Barrier film, laminate, wavelength conversion sheet, backlight member, and display device

Abstract

Provided are: a barrier film which has a high luminance retention rate when used in a wavelength conversion sheet and which can improve color unevenness; a wavelength conversion sheet using the barrier film; and a backlight member. A barrier film in which a resin substrate, a first alumina vapor-deposited film, a first coating layer, a second alumina vapor-deposited film, and a second coating layer are laminated in this order, the first coating layer and the second coating layer being a cured product of a resin composition containing an alkoxysilane and a hydroxyl group-containing water-soluble resin, the first alumina vapor deposition film and the second alumina vapor deposition film have a vapor deposition film peak-to-top ratio P of 1.05 or more and 1.60 or less when subjected to X-ray absorption fine structure analysis. P = (intensity peak top near (1572 eV) / (intensity peak top near (1566 eV)

Description

Technical Field

[0001] This invention relates to barrier films, laminates, wavelength conversion sheets, backlight components, and display devices. Background Technology

[0002] Previously, laminated films, which are formed on substrates such as long strips or sheets of plastic, have been used for various applications. For example, a barrier laminate has been developed in which a barrier layer composed of a thin film such as alumina is provided on a plastic film to provide barrier properties against oxygen and water vapor.

[0003] As a method for manufacturing a barrier film with an alumina film, for example, Patent Document 1 discloses a gas barrier film with excellent transparency and gas barrier properties, which is obtained by using a plasma-activated vapor deposition method (so-called plasma-assisted vapor deposition method) to generate high-density plasma in the space between an aluminum evaporation source and a polymer film as a method for manufacturing a barrier film with an alumina film.

[0004] In addition, Patent Document 2 describes a method for manufacturing a gas barrier film having an alumina vapor-deposited film, in which water vapor reacts with aluminum to increase the degree of hydroxide oxidation, and therefore the water vapor partial pressure is preferably 0.001 Pa or less.

[0005] On the other hand, the development of backlight components using quantum dot technology is also progressing, as for the application of the barrier film mentioned above. Quantum dots refer to nanoscale particles of semiconductors. Furthermore, quantum dots achieve size control through a quantum confinement effect (quantum size effect) where electrons and excitons are confined within tiny nanoscale crystals, thereby enabling the adjustment of the emission wavelength across the entire visible spectrum. Quantum dots are phosphors capable of producing strong fluorescence in narrow wavelength bands, thus allowing display devices to be illuminated with light of the three primary colors with excellent color purity. Therefore, by using quantum dot backlights, display devices with excellent color reproduction can be manufactured.

[0006] The wavelength conversion chip used in the backlight source of this display device has a phosphor layer formed by dispersing nano-sized semiconductor particles in a resin layer, and a barrier film stacked on both surfaces of the phosphor layer to suppress its degradation, which is then combined with an LED light source.

[0007] For example, a wavelength conversion sheet and a backlight unit using the wavelength conversion sheet have been developed. The wavelength conversion sheet is formed by stacking a barrier film on a phosphor layer containing a phosphor, wherein the barrier film is a barrier layer stacked on one side of a specified polyethylene terephthalate film (Patent Document 3). By using a wavelength conversion sheet with a barrier film that has excellent barrier properties and transparency, a display device with more natural and vivid colors and excellent color tone can be provided.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2017-177343

[0011] Patent Document 2: Japanese Patent Application Publication No. 2022-052319

[0012] Patent Document 3: WO2015 / 037733 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] In Patent Document 1, plasma assistance during vapor deposition enhances the reactivity of oxygen with aluminum, resulting in improved transparency and barrier properties. However, the barrier film is prone to uneven coloring and noticeable defects. Regardless of plasma assistance, during reactive vapor deposition, the transmittance after deposition is typically measured, and feedback is applied to the amount of aluminum evaporation or oxygen introduction to maintain the transmittance within a certain range, thus ensuring a uniform appearance. However, in high-speed production at hundreds of meters per minute, this feedback may not be timely. If the film is formed with variations in transmittance, it will result in uneven coloring, appearing as a ring-shaped pattern when viewed from the end face of the barrier film roll. This appearance raises concerns about quality uniformity. If plasma assistance is used to form the film in a state of high transparency and barrier properties, significant color unevenness remains, and subsequent reduction of this unevenness is difficult.

[0015] In addition, as described in Patent Document 2, in the alumina vapor deposition process, a cold trap or a cryogenic pump is usually used to reduce the moisture content in the vapor deposition chamber.

[0016] For wavelength conversion sheets like those in Patent Document 3, further improvements in the oxygen and water vapor barrier properties of the barrier film are required to suppress phosphor layer degradation. In particular, the brightness of the wavelength conversion sheet decreases over time due to phosphor layer degradation. Therefore, high barrier properties are especially needed to maintain brightness as a wavelength conversion sheet over a long period.

[0017] The purpose of this invention is to provide a barrier film with an alumina vapor-deposited film, which can improve the color uniformity of the barrier film and has a high brightness maintenance rate when used in a wavelength conversion film.

[0018] Methods for solving problems

[0019] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by focusing on the amount of hydroxyl groups in the alumina film obtained by X-ray absorption fine structure analysis (hereinafter referred to as XAFS), the brightness maintenance rate can be improved when the barrier film is used in the wavelength conversion sheet, and the color unevenness of the barrier film can also be improved, thus completing the present invention.

[0020] Specifically, the present invention provides the following solutions.

[0021] (1) A barrier film comprising, in sequence, a resin substrate, a first alumina vapor-deposited film, a first coating layer, a second alumina vapor-deposited film, and a second coating layer, wherein, The first coating layer and the second coating layer are respectively cured products of a resin composition comprising an alkoxysilane and a hydroxyl-containing water-soluble resin. For both the first and second alumina vapor-deposited films, the peak ratio P of the vapor-deposited film, as defined below, is 1.05 or higher and 1.60 or lower when performing X-ray absorption fine structure analysis from the surface side of the second coating layer of the barrier film.

[0022] P = (Intensity peak near 1572 eV) / (Intensity peak near 1566 eV)

[0023] (2) According to the barrier film of (1), when the barrier film is etched from the surface side opposite to the resin substrate using time-of-flight secondary ion mass spectrometry (TOF-SIMS), the coating intensity ratio X, as defined below, detected in the respective regions of the first coating layer and the second coating layer is 0.50 or more and 1.10 or less.

[0024] X=C2 - Ionic strength / Si - Ionic strength

[0025] (3) The barrier film according to (1), wherein a rough layer is disposed on the side of the resin substrate opposite to the first alumina vapor-deposited film.

[0026] (4) A laminate, wherein the barrier film of (1) is laminated with the support through an adhesive layer.

[0027] (5) The laminate according to (4), wherein a rough layer is disposed on the side of the support opposite to the adhesive layer.

[0028] (6) A wavelength conversion sheet, wherein the barrier film of (3) is disposed on both sides sandwiching a phosphor layer.

[0029] (7) A wavelength conversion sheet, wherein the laminate of (4) is disposed on both sides with a phosphor layer sandwiched between them, and each of the laminates is sequentially disposed from the outermost side with the support, the resin substrate, the coating layer and the phosphor layer.

[0030] (8) A wavelength conversion sheet, wherein the laminate of (4) is disposed on both sides with a phosphor layer sandwiched between them, and each of the laminates is sequentially disposed from the outermost side with the support, the coating layer, the resin substrate and the phosphor layer.

[0031] (9) A wavelength conversion sheet, wherein the laminate of (4) is disposed on both sides with a phosphor layer sandwiched between them, one laminate being disposed sequentially from the outermost side with the support, the resin substrate, the coating layer and the phosphor layer, and the other laminate being disposed sequentially from the outermost side with the support, the coating layer, the resin substrate and the phosphor layer.

[0032] (10) A backlight component comprising a light source, a light guide plate or a diffuser plate, and the wavelength conversion sheet described in (6).

[0033] (11) A display device having a surface-mount configuration with a light guide plate, wherein, The following components are stacked in sequence: a liquid crystal panel, a polarizing light selective reflector, a prism sheet, a wavelength conversion sheet (6), a light guide plate, and a reflector. A light source is disposed on the end face of the light guide plate.

[0034] (12) A display device, which is a direct-lit display device having a diffuser, wherein, The liquid crystal panel, polarizing light selective reflector, prism sheet, wavelength conversion sheet (6), diffuser plate, light source unit, and reflector sheet are stacked in sequence.

[0035] Invention Effects

[0036] When used in wavelength conversion wafers, the barrier film of the present invention can simultaneously improve brightness maintenance and reduce color unevenness of the barrier film. Attached Figure Description

[0037] Figure 1 This is a cross-sectional view showing an example of the barrier film of this embodiment.

[0038] Figure 2 This is a diagram illustrating an example of a film-forming apparatus according to an embodiment of the present invention.

[0039] Figure 3 This is a cross-sectional view showing an example of the plasma pretreatment mechanism of a film formation apparatus.

[0040] Figure 4 This is a top view showing an example of the electrode section and magnetic field forming section of the plasma pretreatment mechanism of the film formation apparatus.

[0041] Figure 5 This is a cross-sectional view showing an example of the electrode section and magnetic field forming section of the plasma pretreatment mechanism of the film formation apparatus.

[0042] Figure 6 This is a cross-sectional view showing an example of the film-forming mechanism of a film-forming apparatus.

[0043] Figure 7 This is a cross-sectional view showing an example of a laminate using the barrier film of the present invention.

[0044] Figure 8 This is a cross-sectional view showing another example of a laminate using the barrier film of the present invention.

[0045] Figure 9 This is a cross-sectional view showing another example of a laminate using the barrier film of the present invention.

[0046] Figure 10 This is a cross-sectional view showing an example of a wavelength conversion sheet using the barrier film of the present invention.

[0047] Figure 11 This is a cross-sectional view showing another example of a wavelength conversion sheet using the barrier film of the present invention.

[0048] Figure 12 This is a perspective view schematically illustrating the configuration of a surface-mount display device according to one embodiment of the present invention.

[0049] Figure 13 yes Figure 10 The diagram shows a cross-sectional view of the display device.

[0050] Figure 14 This is a cross-sectional view schematically illustrating the configuration of a direct-lit display device according to one embodiment of the present invention.

[0051] Figure 15 This is a graph showing the XAFS spectrum of the barrier film of Example 2.

[0052] Figure 16 This is a graph showing the analytical results of the XAFS spectrum of the barrier film of Example 2.

[0053] Figure 17 This is a graph showing the analytical results of the XAFS spectrum of the barrier membrane of Comparative Example 2.

[0054] Figure 18 This is a graph showing the analytical results of the XAFS spectrum of the barrier membrane of Comparative Example 4.

[0055] Figure 19 This is a graph showing the analytical results of the XAFS spectrum of the barrier membrane of Comparative Example 8.

[0056] Figure 20 This is a graph showing the results of the TOF-SIMS spectrum of the barrier film of Example 2.

[0057] Figure 21 This is a graph showing the results of the TOF-SIMS spectrum of the barrier film of Example 3.

[0058] Figure 22 This is a graph showing the results of the TOF-SIMS spectrum of the barrier membrane of Comparative Example 8. Detailed Implementation

[0059] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited to any of the following embodiments and can be implemented with appropriate modifications within the scope of the purpose of the present invention. In addition, in this specification, the expression "A to B" (A and B are arbitrary values) means "Ax or more and B or less".

[0060] Figure 1 This is a cross-sectional view showing an example of the barrier film of this embodiment. The barrier film manufactured using the film-forming apparatus of this embodiment is, for example, as shown in the image. Figure 1 The barrier film 100A shown includes a substrate 120, a first vapor-deposited film 131b, a first coating layer 131a, a second vapor-deposited film 132b, and a second coating layer 132a. Figure 1 In the example shown, the first vapor-deposited film 131b is located on one surface of the substrate 120. Additionally, in Figure 1 In the example shown, the barrier film 100A is sequentially stacked with a substrate 120, a first vapor-deposited film 131b, a first coating layer 131a, a second vapor-deposited film 132b, and a second coating layer 132a, with the second coating layer 132a located on the surface of the barrier film. The barrier layer 130 is constituted by the first vapor-deposited film 131b, the first coating layer 131a, the second vapor-deposited film 132b, and the second coating layer 132a. Hereinafter, the first alumina vapor-deposited film in this invention will be described only as the first vapor-deposited film, and the second alumina vapor-deposited film will be described only as the second vapor-deposited film.

[0061] It should be noted that in this specification, "layered sequentially" means that the substrate, vapor-deposited film and coating layer are stacked in this order, or other layers such as anchoring coatings and primers can be stacked between these layers.

[0062] The following describes each layer that constitutes the barrier membrane 100A.

[0063] [Substrate]

[0064] The substrate 120 is a layer made of resin. There are no particular limitations on the resin; known resin films or sheets can be used. Specifically, it can be a polyester substrate or a polyolefin substrate. As a polyester substrate, for example, polyester-based resins containing polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins, etc., can be used. As a polyolefin substrate, for example, polypropylene resin can be used.

[0065] Among polyester resins, polyethylene terephthalate (PET) resins and polybutylene terephthalate (PET) resins are preferred. The polyester film used as substrate 120 can be stretched in a specified direction. In this case, the polyester film can be a uniaxially stretched film stretched in one specified direction or a biaxially stretched film stretched in two specified directions. For example, when using a film made of polyethylene terephthalate as substrate 1, a biaxially stretched polyethylene terephthalate film can be used.

[0066] When using a film made of polypropylene resin as the substrate 120, a biaxially stretched polypropylene film can be used.

[0067] In the case of polyester films, the film thickness is not particularly limited, as long as the pretreatment or film-forming process can be performed using the film-forming apparatus described later to form the vapor-deposited film 2. However, from the viewpoint of flexibility and shape retention, a thickness of 5 μm or more and 100 μm or less is preferred, and a thickness of 10 μm or more and 50 μm or less is more preferred. If the thickness of the polyester film is within this range, it is not only easy to bend, but also will not break during transport, and is easy to process in the film-forming apparatus used to manufacture the barrier film 2 with improved adhesion.

[0068] In addition to the conventionally known PET film, biomass PET film, recycled PET film, and high-rigidity PET film (tough PET film) can also be used as the substrate 1.

[0069] It can be a single layer or a multi-layered structure with two or more layers. In the case of a multi-layered structure, the layers can be of the same composition or different compositions. In addition, in the case of a multi-layered structure, the layers can be bonded together with adhesive layers or other bonding agents.

[0070] From the viewpoint of flexibility and shape retention, the film thickness in the case of polyolefin films is preferably in the range of 10 μm or more and 100 μm or less, and more preferably in the range of 15 μm or more and 50 μm or less.

[0071] The substrate 120 may have an anchoring coating (also called an AC layer or primer layer) formed on its surface to improve adhesion to the vapor-deposited film. Examples of anchoring coatings include polyurethane resins, polyamide resins, epoxy resins, phenolic resins, (meth)acrylic resins, and polyvinyl acetate resins. Examples of polyurethane resins include urethane acrylate resins and polyester urethane resins.

[0072] The substrate 120 of the wound body is preferably pre-conditioned through a manufacturing process or a conditioning process, thereby improving barrier properties. Furthermore, it prevents substrate breakage during plasma-assisted vapor deposition, as described later. As an example of conditioning conditions, maintaining the substrate at a temperature of 22–30°C and a relative humidity of 40–65%RH for 1–7 days is also recommended. It should be noted that pre-winding the wound body before storage is also effective for conditioning. In this case, the rewinding process is also preferably performed under the aforementioned conditioning conditions.

[0073] [Vapor Deposition Film]

[0074] Next, the first vapor-deposited film 131b and the second vapor-deposited film 132b (hereinafter, they are collectively referred to as vapor-deposited films without distinction) will be described. The vapor-deposited film contains aluminum oxide. Aluminum exists in the vapor-deposited film in a state where at least a portion forms Al2O3. The vapor-deposited film may also contain metal oxides such as silicon oxides, silicon nitrides, silicon oxynitrides, silicon carbides, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide, or their metal nitrides and carbides. The first vapor-deposited film 131b and the second vapor-deposited film 132b may be the same or different.

[0075] The lower limit of the thickness of the vapor-deposited film is preferably 3 nm or more, more preferably 5 nm or more. The upper limit is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 15 nm or less. The first vapor-deposited film 131b and the second vapor-deposited film 132b may be the same or different.

[0076] It should be noted that the "alumina vapor-deposited film" in this invention refers to the "vapor-deposited film containing aluminum oxide" as described above. In addition to aluminum oxide (Al2O3), it may also contain aluminum hydroxide (AlO(OH)) and aluminum hydroxide (Al(OH)3), etc. A detailed description follows.

