WO2024142641A1 - Corps multicouche optique et article - Google Patents

Corps multicouche optique et article Download PDF

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Publication number
WO2024142641A1
WO2024142641A1 PCT/JP2023/041037 JP2023041037W WO2024142641A1 WO 2024142641 A1 WO2024142641 A1 WO 2024142641A1 JP 2023041037 W JP2023041037 W JP 2023041037W WO 2024142641 A1 WO2024142641 A1 WO 2024142641A1
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layer
refractive index
film
resin substrate
barrier layer
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PCT/JP2023/041037
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English (en)
Japanese (ja)
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嗣人 鈴木
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デクセリアルズ株式会社
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Publication of WO2024142641A1 publication Critical patent/WO2024142641A1/fr

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  • the present invention relates to an optical laminate and an article. This application has priority to the contents described in Japanese Patent Application No. 2022-209242 filed in Japan on December 27, 2022.
  • anti-reflection films are sometimes provided on the surfaces of flat panel displays (FPDs), touch panels, solar cells, etc.
  • FPDs flat panel displays
  • solar cells etc.
  • anti-reflection films using optical laminates in which low refractive index layers and high refractive index layers are alternately stacked are known.
  • Patent Document 1 describes the formation of a barrier layer when depositing a dielectric film on a metal film in order to suppress changes in the characteristics of the metal film when the dielectric film is deposited on the metal film.
  • the present invention was made in consideration of the above problems, and aims to provide an optical laminate and article with excellent scratch resistance.
  • the present invention provides the following means to solve the above problems.
  • the article according to the second aspect comprises the optical laminate according to the above aspect.
  • the resin substrate 1 may contain a reinforcing material as long as the optical properties are not significantly impaired.
  • reinforcing materials include cellulose nanofibers and nanosilica.
  • the surface of the resin substrate 1 may be previously subjected to an etching treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, conversion, oxidation, and/or an undercoat treatment. By previously performing these treatments, the adhesion of the hard coat layer 2 formed on the resin substrate 1 is improved. Furthermore, before forming the hard coat layer 2 on the resin substrate 1, the surface of the resin substrate 1 may be subjected to solvent washing, ultrasonic washing, etc., as necessary, to remove dust and clean the surface of the resin substrate 1.
  • an etching treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, conversion, oxidation, and/or an undercoat treatment.
  • thermosetting resin that is the binder resin may be, for example, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, a melamine-urea co-condensation resin, a silicon resin, a polysiloxane resin (including so-called silsesquioxanes such as cage-shaped and ladder-shaped ones), etc.
  • the hard coat layer 2 may contain an organic resin and an inorganic material, or may be an organic-inorganic hybrid material.
  • An example of an organic-inorganic hybrid material is one formed by the sol-gel method.
  • examples of inorganic materials include silica, alumina, zirconia, and titania.
  • examples of organic materials include acrylic resin.
  • the first layer 5 is laminated, for example, on one surface of the barrier layer 4.
  • the first layer 5 is a part of an optical function layer.
  • the first layer 5 and the alternating laminate film 6 form the optical function layer.
  • the optical function layer is a layer that exhibits an optical function.
  • the optical function is a function that controls the properties of light, namely, reflection, transmission, and refraction, and examples of such functions include an anti-reflection function, a selective reflection function, an anti-glare function, and a lens function.
  • Silicon nitride is represented by, for example, SixNy . Silicon nitride is, for example, Si3N4 . When the first layer 5 is made of silicon nitride, the oxygen content of the first layer 5 is 0 atm %.
  • Silicon oxynitride is represented, for example, by Si x N y O z .
  • the oxygen content of the first layer 5 is low, the first layer 5 exhibits performance equivalent to that of a film made of high-hardness silicon nitride, and the scratch resistance of the optical laminate 10 is improved.
  • the alternating laminate film 6 is, for example, a laminate film in which low refractive index layers and high refractive index layers are alternately laminated in order from the side closest to the first layer 5.
  • the low refractive index layer has a lower refractive index than the first layer 5.
  • the high refractive index layer has a higher refractive index than the low refractive index layer.
  • the refractive indexes of the high refractive index layers may be the same or different.
  • the refractive indexes of the low refractive index layers may be the same or different.
  • the low refractive index layer 61 and the low refractive index layer 63 contain, for example, an oxide of Si.
