antistatic performance (conductivity) is provided as well as absorptivity.
- titanium black is used, the absorption can be increased by adding a small amount.
- the fine particles may be metal fine particles.
- metal fine particles noble metals, particularly Au (gold) and / or Ag (silver) are suitable, but Au is most suitable from the viewpoint of corrosion resistance. Since the metal has conductivity, the addition of metal fine particles imparts antistatic performance to the antireflection film as well as absorbency.
- the ratio between the fine particles and the synthetic resin in the layer 3 is selected so as to have the above-mentioned absorbency. Usually, the ratio of the fine particles to the total of the fine particles and the synthetic resin is 0.1 to 60% by volume, Especially 45 to 55 volume. / 0 , especially 47-52 volumes. / 0 is preferable.
- the layer 3 that is only one layer from the outermost layer on the substrate film side may be a layer obtained by blending an organic dye in a synthetic resin to impart light absorbency.
- an organic dye a dye having a property of absorbing light near a wavelength of 550 nm and having a property of being uniformly dispersed or mixed in the synthetic resin is used.
- One layer on the substrate side from the outermost layer may contain conductive fine particles together with the organic dye.
- the conductive fine particles Z n O, ITO, ATO, other S B_ ⁇ 2 of which conductive metal oxide particles, or the like can be used conductive carbon black.
- the content ratio of the organic dye and the conductive fine particles in the layer 3 on the substrate side from the outermost layer is selected so as to have the above-mentioned absorbency, but the content (addition amount) of the organic dye is usually 1 About 50% by volume is preferable.
- the ratio of the conductive fine particles to the total of the conductive fine particles and the synthetic resin is 55% by volume or less, particularly 45 to 55% by volume, particularly 45 to 52% by volume. About volume% is preferable.
- This absorption is preferably such that the attenuation coefficient k at a wavelength of 550 nm satisfies 0.1 ⁇ k ⁇ 5. It is preferable that k is 0.2 ⁇ k, particularly 0.39 ⁇ k.
- the synthetic resin constituting the layer 3 on the substrate film side only one layer from the outermost layer is preferably an ultraviolet curable or electron beam curable synthetic resin, especially an acrylic resin, an epoxy resin, a styrene resin, Most preferably, it is an acrylic resin.
- the thickness of the layer 3 on the substrate film side is preferably 30 to 80 nm, particularly preferably about 40 to 75 nm.
- the outermost layer 4 having a relatively low refractive index is also made of a synthetic resin, particularly an ultraviolet-curable or electron beam-curable synthetic resin.
- the layer 3 on the substrate film side which is only one layer from the outermost layer, has absorptivity, so that the material of the outermost layer 4 does not require a material having a sufficiently low refractive index.
- the refractive index n of the outermost layer is 1.52 or less, particularly preferably 1.40 to 1.52, particularly preferably 1.42 to 1.48.
- the outermost layer 4 preferably contains about 10 to 40% by weight of fine particles of silica, fluororesin or the like in order to lower the refractive index, improve the scratch resistance, and improve the slipping property. In particular, it is preferable to mix fine silica particles in order to enhance the scratch resistance and chemical resistance.
- Outermost layer Preferably has a thickness of 60 to 100 nm.
- an uncured synthetic resin (containing the above-mentioned fine particles and / or dye if necessary) is used. It is preferable to apply and then irradiate ultraviolet rays or electron beams.
- each of the layers 2 to 4 may be coated and cured one by one, or three layers may be coated and then cured together.
- the coating method include a method in which a coating solution in which an acrylic monomer is made into a solution with a solvent such as toluene is coated with a gravure coater or the like, dried, and then cured by irradiation with ultraviolet rays or electron beams.
- a coating solution in which an acrylic monomer is made into a solution with a solvent such as toluene is coated with a gravure coater or the like, dried, and then cured by irradiation with ultraviolet rays or electron beams.
- this coating method there is an advantage that a film can be formed at high speed, uniformly and at low cost. After this coating, curing is performed by, for example, irradiating an ultraviolet ray or an electron beam, whereby the effects of improving the adhesion and increasing the hardness of the film can be obtained.
- This coating method is remarkably inexpensive as compared with sputter-deposition.
