Laminated film and method for producing laminated film

Abstract

The invention relates to a laminated film and a method for manufacturing the laminated film. A laminated film (1) according to one embodiment is provided with: a base film (2); a cured resin layer (3) disposed on one surface in the thickness direction of the base film (2); and an inorganic material layer (4) disposed on one surface in the thickness direction of the cured resin layer (3). One or more protrusions (B) are formed on one surface of the cured resin layer (3) in the thickness direction, and the average area of the protrusions (B) is 80 nm2 or more and 500 nm2 or less. The arithmetic mean height (Sa) of one surface in the thickness direction of the cured resin layer (3) is 1.0 nm or more.

Description

Technical Field

[0001] This invention relates to laminated films and methods for manufacturing laminated films. Background Technology

[0002] An anti-reflective film is provided on the outer surface of the display screen in display devices such as liquid crystal displays and organic EL (Organic Electro-Luminescence) displays to improve the visibility of the displayed image. For example, a known anti-reflective film comprises, in the thickness direction: a film substrate, a hard coating layer, an inorganic oxide primer layer, and an anti-reflective layer (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2022-65437

[0006] In the antireflective film described in Patent Document 1, the hard coating layer contains inorganic oxide particles (silicon dioxide particles). Consequently, the surface of the hard coating layer on the inorganic oxide primer side has surface irregularities. Through the anchoring effect based on these surface irregularities, peeling of the antireflective layer is suppressed.

[0007] However, in the antireflective film of Patent Document 1, the surface of the antireflective layer opposite to the inorganic oxide primer layer also has surface irregularities that follow those of the hard coating layer. Such surface irregularities cause some of the light incident on the antireflective film to scatter. Furthermore, the silica particles within the hard coating layer also cause some of the light incident on the antireflective film to scatter. In other words, such an antireflective film has undesirable optical properties. Summary of the Invention

[0008] The present invention provides a laminated film with good optical properties and improved adhesion, and a method for manufacturing the laminated film.

[0009] The present invention [1] includes a laminated film comprising: a substrate film; and a cured resin layer disposed on one side of the substrate film in the thickness direction, wherein one or more protrusions are formed on one side of the cured resin layer in the thickness direction, and the average area of ​​the protrusions is 80 nm. 2 Above and 500nm 2 Hereinafter, the arithmetic mean height Sa of one side of the cured resin layer in the thickness direction is 1.0 nm or more.

[0010] The present invention [2] includes the laminated film described in [1] above, wherein the average interface length of the protrusion divided by the average area of ​​the protrusion is 0.2 nm. －1above.

[0011] The present invention [3] includes the laminated film described in [1] or [2] above, wherein the total area of ​​the protrusions is 15% or more and 40% or less relative to the total area of ​​one side of the cured resin layer in the thickness direction.

[0012] The present invention [4] includes the laminated film described in any one of [1] to [3] above, wherein the cured resin layer contains an organosilicon compound.

[0013] The present invention [5] includes the laminated film described in any one of [1] to [4] above, wherein one side of the cured resin layer in the thickness direction is a plasma-treated surface.

[0014] The present invention [6] includes the laminated film described in any one of [1] to [5] above, wherein the laminated film further comprises: an inorganic layer disposed on one side of the cured resin layer in the thickness direction.

[0015] The present invention [7] includes the laminated film described above [6], wherein the laminated film further comprises: an antifouling layer disposed on one side of the inorganic layer in the thickness direction.

[0016] The present invention [8] includes a method for manufacturing a laminated film, which is a method for manufacturing a laminated film as described in any one of [1] to [5] above, comprising the following steps: a preparation step, preparing a substrate film with a cured resin layer, the substrate film with the cured resin layer comprising: a strip of the substrate film; and the cured resin layer disposed on one side of the substrate film in the thickness direction; and a plasma treatment step, forming one or more protrusions by plasma treatment of one side of the substrate film with the cured resin layer in the thickness direction.

[0017] The present invention [9] includes a method for manufacturing the laminated film described above [8], wherein the plasma treatment is a treatment using an inductively coupled plasma of oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna.

[0018] The present invention

[10] includes a method for manufacturing a laminated film as described in [8] or [9] above, wherein the method further comprises: a forming step of forming an inorganic layer on one side of the substrate film with a cured resin layer in the thickness direction.

[0019] Invention Effects

[0020] As described above, the laminated film of the present invention comprises: a substrate film; and a cured resin layer disposed on one side of the substrate film in the thickness direction. One or more protrusions are formed on one side of the cured resin layer in the thickness direction, and the average area of ​​the protrusions is 80 nm. 2Above and 500nm 2 Furthermore, the arithmetic mean height Sa of one side of the cured resin layer in the thickness direction is 1.0 nm or more. Therefore, it has good optical properties and can improve adhesion.

[0021] As described above, the method for manufacturing the laminated film of the present invention includes a plasma treatment step, wherein one or more protrusions are formed by plasma treatment of one side of a substrate film having a cured resin layer in the thickness direction. Therefore, a laminated film with good optical properties and improved adhesion can be manufactured. Attached Figure Description

[0022] Figure 1 This is a cross-sectional view of one embodiment of the laminated film of the present invention.

[0023] Figure 2 Is Figure 1 A cross-sectional view of a laminated membrane formed by further laminating inorganic layers and antifouling layers.