[0077] (XAFS spectral analysis)

[0078] XAFS analysis is an X-ray absorption fine structure (XAFS) pattern, in which X-rays are irradiated from the surface side of the vapor-deposited surface of the barrier film (or the coated side if a coating layer is present), and the absorption is measured. Detailed measurement and resolution conditions are described in the examples.

[0079] In particular, XAFS (Extra-Aspect-Frequency Spectroscopy) analysis using soft X-rays provides information not only about a portion of the vapor-deposited film's surface but also about the overall composition of the vapor-deposited film, revealing information about the size of hydroxyl groups within the alumina vapor-deposited film. Furthermore, even when a coating layer exists on the surface of the vapor-deposited film, information about the film can be obtained even with the coating layer present by irradiating it from the surface side through the coating layer. It should be noted that, as... Figure 1 As in the configuration, with the first vapor-deposited film 131b and the second vapor-deposited film 132b present, the XAFS pattern of the main body is obtained by merging the two vapor-deposited films.

[0080] Figure 15 This is one example of the XAFS measurement results performed on a barrier film from one of the embodiments described later. Additionally, Figure 16 These represent the peaks obtained by peak separation of the XAFS spectrum in Example 2. Figure 15 , Figure 16 In the diagram, the vertical axis represents absorption intensity (au), and the horizontal axis represents energy (eV). The peak ratio P of the vapor-deposited film in this invention is, for example, as shown below. Figure 16 The figure shows the ratios obtained from the peaks of the XAFS spectrum after peak separation.

[0081] exist Figure 16 In the peak separation analysis, Experiment is the measured XAFS spectrum, Fit.Peak1 is the separated intensity peak at 1566 eV, Fit.Peak2 is the separated intensity peak at 1568 eV, and Fit.Peak3 is the separated intensity peak at 1572 eV. Fit.Base1 is the baseline at 1566 eV, and Fit.Base2 is the baseline at 1568 eV.

[0082] according to Figure 15 , Figure 16 The XAFS spectrum contains multiple peaks, specifically peak P1 with a vertices around 1566 eV, peak P2 with a vertices around 1568 eV, and peak P3 with a vertices around 1572 eV. It should be noted that "around 1566 eV" refers to values ​​above 1565 eV and below 1567 eV, "around 1568 eV" refers to values ​​above 1567 eV and below 1569 eV, and "around 1572 eV" refers to values ​​above 1571 eV and below 1573 eV.

[0083] Here, it is believed that: P1 is the peak from 4-coordinated alumina, P2 is the peak from 6-coordinated alumina, and P3 is the peak from 6-coordinated aluminum hydroxide and aluminum hydroxide.

[0084] For alumina films, amorphous films are considered to have superior flexibility compared to crystalline films, and therefore, amorphous films are preferred when used as barrier films. However, it is difficult to determine whether a film is crystalline or amorphous, except in cases where a clear crystalline peak can be identified in XRD, a conventional method of X-ray analysis.

[0085] With confirmation of the XAFS spectrum, γ-Al₂O₃ and θ-Al₂O₃ were detected as P1 in the crystalline alumina film, but the P1 peak was not relatively higher than the P2 peak. According to the embodiments of this application described later, such as Example 2 (see...) Figure 15 Therefore, we know that P1 > P2, which confirms that an amorphous film has been formed.

[0086] Furthermore, for the alumina film to withstand the brightness retention test (described in the examples below) when used in wavelength conversion wafers, amorphous properties alone are insufficient, and it is considered necessary to introduce hydroxyl groups. However, for example, in conventional TOF-SIMS depth analysis, the correlation between film formation conditions and film quality cannot be adequately investigated due to the following factors: it is unclear whether the evaluation is for the alumina film or for detecting residual moisture at the interface between the alumina film and the substrate; or sufficient depth resolution cannot be obtained for portions of the alumina film in the presence of a coating.

[0087] According to the present invention, by confirming the XAFS spectrum, the peak ratio of the vapor-deposited film is defined as P = P3 peak / P1 peak = (intensity peak near 1572 eV) / (intensity peak near 1566 eV), thereby obtaining information related to the amount of hydroxyl groups in the alumina vapor-deposited film.

[0088] The inventors discovered that, in order to reduce color unevenness, compared to forming a film immediately after vapor deposition under conditions of high water vapor barrier properties, forming a film in an alumina film with many dangling bonds and low water vapor barrier properties, and then performing oxidation and hydroxide oxidation (mainly hydroxide oxidation) through aging, thereby reducing dangling bonds and exhibiting water vapor barrier properties, is an effective method. Therefore, by confirming XAFS spectra and studying the correlation between moisture content during vapor deposition, film formation conditions including aging, and film quality, this invention was completed.

[0089] This invention discovers that the fading of the barrier film changes depending on the peak ratio P of the vapor-deposited film. Specifically, by setting the peak ratio P of the vapor-deposited film to 1.05 or higher and 1.60 or lower, it is possible to balance improved barrier properties with reduced color uniformity of the barrier film. The lower limit of the peak ratio P is preferably 1.06 or higher, more preferably 1.09 or higher, and particularly preferably 1.20 or higher. The upper limit of the peak ratio P is preferably 1.54 or lower, more preferably 1.40 or lower.

[0090] If the peak ratio P of the vapor-deposited film is less than 1.05, it is a high-oxide film immediately after vapor deposition. Therefore, it is noticeable when color unevenness occurs, has high barrier properties, and is therefore less prone to fading. "Fading" refers to an increase in transparency (transmittance) or a lightening of color due to changes over time after vapor deposition. This transparency or color affects the appearance of the end face (side face) in the wound state. Details are explained in the evaluation of "color unevenness" in the examples. When high-temperature and high-humidity hydrothermal treatment is performed and the peak ratio P exceeds 1.60, excessive hydroxyl groups are introduced, reducing initial barrier properties, especially water vapor barrier properties.

[0091] In this invention, to improve the aforementioned "color unevenness," the improvement is achieved by slightly reducing the brightness retention rate. Specifically, by intentionally adjusting the brightness retention rate to around 90% to 94% instead of setting it above 95% in the embodiments described later, color unevenness can be improved. It should be noted that although the brightness retention rate is qualitatively related to barrier properties, the test conditions for the brightness retention rate involve harsh conditions of standing in a constant temperature and humidity bath at 60°C and 90%RH for 1000 hours. Therefore, even if there is no difference in oxygen and water vapor barrier properties near the measurement limit, the brightness retention rate will still vary.

[0092] It should be noted that the peak ratio P of the vapor-deposited film in the barrier film can be adjusted by controlling the plasma pretreatment, plasma-assisted treatment during vapor deposition, whether a cold trap is used in the film deposition process, and the combination of curing treatment after film deposition and curing treatment after coating layer formation. Specifically, by not using a cold trap in the film deposition process, it is possible to simultaneously improve the brightness retention rate when used as a wavelength conversion wafer and reduce color unevenness of the barrier film. These results are detailed in the following description of the manufacturing process and examples.

[0093] (Covering layer)

[0094] A first coating layer 131a is deposited on the surface of the first alumina vapor-deposited film 131b, and a second coating layer 132a is deposited on the surface of the second alumina vapor-deposited film 132b. These coating layers provide mechanical / chemical protection to the alumina vapor-deposited film and improve the barrier properties of the barrier-resistant laminated film. Hereinafter, the first coating layer 131a and the second coating layer 132a (hereinafter, they are not distinguished and are simply referred to as coating layers) coated to form the barrier-resistant laminated film will be described. It should be noted that in the following description, the materials, compositions, film thicknesses, etc., of the first coating layer 131a and the second coating layer 132a may be the same or different.

[0095] The coating layer is formed by applying a barrier coating agent onto an alumina vapor-deposited film and then curing it. The barrier coating agent consists of metal alkoxides, water-soluble polymers, silane coupling agents added as needed, sol-gel catalysts, acids, etc.

[0096] As a metal alkoxide, the general formula R1 can be exemplified. n M(OR 2 ) m (wherein, R1 and R2 represent organic groups with 1 to 8 carbon atoms, M represents a metal atom, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, and n+m represents the valence of M.) represents at least one metal alkoxide, and the metal atom represented by M as the metal alkoxide can be silicon, zirconium, titanium, aluminum, or others. For example, alkoxysilanes in which M is Si are preferred.

[0097] The alkoxysilanes described above can be represented by, for example, those with the general formula Si(ORa)4 (where Ra represents a lower alkyl group). In the above text, Ra can be represented by methyl, ethyl, n-propyl, n-butyl, or other compounds. Specific examples of the alkoxysilanes described above include tetramethoxysilane Si(OCH3)4, tetraethoxysilane Si(OC2H5)4, tetrapropoxysilane Si(OC3H7)4, tetrabutoxysilane Si(OC4H9)4, and others. Two or more of the above alkoxides can be used together.

[0098] As silane coupling agents, silane coupling agents having reactive groups such as vinyl, epoxy, methacryl, and amino groups can be used. Particularly preferred are organoalkoxysilanes having epoxy groups, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. One or more silane coupling agents as described above can be used.

[0099] Among them, the crosslinking density of cured films using bifunctional coatings such as γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane is lower than that of systems using trialkoxysilane. Therefore, it is an excellent film with gas barrier properties and resistance to hot water treatment, and it is also a flexible cured film with excellent bending resistance, so the gas barrier properties of this barrier film are not easily deteriorated.

[0100] Water-soluble polymers can be used alone or separately as polyvinyl alcohol resins or ethylene / vinyl alcohol copolymers, or a combination of polyvinyl alcohol resins and ethylene / vinyl alcohol copolymers can be used. In the coating layer of this embodiment, polyvinyl alcohol resins are preferred.

[0101] As a polyvinyl alcohol (PVA)-based resin, substances obtained by saponifying polyvinyl acetate are generally used. The PVA-based resin can be a partially saponified PVA-based resin with a residual amount of several tens of percent acetate groups, a fully saponified PVA-based resin without residual acetate groups, or a modified PVA-based resin with OH groups modified. Regarding the degree of saponification, the resin should be a crystallized material with improved film hardness for gas barrier coatings, preferably with a saponification degree of 70% or higher. Furthermore, the degree of polymerization can be within the range used in conventional sol-gel methods (approximately 100 to 5000). Examples of such PVA-based resins include RS resin "RS-110 (Saponification degree = 99%, Degree of polymerization = 1000)" manufactured by KURARAY Co., Ltd., and "Gohsenol NM-14 (Saponification degree = 99%, Degree of polymerization = 1400)" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0102] As an ethylene / vinyl alcohol copolymer, saponified products of copolymers of ethylene and vinyl acetate, or substances obtained by saponifying random copolymers of ethylene and vinyl acetate, can be used. For example, there are no particular limitations, ranging from partially saponified products containing tens of mol% acetate groups to fully saponified products containing only a few mol% acetate groups or no acetate groups remaining. From a barrier properties perspective, a lower limit for the degree of saponification is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. An upper limit is 100% or less.

[0103] Acid or amine compounds are preferred as catalysts for the sol-gel method.

[0104] As acids, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as acetic acid and tartaric acid, can be used.

[0105] The acid content relative to the total molar amount of alkoxy groups in the metal alkoxide is preferably 0.001 to 0.05 mol%, more preferably 0.01 to 0.03 mol%. When it is less than 0.001 mol%, the catalytic effect is too small; when it is more than 0.05 mol%, the catalytic effect is too strong, the reaction rate becomes too fast, and there is a tendency for it to become uneven.

[0106] As an amine compound, a tertiary amine that is substantially insoluble in water but soluble in organic solvents is preferred. Specifically, N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc., can be used, for example. N,N-dimethylbenzylamine is particularly preferred.

[0107] The content of the amine compound is preferably 0.01 to 1.0 parts by mass relative to 100 parts by mass of the metal alkoxide, and particularly preferably 0.03 to 0.3 parts by mass. If it is less than 0.01 parts by mass, the catalytic effect is too small; if it is more than 1.0 parts by mass, the catalytic effect is too strong, the reaction rate becomes too fast, and there is a tendency for it to become uneven.

[0108] As a solvent, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, and other alcohols are preferred.

[0109] The thickness of the barrier coating layer formed as described above is 100–500 nm. If it is within this range, the coating will not break and will fully cover the surface of the vapor-deposited film, which is therefore preferred.

[0110] Regarding the composition of the barrier coating, relative to 100 parts by weight of alkoxysilane, water-soluble polymers such as polyvinyl alcohol resins can be used in the range of 5 to 20 parts by weight, and silane coupling agents can be used in the range of 0 to 10 parts by weight. This maintains the flexibility of the film. However, if more than 20 parts by weight of silane coupling agent are used, the rigidity and brittleness of the formed barrier coating film increase, which is not preferable.

[0111] The lower limit of the IO value (the ratio of the solid content of metal alkoxides such as tetraethoxysilane (SiO2 equivalent) to water-soluble resins such as polyvinyl alcohol) in the coating layer is preferably 1.5 or more, more preferably 1.9 or more. The upper limit is preferably 4.5 or less, more preferably 3.5 or less. If it exceeds 4.5, the coating layer loses its flexibility and is prone to cracking, thereby reducing its barrier properties, which is not preferred. If it is less than 1.5, the condensation of hydrolysates formed from the metal alkoxides cannot proceed sufficiently, reducing its resistance to damp heat, which is also not preferred.

[0112] (Analysis of C2 / Si ratio using TOF-SIMS)

[0113] For the coating, when etching is performed from the surface of the barrier film opposite to the resin substrate using time-of-flight secondary ion mass spectrometry (TOF-SIMS), the coating intensity ratio X, as defined below, detected in the respective regions of the first coating and the second coating is 0.50 or more and 1.10 or less.

[0114] X=C2 - Ionic strength / Si - Ionic strength

[0115] Using Example 2 described later ( Figure 20 The coating strength ratio X of the barrier film coating layer in this embodiment will be explained. Figure 20This demonstrates the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to analyze the surface of the second coating layer 132a (the surface opposite to the substrate). Figure 1 This is an example of a graph analysis showing the intensity of secondary ions reflecting the elemental composition and chemical structure information when the barrier film of Example 2, composed of layers, is etched (depth-direction analysis). The vertical axis of the graph represents the intensity of the detected secondary ions, expressed as a common logarithm. The horizontal axis (Et times) represents the etching time (seconds).

[0116] TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) is a method that uses a pulsed primary ion beam to irradiate the surface of a solid sample to analyze secondary ions sputtered from the sample surface. The secondary ions are then separated by their time-of-flight difference (which is proportional to the square root of their weight) for mass analysis.

[0117] In the case of depth-oriented analysis, specifically, while repeatedly performing soft etching at a certain speed from the outermost surface of the second coating layer 132a using a Cs (cesium) ion gun, a time-of-flight secondary ion mass spectrometer is used to measure the second coating layer 132a and the first coating layer 131a. This allows for the generation of individual curves reflecting the elemental composition and chemical structure of the secondary ions. A specific example would be shown as follows... Figure 20 As shown, this is the detection of C2. - Ions, CN - Ions, Si - Ions, AlO2 - Ions, SiO2 - The ion intensity is presented as a graph of ion intensity. C2 ions from the second coating layer 132a were sequentially observed from the surface side according to the etching time. - Ionic strength and Si - Ionic strength, AlO2 from the second vapor-deposited film 132b - Ion strength, C2 from the first coating layer 131a - Ionic strength and Si - Ionic strength, AlO2 from the first vapor-deposited film 131b - Ionic strength, C2 from PET - Ionic strength.

[0118] In the barrier film of the present invention, the coating strength ratio X, as defined below, detected in the respective regions of the first coating layer 131a and the second coating layer 132a, is 0.50 or more and 1.10 or less.

[0119] X=C2 - Ionic strength / Si - Ionic strength

[0120] Here, the coating strength ratio X is the average value of each coating region. Figure 20 In this example, the region of the second coating layer 132a is calculated as 500–2000 seconds, and the region of the first coating layer 131a is calculated as 3300–4500 seconds. It should be noted that the detailed measurement conditions for TOF-SIMS are those described in the examples.

[0121] If the coating strength ratio X is less than 0.50, the coating loses its flexibility and is prone to cracking, thus reducing its barrier properties, which is not preferred. If it exceeds 1.10, the Si concentration is low, thus reducing its resistance to damp heat, which is also not preferred.