- the antireflection film of the first embodiment can be applied to a PDP of an OA device, a front filter of a liquid crystal panel, or a window material of a vehicle or a special building.
- An acrylic resin coating film for the hard coat layer 2 is formed on a 1888 / im PET film (refractive index: 1.65) by the above-mentioned coating method (jet coating method) and dried. did.
- the refractive index of this hard coat layer is 1.51.
- the layer 3 (high refractive index layer) on the base film side only one layer from the outermost layer in the same manner A coating film was formed and dried.
- a coating film for the outermost layer 4 (low refractive index layer) was formed using a coating liquid for the outermost layer having the composition shown in Table 1, and dried.
- Example 3 carbon black was blended in Example 1 with carbon black, titanium black was blended in Example 2, and metal fine particles (average particle diameter 7 In Comparative Examples 1 and 2, ITO (average particle size: 60 nm) was blended.
- Table 1 shows the mixing ratio.
- the outermost layer 4 contains 60 parts by weight of a multi-sensitive acrylic resin and 40 parts by weight of fine particles of silicic acid in Comparative Example 1, Examples 1, 2, and 3.
- the outermost layer 4 of Comparative Example 2 is a multi-sensitive acryl resin. It contains 20 parts by weight and 80 parts by weight of a fluororesin.
- the thickness of the hard coat layer is about 5 ⁇
- the thickness of the layer on the substrate film side is only about 80 nm
- the thickness of the outermost layer is about 95 nm.
- An antireflection film was produced.
- Example 4 the layer 3 on the substrate side from the outermost layer was 50 parts by weight of carbon black with respect to 25 parts by weight of the multifunctional acryl resin and 2 parts of Nippon Kayaku K AY ASETBlue A-D as an organic dye. 5 parts by weight.
- Other configurations are the same as those of the first to third embodiments.
- Each of the antireflection films was immersed in a 3 wt% NaOH aqueous solution and a 3 wt% HC1 aqueous solution for 30 minutes each, and then visually inspected for chemical resistance.
- the results are shown in Table 1.
- ⁇ indicates that the color of the reflected light does not change
- X indicates that the color of the reflected light changes.
- An antireflection film was manufactured in the same manner as in Comparative Examples 1 and 2, except that the outermost layer was made of a silicone resin (containing no fine particles), and the same measurement was performed. Table 1 shows the results.
- Acrylic ITO nk IX is resin fine resin particle black black fine particle dye Comparative Example 1 60 40 1.49 0 13 8 F 1.68 0 1.01 o ⁇ Comparative Example 2 20 80 1.42 0 13 87 1.68 0 0.27 X ⁇ Comparative Example 3 100 1.49 0 13 87 1.68 0 1.01 ⁇ X
- Example 1 60 40 1.49 0 33 66 1.55 0.33 0.08 ⁇ ⁇ ⁇ Example 2 60 40 1.9 0 30 49 21 1.56 0.41 0 ⁇ ⁇ Example 3 60 40 1.9 0 8 92 1.49 0.45 0.08 o ⁇ Example 4 60 40 1.49 0 25 50 25 1.58 0.22 0.61 ⁇ ⁇
- Comparative Example 1 is a general transparent coating type antireflection film having a high minimum reflectance.
- a fluororesin-containing refractive index layer was used as the outermost layer to lower the minimum reflectance.
- the minimum reflectance was low, but the scratch resistance was poor.
- Comparative Example 3 uses a silicone resin for the outermost layer. In Comparative Example 3, the minimum reflectance was not so low, and the chemical resistance (alkali resistance) was poor.
- Example 1 only one layer of carbon black was blended in the layer on the substrate film side with respect to the outermost layer. The minimum reflectance was very low, and all performances were satisfied.
- Example 2 only one layer of carbon black and titanium black was blended in the layer on the substrate film side from the outermost layer, and the minimum reflectance could be set to zero.
- Example 3 Au fine particles (average particle diameter: 7 nm) were blended in a layer on the substrate film side only one layer from the outermost layer. The minimum reflectance was very low, and all performances were satisfied. In Example 4, only one layer of the organic dye and carbon black was blended in the layer on the substrate film side from the outermost layer, and the minimum reflectance was very low and all performances were satisfied. The antistatic performance was good in each of the examples and comparative examples.