  • the low refractive index layer 61b and the low refractive index layer 63 are layers mainly composed of, for example, SiO 2 (oxide of Si).
  • the low refractive index layer 61 and the low refractive index layer 63 preferably contain an oxide of Si from the viewpoint of availability and cost, are preferably layers mainly composed of SiO 2 (dioxide of Si) or the like, and are preferably composed of SiO 2.
  • the SiO 2 single layer film is colorless and transparent.
  • the main component is a component that occupies 50 mass % or more of the components contained in the layer.
  • the high refractive index layer 62 examples include silicon nitride (SiN, refractive index 2.0), niobium pentoxide (Nb 2 O 5 , refractive index 2.33), titanium oxide (TiO 2 , refractive index 2.33 to 2.55), tungsten oxide (WO 3 , refractive index 2.2), cerium oxide (CeO 2 , refractive index 2.2), tantalum pentoxide (Ta 2 O 5 , refractive index 2.16), zinc oxide (ZnO, refractive index 2.1), indium tin oxide (ITO, refractive index 2.06), zirconium oxide (ZrO 2 , refractive index 2.2), etc.
  • the high refractive index layer 62 is, for example, niobium pentoxide.
  • a low refractive index layer 63 is disposed on the side of the antifouling layer 7.
  • the antireflection performance of the optical functional layer is improved.
  • the total thickness of the entire optical functional layer is, for example, 80 nm or more and 480 nm or less, preferably 160 nm or more and 240 nm or less, and more preferably 165 nm or more and 225 nm or less.
  • the anti-stain layer 7 is, for example, a vapor deposition film formed by vapor-depositing an anti-stain material.
  • the anti-stain layer 7 is formed, for example, by vacuum-depositing a fluorine-based compound as an anti-stain material on one surface of the low refractive index layer 63.
  • the anti-stain layer 7 contains a fluorine-based compound, the sliding of the pen during input becomes smoother and the pen sliding resistance of the optical laminate 10 is further improved.
  • the fluorine-based compound contained in the anti-soiling layer 7 is, for example, a fluorine-based organic compound.
  • the fluorine-based organic compound is, for example, a compound consisting of a fluorine-modified organic group and a reactive silyl group (e.g., alkoxysilane).
  • Commercially available products that can be used for the anti-soiling layer 7 include Optool DSX (manufactured by Daikin Corporation) and the KY-100 series (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a siloxane bond is formed between the silanol group generated from the reactive silyl group of the fluorine-based organic compound and the SiO 2.
  • the siloxane bond enhances the adhesion between the layer-by-layer laminate film 6 and the antifouling layer 7.
  • the thickness of the antifouling layer 7 is, for example, 1 nm or more and 20 nm or less, and preferably 3 nm or more and 10 nm or less. If the thickness of the antifouling layer 7 is 1 nm or more, sufficient abrasion resistance can be ensured when the optical laminate 10 is applied to touch panel applications, etc. If the thickness of the antifouling layer 7 is 20 nm or less, the time required for vapor deposition is short, and the antifouling layer 7 can be produced efficiently.
  • the stain-resistant layer 7 may contain additives such as light stabilizers, ultraviolet absorbers, colorants, antistatic agents, lubricants, leveling agents, defoamers, antioxidants, flame retardants, infrared absorbers, and surfactants, as necessary.
  • additives such as light stabilizers, ultraviolet absorbers, colorants, antistatic agents, lubricants, leveling agents, defoamers, antioxidants, flame retardants, infrared absorbers, and surfactants, as necessary.
  • the anti-fouling layer 7 formed by vapor deposition is firmly bonded to the layer-by-layer film 6 and is dense with few voids. Therefore, the anti-fouling layer 7 formed by vapor deposition exhibits different characteristics from the anti-fouling layer 7 formed by other methods, such as coating with an anti-fouling material.
  • the anti-fouling layer 7 formed by vapor deposition is resistant to wear.
  • Each layer of the optical laminate 10 is, for example, a sputtered film.
  • the primer layer 3, the barrier layer 4, the first layer 5, and the alternating laminate film 6 are, for example, sputtered films.
  • the sputtered film is denser than a film formed using a general vacuum deposition method or a coating method.
  • the water vapor permeability of the optical functional layer is 1.0 g/m 2 /day or less.