[0122] (Film-forming device)

[0123] Next, an example of the film-forming apparatus 10 used in the method for manufacturing the barrier film will be described. For example... Figure 2 As shown, the film-forming apparatus 10 includes: a substrate conveying mechanism 11A for conveying a substrate 1 (equivalent to the substrate 120 described above); a plasma pretreatment mechanism 11B for performing plasma pretreatment on the surface of the substrate 1; and a film-forming mechanism 11C for forming a vapor-deposited film 2. Figure 5 In the example shown, the film-forming apparatus 10 further includes a pressure-reducing chamber 12. The pressure-reducing chamber 12 has a pressure-reducing mechanism, such as a vacuum pump (described later), that adjusts the atmosphere inside at least a portion of the space to below atmospheric pressure.

[0124] exist Figure 2 In the example shown, the decompression chamber 12 includes: a substrate transfer chamber 12A containing the substrate transfer mechanism 11A; a plasma pretreatment chamber 12B containing the plasma pretreatment mechanism 11B; and a film formation chamber 12C containing the film formation mechanism 11C. The decompression chamber 12 is preferably configured to suppress the mixing of atmospheres within each chamber. For example, as... Figure 2 As shown, the decompression chamber 12 is located between the substrate transfer chamber 12A and the plasma pretreatment chamber 12B, between the plasma pretreatment chamber 12B and the film formation chamber 12C, and between the substrate transfer chamber 12A and the film formation chamber 12C, and may have partition walls 35a to 35c separating each chamber.

[0125] The substrate transfer chamber 12A, plasma pretreatment chamber 12B, and film formation chamber 12C will be described. The plasma pretreatment chamber 12B and film formation chamber 12C are respectively grounded to the substrate transfer chamber 12A and each has a portion connected to the substrate transfer chamber 12A. Therefore, the substrate 1 can be transferred between the substrate transfer chamber 12A and the plasma pretreatment chamber 12B, and between the substrate transfer chamber 12A and the film formation chamber 12C, without contact with the atmosphere. For example, between the substrate transfer chamber 12A and the plasma pretreatment chamber 12B, the substrate 1 can be transferred via an opening provided in the partition wall 35a. The substrate transfer chamber 12A and the film formation chamber 12C have the same structure, allowing the substrate 1 to be transferred between them.

[0126] The function of the depressurization mechanism in the depressurization chamber 12 will be explained. The depressurization mechanism of the depressurization chamber 12 is configured to reduce the atmosphere in the space of the film forming apparatus 10, which is equipped with at least the plasma pretreatment unit 11B or the film forming unit 11C, to below atmospheric pressure. The depressurization mechanism can be configured to reduce the pressure of the substrate transfer chamber 12A, the plasma pretreatment chamber 12B, and the film forming chamber 12C, which are divided by partitions 35a to 35c, to below atmospheric pressure respectively.

[0127] The configuration of the depressurization mechanism of the depressurization chamber 12 will be described. The depressurization chamber 12 may, for example, have a vacuum pump connected to the plasma pretreatment chamber 12B. By adjusting the vacuum pump, the pressure inside the plasma pretreatment chamber 12B during the plasma pretreatment described later can be appropriately controlled. Furthermore, by the method described later, the diffusion of plasma supplied to the plasma pretreatment chamber 12B into other chambers can be suppressed. Similar to the vacuum pump connected to the plasma pretreatment chamber 12B, the depressurization mechanism of the depressurization chamber 12 may have a vacuum pump connected to the film formation chamber 12C. As the vacuum pump, a drying pump, turbomolecular pump, cryogenic pump, rotary pump, diffusion pump, etc., can be used.

[0128] The substrate conveying mechanism 11A of the film forming apparatus 10 in this embodiment will be described in conjunction with the conveying path of the substrate 1. The substrate conveying mechanism 11A is a mechanism disposed in the substrate conveying chamber 12A for conveying the substrate 1. Figure 2 In the example shown, the substrate conveying mechanism 11A includes: an unwinding roller 13 on which a roll of substrate 1 is mounted; a winding roller 15 for winding the substrate 1; and guide rollers 14a to 14d. The substrate 1 delivered from the substrate conveying mechanism 11A is then conveyed by a pretreatment roller 20 (described later) disposed in the plasma pretreatment chamber 12B and a film forming roller 25 (described later) disposed in the film forming chamber 12C.

[0129] It should be noted that, although not shown in the figure, the substrate conveying mechanism 11A may further include a tension pickup roller. By including a tension pickup roller in the substrate conveying mechanism 11A, the substrate 1 can be conveyed while adjusting the tension applied to it.

[0130] (Plasma pretreatment mechanism)

[0131] The plasma pretreatment mechanism 11B will be described. The plasma pretreatment mechanism 11B is a mechanism for performing plasma pretreatment on the surface of the substrate 1. Figure 5 The plasma pretreatment unit 11B shown generates plasma P and uses the generated plasma P to perform plasma pretreatment on the surface of the substrate 1. If the surface of the substrate 1 is activated by plasma pretreatment, for example, hydrogen is released from the substrate resin component, generating carbon free radicals. Then, by combining with oxygen and hydrogen in the atmosphere, functional groups such as hydroxyl, carboxyl, and ketone groups are generated. It is believed that by generating such functional groups, the adhesion between the substrate 1 and the vapor-deposited film 2 is improved. Figure 2 The plasma pretreatment mechanism 11B shown includes: a pretreatment roller 20 disposed in the plasma pretreatment chamber 12B; an electrode section 21 opposite to the pretreatment roller 20; and a magnetic field forming section 23 that forms a magnetic field between the pretreatment roller 20 and the electrode section 21.

[0132] The pretreatment roller 20 will be described. Figure 3 It is Figure 2 The enlarged image shows the portion enclosed by the dotted line containing the symbol VI. It should be noted that... Figure 2 The connection is omitted in the text. Figure 2 The power supply wiring 31 of the power source 32 and the electrode section 21 (described later), as well as the plasma P generated by the plasma pretreatment mechanism 11B, are shown. The pretreatment roller 20 has a rotation axis X. The pretreatment roller 20 is configured such that at least the rotation axis X is located within the plasma pretreatment chamber 12B, which is divided by partitions 35a and 35b. A substrate 1 having dimensions in the direction of the rotation axis X is wound on the pretreatment roller 20. In the following description, the dimension of the substrate 1 in the direction of the rotation axis X will also be referred to as the width of the substrate 1. In addition, the direction of the rotation axis X will also be referred to as the width direction of the substrate 1.

[0133] like Figure 2 As shown, the pretreatment roller 20 can be configured such that a portion of it is exposed on the substrate transfer chamber 12A side. Figure 2In the example shown, the plasma pretreatment chamber 12B and the substrate transfer chamber 12A are connected via an opening provided in the partition wall 35a, through which a portion of the pretreatment roller 20 is exposed on the substrate transfer chamber 12A side. A gap exists between the partition wall 35a and the pretreatment roller 20 between the substrate transfer chamber 12A and the plasma pretreatment chamber 12B, through which the substrate 1 can be transferred from the substrate transfer chamber 12A to the plasma pretreatment chamber 12B. Although not shown, the pretreatment roller 20 may also be configured such that its entirety is located within the plasma pretreatment chamber 12B.

[0134] Although not shown, the pretreatment roller 20 may also have a temperature adjustment mechanism for adjusting the temperature of its surface. For example, the pretreatment roller 20 may have a temperature adjustment mechanism inside its interior, which includes piping for circulating a temperature-adjusting medium such as a refrigerant or heat transfer medium. The temperature adjustment mechanism adjusts the surface temperature of the pretreatment roller 20 to a target temperature, for example, within a range of -20°C to 100°C.

[0135] By equipping the pretreatment roller 20 with a temperature adjustment mechanism, the shrinkage and breakage of the substrate 1 caused by heat can be suppressed during plasma pretreatment.

[0136] The pretreatment roller 20 is formed of at least one of stainless steel, iron, copper, and chromium. To prevent scratches, a hard chromium coating or similar treatment can be applied to the surface of the pretreatment roller 20. These materials are easy to process. Furthermore, by using the aforementioned materials as the material for the pretreatment roller 20, the thermal conductivity of the pretreatment roller 20 itself is improved, thus making it easier to control the temperature of the pretreatment roller 20.

[0137] The electrode section 21 will be described below. Figure 2 and Figure 3 In the example shown, the electrode portion 21 has: a first surface 21c facing the pretreatment roller 20; and a second surface 21d located on the opposite side of the first surface 21c. Figure 2 and Figure 3 In the example shown, the electrode portion 21 is a plate-shaped component, with both the first surface 21c and the second surface 21d being planar. The electrode portion 21 generates plasma between itself and the pretreatment roller 20 by applying an alternating voltage. Preferably, the electrode portion 21 forms an electric field between itself and the pretreatment roller 20 such that the generated plasma moves toward the surface of the substrate 1 in a direction perpendicular to the surface of the substrate 1. This allows for efficient pretreatment of the substrate 1.

[0138] The number of electrode portions 21 is preferably two or more. Two or more electrode portions 21 are preferably arranged along the transport direction of the substrate 1. Figure 2 and Figure 3In the example shown, a film-forming apparatus 10 is illustrated with two electrode sections 21. Alternatively, the number of electrode sections 21 may be, for example, 12 or less.

[0139] The effect of arranging two or more electrode sections 21 along the conveying direction of the substrate 1 will be explained. As described above, plasma is generated between the electrode section 21 and the pretreatment roller 20. The area where plasma is generated expands as the size of the electrode section 21 in the conveying direction increases. On the other hand, when the electrode section 21 is a flat plate-shaped component, the larger the size of the electrode section 21 in the conveying direction, the greater the distance from the end of the first surface 21c of the electrode section 21 facing the pretreatment roller 20 in the conveying direction to the pretreatment roller 20, and the lower the processing capacity generated by the plasma.

[0140] In the film-forming apparatus 10, two or more electrode portions 21 are arranged along the conveying direction of the substrate 1. Therefore, even if the size of the electrode portion 21 in the conveying direction of the substrate 1 is small, plasma can be generated over a wide range in the conveying direction. In addition, by reducing the size of the electrode portion 21, the distance from the end of the first surface 21c of the electrode portion 21 in the conveying direction to the pretreatment roller 20 can be reduced, and plasma can be generated uniformly in the conveying direction.

[0141] like Figure 2 and Figure 3 As shown, the electrode portion 21 has a first end portion 21e and a second end portion 21f located on a first surface 21c of the electrode portion 21. The first end portion 21e is the upstream end portion in the conveying direction of the substrate 1, and the second end portion 21f is the downstream end portion in the conveying direction of the substrate 1. As described above, by reducing the size of the electrode portion 21 in the conveying direction of the substrate 1, the distance from the first end portion 21e and the second end portion 21f of the electrode portion 21 in the conveying direction to the pretreatment roller 20 can be reduced. The size of the electrode portion 21 in the conveying direction of the substrate 1 is related to... Figure 3 The angle θ shown corresponds to the angle between the straight line passing through the first end 21e and the rotation axis X and the straight line passing through the second end 21f and the rotation axis X. The angle θ is preferably 20° or more and 90° or less, more preferably 60° or less, and even more preferably 45° or less. By making the angle θ within the above range, when the first surface 21c of the electrode portion 21 is a plane, plasma can be uniformly generated in the conveying direction between the electrode portion 21 and the pretreatment roller 20.

[0142] The material of the electrode part 21 is not particularly limited as long as it is conductive. Specifically, aluminum, copper, and stainless steel are suitable materials for the electrode part 21.

[0143] The thickness L3 of the electrode portion 21 when viewed from a direction perpendicular to the first surface 21c of the electrode portion 21 is not particularly limited, but is, for example, 15 mm or less. By making the thickness of the electrode portion 21 the above value, a magnetic field can be effectively formed between the pretreatment roller 20 and the electrode portion 21 by means of the magnetic field forming section 23. In addition, the thickness L3 of the electrode portion 21 is, for example, 3 mm or more.

[0144] The magnetic field forming part 23 will be explained. For example... Figure 2 and Figure 3 As shown, the magnetic field forming section 23 is located on the opposite side of the electrode section 21 from the side facing the pretreatment roller 20. The magnetic field forming section 23 is a component that forms a magnetic field between the pretreatment roller 20 and the electrode section 21. Regarding the magnetic field between the pretreatment roller 20 and the electrode section 21, for example, when using the plasma pretreatment mechanism 11B to generate plasma, it helps to generate higher density plasma. Figure 2 and Figure 3 The magnetic field forming part 23 shown has a first magnet 231 and a second magnet 232 disposed on the second surface 21d of the electrode part 21.

[0145] The number of magnetic field forming sections 23 is preferably two or more. In the case where the plasma pretreatment mechanism 11B has two or more electrode sections 21 and two or more magnetic field forming sections 23, the two or more magnetic field forming sections 23 are preferably disposed on the opposite side of each of the two or more electrode sections 21 to the side facing the pretreatment roller 20. Figure 2 and Figure 3 In the example shown, two magnetic field forming parts 23 are respectively disposed on the second surface 21d of the two electrode parts 21.

[0146] The structure of the first magnet 231 and the second magnet 232 in the normal direction of the second surface 21d of the electrode section 21 will be described. For example... Figure 2 and Figure 3 As shown, the first magnet 231 and the second magnet 232 have N poles and S poles, respectively. Figure 2 and Figure 3 The symbol N shown indicates the N pole of the first magnet 231 or the second magnet 232. Additionally, Figure 2 and Figure 3 The symbol S indicates the S pole of either the first magnet 231 or the second magnet 232. One of the N pole or S pole of the first magnet 231 is located on the substrate 1 side relative to the other. Similarly, one of the N pole or S pole of the second magnet 232 is located on the substrate 1 side relative to the other. Figure 2 and Figure 3In the example shown, the N pole of the first magnet 231 is located on the substrate 1 side relative to the S pole of the first magnet 231, and the S pole of the second magnet 232 is located on the substrate 1 side relative to the N pole of the second magnet 232. Although not shown, it is also possible that the S pole of the first magnet 231 is located on the substrate 1 side relative to the N pole of the first magnet 231, and the N pole of the second magnet 232 is located on the substrate 1 side relative to the S pole of the second magnet 232.

[0147] Next, the structure of the first magnet 231 and the second magnet 232 in the surface direction of the second surface 21d of the electrode section 21 will be described. Figure 4 Observed from the 23rd side of the magnetic field forming part Figure 2 Top view of electrode section 21 and magnetic field forming section 23 shown. Figure 5 It shows along Figure 4 A cross-sectional view of line VIII-VIII. Additionally, Figure 4 In the diagram, direction D1 is the direction in which the rotation axis X of the pretreatment roller 20 extends.

[0148] like Figure 4 and Figure 5 As shown, the first magnet 231 has a first axial portion 231c. (As indicated...) Figure 4 As shown, the first axial portion 231c extends along direction D1, that is, along the rotation axis X of the pretreatment roller 20. The first magnet 231 disposed on one electrode portion 21 may have one first axial portion 231c, or it may have two or more first axial portions 231c. Figure 4 In the example shown, the first magnet 231 disposed on an electrode portion 21 has a first axial portion 231c.

[0149] In addition, such as Figure 4 and Figure 5 As shown, the second magnet 232 has a second axial portion 232c. (As indicated...) Figure 7 As shown, the second axial portion 232c also extends along direction D1, i.e. along the rotation axis X, just like the first axial portion 231c.

[0150] By including portions extending along the rotation axis X in both the first magnet 231 and the second magnet 232, the uniformity of the magnetic field strength formed around the substrate 1 in the width direction of the substrate 1 can be improved. This, in turn, improves the uniformity of the plasma distribution density formed around the substrate 1 in the width direction of the substrate 1.

[0151] The second magnet 232 disposed on one electrode portion 21 may have one second axial portion 232c, or it may have two or more second axial portions 232c. Figure 4 and Figure 5In the example shown, the second magnet 232 provided on one electrode portion 21 has two second axial portions 232c. The two second axial portions 232c can be positioned to clamp the first axial portion 231c in a direction D2 orthogonal to the rotation axis X in the surface direction of the second surface 21d of the electrode portion 21.

[0152] Figure 5 The dimensions L4 of the first axial portion 231c and L5 of the second axial portion 232c in the conveying direction of the substrate 1 shown are not particularly limited. Furthermore, the ratio of the dimensions L4 of the first axial portion 231c to L5 of the second axial portion 232c in the conveying direction of the substrate 1 is not particularly limited. The dimensions L4 of the first axial portion 231c may be equal to the dimensions L5 of the second axial portion 232c, or the dimensions L4 of the first axial portion 231c may be larger than the dimensions L5 of the second axial portion 232c.

[0153] The distance L6 between the first axial portion 231c and the second axial portion 232c in direction D2 is set such that a magnetic field generated by the first axial portion 231c and the second axial portion 232c is formed between the pretreatment roller 20 and the electrode portion 21.