- the antireflection property is excellent, and the selection range of materials usable as the low refractive index layer material can be expanded.
- the use of an inexpensive acrylic resin with excellent chemical resistance, adhesion and weather resistance for the outermost layer provides a low-cost anti-reflection film with excellent anti-reflection performance and abrasion resistance. You can also.
- FIG. 2 is a sectional view showing an example of the antireflection film of the second embodiment.
- the anti-reflection film 10 is formed by applying a coating on the transparent base film 11 to form a hard coat layer 12, a transparent conductive layer 13, a light absorption layer 14, and a low refractive index layer 15 in this order. It is.
- the transparent base film 11 examples include polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), acrylic, polycarbonate (PC), polystyrene, triacetate, polyvinyl alcohol, Transparent films of polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane, cellophane, and the like, preferably PET, PC, and PMMA.
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- PC polycarbonate
- PC polystyrene
- triacetate polyvinyl alcohol
- Transparent films of polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane, cellophane, and the like preferably PET, PC, and PMMA.
- Transparent substrate film 11 The required thickness depends on the intended use of the anti-reflection film. (Eg, strength, thin-film properties), etc., but usually ⁇ ⁇ ! The range is ⁇ 1 O mm.
- the hard coat layer 12 on the transparent substrate film 11 can be formed by applying a normal hard coat agent such as an acrylic resin or a silicone resin. If necessary, a known UV absorber may be added to the hard coat layer in an amount of about 0.005 to 5% by weight to impart UV cut performance.
- the thickness of the hard coat layer 12 is preferably about 2 to 20 im.
- the mixing ratio of the conductive fine particles and the binder resin in the coating liquid is appropriately determined according to the refractive index of the transparent conductive layer 13 to be formed.
- the mixing ratio of the conductive fine particles and the binder resin it is possible to form the transparent conductive layer 13 having a refractive index n of 1.58 to 1.75 for light having a wavelength of 550 nm. preferable.
- the film thickness of the transparent conductive layer 13 should be 0.25 ⁇ or more, particularly 0.3 to 0.6 mm, and especially 0.3 to 0.55 for light with a wavelength of 550 nm. Is preferred. If the thickness of the transparent conductive layer 13 is smaller than this range, sufficient conductivity cannot be obtained, and the surface resistance of the obtained antireflection film increases. If the transparent conductive layer 13 is too thick, the optical performance (anti-reflection performance) is extremely reduced.
- the conductive fine particles used for forming the transparent conductive layer 13 preferably have an average particle size of 5 to 100 ⁇ m.
- the light-absorbing layer 14 is preferably formed by forming at least one kind of light-absorbing fine particles selected from the group consisting of metal oxides, metal nitrides, and carbon on the transparent conductive layer 13 by using acrylic or the like. It is formed by applying a coating liquid mixed with the above binder resin onto the transparent conductive layer 13 and subjecting the obtained coating film to heat or curing, preferably light curing. The mixing ratio of the light-absorbing fine particles and the binder resin in the coating liquid is appropriately determined by the attenuation coefficient of the light-absorbing layer 14 to be formed.
- the thickness of the light absorbing layer 14 is preferably 0.25 ⁇ or less, particularly preferably 0.12 to 0.22 mm for light having a wavelength of 550 nm. If the thickness of the light absorbing layer 14 is larger than this range, the transmittance will decrease. However, if the film thickness of the light absorbing layer 14 is excessively thin, sufficient antireflection performance cannot be obtained, which is not preferable.
- titanium oxide or the like can be used, and as the metal nitride, titanium nitride or the like can be used. A mixture of the two, for example, titanium plaque is preferable.
- the average particle size of the light absorbing fine particles is preferably from 5 to 100 nm.
- the low-refractive-index layer 15 formed on the light-absorbing layer 14 preferably has an attenuation coefficient k for light having a wavelength of 550 nm of approximately 0 and a refractive index n of 1.38 to 1.55.
- the refractive index n of the low refractive index layer 15 is less than 1.38, the film strength becomes extremely poor, and when it exceeds 1.55, the antireflection performance is lowered.