[0024] Figures 3A to 3D This is one embodiment of the method for manufacturing the laminated film of the present invention. Figure 3A This indicates the process of preparing a substrate film with a cured resin layer. Figure 3B This indicates a process of plasma treatment on one side of the substrate film with a cured resin layer in the thickness direction. Figure 3C This indicates the process of forming an inorganic layer. Figure 3D This refers to the process of forming an antifouling layer.

[0025] Figure 4 This is a cross-sectional view of a first modified example of the laminated film of the present invention.

[0026] Figure 5 This is a schematic diagram of the apparatus used in the process of manufacturing laminated films, including the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process.

[0027] Figure 6 It means Figure 6 A three-dimensional view showing the positional relationship between the low-inductance antenna and the substrate film with a cured resin layer in the plasma processing chamber.

[0028] Figure 7 It means Figure 7 A cross-sectional view showing the positional relationship between the low-inductance antenna and the substrate film with a cured resin layer in the plasma processing chamber.

[0029] Figure 8 These are photographs of surface SEM images and binarized images of one side (plasma-treated surface) of the cured resin layer of the laminated film of Example 1, Comparative Example 1, and Comparative Example 3 in the thickness direction.

[0030] Figure 9 It means Figure 8 A diagram illustrating the method for measuring the convex portion in region X of one side of the cured resin layer in the thickness direction of the binary image of Example 1.

[0031] Explanation of reference numerals in the attached figures

[0032] 1: Laminated film; 2: Substrate film; 3: Cured resin layer; 4: Inorganic layer; 5: Antifouling layer; B: Raised portion. Detailed Implementation

[0033] 1. Laminated film

[0034] (1) First implementation method

[0035] Reference Figure 1 An embodiment of the laminated film 1 of the present invention will be described.

[0036] like Figure 1 As shown, the laminated film 1 includes: a substrate film 2; and a cured resin layer 3 disposed on one side of the substrate film 2 in the thickness direction.

[0037] The laminated film 1 extends in a plane direction orthogonal to the thickness direction.

[0038] <Substrate Film>

[0039] The substrate film 2 is the bottom layer of the laminated film 1 and serves as a support film to ensure the strength of the laminated film 1.

[0040] The substrate film 2 has a film shape (including a sheet shape). Furthermore, the substrate film 2 is, for example, a flexible, transparent resin film.

[0041] Examples of materials used for the substrate film 2 include: polyester resin, polyolefin resin, cellulose resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, and polystyrene resin. Examples of polyester resins include: polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include: polyethylene, polypropylene, and cyclic olefin polymers (COP). Examples of cellulose resins include: cellulose triacetate (TAC).

[0042] The material of the substrate film 2 can be used alone or in combination of two or more materials.

[0043] From the viewpoint of transparency and strength, the substrate film 2 is preferably at least one selected from the group consisting of polyester resin film, polyolefin resin film, and cellulose resin film. More preferably, it is at least one selected from the group consisting of PET film, COP film, and TAC film. Even more preferably, it is a TAC film.

[0044] The substrate film 2 preferably does not contain particles (e.g., metal oxide particles described later).

[0045] From the viewpoint of strength and operability, the thickness of the substrate film 2 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 30 μm or more, and furthermore, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0046] The total light transmittance (JIS K 7375:2008) of the substrate film 2 is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and, for example, 100% or less.

[0047] If the total light transmittance of the substrate film 2 is above the lower limit mentioned above, good transparency can be ensured in the laminated film 1.

[0048] It should be noted that, in the case where the cured resin layer 3 described later is disposed on either one side of the substrate film 2 in the thickness direction or the other side in the thickness direction, in order to ensure the transportability and operability of the substrate film 2 in the roll-to-roll process, a carrier film (illustration omitted) may also be attached to the side of the substrate film 2 opposite to the side where the cured resin layer 3 is disposed.

[0049] <Curing Resin Layer>

[0050] The cured resin layer 3 is a layer that improves mechanical properties. The cured resin layer 3 is in contact with one side of the substrate film 2 in the thickness direction. It should be noted that the cured resin layer 3 may also be further disposed on the other side of the substrate film 2 in the thickness direction as needed.

[0051] In this embodiment, the surface of the cured resin layer 3 along its thickness direction is the plasma-treated surface 3a. The plasma-treated surface 3a is the surface that has undergone plasma treatment. The plasma treatment will be described in detail later. From the viewpoint of controlling the surface state of the plasma-treated surface 3a, treatment using plasma that utilizes an oxygen-containing gas-generated inductively coupled plasma (oxygen LIA treatment) generated by applying high-frequency power to a low-inductance antenna (LIA) is preferred. That is, the surface of the cured resin layer 3 along its thickness direction is the plasma-treated surface 3a using an oxygen-containing gas-generated inductively coupled plasma. The oxygen LIA treatment is described in detail in the method for manufacturing the laminated film. It should be noted that the surface of the cured resin layer 3 along its thickness direction before plasma treatment is the untreated surface 3a'.

[0052] Examples of curable resin layers 3 include hard coatings, optical adjustment layers, and anti-adhesion layers. Hard coatings, for example, prevent scratches from forming on the exposed surface of the substrate film 2. Optical adjustment layers, for example, adjust the optical properties (e.g., refractive index) of the laminated film 1. Anti-adhesion layers, for example, impart anti-adhesion properties to the surfaces of multiple laminated films 1 in contact with each other, when the laminated films 1 are stacked in the thickness direction.