[0154] When the magnetic field forming section 23 is viewed along the normal direction of the second surface 21d of the electrode section 21, the second magnet 232 can surround the first magnet 231. For example, Figure 4 As shown, the second magnet 232 may have two second axial portions 232c and two connecting portions 232d arranged in such a way as to connect the two second axial portions 232c.

[0155] Examples of magnets used as the magnetic field forming part 23, such as the first magnet 231 and the second magnet 232, include permanent magnets such as ferrite magnets, neodymium magnets, and rare-earth magnets such as samarium cobalt magnets. Alternatively, an electromagnet can also be used as the magnetic field forming part 23.

[0156] The magnetic flux density of the magnets in the magnetic field forming section 23, such as the first magnet 231 and the second magnet 232, is, for example, between 100 Gauss and 10,000 Gauss. If the magnetic flux density is 100 Gauss or higher, a sufficiently strong magnetic field can be formed between the pretreatment roller 20 and the electrode section 21, which can generate a high-density plasma and form a good pretreatment surface at high speed. On the other hand, in order to make the magnetic flux density on the surface of the substrate 1 higher than 10,000 Gauss, expensive magnets or magnetic field generating mechanisms are required.

[0157] Although not shown, the plasma pretreatment apparatus 11B may also include a plasma feed gas supply unit. The plasma feed gas supply unit supplies gas, which serves as the feed gas for plasma, into the plasma pretreatment chamber 12B. The configuration of the plasma feed gas supply unit is not particularly limited. For example, the plasma feed gas supply unit includes a hole provided on the wall of the plasma pretreatment chamber 12B for ejecting the gas, which serves as the feed gas for plasma. Alternatively, the plasma feed gas supply unit may have a nozzle for releasing the plasma feed gas at a position closer to the substrate 1 than the wall of the plasma pretreatment chamber 12B. The plasma feed gas supplied by the plasma feed gas supply unit may be, for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide, or ethylene, or a mixture of these gases. As the plasma feed gas, one inert gas may be used alone, one active gas may be used alone, or a mixture of two or more gases included in an inert gas or an active gas may be used. As the plasma feed gas, a mixture of an inert gas such as argon and an active gas is preferred. As an example, the plasma feed gas supply unit supplies a mixture of argon (Ar) and oxygen (O2).

[0158] For example, the plasma pretreatment unit 11B uses a plasma density of 100 W·sec / m 2 Above 8000W·sec / m 2 The following plasma is supplied between the pretreatment roller 20 and the electrode section 21.

[0159] exist Figure 2 In the example shown, the plasma pretreatment unit 11B is disposed within a plasma pretreatment chamber 12B, which is separated from the substrate transfer chamber 12A and the film formation chamber 12C by a partition wall. By separating the plasma pretreatment chamber 12B from other areas such as the substrate transfer chamber 12A and the film formation chamber 12C, the atmosphere of the plasma pretreatment chamber 12B can be easily adjusted independently. As a result, for example, the concentration of plasma raw material gas in the space facing the pretreatment roller 20 and the electrode section 21 can be easily controlled, and the productivity of the laminated film is improved.

[0160] (film-forming mechanism)

[0161] Next, the film-forming mechanism 11C will be described. Figure 2 In the example shown, the film-forming mechanism 11C has a film-forming roller 25 and an evaporation mechanism 24 disposed in the film-forming chamber 12C.

[0162] The film-forming roller 25 will be described. The film-forming roller 25 is a roller that winds and transports the substrate 1, which has been pretreated in the plasma pretreatment unit 11B, with the treatment surface facing outwards.

[0163] The material of the film-forming roller 25 will be described. The film-forming roller 25 is preferably formed of a material comprising at least one of stainless steel, iron, copper, and chromium. To prevent scratches, a hard chromium coating or similar treatment can be applied to the surface of the film-forming roller 25. These materials are easy to process. Furthermore, by using the aforementioned materials as the material of the film-forming roller 25, the thermal conductivity of the film-forming roller 25 itself is improved, thus resulting in excellent temperature control. The average surface roughness Ra of the surface of the film-forming roller 25 is, for example, 0.1 μm or more and 10 μm or less.

[0164] Additionally, although not shown, the film-forming roller 25 may also have a temperature adjustment mechanism for adjusting the surface temperature of the film-forming roller 25. The temperature adjustment mechanism may, for example, have a circulation path inside the film-forming roller 25 for circulating a cooling medium or a heat source medium. The cooling medium (refrigerant) may be, for example, an aqueous solution of ethylene glycol, and the heat source medium (heat medium) may be, for example, silicone oil. The temperature adjustment mechanism may have a heater located opposite the film-forming roller 25. When the film-forming mechanism 11C forms a film by vapor deposition, considering the limitations of the heat resistance of the relevant mechanical components and versatility, it is preferable that the temperature adjustment mechanism adjusts the surface temperature of the film-forming roller 25 to a target temperature within the range of -20°C to 200°C. By equipping the film-forming roller 25 with a temperature adjustment mechanism, temperature fluctuations in the substrate 1 caused by heat generated during film formation can be suppressed.

[0165] The evaporation mechanism 24 will be described. Figure 6 Will Figure 2 The enlarged portion enclosed by the dotted-dash line containing the symbol IX shows... Figure 5 The specific manner in which the evaporation mechanism 24 is omitted is shown in the figure. Figure 2 The figure omitted shows the vapor deposition material supply section 61, which supplies the vapor deposition material. It should be noted that... Figure 6 The description of the pressure-reducing chamber 12 and partitions 35b and 35c is omitted. The evaporation mechanism 24 is a mechanism for evaporating a vapor-deposited material containing aluminum. By adhering the evaporated vapor-deposited material to the substrate 1, an aluminum-containing vapor-deposited film is formed on the surface of the substrate 1. In this embodiment, the evaporation mechanism 24 employs a resistance heating type. Figure 6 In the example shown, the evaporation mechanism 24 has a boat 24b. In this embodiment, the boat 24b has a power source (not shown) and a resistor (not shown) electrically connected to the power source. Multiple boats 24b may be arranged in the width direction of the substrate 1.

[0166] like Figure 6 As shown, the film-forming mechanism 11C may have a vapor deposition material supply section 61 that supplies vapor deposition material to the evaporation mechanism 24. Figure 6 The image shows an example of aluminum metal wires being continuously fed out by the vapor deposition material supply unit 61.

[0167] Although not shown, the film-forming mechanism 11C includes a gas supply mechanism. This gas supply mechanism supplies gas between the evaporation unit 24 and the film-forming roller 25. The gas supply mechanism supplies at least oxygen. The oxygen reacts with or combines with the evaporated material, such as aluminum, which is evaporated by the evaporation unit 24 and directed towards the substrate 1 on the film-forming roller 25. As a result, an aluminum oxide-containing vapor-deposited film can be formed on the surface of the substrate 1.

[0168] Additionally, the film-forming mechanism 11C includes a plasma supply mechanism 50 for supplying plasma between the surface of the substrate 1 and the evaporation mechanism 24. Figure 2 and Figure 6 In the example shown, the plasma supply mechanism 50 has a hollow cathode 51. In this embodiment, the hollow cathode 51 is a cathode with a partially open cavity. The hollow cathode 51 is capable of generating plasma within the cavity. Figure 6 In the example shown, the hollow cathode 51 is configured such that the opening of the hollow portion of the hollow cathode 51 is located obliquely above the boat 24b. Furthermore, although not shown, the plasma supply mechanism 50 of this embodiment has an anode facing the opening from which plasma is drawn out. The plasma supply mechanism 50 of this embodiment generates plasma within the hollow portion of the hollow cathode 51 and draws this plasma out between the surface of the substrate 1 and the evaporation mechanism 24 using the facing anode, thereby generating a strong plasma between the surface of the substrate 1 and the evaporation mechanism 24. Regarding the position of the facing anode, there is no particular limitation as long as plasma can be drawn out from the opening of the hollow portion of the hollow cathode 51 using the facing anode and supplied to the surface of the substrate 1 and the evaporation mechanism 24. In this embodiment, the case where the facing anodes are arranged on both sides of the substrate 1 in the width direction of the boat 24b will be described. In this case, the film-forming mechanism 11C has two or more boats 24b and two or more opposing anodes, which can be arranged alternately along the width direction of the substrate 1. Although not shown, the plasma supply mechanism 50 may have a raw material supply device for supplying plasma raw material gas into at least the cavity of the hollow cathode 51. The plasma raw material gas supplied as the raw material supply device can be, for example, the same gas that can be used as the plasma raw material gas supplied by the plasma raw material gas supply unit of the plasma pretreatment mechanism 11B.

[0169] By supplying plasma to the surface of the substrate 1 and the evaporation unit 24 through the plasma supply mechanism 50, plasma assistance is provided during the vapor deposition process. This activates the aluminum and oxygen evaporated in the evaporation unit 24, promoting the reaction or combination of aluminum and oxygen. As a result, the proportion of aluminum as alumina in the vapor-deposited film 2 formed on the surface of the substrate 1 can be increased, thereby stabilizing the properties of the vapor-deposited film 2.

[0170] Although not shown in the figure, the film forming apparatus 10 may also include a substrate charge removal unit, which performs post-processing on the portion of the substrate transfer chamber 12A located downstream of the film forming chamber 12C in the transport direction closer to the substrate 1. This post-processing utilizes the charge removal generated on the substrate 1 caused by film formation by the film forming mechanism 11C. The substrate charge removal unit may be configured to remove charge from one side of the substrate 1 or to remove charge from both sides of the substrate 1.

[0171] The apparatus used for removing the charged material from the substrate 1 as a post-processing unit is not particularly limited, and can be, for example, a plasma discharge apparatus, an electron beam irradiation apparatus, an ultraviolet irradiation apparatus, a scavenging rod, a glow discharge apparatus, a corona treatment apparatus, etc.

[0172] When performing post-processing by forming a discharge using a plasma treatment device or a glow discharge device, a single discharge gas such as argon, oxygen, nitrogen, or helium, or a mixture thereof, can be supplied to the vicinity of the substrate 1. Post-processing can be performed using any discharge method such as alternating current (AC) plasma, direct current (DC) plasma, arc discharge, microwave, or surface wave plasma. Under reduced pressure, it is most preferable to use a plasma discharge device for post-processing.

[0173] The substrate charge removal unit is located in the substrate conveying chamber 12A, downstream of the film forming chamber 12C in the conveying direction of the substrate 1. This removes the charge from the substrate 1, allowing it to quickly leave the film forming roller 25 at a predetermined position and be conveyed. Therefore, the substrate can be conveyed stably, preventing damage and quality degradation caused by charge buildup. Furthermore, improved wettability of the substrate surface and interior enhances its adaptability for subsequent processing.

[0174] (power supply)

[0175] exist Figure 2 In the example shown, the film-forming apparatus 10 further includes a power supply 32 electrically connected to the pretreatment roller 20 and the electrode section 21. Figure 5 In the example shown, the power supply 32 is electrically connected to the pretreatment roller 20 and the electrode section 21 via the power supply wiring 31. The power supply 32 is, for example, an AC power supply. When the power supply 32 is an AC power supply, the power supply 32 can apply an AC voltage with a frequency of, for example, 20 kHz to 500 kHz between the pretreatment roller 20 and the electrode section 21. The applied power (the power that can be applied to each 1 m width of the electrode section 21 in the width direction of the substrate 1) is not particularly limited, for example, 0.5 kW / m to 20 kW / m. The pretreatment roller 20 can be electrically set to ground level or electrically set to a non-fixed level.

[0176] (Method for manufacturing barrier film)

[0177] Next, the film-forming apparatus 10 described above is used to manufacture... Figure 1 The method for forming the barrier film shown will be described. First, the first film-forming step (hereinafter also referred to as the film-forming step) for forming a first vapor-deposited film on the surface of the substrate 1 will be described. In the film-forming process using the film-forming apparatus 10, a plasma pretreatment step is performed in which the substrate 1 is conveyed along the aforementioned conveying path of the substrate 1 while the surface of the substrate 1 is subjected to plasma pretreatment using the plasma pretreatment unit 11B, and a film-forming step is performed in which the vapor-deposited film is formed on the surface of the substrate 1 using the film-forming unit 11C. The conveying speed of the substrate 1 is preferably 200 m / min or more, more preferably 400 m / min or more and 1000 m / min or less.

[0178] (Plasma pretreatment process)

[0179] The plasma pretreatment process is performed, for example, by the following method. First, plasma feed gas is supplied into the plasma pretreatment chamber 12B. Next, the aforementioned alternating voltage is applied between the pretreatment roller 20 and the electrode section 21. When applying the alternating voltage, power control or impedance control can be performed.

[0180] For the plasma feed gas supplied in the pretreatment, oxygen alone or a mixture of oxygen and an inert gas is supplied from the gas storage unit while the gas flow rate is measured by a flow controller. Examples of inert gases include one or more gases selected from argon, helium, and nitrogen.

[0181] As for plasma treatment, the mixing ratio of oxygen to the inert gas, the oxygen / inert gas ratio is preferably 6 / 1 to 1 / 1, more preferably 5 / 2 to 3 / 2.5.

[0182] By setting the mixing ratio to 6 / 1 to 1 / 1, the energy for forming the aluminum vapor-deposited film on the resin substrate is increased. Furthermore, by setting it to 5 / 2 to 3 / 2, the oxidation degree of the aluminum vapor-deposited film can be improved, thereby ensuring the adhesion between the aluminum vapor-deposited film and the substrate.

[0183] By applying an alternating voltage, plasma is generated simultaneously with glow discharge, and the plasma P is concentrated between the pretreatment roller 20 and the magnetic field forming section 23. In this way, plasma P can be supplied between the pretreatment roller 20 and the magnetic field forming section 23. With this plasma P, plasma (ion) pretreatment can be performed on the surface of the substrate 1.

[0184] The plasma intensity per unit area in plasma processing is 50 W·sec / m. 2 Above and 8000 W·sec / m 2 Below, at 50 W·sec / m2 The effect of plasma pretreatment is not visible below this point. Additionally, at 8000 W·sec / m 2 During the above processes, there is a tendency for the resin substrate to deteriorate due to plasma, such as consumption, breakage, discoloration, and firing. In particular, for the formation of the alumina layer, the plasma intensity used as a plasma pretreatment is preferably 100 W·sec / m. 2 Above 1000W·sec / m 2 the following.

[0185] When an AC voltage is applied between the pretreatment roller 20 and the electrode section 21, the gas pressure inside the plasma pretreatment chamber 12B is reduced to below atmospheric pressure by the depressurization chamber 12. In this case, the gas pressure inside the plasma pretreatment chamber 12B can be adjusted, for example, so that a glow discharge can be generated between the pretreatment roller 20 and the electrode section 21 by applying an AC voltage. The pressure inside the plasma pretreatment chamber 12B when an AC voltage is applied between the pretreatment roller 20 and the electrode section 21 can be set and maintained at approximately 0.1 Pa or more and 100 Pa or less, and is particularly preferably 1 Pa or more and 20 Pa or less.

[0186] The function of the magnetic field forming unit 23 in the plasma pretreatment process will be explained. The magnetic field forming unit 23 forms a magnetic field between the pretreatment roller 20 and the electrode unit 21. The magnetic field functions to capture and accelerate electrons present between the pretreatment roller 20 and the electrode unit 21. Therefore, in the region where the magnetic field is formed, the collision frequency between electrons and the plasma feed gas can be increased, the plasma density can be increased, and the plasma can be localized, thereby improving the efficiency of plasma pretreatment.

[0187] (First film-forming process)

[0188] In the film-forming process, a film-forming mechanism 11C is used to form a film on the surface of the substrate 1. As an example of the film-forming process, a film is formed on the surface of the substrate 1 using... Figure 6 The film-forming mechanism 11C with evaporation mechanism 24 shown here will be used to describe the formation of an aluminum oxide vapor deposition film.

[0189] First, an aluminum-containing vapor deposition material is supplied to the boat 24b of the evaporation unit 24 in an orientation opposite to the film-forming roller 25. Aluminum metal wire can be used as the vapor deposition material. Figure 6 In the example shown, aluminum wire is continuously fed into boat 24b by vapor deposition material supply unit 61, thereby supplying vapor deposition material to boat 24b.

[0190] The aluminum is evaporated inside boat 24b by heating. Figure 6For convenience, the evaporated aluminum vapor 63 is illustrated in the diagram. The oxygen used to oxidize the aluminum can be elemental oxygen or a mixture of oxygen and an inert gas such as argon. By controlling the amount of oxygen, both barrier properties and transparency can be achieved. The pressure at this point is preferably 0.05 Pa or higher and 8.00 Pa or lower.