  • a dense sputtered film has a low water vapor permeability.
  • the sputtered film is dense and does not easily leave a sliding mark. For example, even if a part of the antifouling layer 7 is peeled off due to pen sliding, the optical functional layer is dense, so that the pen sliding mark is not easily left.
  • a resin substrate 1 is prepared.
  • the resin substrate 1 can be obtained, for example, by purchasing a commercially available product.
  • the resin substrate 1 does not need to be subjected to a degassing process.
  • a hard coat layer 2 is formed on one surface of the resin substrate 1.
  • a slurry containing a material for the hard coat layer 2 is applied onto the resin substrate 1, and the material for the hard coat layer 2 is cured by a known method to obtain the hard coat layer 2.
  • the surface Before forming the hard coat layer 2 on the resin substrate 1, the surface may be washed as necessary. Examples of methods for washing the surface of the resin substrate 1 include solvent washing and ultrasonic washing. Washing the resin substrate 1 is preferable because it removes dust from the surface of the resin substrate 1 and cleans the surface. Alternatively, a commercially available resin substrate 1 with a hard coat layer 2 formed thereon may be purchased.
  • the primer layer 3 is formed on the hard coat layer 2.
  • the method for manufacturing the primer layer 3 is not particularly limited, and it can be manufactured using a known manufacturing method.
  • the primer layer 3 can be formed, for example, by a sputtering method.
  • the primer layer 3 is produced by using a silicon target and performing sputtering in an atmosphere of a mixed gas of argon and oxygen.
  • the barrier layer 4 is formed on the primer layer 3.
  • the method for manufacturing the barrier layer 4 is not particularly limited, and it can be manufactured using a known manufacturing method.
  • the barrier layer 4 can be formed, for example, by a sputtering method.
  • the barrier layer 4 is produced by sputtering using a silicon target in an atmosphere of a mixed gas of argon and oxygen.
  • the manufacturing method of the first layer 5 is not particularly limited, and it can be manufactured using a known manufacturing method.
  • the first layer 5 can be formed by, for example, a sputtering method.
  • the first layer 5 is produced by sputtering using a silicon target in an atmosphere of a mixed gas of argon and nitrogen.
  • the alternating laminate film 6 is formed on the first layer 5.
  • the alternating laminate film 6 is formed, for example, in the order of a low refractive index layer 61, a high refractive index layer 62, and a low refractive index layer 63. These layers are produced, for example, by using a sputtering method. Examples of power supply methods for the sputtering method include DC (direct current), RF (high frequency), and MF (medium frequency).
  • DC direct current
  • RF high frequency
  • MF medium frequency
  • the frequency during sputtering is preferably 20 KHz to 60 KHz.
  • the degree of vacuum during sputtering is, for example, 1.0 Pa or less.
  • the conveying speed (line speed) is, for example, 0.5 m/min or more and 20 m/min or less.
  • an antifouling layer 7 is formed on the layer-by-layer film 6.
  • a plasma treatment it is preferable to perform a plasma treatment on the surface of the layer-by-layer film 6. Modifying the surface of the low refractive index layer 63 by the plasma treatment increases the adhesion between the layer-by-layer film 6 and the antifouling layer 7.
  • the anti-fouling layer 7 is formed, for example, by vapor deposition. Vapor deposition is performed by heating the material that will become the anti-fouling layer 7 to its vapor pressure temperature. The degree of vacuum during vapor deposition is, for example, 1.0 Pa or less. When the anti-fouling layer 7 is formed under these conditions, it becomes dense and less susceptible to wear.
  • the deposition of the primer layer 3, barrier layer 4, first layer 5, alternating laminate film 6, and antifouling layer 7 is preferably performed roll-to-roll in a reduced pressure environment.
  • the optical laminate 10 can be produced.
  • the optical laminate 10 has a barrier layer 4, and therefore can suppress outgassing from the resin substrate 1 from adversely affecting the first layer 5.
  • the barrier layer 4 can prevent oxygen from being taken up into the first layer 5.
  • oxygen is taken up into the first layer 5
  • the refractive index of the first layer 5 decreases, and the hardness also decreases.
  • the refractive index of the first layer 5 decreases, the optical properties of the optical laminate 10 decrease.