[0053] The cured resin layer 3 is preferably a hard coating. If the cured resin layer 3 is a hard coating, scratches can be suppressed on the surface (exposed surface) of the inorganic layer 4 formed on the surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3 or on the surface (exposed surface) of the antifouling layer 5 formed on the surface (exposed surface) in the thickness direction of the inorganic layer 4.

[0054] The cured resin layer 3 is a cured product of the curable resin composition. Specifically, the cured resin layer 3 is formed by coating the curable resin composition onto one side of the substrate film 2 in the thickness direction, drying it as needed, and then curing it.

[0055] Examples of curable resin compositions include, for example, compositions comprising a UV-curable resin (UV-curable resin composition) and compositions comprising a thermosetting resin. From the viewpoint of manufacturing efficiency, a UV-curable resin composition is preferred as the curable resin composition. That is, the cured resin layer 3 is a cured layer of the UV-curable resin composition.

[0056] Examples of UV-curable resins include (meth)acrylate resins. Acrylate resins are preferred. Examples of acrylate resins include urethane acrylate resins and acrylic resins (excluding urethane acrylate resins). Urethane acrylate resins are preferred. Furthermore, copolymers of urethane acrylate resins and polyfunctional acrylates may also be used. Two or more UV-curable resins may be used alone or in combination. It should be noted that (meth)acrylate resins are methacrylate resins and / or acrylate resins.

[0057] That is, the cured resin layer 3 preferably contains acrylate resin. More preferably, it contains urethane acrylate resin. In addition, the cured resin layer 3 may also contain a copolymer of urethane acrylate resin and polyfunctional acrylate.

[0058] It should be noted that the cured resin layer 3 may also contain other UV-curable resins.

[0059] Other UV-curable resins include, for example, polyester resins, urethane resins (excluding acrylic urethane resins), amide resins, epoxy resins, and melamine resins. Other UV-curable resins can be used alone or in combination of two or more.

[0060] The UV-curable resin composition may also contain particles. Preferably, it does not contain particles. That is, the cured resin layer 3 preferably does not contain particles.

[0061] If the cured resin layer 3 does not contain particles, the total reflectance (light reflectance ratio) can be improved. That is to say, the laminate 1 has excellent optical properties.

[0062] As particles, examples include organic particles and inorganic particles.

[0063] Materials that are organic particles include, for example, polymethyl methacrylate, polystyrene, acrylic / styrene copolymers, and polycarbonate.

[0064] Inorganic particles can be exemplified by inorganic oxide particles. Materials that are inorganic oxide particles can include, for example, metal oxides and quasi-metal oxides, specifically: silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. It should be noted that the inorganic oxide particles can also be metal composite oxides composed of the aforementioned metal oxides. Furthermore, to improve adhesion and affinity with resins, functional groups such as acryloyl groups and epoxy groups can be introduced onto the surface of the inorganic oxide particles.

[0065] The average particle size is not particularly limited, but is, for example, less than 500 nm, preferably less than 300 nm, and more preferably less than 100 nm.

[0066] It should be noted that the average particle size can be determined by the specific surface area (BET) method.

[0067] The proportion of particles in the UV-curable resin composition (solid component) is, for example, 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and especially preferably 0% by mass.

[0068] If the proportion of particles in the UV-curable resin composition (solid component) is below the above-mentioned upper limit, the scattering of light incident on the laminated film 1 caused by particles in the laminated film 1 can be suppressed.

[0069] Furthermore, the curable resin composition may include, for example, a leveling agent. The leveling agent is used to modify the surface shape of the cured resin layer 3. Examples of leveling agents include those containing organosilicon compounds.

[0070] That is to say, the cured resin layer 3 preferably contains an organosilicon compound.

[0071] Organosilicon compounds include, for example, compounds having a siloxane structure. Compounds having a dimethylsiloxane structure are preferred examples.

[0072] Examples of compounds having a siloxane structure include: polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyether ester-modified hydroxyl-containing polydimethylsiloxane, polyether-modified acryloyl-containing polydimethylsiloxane, polyester-modified acryloyl-containing polydimethylsiloxane, polymethylalkylsiloxane, and epoxy-modified polydimethylsiloxane. Preferably, examples include: polyether-modified polydimethylsiloxane, polyether ester-modified hydroxyl-containing polydimethylsiloxane, polyether-modified acryloyl-containing polydimethylsiloxane, polyester-modified acryloyl-containing polydimethylsiloxane, and epoxy-modified polydimethylsiloxane.

[0073] Leveling agents may also contain other components (such as (meth)acrylate resins).

[0074] When the cured resin layer 3 contains an organosilicon compound, when the untreated surface 3a' of the cured resin layer 3 is subjected to plasma treatment, -Si-O- is formed on the plasma-treated surface 3a of the cured resin layer 3. When an inorganic layer 4 is laminated onto the plasma-treated surface 3a of the cured resin layer 3, the -Si-O- of the plasma-treated surface 3a of the cured resin layer 3 bonds with the inorganic atoms of the inorganic layer 4, thereby improving the adhesion.