[0191] It should be noted that a cold trap (not shown) may also be provided within the film-forming mechanism 11C. The cold trap is a device that removes moisture from the film-forming mechanism 11C through cooling. Generally, reducing the moisture content in the vapor deposition chamber is fundamental during the film-forming process; therefore, operating the cold trap to reduce moisture content is a basic configuration in vapor deposition machines used in production. However, according to the inventors' understanding, it has been determined that the moisture content in the polyester substrate is also reduced due to the operation of the cold trap, thereby reducing the effect of hydroxyl group introduction achieved by the curing treatment after the film-forming process described later.

[0192] Therefore, in manufacturing the barrier film of the present invention, in order to prevent the cold trap from operating due to the residual moisture contained in the polyester substrate, that is, by combining a plasma pretreatment before film formation that can effectively remove moisture only from the surface of the polyester substrate, a film formation process that prevents the cold trap from operating, and a curing treatment after film formation, it is successfully achieved that the curing treatment after film formation is effective, and at the same time, the barrier properties and transparency are improved.

[0193] (Plasma-assisted deposition)

[0194] The plasma-assisted process during the following vapor deposition is not necessary in the manufacture of the barrier film of the present invention.

[0195] The method of supplying plasma between the surface of the substrate 1 and the evaporation unit 24 via the plasma supply mechanism 50, i.e., plasma-assisted vapor deposition, will be described. Plasma is generated within the cavity of the hollow cathode 51 of the plasma supply mechanism 50. Then, a discharge is generated between the hollow cathode 51 and the opposing anode, drawing the plasma within the cavity of the hollow cathode 51 out to the area between the surface of the substrate 1 and the evaporation unit 24.

[0196] The discharge generated between the hollow cathode 51 and the opposing anode is called an arc discharge. An arc discharge, for example, refers to a discharge with a current value of 10A or more.

[0197] While supplying plasma between the surface of the substrate 1 and the evaporation mechanism 24, aluminum is evaporated, thereby supplying plasma to the aluminum vapor 63. By supplying plasma, the reaction or combination of aluminum vapor 63 with oxygen can be promoted. As a result, aluminum vapor 63 can be oxidized before it reaches the surface of the substrate 1. By adhering the evaporated and oxidized aluminum to the substrate 1, an aluminum oxide film can be deposited on the surface of the substrate 1, thus creating a barrier film.

[0198] The plasma feed gas supplied by the plasma supply unit 50 is preferably argon.

[0199] (Curing treatment after film formation)

[0200] The barrier film winding after the above film-forming process is subjected to a curing treatment (heating treatment) for a specified time. As a result, hydroxyl groups are introduced into the alumina vapor-deposited film, forming a vapor-deposited film with excellent barrier properties, especially with excellent water vapor barrier properties.

[0201] The aging temperature is preferably 50°C or higher and 60°C or lower. The minimum aging time is 24 hours (1 day) or higher, more preferably 48 hours (2 days) or higher. The maximum aging time is 144 hours (6 days) or lower, more preferably 96 hours (4 days) or lower. It should be noted that there is no particular limitation on the aging humidity; it does not need to be high humidity. A relative humidity of 40% or higher and 70% or lower is generally sufficient.

[0202] (Coating formation process)

[0203] (First coating layer formation process)

[0204] In the first coating layer forming process (hereinafter also referred to as the coating layer forming process), the first coating layer can be manufactured by the following method. First, a barrier coating agent is prepared by mixing the above-mentioned metal alkoxide, water-soluble polymer, silane coupling agent added as needed, sol-gel catalyst, acid, and organic solvents such as water, methanol, ethanol, and isopropanol as solvents. Next, the above-mentioned barrier coating agent is coated on the alumina vapor-deposited film by conventional methods and dried. Through this drying process, the silanol generated by the above-mentioned metal alkoxide and silane coupling agent is further polycondensed to form a coating film. As the above-mentioned drying conditions, a heat treatment is performed for 3 seconds to 10 minutes at a temperature of 20 to 200°C and below the melting point of the plastic substrate, preferably in the range of 50 to 180°C. As a result, a coating layer based on the above-mentioned barrier coating agent can be formed on the alumina vapor-deposited film. It should be noted that the above-mentioned coating operation can also be repeated on the first coating film to form multiple coating films consisting of two or more layers.

[0205] The barrier film winding that has undergone the above-mentioned coating formation process is subjected to a curing treatment (heating treatment) for a specified time. By appropriately condensing the coating, a barrier film with barrier properties that are not easily reduced can be obtained.

[0206] The lower limit of the curing temperature after the coating formation process is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 100°C or lower, more preferably 70°C or lower. The lower limit of the curing time is 24 hours (1 day) or higher, more preferably 48 hours (2 days) or higher. The upper limit is 144 hours (6 days) or lower, more preferably 96 hours (4 days) or lower. It should be noted that the curing humidity is not particularly limited and does not need to be high; a relative humidity of 40% or higher and 70% or lower is generally sufficient.

[0207] (Second film-forming process)

[0208] An aluminum oxide vapor-deposited film is further formed on the first coating layer to form... Figure 1 The second vapor-deposited film 132b is formed under the same conditions as the plasma pretreatment process, the first film formation process, and the curing process described above. The first vapor-deposited film and the second vapor-deposited film can be formed under the same conditions or under different conditions.

[0209] (Second coating layer formation process)

[0210] Furthermore, a further film is formed on the alumina vapor-deposited film deposited through the second film-forming process described above. Figure 1 The second coating layer 132a is formed. The film can be formed under the same conditions as the first coating layer forming process described above. The first coating layer and the second coating layer can be formed under the same conditions or under different conditions.

[0211] <<Layered Structures>>>

[0212] Next, the laminate of the present invention using a barrier film will be described. Figure 7 The laminate 100B is shown to use Figure 1 An example of a laminated barrier membrane. (And...) Figure 1 Compared to the barrier film 100A, a rough layer 160 is formed on the surface of the substrate 120 opposite to the first vapor-deposited film 131b. The laminate of the present invention is suitable for use in wavelength conversion sheets, etc.

[0213] Figure 8 In the laminate 100C, the substrate 120 of the barrier film 100A is laminated with the support 150 through an adhesive layer or bonding agent layer 140 (hereinafter referred to as adhesive bonding layer 140). As for the rough layer 160, a rough layer 160 is formed on the surface of the support 150 opposite to the barrier film 100A.

[0214] Figure 9 In the laminate 100D, the barrier layer 130 of the barrier film 100A is laminated with the support 150 through an adhesive layer or bonding agent layer 140 (hereinafter referred to as the adhesive bonding layer 140). That is, the barrier film 100A is configured in reverse. Figure 8 different.

[0215] Thus, the roughening layer 160 can be formed on the side of the substrate 120 opposite to the first alumina vapor-deposited film 131b. Specifically, it can be formed on one surface of the substrate 120. In this case, it includes not only forming the roughening layer directly on the surface, but also forming the roughening layer through a primer layer or the like. Alternatively, it can be formed on one side of the substrate 120 through other supports 150 or the like.

[0216] The following describes each layer that constitutes laminates 100B, 100C, and 100D.

[0217] [Rough layer]

[0218] The roughening layer 160 is a layer with an uneven surface, such as an adhesion prevention layer or a light diffusion layer. The roughening layer can effectively suppress the adhesion between the wavelength conversion sheet and the light guide plate 330, the diffuser plate 370, etc., or diffuse the light incident on the wavelength conversion sheet and the emitted light, thereby further improving the optical wavelength conversion efficiency.

[0219] exist Figures 7-9 In this context, the rough layer 160 is a layer comprising resin 161 and particles 162. The surface of the rough layer 160 contains particles, at least a portion of which protrudes to form an uneven surface shape. Here, the term "rough layer with at least a portion of particles protruding" means that the surface of the rough layer is not a uniformly flat shape, but rather a state in which the particles form undulations on the surface of the rough layer and / or at least a portion of the particles are exposed from the surface of the rough layer.

[0220] It should be noted that as long as an uneven shape can be formed on the surface, the rough layer can also be without particles.

[0221] <Adhesive Prevention Layer>

[0222] When the rough layer 160 is an adhesion prevention layer, it can effectively suppress the adhesion of the wavelength conversion sheet to the light guide plate 330, the diffuser plate 370, etc., and can also prevent damage to the convex part of the prism sheet 340 caused by friction.

[0223] Furthermore, by providing an anti-adhesion layer on the barrier film, it is possible to prevent the barrier film or wavelength conversion sheet from sticking together when it is rolled into a roll. Therefore, the barrier film or wavelength conversion sheet can be made into a roll for storage or transportation.

[0224] In particular, when transporting a display device in which a light guide plate is positioned on the surface of the wavelength conversion sheet's adhesive resist layer, the adhesive resist layer may sometimes rub against the light guide plate, causing damage to the adhesive resist layer. Alternatively, the adhesive resist layer may rub against the light guide plate, causing fragments to be generated from the adhesive resist layer, which can damage both the adhesive resist layer and the light guide plate. Such damage to the adhesive resist layer and the light guide plate can result in cosmetic defects in the display device.

[0225] Therefore, in the laminate of this embodiment, the proportion of particles protruding from the adhesive prevention layer whose diameter is more than twice the thickness of the adhesive prevention layer—that is, the proportion of particles whose diameter is visually perceived as more than twice the thickness of the adhesive prevention layer when viewed from above—is preferably 20% to 80% of the total number of particles protruding from the adhesive prevention layer. If the proportion of these particles is less than 20%, the damage resistance of the roughening layer deteriorates, and sometimes it is not possible to effectively suppress the adhesion of the wavelength conversion sheet and the light guide plate, etc. Furthermore, if the proportion of these particles exceeds 80%, the damage resistance of the roughening layer sometimes deteriorates. Here, the thickness of the adhesive prevention layer refers to the thickness of the resin 161 layer constituting the adhesive prevention layer.

[0226] Furthermore, in this embodiment, the laminate is preferably bonded to prevent the layer from being viewed from below at a depth of 1 mm. 2 The total number of particles within the square is over 1800. Therefore, it can sometimes effectively suppress the adhesion of wavelength conversion sheets and light guide plates, improving the damage resistance of the adhesion-preventing layer. It should be noted that the adhesion-preventing layer is 1mm thick when viewed from above. 2 There is no particular upper limit to the total number of particles within the square, but it is preferably 20,000 or less, and more preferably 15,000 or less. Here, the adhesive-resistant layer is 1 mm in top view. 2 The total number of particles within the square refers to the total number of particles visible on the surface of the adhesive layer when viewed from the surface side, excluding the number of particles that are buried in the adhesive layer and cannot be visually identified from the surface.

[0227] The proportion of particles whose diameter is visually perceived to be more than twice that of the target particle can be determined, for example, by observing the surface of a specified area (e.g., 258 × 260 μm) of the anti-adhesion layer from above using a microscope (e.g., a laser microscope, scanning electron microscope) or a microscope. It should be noted that the measurement screen is adjusted as needed to make the planar portion horizontal. Then, an image is acquired, and the brightness is adjusted to allow for the extraction of the particle portion. The particles and their diameters are calculated based on this brightness-adjusted image. Then, based on the thickness of the anti-adhesion layer calculated from the coating amount, the proportion of particles whose diameter is visually perceived to be more than twice that of the thickness of the anti-adhesion layer is calculated.

[0228] 1mm of adhesive backing layer as seen from above 2 The total number of particles within a square can be calculated by converting the total number of particles in the specified area (e.g., 258 × 260 μm) to 1 × 1 mm.

[0229] It should be noted that the 1mm diameter viewed from above is used to determine the particle size distribution. 2 The total number of particles within a square can be determined using a microscope, for example, an Olympus laser microscope, namely the OLS4000.

[0230] By using an adhesive-resistant layer with a proportion of particles protruding from the adhesive-resistant layer and a total number of particles of a specified area within the range described above, damage to the adhesive-resistant layer and the light guide plate (diffuser plate) can be effectively suppressed.

[0231] It should be noted that the same applies when an anti-adhesion layer is laminated on the surface of the wavelength conversion sheet opposite to the light guide plate (diffuser plate) side, and the anti-adhesion layer is in contact with the optical film. That is, by having an anti-adhesion layer with a proportion of particles protruding from the anti-adhesion layer and a total number of particles of a specified area within the above-mentioned range, damage to the anti-adhesion layer and the optical film can be effectively suppressed.

[0232] In particular, when the optical film is a prism sheet, the prism is damaged due to the shape of the prism sheet, so it can be said that the optical film is more likely to be damaged than other optical films.

[0233] Therefore, when using a prism sheet as an optical film, by stacking an adhesive layer on the surface of the wavelength conversion sheet opposite to the light guide plate (diffuser plate) side, with the proportion of particles protruding from the adhesive layer and the total number of particles of a specified area set within the range described above, damage to the optical film (prism sheet) can be effectively suppressed.

[0234] In addition, the particle 162 preferably contains particles with a compressive strength of 2.8 kgf / mm². 2 The above-mentioned resin. More preferably, the compressive strength of this resin is 3.0 kgf / mm². 2 The above is further preferred to be 4.0 kgf / mm 2 above. 2.8kgf / mm 2 Examples of resins mentioned above include acrylic resins. The compressive strength of particles 162 is achieved to be 2.8 kgf / mm². 2The above features reduce the likelihood of particles being crushed or cut by foreign objects, and prevent foreign objects from directly damaging the surface of the adhesive layer, thus improving damage resistance. Acrylic resins are polymers containing at least one olefinically unsaturated monomer having a carboxyl or carboxylic acid ester group selected from the group consisting of methacrylic acid, acrylic acid, methacrylates, and acrylates as a monomer component. If the compressive strength of particle 162 is less than 2.8 kgf / mm²... 2 If foreign matter is mixed in, the particles will be crushed or cut, and the foreign matter can easily form scratches on the surface of the adhesive layer, reducing its damage resistance. Therefore, it is not preferred.

[0235] The thickness of the anti-adhesion layer is not particularly limited as long as it achieves the effect of the present invention. For example, it is preferably 1.0 μm or more and 50.0 μm or less, more preferably 1.5 μm or more and 10.0 μm or less. It should be noted that the thickness of the anti-adhesion layer refers to the thickness of the resin portion other than the particles in the anti-adhesion layer, excluding the thickness of the portion of the particles exposed on the resin. The thickness of the anti-adhesion layer can be measured, for example, by observing the cross-section using a scanning electron microscope or the like.

[0236] To ensure the thickness of the adhesive resist layer falls within the aforementioned range, the coating weight of the adhesive resist layer after drying is preferably set to 1.0 g / m². 2 Above and 3.6g / m 2 The following applies. If the coating thickness is within this range, it can suppress particle embedding in the adhesive layer and prevent impurities from entering between the adhesive layer and the light guide plate. If the coating weight of the adhesive layer after drying is less than 1.0 g / m²... 2 If the adhesive layer becomes thinner relative to the particles, impurities can enter between the adhesive layer and the light guide plate (diffuser plate), potentially damaging the roughening layer and the light guide plate (diffuser plate). If the coating weight of the adhesive layer after drying exceeds 3.6 g / m²... 2 If particles are embedded in the adhesive-resistant layer, it may impair the function of the adhesive-resistant layer.

[0237] The haze value of the anti-adhesion layer is preferably 10% or more and 35% or less, and more preferably 10% or more and 25% or less. With a haze value of 10% or more, the number of particles contained in the anti-adhesion layer becomes sufficient, improving the damage resistance of the anti-adhesion layer and effectively suppressing adhesion between the anti-adhesion layer and the light guide plate, etc. With a haze value of 35% or less, the damage resistance of the anti-adhesion layer is improved, enhancing its functionality as a display device.

[0238] If the haze value of the anti-adhesion layer is less than 10%, the number of particles contained in the anti-adhesion layer is insufficient, thus reducing its damage resistance and sometimes failing to effectively prevent adhesion between the anti-adhesion layer and the light guide plate. If the haze value of the anti-adhesion layer exceeds 35%, its damage resistance also decreases, resulting in an excessively high haze value and reduced functionality as a display device. It should be noted that the haze value can be measured using a haze meter according to JIS K7136. The haze value of the roughened layer (anti-adhesion layer) can be calculated as follows: measure the haze value after the anti-adhesion layer is formed on a substrate such as PET film, and calculate the difference between the haze value of the anti-adhesion layer and the haze value of the PET film alone.

[0239] (resin)

[0240] The resin 161 contained in the adhesive-resistant layer is not particularly limited as long as it can achieve the purpose of the adhesive-resistant layer. Examples include acrylic resins, epoxy resins, polyurethane resins, polyester resins, polyester acrylate resins, polyurethane acrylate resins, urethane acrylate resins, and epoxy acrylate resins. Among these, acrylic resins are preferred from the viewpoint of having hardness.