  • the scratch resistance of the optical laminate 10 decreases.
  • the optical laminate 10 may have layers other than the resin substrate 1, the hard coat layer 2, the primer layer 3, the barrier layer 4, the first layer 5, the alternating laminate film 6, and the antifouling layer 7.
  • the optical laminate 10 may also have layers having various properties as necessary on the surface of the resin substrate 1 opposite the surface on which the barrier layer 4 and the like are formed.
  • an adhesive layer used for adhesion to other members may be provided.
  • another optical film may be provided via this adhesive layer. Examples of other optical films include a polarizing film, a retardation compensation film, a film that functions as a 1/2 wavelength plate, or a 1/4 wavelength plate.
  • a layer having functions such as anti-reflection, selective reflection, anti-glare, polarization, phase difference compensation, viewing angle compensation or expansion, light guiding, diffusion, brightness improvement, hue adjustment, and electrical conductivity may be formed on one side of the resin substrate 1.
  • a nano-order uneven structure that exhibits moth-eye and anti-glare functions may be formed on the surface of the optical laminate 10.
  • Micro to millimeter-order geometric shapes such as lenses and prisms may be formed on the surface of the optical laminate 10.
  • the optical laminate 10 can also be applied to a variety of products.
  • the optical laminate 10 may be provided on the screen of an image display unit, such as a liquid crystal display panel or an organic EL display panel. This allows, for example, the touch panel display unit of a smartphone or other operating device to exhibit high scratch resistance, resulting in an image display device that is suitable for practical use.
  • the article is not limited to image display devices, and the optical laminate 10 can be applied to window glass, goggles, the light receiving surface of a solar cell, the screen of a smartphone or a personal computer display, information input terminals, tablet terminals, AR (augmented reality) devices, VR (virtual reality) devices, electronic display boards, glass table surfaces, gaming machines, operation support devices for aircraft and trains, navigation systems, instrument panels, the surface of optical sensors, etc.
  • AR augmented reality
  • VR virtual reality
  • Example 1 In Example 1, the change in composition of the first layer 5 when the thickness of the barrier layer 4 was changed was measured.
  • a primer layer 3 represented by SiOx (0 ⁇ x ⁇ 2) was formed on the hard coat layer 2 to a thickness of 4 nm by a reactive sputtering method using a Si target as a sputtering target and a mixed gas of Ar gas and O2 gas.
  • a barrier layer 4 represented by SiO2 was formed on the primer layer 3 by reactive sputtering using a mixed gas of Ar gas and O2 gas, using a Si target as the sputtering target.
  • the deposition pressure was 0.3 Pa
  • the Ar flow rate during deposition was 3.2 sccm
  • the O2 flow rate was 1.8 sccm
  • the configuration of the barrier layer 4 of each sample is shown below.
  • Sample 1 0 nm (barrier layer 4 was not formed)
  • Sample 2 1 0 nm (barrier layer 4 was not formed)
  • Sample 2 1 nm
  • Sample 3 2 nm
  • Sample 4 4 nm
  • Sample 5 6 nm
  • Sample 6 8 nm
  • Sample 7 10 nm
  • a first layer 5 was formed on the barrier layer 4 by reactive sputtering using a Si target as a sputtering target and a mixed gas of Ar gas and N2 gas.
  • the film formation pressure was 0.3 Pa, and the film thickness of the first layer 5 was 50 nm.
  • an X-ray photoelectron spectroscopy device (Electron Spectroscopy for Chemical Analysis, ESCA; Versaprobe III, manufactured by ULVAC-PHI, Inc.) was used to analyze the composition of the first layer 5 of each of the prepared samples 1 to 7.
  • a comparative sample (sample 8) was also prepared in which the first layer 5 was prepared under the same conditions as sample 1, using a resin substrate 1 that had been degassed for 18 hours.
  • the composition of the first layer 5 of sample 8 was also measured using ESCA.
  • sample 8 which underwent a degassing process, there was little outgassing from the resin substrate 1, so the first layer 5 was a silicon nitride film. In contrast, it was confirmed that even in samples 1 to 7, which did not undergo a degassing process, if the thickness of the barrier layer 4 was 4 nm or more, the film had a composition that could be roughly considered to be silicon nitride.
  • Example 2 In Example 2, changes in the characteristics of the first layer 5 due to differences in the oxygen content of the first layer 5 were measured.