[0075] When the cured resin layer 3 comprises a UV-curable resin and a leveling agent, the amount of leveling agent relative to 100 parts by weight of the UV-curable resin is, for example, 0.01 parts by weight or more, preferably 0.02 parts by weight or more, more preferably 0.03 parts by weight or more, and furthermore, for example, 1 part by weight or less, preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, even more preferably 0.08 parts by weight or less, and especially preferably 0.06 parts by weight or less.

[0076] If the amount of leveling agent is below the above-mentioned upper limit relative to 100 parts by mass of UV-curable resin, the total reflectance (light reflectance ratio) in the laminate 1 can be further improved.

[0077] Furthermore, when the curable resin composition is an ultraviolet-curable resin composition, it is preferable to include a photopolymerization initiator.

[0078] Furthermore, the curable resin composition may also contain additives such as solvents, thixotropic agents, and antistatic agents.

[0079] The thickness of the cured resin layer 3 is, for example, 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 5 μm or more. In addition, it is, for example, 40 μm or less, preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0080] If the thickness of the cured resin layer 3 is above or above the aforementioned lower limit, the cured resin layer 3 can be easily formed, and its function can be fully realized. Furthermore, if the thickness of the cured resin layer 3 is below or below the aforementioned upper limit, the laminated film 1 can be thinned.

[0081] It should be noted that when the cured resin layer 3 is disposed on both sides of the substrate film 2 in the thickness direction, the thickness of the cured resin layer 3 mentioned above is the thickness of the cured resin layer 3 on one side disposed in the thickness direction of the substrate film 2, and not the total thickness of the cured resin layer 3.

[0082] As described in the following embodiments Figure 8 , 9 As shown, one or more protrusions B are formed on one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a). The one or more protrusions B are included in the unevenness formed during plasma treatment of the surface of the cured resin layer 3 in the thickness direction. Figure 9 express Figure 8The parameters of the convex portions in the X region of the binarized image of Example 1 are shown. Solid lines a1 to a4 enclose the convex portions B1 to B4, and the length of solid lines a1 to a4 represents the interface length of the convex portions B1 to B4. The diagonal lines A1 to A4 represent the area of ​​the convex portions B1 to B4. The shape of the convex portion B is not particularly limited; however, from the viewpoint of fit, it is preferable to... Figure 9 The protrusions B1, B2, and B4 are elongated shapes formed by the fusion of multiple protrusions B. It should be noted that the area and interface length of the protrusions B on the thickness direction side of the cured resin layer 3 are calculated based on the image obtained by binarizing the surface SEM image using image analysis software.

[0083] The average area A of the protrusion B on one side of the thickness direction of the cured resin layer 3 (plasma-treated surface 3a) ave 80nm 2 Above and 500nm 2 Below. The average area A of the convex part B. ave Preferably 100nm 2 The above, preferably 150nm 2 The above is further preferred to be 200nm. 2 In addition, 450nm is preferred. 2 The following is more preferably 400nm 2 Below. By measuring the average area A of the convex portion B. ave Setting it above the aforementioned lower limit improves the seal. Furthermore, by adjusting the average area A of the protrusion B... ave Setting the value below the aforementioned upper limit can improve optical properties.

[0084] The average area A of the convex part B ave Based on the areas A1 to A1 of the n convex parts B existing within the measured field of view. n The total is calculated by dividing the sum by n.

[0085] The average interface length a of the protrusion B on one side of the thickness direction of the cured resin layer 3 (plasma-treated surface 3a) ave For example, the wavelength is 20 nm or more, preferably 40 nm or more, more preferably 60 nm or more, and even more preferably 70 nm or more. Furthermore, for example, the wavelength is 800 nm or less, preferably 400 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. This is achieved by measuring the average interface length a of the protrusion B. ave Setting it above the aforementioned lower limit improves the sealing performance. Furthermore, by increasing the average interface length a of the convex portion B... ave Setting the value below the aforementioned upper limit can improve optical properties.

[0086] like Figure 8As shown, the interface length of convex part B is a1~a n Let be the perimeter of each convex part B. Let be the average interface length 'a' of convex part B. ave Based on the interface lengths a1 to a2 of the n protrusions B present in the measurement field of view. n The total is calculated by dividing the sum by n.

[0087] The average interface length a of the protrusion B on one side of the thickness direction of the cured resin layer 3 (plasma-treated surface 3a) ave Divide by the average area A of the convex part B ave The obtained value (average interface length a of convex part B) ave / Average area of ​​convex part B A ave For example, 0.10nm －1 The preferred size is 0.15nm. －1 The above, more preferably 0.20nm －1 The above is further preferred to be 0.25nm. －1 In addition, for example, 0.80nm －1 The preferred size is 0.60nm. －1 The preferred value is 0.50nm. －1 Hereinafter, 0.40nm is further preferred. －1 Below. The average interface length a of the protrusion B on one side of the cured resin layer 3 in the thickness direction is... ave Divide by the average area A of the convex part B ave Setting the obtained value within the above range can improve the tightness.