[0241] When acrylic resin is included, the proportion of acrylic resin is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, relative to 100 parts by mass of resin contained in the adhesive resist layer.

[0242] (Particles)

[0243] The particles are formed into spherical shapes to inhibit adhesion between the light guide plate and the wavelength conversion sheet. There are no particular limitations on the type of particles; examples include acrylic resins, polystyrene resins, and polyethylene resins. Preferably, the particles contain a compressive strength of 2.8 kgf / mm² as measured according to JIS A 9511. 2 Examples of the resins mentioned above include acrylic resins and polystyrene resins.

[0244] In addition to the aforementioned acrylic and polystyrene resins, granules can also be made of silica microparticles, melamine, nylon, benzoguanamine microparticles, etc. It should be noted that the hardness of these materials, from highest to lowest, is as follows: silica microparticles, melamine, nylon, polystyrene resin, acrylic resin, and polyethylene resin.

[0245] The average particle size is preferably 1 μm or more and 50 μm or less, more preferably 1.5 μm or more and 10 μm or less. By making the average particle size 1 μm or more, at least a portion of the particles are exposed from the surface of the adhesive prevention layer, which can more effectively suppress the adhesion between the adhesive prevention layer and the light guide plate 330, and can improve the damage resistance of the adhesive prevention layer. By making the average particle size 50 μm or less, the functional reduction of the adhesive prevention layer caused by particles detaching from the adhesive prevention layer and the damage to the adhesive prevention layer caused by detached particles can be suppressed.

[0246] The average particle size is obtained, for example, as the D50 value in particle size distribution determination based on JIS Z8820 and Z8822. The average particle size can be determined, for example, by dynamic light scattering, laser diffraction scattering, or SEM / TEM observation.

[0247] The particle content is preferably 5% by mass or more and 50% by mass or less relative to the total amount of the adhesive-resistant layer, more preferably 10% by mass or more and 40% by mass or less. A content of 5% by mass or more effectively prevents the adhesive-resistant layer from adhering to other components such as the light guide plate. A content of 50% by mass or less ensures a sufficient amount of resin for forming the film-forming adhesive-resistant layer, thus improving the film-forming properties of the adhesive-resistant layer.

[0248] The content of particles protruding from the adhesive layer relative to the total amount of the adhesive layer is preferably 2% to 25% by mass, more preferably 5% to 20% by mass.

[0249] The refractive index difference between the refractive index of the particles and the refractive index of the resin contained in the adhesive prevention layer is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less.

[0250] (additive)

[0251] In the adhesive prevention layer of this embodiment, stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, and other additives may be added as needed.

[0252] <Light Diffuse Layer>

[0253] When the roughened layer is a light-diffusing layer, the light incident on the wavelength conversion plate and the emitted light can be diffused, further improving the wavelength conversion efficiency. It should be noted that as long as an uneven shape can be formed on the surface, the light-diffusing layer can also be without particles.

[0254] In cases where the light-diffusing layer contains resin and particles, the same material as the resin and particles contained in the adhesive-resistant layer can be used, so a description is omitted here.

[0255] [Support]

[0256] In the laminated body of this embodiment, such as Figure 8 , 9 As shown, a support 150 may be disposed between the barrier film and the roughened layer 160. The support 150 is a layer mainly comprising resin, and the resin may be the same as the resin described in the substrate 120.

[0257] exist Figure 8 , 9 In the laminated structure, the thickness of the support 150 is preferably more than 25 μm and less than 200 μm, more preferably more than 38 μm and less than 175 μm, and even more preferably more than 50 μm and less than 150 μm. By making the thickness of the support 150 more than 25 μm and less than 200 μm, the flexibility of the wavelength conversion sheet is improved, and the processability when combined with the backlight source of the display device is improved.

[0258] To prevent light from the backlight source from being blocked, the support preferably has a high total light transmittance as measured by JIS K 7361. Specifically, the total light transmittance of the support as measured by JIS K 7361 is preferably 85% or more, and more preferably 90% or more.

[0259] [Adhesive Layer]

[0260] like Figure 8 , 9 As shown, in this embodiment, an adhesive layer 140 may be disposed between the barrier film and the support 150. The adhesive layer refers to an adhesive layer or bonding agent layer. Examples of adhesives constituting the adhesive layer 140 include polyvinyl acetate adhesives, homopolymers of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., or copolymers thereof with methyl methacrylate, acrylonitrile, styrene, etc., polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives consisting of copolymers of ethylene with monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives consisting of urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth)acrylic adhesives, rubber adhesives consisting of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, inorganic adhesives consisting of alkali metal silicates, low melting point glass, etc.

[0261] As an adhesive constituting the bonding layer, there are no particular limitations as long as it has the desired adhesive strength. Examples include acrylic, urethane, rubber, and silicone adhesives. Among these, acrylic adhesives with excellent heat resistance and other durability, transparency, and low cost are preferred. Examples of acrylic adhesives include acrylate copolymers formed by copolymerizing acrylates with other monomers. Examples of acrylates include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, hydroxyethyl acrylate, propylene glycol acrylate, acrylamide, and glycidyl acrylate. These can be used alone or in combination of two or more.

[0262] Other monomers mentioned above include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, propylene glycol acrylate, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and n-ethylhexyl methacrylate, which can be used alone or in combination of two or more.

[0263] The composition system of the adhesive layer can be any combination form such as water-based, solution-based, emulsion-based, or dispersion-based. In addition, its properties can be any form such as film / sheet, powder, or solid. Furthermore, the bonding mechanism can be any form such as chemical reaction, solvent evaporation, thermal melting, or hot pressing.

[0264] The adhesive layer can be applied by methods such as roller coating, gravure coating, doctor blade coating, dip coating, spraying, other coating methods, or printing. The preferred coating amount is 0.1 g / m³. 2 Above and 10g / m 2 The following (dry state).

[0265] It should be noted that, instead of the adhesive layer formed by the aforementioned adhesive, a resin layer formed by laminating a thermosetting resin or a thermoplastic resin containing a crosslinking agent can be used. Furthermore, the following method can also be used: melting a thermoplastic resin such as EVA, ionomer, polyvinyl butyral (PVB), or polyethylene-based resin, extruding and laminating the molten thermoplastic resin, and bonding by extrusion lamination.

[0266] Wavelength Conversion Plate

[0267] Figure 10 , 11 This is a cross-sectional view illustrating an example of the wavelength conversion plate of the present invention. Specifically, Figure 10In the wavelength conversion chip 200B, a phosphor layer 110 containing a phosphor 112 and a sealing resin 111 is laminated with a laminate 100B on both surfaces of the phosphor layer 110, separated by an adhesive layer or bonding agent layer 170 (hereinafter referred to as the adhesive bonding layer 170). Additionally, Figure 11 In the wavelength conversion sheet 200D, a phosphor layer 110 containing phosphor 112 and sealing resin 111 is laminated with a laminate 100D across the two surfaces of the phosphor layer 110, separated by an adhesive layer 170. By laminating the laminate of the present invention across the two surfaces of the phosphor layer 110, barrier properties are imparted to the phosphor layer. It should be noted that, in this specification, the two surfaces of the phosphor layer refer to the two surface sides opposite to the side where the light source is disposed (light incident surface side) and the side where the backlight source is disposed (light emitting surface side) when the wavelength conversion sheet is used as a backlight source.

[0268] Figure 10 , 11 The wavelength conversion sheet has roughened layers disposed on the two outermost layers of the laminate, but it is not limited to this. It may also be configured such that the laminate of the present invention is laminated only on the surfaces of the light guide plate and the diffuser plate (not shown). Alternatively, it may be configured such that the laminate of the present invention is laminated only on the surface of the light-emitting side (visual recognition side) (not shown). Alternatively, it may be possible to omit the roughened layers and instead... Figure 1 Such a barrier film is stacked alone on at least one side of the phosphor layer.

[0269] [Fluorescent layer]

[0270] The phosphor layer 110 is a layer used to adjust the emission wavelength of light emitted from the backlight source. The phosphor layer 110 contains one or more phosphors composed of quantum dots.

[0271] The quantum dots forming phosphor 112 are semiconductor particles of a specified size exhibiting a quantum confinement effect. When a quantum dot absorbs light from an excitation source and reaches an excited state, it releases energy corresponding to its band gap. By adjusting the size of the quantum dot or its composition, the band gap can be adjusted, allowing for the acquisition of energy at various wavelengths. In particular, quantum dots can produce strong fluorescence in a narrow wavelength range. Therefore, the display device can be illuminated with light of the three primary colors with excellent color purity, thus achieving excellent color reproduction.

[0272] There are no particular limitations on the phosphor, and examples include particles comprising at least one of the group consisting of group II-VI compounds, group III-V compounds, group IV-VI compounds, and group IV compounds. From the viewpoint of luminescence efficiency, the phosphor preferably comprises a compound containing at least one of Cd and In.

[0273] Specific examples of II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, etc.

[0274] Specific examples of III-V group compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, etc.

[0275] Specific examples of group IV-VI compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, etc.

[0276] Specific examples of group IV compounds include Si, Ge, SiC, and SiGe.

[0277] As quantum dot phosphors, those with a core-shell structure are preferred. By making the band gap of the compound constituting the shell wider than that of the compound constituting the core, the quantum efficiency of the phosphor can be further improved. Examples of core-shell combinations (core / shell) include CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, and CdTe / ZnS.

[0278] Furthermore, as a phosphor, it can be a quantum dot phosphor with a so-called core-shell structure, which has a multi-layered shell. By stacking one or more narrow-bandgap shells on a wide-bandgap core, and then further stacking wide-bandgap shells on top of those shells, the quantum efficiency of the phosphor can be further improved.

[0279] The phosphor layer 110 can be formed by laminating a sealing resin 111 containing phosphor 112. For example, it can be formed by coating a mixture containing phosphor 112 and sealing resin 111 onto the surface of a substrate layer and then curing it. Examples of sealing resin 111 include photopolymer resins of acrylic resins such as polyester (meth)acrylate, urethane (meth)acrylate, polyester-urethane (meth)acrylate, polyether (meth)acrylate, polyol (meth)acrylate, melamine (meth)acrylate, isocyanurate (meth)acrylate, epoxy (meth)acrylate, (meth)acrylate resin, etc.; thermosetting resins such as phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, polyester resin, silicone resin, polyurethane resin, etc.; or thermoplastic resins such as EVA, ionomer, polyvinyl butyral (PVB), polyethylene resin, etc., containing crosslinking agents. From the perspective of ensuring adhesion between the phosphor layer and the substrate layer, it is preferable to use at least one resin selected from the group consisting of acrylic resins, epoxy resins, urethane resins, and polyester resins. Furthermore, these resins can be used individually or in combination. Additionally, an adhesive layer can be formed to improve adhesion.

[0280] [Adhesive Layer]

[0281] like Figure 3 As shown, in this embodiment, an adhesive layer 170 can be disposed between the laminate and the phosphor layer 110. The adhesive layer 170 can be the same adhesive described in the adhesive layer 140, therefore its description is omitted here.

[0282] <Manufacturing Method of Wavelength Conversion Plate>

[0283] For example, an adhesive layer 170 is formed on the surface of the coating layer 130a side of two laminates 100B. A mixture (ink) containing phosphor 110 and sealant 111 is coated on the surface of the adhesive layer of either laminate 100B. Then, the mixture (ink) is brought into contact with the surface of the adhesive layer 170 of the other laminate 100B to cure, thereby enabling the fabrication of a wavelength conversion sheet. Figure 10 The wavelength conversion chip 200B shown is shown. Figure 11The wavelength conversion sheet 200D shown can also be manufactured in the same way. It should be noted that, instead of forming the adhesive layer 170, a mixture (ink) containing phosphor 110 and sealant resin 111 can be directly coated on the surface of the laminate.

[0284] <<Display Devices>>>

[0285] use Figures 12-14 A display device equipped with the aforementioned wavelength conversion chip will be described.

[0286] Figure 12 This is a perspective view schematically illustrating the configuration of a surface-mount display device according to one embodiment of the present invention.

[0287] Figure 13 yes Figure 12 The diagram shows a cross-sectional view of the display device. Figure 13 The cross-sectional view shown is a cross-sectional view at a section that is parallel to the stacked direction of the wavelength conversion sheet 200B (200D) constituting the display device and parallel to the direction in which the light source section and the light guide plate are arranged (the direction in which the light emitted from the light source section travels).

[0288] Figure 14 This is a cross-sectional view schematically illustrating the configuration of a direct-lit display device according to one embodiment of the present invention.

[0289] Figure 12 and Figure 13 The display device 300A shown comprises, in sequence, an LCD panel 360, a polarizing light selective reflector 350, a prism sheet 340, a wavelength conversion sheet 200B (200D), a light guide plate 330, and a reflector 320. Furthermore, in the display device 300A, a light source unit 310 is arranged along at least one end face (side face) of the light guide plate 330. The backlight component of the present invention is constituted by the light source unit 310, the light guide plate 330 or the diffuser plate 370 described later, and the wavelength conversion sheet 200B (200D).

[0290] The LCD panel 360 is formed by a transmissive liquid crystal display element, which is a transmissive display section that forms image information on its display surface.

[0291] The polarizing selective reflector 350 is a sheet-like component that allows light of a specific polarization state to pass through and reflects light of other polarization states. For example, the DBEF series (manufactured by Sumitomo 3M Corporation) can be used. When using such a polarizing selective reflector 350, from the perspective of improving brightness and light utilization efficiency, it is preferable to arrange the polarizing selective reflector 350 so that its transmission axis is parallel to the transmission axis of a polarizer (not shown) located on the light incident side of the LCD panel 360.

[0292] The prism sheet 340 is an optical sheet that deflects (converges) the direction of light emitted from the upper surface of the light guide plate 330 toward the front direction (the normal direction of the panel surface of the LCD panel).

[0293] The light guide plate 330 is a generally flat plate component that guides light. The light emitted from the light source 310 enters from one end face of the flat plate and is guided by total internal reflection on the upper and lower surfaces of the light guide plate 330, and is appropriately emitted from the upper surface of the light guide plate 330 toward the prism sheet 340.

[0294] The reflector 320 is a sheet-like component capable of reflecting light. It is disposed on the side of the light guide plate 330 opposite to the prism sheet 340 and has the function of reflecting light emitted from the lower surface of the light guide plate 330 back into the light guide plate 330, thereby improving the utilization efficiency of light emitted from the light source 310. From the perspective of improving light utilization efficiency, the reflector 320 preferably has primarily specular reflectivity (positive reflectivity). The reflector 320 can be, for example, a sheet-like component with at least the reflective surface (the surface on the side of the light guide plate 330) made of a material with high reflectivity such as metal, or a sheet-like component containing a thin film (e.g., a metal thin film) made of a material with high reflectivity as a surface layer. It should be noted that, not limited to these, the reflector 320 can also be made, for example, a sheet-like component made of white resin that primarily has diffuse reflectivity and high reflectivity.

[0295] The light source unit 310 is a light source that emits light to illuminate the LCD panel 360. From the perspective of uniformly incident light onto one end face of the light guide plate 330, the light source unit 310 is formed, for example, by arranging a plurality of point light sources at predetermined intervals. These point light sources may be, for example, LED (light-emitting diode) light sources or organic EL (electroluminescent) light sources.

[0296] Figure 12 and Figure 13 The display device 300A is a surface-mount display device, in which light emanating from a backlight source, i.e., a light source unit 310, disposed on the end face of a light guide plate 330 is incident on the light guide plate 330 and guided within the light guide plate, causing light emitted from the upper surface of the light guide plate 330 to be sequentially transmitted through a wavelength conversion sheet 200B (200D), a prism sheet 340, a polarizing light selective reflector 350, and an LCD panel 360. It should be noted that a reflector 320 is provided as needed.

[0297] In the so-called surface-mount display device 300A, the wavelength conversion sheet 200B (200D) is configured to contact the light guide plate 330. Here, in the case of conventional wavelength conversion sheets using a barrier film or wavelength conversion film, the barrier film adheres to the light guide plate, becoming a major cause of significant degradation in the display characteristics of the liquid crystal display device. Furthermore, during handling of the display device, friction between the wavelength conversion sheet and the light guide plate causes damage to the wavelength conversion sheet and / or the light guide plate, also becoming a major cause of degradation in the display characteristics of the display device.

[0298] However, for display devices with a light guide plate on the rough layer of the wavelength conversion sheet, even surface-mount display devices can effectively prevent the barrier film from adhering to the light guide plate, and at the same time prevent damage to the wavelength conversion sheet and / or the light guide plate.