- the low refractive index layer 15 is formed of a fluorine-containing acryl resin, it is not possible to obtain a good antireflection film in terms of scratch resistance.
- the low refractive index layer 15 is preferably formed of a silica-containing acrylic resin having excellent scratch resistance.
- a coating liquid obtained by mixing fine silica particles with an acrylic binder resin is used as a light absorbing layer. It is preferable that the composition is formed by coating on the substrate 14 and subjecting the obtained coating film to heat or curing, preferably to light curing.
- the mixing ratio of the silica fine particles and the binder resin in the coating liquid is appropriately determined depending on the refractive index of the low refractive index layer 15 to be formed and the like.
- binder-resin 20 to 400 100 (weight ratio)
- the low refractive index layer 15 satisfying the above-described refractive index is formed. It is preferred that
- the thickness of the low refractive index layer 15 is preferably 0.10 to 0.20 ⁇ with respect to light having a wavelength of 550 nm. If the thickness of the low refractive index layer 15 is smaller than this range, the antireflection performance If it is thicker, the anti-reflective performance will be lower.
- the silica fine particles used for forming the low refractive index layer 15 preferably have an average particle size of 5 to 20 nm.
- the antireflection film of the second embodiment has excellent luminous reflectance of 0.5% or less and excellent antireflection performance, and also has a surface resistance of 1 ⁇ 10 8 ⁇ / port or less, and further 9 ⁇ 10 7 ⁇ / port or less It is particularly suitable as an anti-reflection film for CR films because of its low antistatic performance, but it is not limited to an anti-reflection film for CR films, and is also useful as a plasma television and liquid crystal television. It is.
- ITO fine particles having an average particle diameter of 50 nm are used, carbon fine particles having an average secondary particle diameter of 100 nm are used, and titanium plaque fine particles having an average particle diameter of 60 nm are used.
- the silica fine particles used had an average particle diameter of 12 nm. ⁇ is 550 nm.
- the antireflection film thus manufactured was evaluated for conductivity, scratch resistance, minimum reflectance, and luminous reflectance by the following methods, and the results are shown in Table 2.
- the surface resistance was measured using “Hiresta UP” manufactured by Mitsubishi Chemical Corporation and evaluated according to the following criteria. .
- the conductivity is remarkably excellent when the surface resistance is 8.0 ⁇ 10 7 ⁇ / port or less.
- the surface resistance is more than 8.0 ⁇ 10 7 ⁇ / port and less than 2 ⁇ 10 8 ⁇ . Excellent in conductivity.
- the surface resistance exceeds 2 ⁇ 10 8 ⁇ / port and the conductivity is low.
- the outermost surface of the anti-reflection film was rubbed with an eraser at a constant load, and was rated as “ ⁇ ” if it did not scratch even after more than 50 times, and “X” if it scratched less than 50 times.
- a black tape was applied to the back side of the anti-reflection film and measured with a Hitachi spectrophotometer, and evaluated according to the following criteria.
- the antireflection performance was slightly inferior at 0.5 to 0.6%.
- the antireflection performance is poor at 0.6% or more.
- An antireflection film was produced in the same manner as in Example 5 except that the film thickness of the transparent conductive layer was changed to the film thickness shown in Table 2, and the conductivity, abrasion resistance, minimum reflectance, and luminosity were similarly calculated. The reflectance was evaluated, and the results are shown in Table 2.
- the anti-reflection film thus manufactured was evaluated for conductivity, scratch resistance, minimum reflectance, and luminous reflectance in the same manner as in Example 5, and the results are shown in Table 2.
- a high pressure mercury lamp at an integrated light intensity of 50 Omj / cm 2 under conditions of an oxygen concentration of 200 ppm or less.
- a light absorbing layer having a film thickness of about 0.16 and an attenuation coefficient k of 0.20 was formed.
- the conductivity, the scratch resistance, the minimum reflectance, and the visual sensitivity reflectance were evaluated in the same manner as in Example 5, and the results are shown in Table 2.
- a hard coat layer and a transparent conductive layer were formed on a PET film in the same manner as in Example 10.
- An absorption layer was formed.
- An anti-reflection film was produced in the same manner as in Example 5, except that the light-absorbing layer was not formed and the low-refractive-index layer was formed to have a film thickness of about 0.25 ⁇ .