[0088] The ratio of the total area of ​​the protrusions B to the total area of ​​one side of the cured resin layer 3 in the thickness direction is, for example, 10% or more, preferably 15% or more, more preferably 20% or more, and further preferably, 50% or less, preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less. Setting the ratio of the total area of ​​the protrusions B to the total area of ​​one side of the cured resin layer 3 in the thickness direction to the aforementioned lower limit improves adhesion. Furthermore, setting the ratio of the total area of ​​the protrusions B to the total area of ​​one side of the cured resin layer 3 in the thickness direction to the aforementioned upper limit improves optical properties.

[0089] The ratio of the total area of ​​the protrusions B to the total area of ​​one side of the cured resin layer 3 in the thickness direction is based on the areas A1 to A1 of the n protrusions B present in the measurement field of view. n The total is calculated by dividing the area of ​​the measured field of view by the sum of the sums.

[0090] The arithmetic mean height Sa (ISO 25178-2:2012) of one side (plasma-treated surface 3a) of the cured resin layer 3 in the thickness direction is 1.0 nm or more. More preferably, it is 1.6 nm or more, even more preferably 2.2 nm or more, and furthermore, for example, it is 5.0 nm or less, preferably 4.0 nm or less, and more preferably 3.0 nm or less. By setting the arithmetic mean height Sa to the lower limit or above mentioned above, the adhesion can be improved. Furthermore, by setting the arithmetic mean height Sa to the upper limit mentioned above, the optical properties can be improved.

[0091] The arithmetic mean height Sa of one side of the cured resin layer in the thickness direction can be measured by atomic force microscopy (AFM).

[0092] (Effects)

[0093] As described above, the laminated film 1 includes: a substrate film 2; and a cured resin layer 3 disposed on one side of the substrate film 2 in the thickness direction. One or more protrusions B are formed on one side of the cured resin layer 3 in the thickness direction, and the average area of ​​the protrusions B is 80 nm. 2 Above and 500nm 2 Furthermore, the arithmetic mean height Sa of the surface of the cured resin layer 3 in the thickness direction is 1.0 nm or more. Therefore, in the laminated film 1, the adhesion between the cured resin layer 3 and layers further laminated on its thickness direction, such as the inorganic layer 4, can be improved.

[0094] Furthermore, the total reflectance (light reflectance ratio) of the laminated film 1, when an inorganic layer is laminated on one side of the thickness direction of the cured resin layer 3, under illumination of light with a wavelength of 380 nm to 780 nm from a standard light source D65, is 0.40% or less. In other words, the laminated film 1 exhibits excellent optical properties.

[0095] Therefore, the above-mentioned laminated film 1 has good optical properties and can improve the sealing performance.

[0096] (2) Second implementation method

[0097] As needed, such as Figure 2 As shown, the laminated film 1a includes: an inorganic layer 4 disposed on one side of the cured resin layer 3 in the thickness direction; and an antifouling layer 5 disposed on one side of the inorganic layer 4 in the thickness direction. In this embodiment, the laminated film 1a sequentially includes: a substrate film 2, a cured resin layer 3, an inorganic layer 4, and an antifouling layer 5 on the side facing the thickness direction. In the laminated film 1a, the substrate film 2 and the cured resin layer 3 are the same as in the first embodiment.

[0098] <Inorganic Layer>

[0099] As an inorganic layer 4, examples include anti-reflective layers and conductive layers. An anti-reflective layer is a layer that suppresses the intensity of external light reflection. A conductive layer is a layer that is conductive.

[0100] It should be noted that when the inorganic layer 4 has an anti-reflective layer, the laminated film 1a is an anti-reflective film. Furthermore, when the inorganic layer 4 has a conductive layer, the laminated film 1a is a conductive film.

[0101] The inorganic layer 4 can consist of a single layer with a single function, or it can be a composite layer consisting of multiple layers with different functions. For example... Figure 2 As shown, the inorganic layer 4 in this embodiment has an anti-reflective layer 41.

[0102] In this embodiment, the inorganic layer 4 is a layer formed by a dry coating method (dry coating layer). Examples of dry coating methods include sputtering, vacuum evaporation, and CVD. Sputtering is preferred. That is, the inorganic layer 4 is preferably a dry coating layer. It is more preferably a sputtered layer.

[0103] [Anti-reflective layer]

[0104] The antireflective layer 41 is disposed, for example, on one side of the cured resin layer 3 in the thickness direction. The antireflective layer 41 may include, for example, a plurality of transparent inorganic oxide films stacked in the thickness direction.

[0105] The anti-reflective layer 41 is, for example, an alternating stack of high-refractive-index and low-refractive-index layers. The number of alternating layers is not particularly limited, for example, four layers.

[0106] Specifically, Figure 2 The anti-reflective layer 41 shown has, in sequence, a high refractive index layer 41a, a low refractive index layer 41b, a high refractive index layer 41c, and a low refractive index layer 41d on the side facing the thickness direction.

[0107] The high refractive index layer 41a is in contact with the cured resin layer 3. The high refractive index layer 41a is in contact with the low refractive index layer 41b. The low refractive index layer 41b is in contact with the high refractive index layer 41c. The high refractive index layer 41c is in contact with the low refractive index layer 41d.

[0108] High refractive index layers 41a and 41c are layers with relatively large refractive indices, while low refractive index layers 41b and 41d are layers with relatively small refractive indices.

[0109] In this layered structure, the intensity of reflected light is attenuated through interference between reflected light at multiple interfaces of the high-refractive-index layers 41a and 41c and the low-refractive-index layers 41b and 41d. This interference effect can be achieved by adjusting the optical film thickness (the product of the film's refractive index and thickness) of each layer of the antireflective layer 41.