[0299] In addition, conventional light guide plates can be used, but in order to more effectively prevent the barrier film from sticking to the light guide plate, the surface of the light guide plate that contacts the barrier film can be made wedge-shaped.

[0300] use Figure 14 Other display devices equipped with the aforementioned wavelength conversion chip will be described. Figure 14 The display device 300B is a so-called direct-lit display device, wherein a light source 380 is arranged on the back side of the diffuser 370, and a wavelength conversion plate 200B (200D) is arranged on the side of the diffuser 370 opposite to the light source 380, so that light irradiated from the light source 380 is irradiated onto the wavelength conversion plate 200B (200D) through the diffuser 370.

[0301] In this embodiment, on the side of the wavelength conversion plate 200B (200D) opposite to the diffuser plate 370, as described above... Figure 9 and Figure 10 The display device 300A shown also sequentially stacks a prism sheet 340, a polarizing light selective reflector 350, and an LCD panel 360. Furthermore, a reflector 320 is provided on the side of the light source unit 380 opposite to the diffuser plate 370, so that light emitted from the light source unit 380 that did not incident on the diffuser plate 370 and was reflected back towards the diffuser plate 370, thereby improving light utilization efficiency. It should be noted that... Figure 11 The light source section 380 shown is formed by arranging multiple point light sources (LEDs) at equal intervals in a grid pattern along the surface of the diffuser plate 370.

[0302] In the so-called direct-lit display device 300B, the wavelength conversion sheet 200B (200D) is configured to contact the diffuser plate 370. By arranging the diffuser plate 370 on the surface of the roughened layer 160 of the wavelength conversion sheet 200B (200D), for the same reasons as in the aforementioned display device 300A, it is possible to effectively prevent the barrier film from adhering to the diffuser plate, and at the same time, to prevent damage to the wavelength conversion sheet and / or the diffuser plate.

[0303] <Manufacturing Method of Display Device>

[0304] The display device can be manufactured by a process of placing a light guide plate or a diffuser plate on the surface of the roughened layer of the wavelength conversion sheet.

[0305] Example

[0306] The present invention will be described in more detail below through examples, but the present invention is not limited thereto in any way described herein. First, barrier films of Examples 1 to 7 and Comparative Examples 1 to 9 were manufactured using the film-forming apparatus 10 and film-forming method described in this embodiment. Pretreatment conditions, vapor deposition conditions, etc. are summarized in Tables 1 and 2.

[0307] (Example 1)

[0308] As substrate 1, a 12μm thick biaxially stretched polyethylene terephthalate film (PET film, trade name: Unitika PET-F) was used. Figure 2 The film-forming apparatus 10 shown performs a plasma pretreatment process and a film-forming process.

[0309] First, in the conditioning process, the roll material is rewound at 25°C and 50%RH, and then stored at 25°C and 50%RH for 3 days to condition the moisture, which is then used as the PET substrate.

[0310] In the pretreatment process, use Figure 2 and Figure 3 The plasma pretreatment unit 11B shown performs plasma pretreatment on the surface of the substrate 1. Specifically, firstly, plasma-generating gas is supplied to the plasma pretreatment chamber 12B using a plasma feed gas supply unit, while the gas pressure inside the plasma pretreatment chamber 12B is adjusted using a depressurization chamber 12. Next, a voltage is applied between the pretreatment roller 20 and the electrode unit 21 to generate plasma, thereby performing plasma pretreatment on the surface of the substrate 1. The conditions for plasma pretreatment are as follows.

[0311] <Preprocessing conditions>

[0312] Substrate conveying speed: 670m / min

[0313] High-frequency power output: 4kW

[0314] High-frequency power supply frequency: 40kHz

[0315] Plasma intensity: 550 W·sec / m 2

[0316] Plasma-forming gases: Oxygen 100 (sccm), Argon 1000 (sccm)

[0317] Magnetic forming unit: 1000 Gauss permanent magnet

[0318] Voltage applied between the pretreatment drum and the plasma supply nozzle: 420V

[0319] Pressure in the pre-processing zone: 2.0 × 10 -1 Pa

[0320] In the film-forming process, using Figure 6 The resistance heating evaporation mechanism 24 shown (denoted as RH in Table 1) forms an aluminum oxide-containing vapor-deposited film 2 by vacuum vapor deposition. Specifically, while supplying aluminum metal wire as a vapor deposition material into the boat 24b, the resistance heating evaporation mechanism 24 heats the vapor deposition material in the boat 24b, causing the aluminum to evaporate and reach the surface of the substrate 1. At the same time, oxygen is supplied, and a vapor-deposited film 2 is formed on the surface of the substrate 1.

[0321] In addition, as a plasma supply mechanism 50, a device with... Figure 6 The hollow cathode 51 and the anode (not shown) are arranged on both sides of the substrate 1 in the width direction, facing the opening of the hollow portion of the hollow cathode 51, as viewed from boat 24b. Plasma feed gas (argon) is supplied to the hollow portion of the hollow cathode 51, causing it to discharge and generate plasma. This plasma is then led out through the opposing anode between the surface of the substrate 1 and the evaporation mechanism 24 for plasma-assisted deposition. The conditions for plasma assistance are: argon gas supply to the hollow cathode is 80 sccm, anode current is 47 A, and anode voltage is 21 V. It should be noted that film formation occurs without the plasma-assisted deposition process following the plasma post-treatment step when the cold trap is not operating.

[0322] A first vapor-deposited film is deposited on substrate 1 using the method described above. The conveyor speed is 670 m / min, and the thickness of the vapor-deposited film is 8.0 nm. The transmittance at 366 nm, measured online after vapor deposition, is used as a baseline for pre-treatment of substrate 1, setting the transmittance of the undeposited state as 100%. Vapor deposition then begins, with oxygen supply controlled by feedback to achieve a transmittance of 99.7%. The pressure during vapor deposition is 1.1 Pa.

[0323] The barrier film windings that have undergone the above film-forming process are then cured at 25°C and 50%RH for 3 days.

[0324] Next, a first coating layer is deposited on the first vapor-deposited film. Polyvinyl alcohol (PVA), a water-soluble polymer with a saponification degree of 99% or higher and a polymerization degree of 2400, is mixed with water and isopropanol in a 95 / 5 ratio to obtain solution A, with a solid content adjusted to 4%. Water, isopropanol, and 1N hydrochloric acid are mixed in a 65 / 34 / 1 ratio to obtain adjusted solution B. Tetraethoxysilane, a metal alkoxide, is prepared as solution C. The liquid obtained by adjusting the ratio of solution B to solution C is solution D, and the liquid obtained by adjusting the ratio of solution A to solution D is a barrier coating. The ratios of solution B to solution C and solution A to solution D are adjusted such that the solid content of the barrier coating mixture is 5%, and the SiO2 equivalent mass of tetraethoxysilane is 2.0 relative to the solid content of PVA. This barrier coating is then used as solution X.

[0325] The barrier coating prepared above is applied to the first vapor-deposited film using a direct gravure method. Then, it is dried at 140°C to form a 200nm thick coating layer. Finally, it is cured at 25°C and 50%RH for 3 days to form the first coating layer. It should be noted that the thickness of the dried film is controlled by changing the gravure printing process.

[0326] Next, under the same conditions as the first vapor-deposited film described above, a second vapor-deposited film is formed on the first coated layer, and the film thickness of the coated layer on the second vapor-deposited film is set to 230 nm. Otherwise, the second coated layer is formed under the same conditions as the first coated layer described above, thereby manufacturing the barrier film of Example 1.

[0327] (Example 2)

[0328] Without plasma assistance, the conveying speed of the film-forming process was set to 600 m / min, the transmittance was set to 94.0, and the pressure was set to 0.30 Pa. Otherwise, the barrier film of Example 2 was manufactured in the same manner as in Example 1.

[0329] (Example 3)

[0330] In the film-forming process, a 12 μm thick biaxially stretched polyethylene terephthalate film (PET film, trade name: Toray Industries P60) was used as substrate 1. An anchoring coating of urethane resin with an acrylate thickness of 200 nm was formed on substrate 1 (denoted as AC in Table 1). In the film-forming process of vapor deposition, EB (electron beam) heating (denoted as EB in Table 1) was used instead of resistance heating. No plasma pretreatment was performed. The film thickness was set to 10.0 nm at a conveying speed of 480 m / min. The oxygen supply was controlled by feedback so that the transmittance at a wavelength of 366 nm measured online after vapor deposition was 88.0%. The pressure during vapor deposition was set to 0.2 Pa. No plasma assistance was performed. Otherwise, the film-forming process and curing treatment were performed in the same manner as in Example 1. It should be noted that the transmittance at a wavelength of 366 nm measured online after vapor deposition was set based on a transmittance of 100% for the substrate 1 and the anchoring coating in the undeposited state.

[0331] In the coating formation process, solution Z was used. When mixing solutions B and C, 15% of 1,3,5-tris(3-trialkoxysilylpropyl)isocyanurate was added relative to the weight of tetraethoxysilane to obtain a coating. The ratio of solution B to solution C and the ratio of solution A to solution D were adjusted such that the mass of tetraethoxysilane converted to SiO2 was 7% and the mass of the SiO2 of tetraethoxysilane was 4.0 relative to the solid content of PVA. The barrier coating thus mixed was used as solution Z, and the film thicknesses were set to 210 nm for the first coating and 210 nm for the second coating. The curing treatment after coating formation was set to 3 days at 55°C and 50%RH. Otherwise, the barrier film of Example 3 was manufactured in the same manner as in Example 1.

[0332] (Example 4)

[0333] In the coating layer formation process, the film thickness was set to 200 nm for the first coating layer and 160 nm for the second coating layer. Otherwise, the barrier film of Example 4 was manufactured in the same manner as in Example 3.

[0334] (Example 5)

[0335] In the humidification process, the film was rewound at 30°C and 60%RH, and then stored at 30°C and 60%RH for 3 days for humidification. Otherwise, the barrier film of Example 5 was manufactured in the same manner as in Example 2.

[0336] (Example 6)

[0337] In the film-forming process, the curing treatment after film formation was set to be carried out at 60°C and 50%RH for 4 days. Otherwise, the barrier film of Example 6 was manufactured in the same manner as in Example 5.

[0338] (Example 7)

[0339] In the film-forming process, the plasma-assisted conditions were set to an anode current of 56A. Otherwise, the barrier film of Example 7 was manufactured in the same manner as in Example 1.

[0340] (Comparative Example 1)

[0341] In the first vapor deposition film formation process, the conveying speed was set to 600 m / min, the film thickness was set to 8.9 nm, the cold trap was operated, and the plasma-assisted conditions were set to an anode current of 155 A and an anode voltage of 20 V. No post-deposition curing treatment was performed. Otherwise, it was the same as in Example 1. Furthermore, a second vapor deposition film was not formed.

[0342] In the first coating layer formation process, solution Y was used. When mixing solutions B and C, 5% glycidoxypropyltrimethoxysilane was added relative to the weight of tetraethoxysilane to form the coating layer. The ratio of solution B to solution C and the ratio of solution A to solution D were adjusted such that the solid content was 5% and the mass of tetraethoxysilane converted to SiO2 was 3.4 relative to the solid content of PVA. This mixed barrier coating was used as solution Y, and the thickness of the first coating layer was adjusted to 300 nm. No second coating layer was formed, thus producing the barrier film of Comparative Example 1.

[0343] (Comparative Example 2)

[0344] In the film-forming process, the curing treatment after film formation was set to be carried out at 50°C and 50%RH for 2 days. Otherwise, the barrier film of Comparative Example 2 was manufactured in the same manner as Comparative Example 1.

[0345] (Comparative Example 3)

[0346] In the film-forming process, the curing treatment after film formation was set to be carried out at 55°C and 50%RH for 3 days. Otherwise, the barrier film of Comparative Example 3 was manufactured in the same manner as Comparative Example 1.

[0347] (Comparative Example 4)

[0348] In the film-forming process, no second vapor-deposited film was formed; in the coating layer formation process, no second coating layer was formed. Otherwise, the barrier film of Comparative Example 4 was manufactured in the same manner as in Example 2.

[0349] (Comparative Example 5)

[0350] In the first vapor deposition film formation process, the EB heating method (denoted as EB in Table 1) was used instead of the resistance heating method, so that the light transmittance was 88.0% and the pressure was 0.2 Pa. Otherwise, the process was carried out in the same way as Comparative Example 4, and the barrier film of Comparative Example 5 was manufactured.

[0351] (Comparative Example 6)

[0352] In the film formation process, the cold trap was operated and the plasma-assisted conditions were set to an anode current of 168A and an anode voltage of 23V. Otherwise, the barrier film of Comparative Example 6 was manufactured in the same manner as in Example 1.

[0353] (Comparative Example 7)

[0354] In the film-forming process, the plasma-assisted conditions were set to an anode current of 155A and an anode voltage of 20V. Otherwise, the barrier film of Comparative Example 7 was manufactured in the same manner as Comparative Example 6.

[0355] (Comparative Example 8)

[0356] In the film-forming process, the conveying speed was set to 530 m / min, the film thickness was set to 10.0 nm, the transmittance was set to 98.0%, and the pressure was set to 1.0 Pa. Otherwise, it was carried out in the same manner as Comparative Example 7. In the film-forming process, the film thickness was set to 300 nm using solution Y, and the curing treatment after the coating layer was formed was carried out at 55°C and 50% RH for 3 days. Otherwise, the barrier film of Comparative Example 8 was manufactured in the same manner as Comparative Example 7.

[0357] (Comparative Example 9)

[0358] In the film formation process, the plasma-assisted conditions were set as follows: anolyte current of 141A, anolyte voltage of 22V, conveying speed of 530m / min, film thickness of 10.0nm, light transmittance of 98.0%, and pressure of 1.0Pa. Otherwise, the barrier film of Comparative Example 9 was manufactured in the same manner as Comparative Example 7.

[0359] (Comparative Example 10)

[0360] In the film formation process of the first vapor-deposited film in Example 2, a curing treatment was performed for 5 days at 60°C and 80%RH. As a result, the film broke during the roll-out process to form the first coating layer, and therefore the formation of the first coating layer, the second vapor-deposited film, and the second coating layer was not performed. The barrier film was collected from the outermost layer of the roll that had undergone the curing treatment at 60°C and 80%RH and evaluated using XAFS.

[0361] [Table 1]

[0362] [Table 2]

[0363] [Acquisition and parsing of XAFS graphs]

[0364] For the barrier films of Examples 1 to 7 and Comparative Examples 1 to 10, XAFS spectra were obtained under the following measurement conditions. Among them, the results of Example 2 are shown in Figure 15 . The vertical axis in the figure is the intensity of the generated fluorescent X-ray (recorded as absorption intensity (a.u) in the figure), and the horizontal axis is the light (or X-ray) energy (eV).

[0365] <XAFS Spectrum Acquisition>

[0366] · Utilized line: Aichi Synchrotron Radiation Center BL1N2

[0367] · Accelerating energy: 1.2 GeV

[0368] · Beam size: 1.0 mm in the horizontal direction × 1.0 mm vertically

[0369] · Incident angle to the sample: 22.5° (the direction perpendicular to the sample is set as 0°)

[0370] · Entrance slit: 30 μm

[0371] · Exit slit: 30 μm

[0372] · Measurement method: Partial fluorescence yield method

[0373] · Energy range (Al K-edge): 1500 - 1700 eV

[0374] · Energy level: 1500 - 1550 eV: 2.0 eV / step 1550 - 1555 eV: 1.0 eV / step 1555 - 1575 eV: 0.2 eV / step 1575 - 1600 eV: 0.5 eV / step 1600 - 1680 eV: 1.0 eV / step 1680 - 1700 eV: 2.0 eV / step (Integration time: 10 s / point in total) · Energy calibration: Energy calibration using Au 4f 7 / 2 of the Au plate (calibration is performed by subtracting the theoretical value of 1500 eV from the measured value) <XAFS Spectrum Analysis> Peak separation method The intensity values were normalized such that the absorption spectrum intensity value at an X-ray absorption energy value of 1540 eV was 0 and the absorption spectrum intensity value at an X-ray absorption energy value of 1680 eV was 1.

[0375] [Equation 1]

[0376] Extract the data points from 1555 eV to 1575 eV and from 1595 eV to 1605 eV after standardization, fit the function of f(x) above, and find each coefficient. Among them, the limiting conditions of k1 = k2, K1 = X1, and K2 = X2 are added. The fitting is performed by the least squares method. At this time, use the least squares function of the scipy library in Python, and assign values as shown in the following table for the initial values of the coefficients to find. The definitions of the symbols of the above function are as follows.