- the properties, minimum reflectance, and luminous reflectance were evaluated, and the results are shown in Table 2.
- Example 5 a light-absorbing layer was not formed, a fluorine-containing acrylic resin was applied on the transparent conductive layer, and light irradiation was performed with a high-pressure mercury lamp under an oxygen concentration of 200 ppm or less at an integrated light amount of 500 mj / cm 2.
- An antireflection film was produced in the same manner as in Example 5, except that the transparent conductive layer was not formed and the low refractive index layer was formed to have a thickness of about 0.2 ⁇ .
- the abrasion, minimum reflectance, and luminous reflectance were evaluated, and the results are shown in Table 2. Structure of anti-reflection film Evaluation result
- Comparative Examples 4 and 5 without the light absorbing layer have high minimum reflectance and high luminous reflectance.
- Comparative Example 5 in which a fluorine-containing acrylic low refractive index layer was used on the outermost surface, the antireflection performance was high, but the abrasion resistance was significantly reduced. Comparative Examples 4 and 5 both have poor conductivity.
- the antireflection film of Comparative Example 6 which did not have the transparent conductive layer, had a low minimum reflectance and a high luminous reflectance, but had poor conductivity.
- Examples 5 to 9 show a change in conductivity when a transparent conductive layer and a light absorbing layer were provided and the thickness of the transparent conductive layer was gradually increased. Since the extinction coefficient k is as high as 0.32, all show good antireflection performance. Further, the thickness of the transparent conductive layer 0.3 When the above example, it is possible to achieve the following 1 X 1 0 8 ⁇ / mouth goal.
- the thickness of the transparent conductive layer was sufficiently increased (0.5 mm), and the ratio of the carbon fine particles and the titanium black fine particles to the ataryl binder in the light absorbing layer was changed to prevent reflection. It was found that when the attenuation coefficient k of the light absorbing layer was 0.25 or more, sufficient antireflection performance was obtained for both the minimum reflectance and the luminous reflectance.
- a low-cost, coated antireflection film having an extremely excellent antireflection performance and antistatic performance.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004541229A JP4400458B2 (ja) | 2002-10-02 | 2003-09-19 | 反射防止フィルム |
AU2003264510A AU2003264510A1 (en) | 2002-10-02 | 2003-09-19 | Anti-reflection film |
EP03799113A EP1548469A4 (en) | 2002-10-02 | 2003-09-19 | ANTIREFLET FILM |
US11/091,505 US20050233131A1 (en) | 2002-10-02 | 2005-03-29 | Antireflective film |
Applications Claiming Priority (8)
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JP2002-290170 | 2002-10-02 | ||
JP2002-290168 | 2002-10-02 | ||
JP2002290169 | 2002-10-02 | ||
JP2002290168 | 2002-10-02 | ||
JP2002290170 | 2002-10-02 | ||
JP2002-290169 | 2002-10-02 | ||
JP2002318349 | 2002-10-31 | ||
JP2002-318349 | 2002-10-31 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/091,505 Continuation US20050233131A1 (en) | 2002-10-02 | 2005-03-29 | Antireflective film |
Publications (1)
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WO2004031813A1 true WO2004031813A1 (ja) | 2004-04-15 |
Family
ID=32074566
Family Applications (1)
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PCT/JP2003/011969 WO2004031813A1 (ja) | 2002-10-02 | 2003-09-19 | 反射防止フィルム |
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US (1) | US20050233131A1 (ja) |
EP (1) | EP1548469A4 (ja) |
JP (1) | JP4400458B2 (ja) |
AU (1) | AU2003264510A1 (ja) |
WO (1) | WO2004031813A1 (ja) |
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US10310143B2 (en) | 2013-12-03 | 2019-06-04 | Fujifilm Corporation | Anti-reflection optical member |
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Also Published As
Publication number | Publication date |
---|---|
EP1548469A4 (en) | 2010-12-15 |
JPWO2004031813A1 (ja) | 2006-02-02 |
JP4400458B2 (ja) | 2010-01-20 |
AU2003264510A1 (en) | 2004-04-23 |
US20050233131A1 (en) | 2005-10-20 |
EP1548469A1 (en) | 2005-06-29 |
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