[0110] The high refractive index layer 41a (first high refractive index layer) is, for example, composed of a high refractive index material with a refractive index of 1.9 or higher at a wavelength of 550 nm. Examples of high refractive index materials include niobium oxide (Nb₂O₅), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO). From the viewpoint of balancing high refractive index and low absorption of visible light, niobium oxide (refractive index 2.33) is preferred as the high refractive index material.

[0111] The thickness of the high refractive index layer 41a is, for example, 1 nm or more, preferably 5 nm or more, and furthermore, for example, 50 nm or less, preferably 30 nm or less. Furthermore, the optical film thickness of the high refractive index layer 41a is, for example, 20 nm or more, and furthermore, for example, 55 nm or less.

[0112] The low-refractive-index layer 41b (first low-refractive-index layer) is, for example, made of a low-refractive-index material with a refractive index of 1.6 or less at a wavelength of 550 nm. Examples of low-refractive-index materials include silicon dioxide (SiO2) and magnesium fluoride. From the viewpoint of balancing low refractive index and low absorption of visible light, silicon dioxide (refractive-index 1.46) is preferred as the low-refractive-index material.

[0113] The thickness of the low refractive index layer 41b is, for example, 5 nm or more, preferably 10 nm or more, and furthermore, for example, 80 nm or less, preferably 50 nm or less. Furthermore, the optical film thickness of the low refractive index layer 41b is, for example, 15 nm or more, and furthermore, for example, 70 nm or less.

[0114] The high refractive index layer 41c (second high refractive index layer) is, for example, made of a high refractive index material with a refractive index of 1.9 or higher at a wavelength of 550 nm. Examples of high refractive index materials include those mentioned above related to the high refractive index layer 41a, with niobium oxide being a preferred example.

[0115] The thickness of the high refractive index layer 41c is, for example, 30 nm or more, preferably 50 nm or more, and furthermore, for example, 200 nm or less, preferably 150 nm or less. Furthermore, the optical film thickness of the high refractive index layer 41c is, for example, 60 nm or more, and furthermore, for example, 330 nm or less.

[0116] The low-refractive-index layer 41d (second low-refractive-index layer) is, for example, made of a low-refractive-index material with a refractive index of 1.6 or less at a wavelength of 550 nm. Examples of low-refractive-index materials include those described above related to the low-refractive-index layer 41b, with silicon dioxide being a preferred example.

[0117] The thickness of the low refractive index layer 41d is, for example, 20 nm or more, preferably 40 nm or more, and furthermore, for example, 200 nm or less, preferably 120 nm or less. Furthermore, the optical film thickness of the low refractive index layer 41d is, for example, 100 nm or more, and furthermore, for example, 160 nm or less.

[0118] The total thickness of the antireflective layer 41 is, for example, 100 nm or more, preferably 150 nm or more, more preferably 200 nm or more, and furthermore, for example, 800 nm or less, preferably 500 nm or less, more preferably 400 nm or less. In this embodiment, the total thickness of the antireflective layer 41 refers to the sum of the thicknesses of the high refractive index layers 41a and 41c and the low refractive index layers 41b and 41d.

[0119] If the total thickness of the anti-reflective layer 41 is above the aforementioned lower limit, the function of attenuating the intensity of reflected light can be ensured in the anti-reflective layer 41. If the total thickness of the anti-reflective layer 41 is below the aforementioned upper limit, cracks in the anti-reflective layer 41 can be suppressed.

[0120] [Conductive layer]

[0121] A conductive layer, for example, replaces the aforementioned anti-reflective layer 41 and is disposed on one side of the cured resin layer 3 in the thickness direction. The conductive layer is, for example, a layer formed of a conductive material. Examples of conductive materials include metals and metal oxides.

[0122] Examples of metals include copper, silver, gold, aluminum, and their alloys. Examples of metal oxides include indium-containing conductive oxides, antimony-containing conductive oxides, and zinc-containing conductive oxides. Examples of indium-containing conductive oxides include indium-tin oxide (ITO), indium-zinc oxide (IZO), indium-gallium oxide (IGO), and indium-gallium-zinc oxide (IGZO). Examples of antimony-containing conductive oxides include antimony-tin oxide (ATO). Examples of zinc-containing conductive oxides include zinc-aluminum oxide (AZO).

[0123] The thickness of the conductive layer is, for example, 10 nm or more, preferably 15 nm or more, more preferably 20 nm or more, and furthermore, for example, 1000 nm or less, preferably 800 nm or less, more preferably 500 nm or less, and even more preferably 200 nm or less.

[0124] <Anti-fouling layer>

[0125] The antifouling layer 5 prevents pollution from the external environment and facilitates the removal of adhering pollutants. Furthermore, the antifouling layer 5 has water vapor barrier properties.

[0126] The antifouling layer 5 is disposed on one side of the inorganic layer 4 in the thickness direction as needed. In this embodiment, the laminated film 1a includes the antifouling layer 5.

[0127] The antifouling layer 5 is in contact with the inorganic layer 4 on one side in the thickness direction. The antifouling layer 5 is the uppermost layer of the laminated film 1a.