[0377] Mi: The weighting factor of the Gaussian function and Lorentz function of the i-th absorption peak

[0378] Xi: The peak center of the i-th absorption peak

[0379] hi: The peak intensity factor of the i-th absorption peak

[0380] βi: The peak width factor of the i-th absorption peak

[0381] kj: The baseline intensity factor in the j-th baseline

[0382] Kj: The midpoint position of the baseline intensity of the j-th baseline

[0383] [Table 3]

[0384] The results of peak separation of the XAFS spectra of Example 2, Comparative Examples 2, 4, and 8 are shown respectively in Figures 16 to 19 . Figure 16 is the analysis result of XAFS peak separation of Example 2, Figure 17 is the analysis result of XAFS peak separation of Comparative Example 2, Figure 18 is the analysis result of XAFS peak separation of Comparative Example 4, Figure 19 is the analysis result of XAFS peak separation of Comparative Example 8.

[0385] Experiment is the measured XAFS spectrum, Fit.Peak1 is the intensity peak near 1566 eV separated, Fit.Peak2 is the intensity peak near 1568 eV separated, and Fit.Peak3 is the intensity peak near 1572 eV separated. For the barrier films of Examples 1 to 7 and Comparative Examples 1 to 10, calculate the XAFS peak top ratio P = (intensity peak top near 1572 eV) / (intensity peak top near 1566 eV), and show the results in Table 4.

[0386] <TOF-SIMS Analysis>

[0387] For the barrier membranes of Examples 1-7 and Comparative Examples 1-9, the C2 content in the barrier membranes was determined using time-of-flight secondary ion mass spectrometry (TOF-SIMS). - Ions (mass number 24,000), CN - Ions (mass number 26.0003), Si - Ions (mass number 27.9777), AlO2 - Ions (mass number 58.971), SiO2 - The intensity of the ion (mass number 59.9666) was determined. Specifically, a time-of-flight secondary ion mass spectrometer (ION TOF, TOF.SIMS5) was used. Simultaneously, a Cs (cesium) ion gun was used to repeatedly perform soft etching from the surface of the barrier film towards the PET film side at a certain speed, while mass spectrometry analysis of various ions in each layer was performed. The coating layer intensity ratio X = C² was obtained. - Ionic strength / Si - The ionic strengths are shown in Table 4 (C2 / Si strength ratio in Table 4).

[0388] TOF-SIMS Measurement Conditions

[0389] Primary ion types: Bi 3++ (0.2pA, 100μs)

[0390] • Measurement area: 150×150μm 2

[0391] • Scan: 128 pixels × 128 pixels × 1 scan

[0392] • Types of etching guns: Cs (1keV, 60nA)

[0393] • Etching area: 600×600μm 2

[0394] • Etching rate: 10 sec / cycle

[0395] • Vacuuming time: 1×10 -6 More than 15 hours below mbar

[0396] • TOF-SIMS measurements were performed within 30 hours of the start of vacuuming.

[0397] The measurement results are illustrated in the following charts: Figures 20 to 22 . Figure 20 These are the measurement results from Example 2. Figure 21 These are the measurement results from Example 3. Figure 21The results are from Comparative Example 8. In the figure, the vertical axis represents the intensity of secondary ions, and the horizontal axis represents the number of seconds for etching.

[0398] [Table 4]

[0399] <Evaluation of uneven color on the outer surface of the barrier film>

[0400] For the barrier films of Examples 1-7 and Comparative Examples 1-9, a visual inspection was performed on the end face of the wound body. Furthermore, for Comparative Examples 1, 3-5, the "color difference" of the barrier films collected from the wound body was evaluated. The results are shown in Table 4.

[0401] Here, "end-face visual appearance" refers to the visual evaluation of color unevenness when viewed from the end face (side face) of the wound body.

[0402] The evaluation of "color difference" was conducted as follows. The barrier film roll was observed from the end face, and samples were collected from the darker (A) and lighter (B) portions of the barrier film. Using a Konica Minolta CM-600d spectrophotometer, one sample of the darker (A) portion of the barrier film was placed on a standard white plate with the film side facing upwards. Measurements were performed under SCI (including positive reflection), 10° field of view, and D65 light source conditions. Measurements were also performed on the lighter (B) portion. The measured L... a b The value is used to calculate the color difference between the darker area (A) and the lighter area (B).

[0403] It was confirmed that when the color difference of a single barrier film is greater than 0.3, it is determined by visual inspection that the color is significantly uneven when viewed from the end face of the wound body.

[0404] [Table 5]

[0405] <Determination of the Barrier Properties of Barrier Membranes>

[0406] The water vapor permeability and oxygen permeability of the barrier membranes in Examples 1-7 and Comparative Examples 1-9 were measured.

[0407] Water vapor transmission rate (g / (m) 2 •day), indicated as "WVTR" in the table, was measured using a water vapor transmission rate measuring device (MOCON, product name "PERMATORAN-W 3 / 31") under measurement conditions of 40°C and 100% RH, according to JIS K7129 B method. Additionally, oxygen transmission rate (cc / (m))2 The oxygen permeability (day·atm), indicated as "OTR" in the table, was measured using an oxygen permeability measuring device (manufactured by MOCON, product name "OX-TRAN 2 / 20") under the conditions of 23°C and 90%RH, according to JIS K7126-2. The results are shown in Table 6.

[0408] <Evaluation of brightness maintenance>

[0409] For the barrier films of Examples 1-7 and Comparative Examples 1-9, wavelength conversion sheets with the following layer configuration were fabricated.

[0410] First, after forming a roughened layer 160 on one side of the support 150 (biaxially stretched PET film, 38 μm thick), an adhesive layer 140 (a two-component curing polyurethane adhesive, 5 μm thick when dry) is applied using a gravure roller coating method and dried. This layer is then laminated to the surface of the barrier film 130 of Example 1 above to obtain two sheets. Figure 9 The stack shown is 100D.

[0411] Regarding the rough layer 160, the spherical particles containing polyacrylic acid resin (Epostar MA (acrylic crosslinked polymer with a compressive strength of 2.8 kgf / mm²) will be used as particles 162. 2 The above-mentioned resin (average particle size 4 μm) is mixed with an acrylic resin to prepare a coating agent for forming a rough layer. This agent is then applied to a substrate using a gravure roller coating method (particle content 1.7% by mass, coating weight at drying 1.6 g / m²). 2 (Rough layer thickness 1.5μm).

[0412] Next, the adhesive layer coating liquid described below is applied to the substrate 120 and dried to form the adhesive layer 170.

[0413] <Adhesive Layer Coating Liquid>

[0414] ·50 parts by weight of polyester polyol

[0415] (Hydroxy value: 62 mg KOH / g, solid content 20% by mass)

[0416] · 1 part by weight of silane coupling agent

[0417] (3-Epoxypropoxypropylmethyldimethoxysilane)

[0418] · 1 part by weight of silica filler

[0419] (Average particle size 5μm)

[0420] · 1 part by weight of curing agent

[0421] (1,6-Hexamethylene diisocyanate, 35% by weight of solids)

[0422] · Solvent 50 parts by weight

[0423] (Methyl ethyl ketone)

[0424] Next, a phosphor coating liquid containing phosphor 112 is applied to the adhesive layer 170 surface on the substrate 120 surface of a laminate 100D, and then dried to form a phosphor layer 110 that has not been irradiated with ionizing radiation. Then, the phosphor layer 110 and another laminate 100D are laminated with their substrates 120 facing each other, irradiated with ultraviolet light, and two laminates 100D are stacked with the phosphor layer 110 having a thickness of 30 μm in between, to manufacture... Figure 11 The wavelength conversion chip shown is 200D.

[0425] <Fluorescent Dispersion>

[0426] Quantum dots and amino-modified silicone were mixed in a glove box purged with nitrogen to an oxygen concentration of less than 300 ppm, and stirred with a magnetic stirrer for 4 hours while being heated in a water bath at 90°C. The mixture was then filtered through a polypropylene filter with a pore size of 0.2 μm to obtain a CdSe / ZnS core-shell quantum dot dispersion.

[0427] ·0.9 parts by mass of quantum dots

[0428] (Emission peak: 540nm, manufactured by Sigma-Aldrich)

[0429] ·0.9 parts by mass of quantum dots

[0430] (Emission peak: 630nm, manufactured by Sigma-Aldrich)

[0431] 99 parts by weight of amino-modified silicone

[0432] (Genesee, GP-344, viscosity: 670 mPa·s)

[0433] <Fluorescent Coating Solution>

[0434] · 58.11 parts by weight of multifunctional acrylate compounds

[0435] (Ethoxylated bisphenol A diacrylate; trade name "ABE-300" by Shin-Nakamura Chemical Industry Co., Ltd.)

[0436] · 38.74 parts by weight of polyfunctional thiols

[0437] (Pentaerythritol tetra(3-mercaptopropionate); trade name "PEMP" from SC Organic Chemistry)

[0438] • 0.5 parts by weight of photopolymerization initiator

[0439] (IGM Resins BV's product name "Omnirad TPO H")

[0440] 1.61 parts by weight of the above-mentioned phosphor dispersion

[0441] Acetic acid 0.79 parts by weight

[0442] 0.25 parts by weight of titanium dioxide

[0443] (Chemours' trade name "Ti-Pure R-706"; particle size 0.36μm)

[0444] Similarly, wavelength conversion sheets using the barrier films of Examples 2 to 4 and Comparative Examples 1 to 10 instead of the barrier film 130 of Example 1 were manufactured. After manufacturing, the wavelength conversion sheets were wound into rolls.

[0445] The wavelength conversion plates obtained above were cut into 100mm wide and 100mm long dimensions to obtain evaluation samples. Then, the spectroradiometer SR-LEDW (TOPCON) was used to measure the spectroradiometer brightness of the evaluation samples. The brightness of the peaks near 449nm, 535nm, and 627nm was set as blue, green, and red brightness, respectively. The spectroradiometer was set at the top, and the DBEF (Dual Brightness Enhancement Film), BEF (Brightness Enhancement Film), evaluation sample, diffuser plate, and blue LED light source were sequentially arranged under the objective lens of the spectroradiometer for measuring the spectroradiometer brightness. The measurement angle was set to 0.1°.

[0446] The evaluation samples tested above were placed in a constant temperature and humidity bath at 60°C and 90%RH for 1000 hours of damp heat testing. Brightness was then measured using the same method as described above. Next, the brightness retention rate of the evaluation samples was calculated according to the following formula. The results are shown in Table 5.

[0447] Brightness maintenance (535nm) = (Ga / Ba) / (Gb / Bb) × 100%

[0448] Brightness maintenance (627nm) = (Ra / Ba) / (Rb / Bb) × 100%

[0449] Ba: Luminescence intensity (brightness) at the peak near 449 nm after the damp heat test.

[0450] Ga: Luminescence intensity (brightness) at the peak near 535 nm after the damp heat test.

[0451] Ra: Luminescence intensity (brightness) at the peak near 627 nm after the damp heat test.

[0452] Bb: Luminescence intensity (brightness) at the peak near 449 nm before the damp heat test.

[0453] Gb: Luminescence intensity (brightness) at the peak near 535 nm before the damp heat test.

[0454] Rb: Luminescence intensity (brightness) at the peak near 627nm before the damp heat test.

[0455] [Table 6]

[0456] As can be understood from Tables 4 to 6, the laminate of the barrier film of this embodiment, which uses a peak ratio P of 1.05 or higher and 1.60 or lower obtained from the XAFS spectrum, does not have color unevenness of the barrier film and has a high brightness retention rate when used as a wavelength conversion sheet.

[0457] Explanation of reference numerals in the attached figures

[0458] 100A barrier film

[0459] 100B~100D laminates

[0460] 110 Fluorescent Layer

[0461] 111 Sealing Resin

[0462] 112 Fluorescent

[0463] 1. 120 substrate

[0464] 131b First vapor deposition film

[0465] 131a First Covering Layer

[0466] 132b Second Evaporation Film

[0467] 132a Second Cover Layer

[0468] 140 Adhesive layer or bonding agent layer

[0469] 150 Support

[0470] 160 rough layer

[0471] 161 Resin

[0472] 162 particles

[0473] 170 Adhesive layer or bonding agent layer

[0474] 200B and 200D wavelength conversion sheets

[0475] 300A and 300B display devices

[0476] 310, 380 Light Source Section

[0477] 320 reflective sheet

[0478] 330 light guide plate

[0479] 340 prism sheet

[0480] 350° polarized selective reflector

[0481] 360° LCD Panel

[0482] 370 Diffuser

[0483] 10 Film Forming Device

[0484] P plasma

[0485] X Rotation Axis

[0486] 11A Substrate Conveying Mechanism

[0487] 11B Plasma Pretreatment Unit

[0488] 11C film-forming mechanism

[0489] 12 Decompression Chamber

[0490] 12A Substrate Transfer Chamber

[0491] 12B Plasma Pretreatment Chamber

[0492] 12C film-forming chamber

[0493] 13 Unwinding Rollers

[0494] 14a~d guide rollers

[0495] 15 winding rollers

[0496] 20 Pretreatment Rollers

[0497] 21 Electrode section

[0498] 23 Magnetic field forming section

[0499] 23a First page

[0500] 23b Second page

[0501] 231 First Magnet

[0502] 231c First Axial Section

[0503] 232 Second Magnet

[0504] 232c Second Axial Section

[0505] 232d connection part

[0506] 24 Evaporation Mechanism

[0507] 24b Boat

[0508] 25 Film-forming rollers

[0509] 31 Power supply wiring

[0510] 32 power supplies

[0511] 35a~35c next door

[0512] 50 Plasma supply mechanism

[0513] 51 Hollow Cathode

[0514] 61. Vapor Deposition Material Supply Department

[0515] 63 Aluminum vapor

Claims

1. A barrier film comprising, in sequence, a resin substrate, a first alumina vapor-deposited film, a first coating layer, a second alumina vapor-deposited film, and a second coating layer, wherein, The first coating layer and the second coating layer are respectively cured products of a resin composition comprising an alkoxysilane and a hydroxyl-containing water-soluble resin. For both the first and second alumina vapor-deposited films, the peak ratio P of the vapor-deposited film, as defined below, is 1.05 or higher and 1.60 or lower when performing X-ray absorption fine structure analysis from the surface side of the second coating layer of the barrier film. P = (intensity peak near 1572 eV) / (intensity peak near 1566 eV).

2. The barrier membrane according to claim 1, wherein, When the barrier film was etched using time-of-flight secondary ion mass spectrometry (TOF-SIMS) from the surface opposite to the resin substrate, the coating intensity ratio X detected in the respective regions of the first and second coating layers, as defined below, was 0.50 or higher and 1.10 or lower. X=C2 - Ionic strength / Si - Ionic strength.

3. The barrier membrane according to claim 1, wherein, A rough layer is disposed on the side of the resin substrate opposite to the first alumina vapor-deposited film.

4. A layered body, wherein, The barrier film and the support body as described in claim 1 are stacked together with an adhesive layer in between.

5. The laminated body according to claim 4, wherein, A rough layer is disposed on the side of the support opposite to the adhesive layer.

6. A wavelength conversion plate, wherein, The barrier film of claim 3 is disposed on both sides with a phosphor layer sandwiched between them.

7. A wavelength conversion plate, wherein, The laminate of claim 4 is disposed on both sides with a phosphor layer sandwiched between them, and each of the laminates is provided with the support, the resin substrate, the coating layer and the phosphor layer in sequence from the outermost side.

8. A wavelength conversion plate, wherein, The laminate of claim 4 is disposed on both sides with a phosphor layer sandwiched between them, and each of the laminates is provided with the support, the coating layer, the resin substrate and the phosphor layer in sequence from the outermost side.

9. A wavelength conversion plate, wherein, The laminate of claim 4 is disposed on both sides with a phosphor layer sandwiched between them. One laminate is disposed sequentially from the outermost side with the support, the resin substrate, the coating layer, and the phosphor layer, and the other laminate is disposed sequentially from the outermost side with the support, the coating layer, the resin substrate, and the phosphor layer.

10. A backlight component comprising a light source, a light guide plate or a diffuser plate, and a wavelength conversion sheet as described in claim 6.

11. A display device, which is a surface-mount display device having a light guide plate, wherein, The light guide plate and the reflective sheet are stacked in sequence as follows: a liquid crystal panel, a polarizing light selective reflector, a prism sheet, a wavelength conversion sheet as described in claim 6, and the reflective sheet. A light source is disposed on the end face of the light guide plate.

12. A display device, which is a direct-lit display device having a diffuser plate, wherein, The liquid crystal panel, polarizing light selective reflector, prism sheet, wavelength conversion sheet as described in claim 6, diffuser plate, light source unit, and reflector sheet are stacked in sequence.

Images