  • the resin substrate 1 on which the hard coat layer 2 was formed was depressurized to 1.0E-4 Pa or less, and a degassing process was carried out for 18 hours.
  • the configurations of the resin substrate 1 and the hard coat layer 2 were the same as in Example 1.
  • a primer layer 3 and a barrier layer 4 were formed on the hard coat layer 2.
  • the configurations of the primer layer 3 and the barrier layer 4 were the same as in Example 1.
  • a first layer 5 represented by Si x N y O z was produced on the barrier layer 4 by reactive sputtering using a Si target as a sputtering target and a mixed gas of Ar gas, N 2 gas and O 2 gas.
  • the film formation pressure was 0.3 Pa, and the film formation time was 1818 seconds to produce the first layer 5.
  • the film thickness of the first layer 5 was about 200 nm.
  • the Ar flow rate during film formation was 3 sccm
  • the N 2 flow rate was 2 sccm
  • the O 2 flow rate was changed to prepare several samples with different oxygen contents.
  • the O 2 flow rate during the production of each sample and the composition ratio of the first layer 5 after production are shown in Table 3 below.
  • the composition of the first layer 5 of each sample was analyzed by ESCA.
  • Figure 3 shows the composition analysis results of each sample measured in Example 2.
  • the vertical axis of Figure 3 shows the energy of the Si 2p electrons measured by ESCA.
  • the horizontal axis of Figure 3 shows the oxygen content of the first layer 5.
  • the first layer 5 can be considered as a nitride film, and if the oxygen content in the first layer 5 is high, the first layer 5 becomes an oxide film. If the oxygen content in the first layer 5 is 40 atm% or less, the first layer 5 can be said to be a film whose composition can be roughly considered as silicon nitride.
  • Example 3 In Example 3, the first layer 5 represented by Si x N y O z was formed on a slide glass under the same conditions as the samples of the first layer 5 prepared in Example 2, and the Martens hardness of the first layer 5 formed on the slide glass plate was measured.
  • FIG. 4 shows the Martens hardness of each sample in Example 3. The Martens hardness was measured at a load of 0.05 mN using a microcompression tester (ENT-NEXUS manufactured by Elionix Co., Ltd., measuring indenter: Berkovich indenter) in accordance with ISO14577-1. As shown in FIG. 4, the Martens hardness decreases as the oxygen content in the first layer 5 increases. If the oxygen content of the first layer 5 is 40 atm% or less, the first layer 5 exhibits a hardness of 5000 N/cm 2 or more.
  • the refractive index of the first layer 5 of each of the prepared samples was measured.
  • the refractive index of the first layer 5 was measured using a J. A. Woollam M-2000 spectroscopic ellipsometer.
  • Figure 5 shows the refractive index of the first layer 5 of each sample in Example 3. As shown in Figure 5, the refractive index of the first layer 5 decreases as the oxygen content in the first layer 5 increases.
  • the scratch resistance test was conducted as follows. First, the optical laminate 10 was attached to a 1 mm thick glass plate using a transparent adhesive sheet (manufactured by Lintec Corporation) so that the low refractive index layer 63 of the optical laminate 10 was on the surface. Then, a linear sliding test was conducted using a stylus pen tip (refill for Bamboo Sketch/Bamboo Tip (medium type) manufactured by Wacom Corporation). The load was 250 gf, the number of sliding strokes was 20,000 (10,000 back and forth strokes), the back and forth distance was 50 mm, and the back and forth speed was two strokes per second (one back and forth stroke).

Abstract

L'invention concerne un corps multicouche optique comprenant un matériau de base en résine, une couche barrière et une première couche. La couche barrière est prise en sandwich entre le matériau de base en résine et la première couche. La couche barrière contient de l'oxyde de silicium, tandis que la première couche contient du nitrure de silicium ou de l'oxynitrure de silicium. L'épaisseur de film de la couche barrière est de 4 nm ou plus. La teneur en oxygène de la première couche est inférieure ou égale à 40 atm %.
PCT/JP2023/041037 2022-12-27 2023-11-15 Corps multicouche optique et article WO2024142641A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2022-209242 2022-12-27

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Publication Number Publication Date
WO2024142641A1 true WO2024142641A1 (fr) 2024-07-04

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