[0128] As a material for the antifouling layer 5, examples include organofluorine compounds. As an organofluorine compound, alkoxysilane compounds having a perfluoropolyether group are preferred. As an alkoxysilane compound having a perfluoropolyether group, examples include compounds represented by the following general formula (1).

[0129] R 1 -R 2 -X-(CH2)m-Si(OR) 3 )3(1)

[0130] In general formula (1), R 1 A fluoroalkyl group (with one or more hydrogen atoms of an alkyl group replaced by fluorine atoms) is described as having a straight-chain or branched structure (with a carbon number of, for example, 1 or more and 20 or less). Preferably, a perfluoroalkyl group is described as having all hydrogen atoms of the alkyl group replaced by fluorine atoms.

[0131] R 2 This represents a structure containing at least one repeating perfluoropolyether (PFPE) group. Preferably, it represents a structure containing two repeating PFPE groups. Examples of repeating PFPE groups include repeating structures with linear PFPE groups and repeating structures with branched PFPE groups. Examples of repeating structures with linear PFPE groups include –(OC…) n F 2n ) p The structure shown is (n represents an integer greater than 1 and less than 20, p represents an integer greater than 1 and less than 50. The same applies below). For example, a repeating structure of a branched PFPE base can be enumerated as –(OC(CF3)2). p The structure shown is - (OCF2CF(CF3)CF2) p The structure shown is shown in the diagram. As repeating structures of the PFPE group, linear repeating structures of the PFPE group are preferred, and (OCF2) repeating structures are more preferred. p - and - (OC2F4) p -.

[0132] R 3 The alkyl group has 1 or more but less than 4 carbon atoms, and preferably methyl.

[0133] X represents an ether group, carbonyl group, amino group, or amide group. Preferably, it represents an ether group.

[0134] m represents an integer greater than or equal to 1. Furthermore, m preferably represents an integer less than or equal to 20, more preferably an integer less than or equal to 10, and even more preferably an integer less than or equal to 5.

[0135] Among such alkoxysilane compounds having a perfluoropolyether group, compounds represented by the following general formula (2) are preferred.

[0136] CF3-(OCF2) q -(OC2F4) r -O-(CH2)3-Si(OCH3)3(2)

[0137] In general formula (2), q represents an integer greater than 1 and less than 50, and r represents an integer greater than 1 and less than 50.

[0138] Furthermore, alkoxysilane compounds with perfluoropolyether groups can be used alone or in combination of two or more.

[0139] In this embodiment, the antifouling layer 5 is a layer formed by a dry coating method (dry coating layer). Examples of dry coating methods include sputtering, vacuum evaporation, and CVD. Vacuum evaporation is preferred. That is, the antifouling layer 5 is preferably a dry coating layer. More preferably, it is a vacuum evaporation layer.

[0140] The thickness of the antifouling layer 5 is, for example, 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and, for example, 25 nm or less, preferably 20 nm or less, more preferably 15 nm or less.

[0141] The thickness of the laminate 1a is, for example, 5 μm or more, preferably 10 μm or more, more preferably 30 μm or more, and furthermore, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0142] The total reflectance of the light irradiated by the standard light source D65 with a wavelength of 380 nm to 780 nm from the side of the inorganic layer 4 (the side of the thickness direction of the laminate 1a) to the laminate 1a is 0.40% or less, preferably 0.35% or less, more preferably 0.33% or less, and even more preferably 0.31% or less.

[0143] (Effects)

[0144] As described above, the laminated film 1a includes: a substrate film 2; and a cured resin layer 3 disposed on one side of the substrate film 2 in the thickness direction. One or more protrusions B are formed on one side of the cured resin layer 3 in the thickness direction, and the average area of ​​each protrusion B is 80 nm. 2 Above and 500nm 2Furthermore, the arithmetic mean height Sa of the surface of the cured resin layer 3 along its thickness direction is 1.0 nm or more. Therefore, in the laminated film 1a, the adhesion between the cured resin layer 3 and the inorganic layer 4 laminated on its thickness direction surface can be improved.

[0145] Furthermore, the total reflectance (light reflectance ratio) of the standard light source D65 irradiating the laminated film 1a from the thickness direction of the inorganic layer 4 to the laminated film 1a is less than 0.40%. In other words, the laminated film 1a has excellent optical properties.

[0146] Therefore, the above-mentioned laminated film 1a has good optical properties and can improve the sealing performance.

[0147] 2. Manufacturing method of laminated films

[0148] One embodiment of a method for manufacturing a laminated film will be described: Refer to Figure 3A and Figure 3B After manufacturing the above-mentioned laminated film 1, further refer to Figure 3C and Figure 3D The above-mentioned laminated film 1a is manufactured.

[0149] A method for manufacturing a laminated film includes, for example, the following steps: a preparation step, preparing a substrate film 10' with a cured resin layer, the substrate film 10' having: a strip of substrate film 2; and a cured resin layer 3 disposed on one side of the substrate film 2 in the thickness direction. Figure 3A ); and a plasma treatment process, wherein one or more protrusions B are formed by plasma treatment of one side of the substrate film 10' with the cured resin layer in the thickness direction. Figure 3B Furthermore, in this embodiment, the method for manufacturing the laminated film further includes: an inorganic layer forming step, wherein an inorganic layer 4 is formed on one side of the laminated film 1 in the thickness direction. Figure 3C ); and the antifouling layer forming process, wherein an antifouling layer 5 is formed on one side of the inorganic layer 4 in the thickness direction. Figure 3D It should be noted that the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process use, for example... Figure 5 The device Z shown is implemented sequentially.

[0150] (Preparation process)

[0151] In the preparation process, such as Figure 3AAs shown, a strip of substrate film 10' with a cured resin layer is prepared. This strip of substrate film 10' includes: a flexible substrate film 2; and a cured resin layer 3 disposed on one side of the substrate film 2 in the thickness direction. In the strip of substrate film 10' with a cured resin layer, the side of the cured resin layer 3 in the thickness direction is not subjected to plasma treatment. That is, the strip of substrate film 10' with a cured resin layer has a plasma-untreated surface 3a', and the side of the strip of substrate film 10' with a cured resin layer in the thickness direction is the plasma-untreated surface 3a'.

[0152] Specifically, in the preparation process, a flexible substrate film 2 is prepared, and the above-mentioned ultraviolet curable resin composition is coated on one side of the substrate film 2 in the thickness direction. After the coating is formed, the coating is cured to form a cured resin layer 3, and a substrate film 10' with a cured resin layer is prepared.

[0153] From a manufacturing point of view, the UV-curable resin composition preferably contains a solvent. Examples of solvents include butyl acetate, ethyl acetate, toluene, and cyclopentanone. Butyl acetate and cyclopentanone are preferred.

[0154] In the case where the UV-curable resin composition contains a solvent, the coating on the substrate film 2 is dried after the UV-curable resin composition is applied.

[0155] The drying temperature is, for example, above 50°C, and also, for example, below 120°C. The drying time is, for example, above 10 seconds, and also, for example, below 10 minutes.

[0156] The coating on one side of the substrate film 2 along its thickness direction is cured by ultraviolet (UV) irradiation. Examples of UV light sources include high-pressure mercury lamps and LED lamps. The cumulative UV irradiation intensity is, for example, 100 mJ / cm². 2 In addition, for example, 500mJ / cm 2 the following.

[0157] A strip of substrate film 10' with a cured resin layer is prepared as described above. In this embodiment, a roll of the strip of substrate film 10' with a cured resin layer is prepared. Specifically, the strip of substrate film 10' with a cured resin layer is wound such that one side of the substrate film 10' with the cured resin layer (the plasma-untreated surface 3a') faces radially inward.

[0158] [Device Z]

[0159] In the method for manufacturing a laminated film, a substrate film 10' with a cured resin layer is then conveyed as a working film W in a roll-to-roll manner under reduced pressure, while a plasma treatment process, an inorganic layer formation process, and an antifouling layer formation process are sequentially performed. (Refer to...) Figure 5 The apparatus Z will be described as an example of an apparatus for performing a plasma processing step, an inorganic layer formation step, and an antifouling layer formation step.

[0160] It should be noted that the working film W before the plasma treatment process is a substrate film 10' with a cured resin layer, the working film W after the plasma treatment process and before the inorganic layer formation process is a laminated film 1, and the working film W after the antifouling layer formation process is a laminated film 1a.

[0161] The apparatus Z comprises: an extraction chamber R1, a winding chamber R2, a connecting chamber P1, a plasma treatment chamber P2, a connecting chamber P3, a first film-forming chamber P4, a connecting chamber P5, a second film-forming chamber P6, a connecting chamber P7, and a PEM device (illustration omitted).

[0162] The extraction chamber R1 is equipped with an extraction roller 51 for extracting the working film W. A strip of substrate film 10' with a cured resin layer is mounted on the extraction roller 51 as the working film W. In addition, a predetermined number of guide rollers G are provided in the extraction chamber R1 for guiding the working film W.

[0163] The winding chamber R2 is equipped with a winding roller 52 for winding the working film W. A predetermined number of guide rollers G are provided inside the winding chamber R2 for guiding the working film W.

[0164] A connecting chamber P1 is positioned between the extraction chamber R1 and the plasma processing chamber P2 in the direction of travel of the working membrane W. A predetermined number of guide rollers G are provided within the connecting chamber P1 to guide the working membrane W. The connecting chamber P1 is connected to a vacuum pump (not shown) and is configured to regulate the pressure within the chamber. When the device Z is operated, the pressure within the connecting chamber P1 is maintained at a predetermined pressure between the pressure in the extraction chamber R1 and the pressure in the plasma processing chamber P2. This ensures the pressure difference between the extraction chamber R1 and the plasma processing chamber P2.

[0165] The plasma treatment chamber P2 is positioned between the connecting chambers P1 and P3 in the direction of travel of the working membrane W. The plasma treatment process is performed in the plasma treatment chamber P2.

[0166] The plasma processing chamber P2 is equipped with multiple LIA71 antennas. LIAs are antennas with low inductance (below 7.5 μH) and capable of generating inductively coupled plasma by applying high-frequency power. In this embodiment, as... Figure 6 and Figure 7 As shown, LIA71 is supported by mounting component 72 and covered by cover block 73 (in Figure 6 (The text is omitted) Under the condition of being covered, it is configured in the indoor space of plasma processing chamber P2 ( Figure 6 (This refers to the case where the number of LIA71 is 4).

[0167] Multiple LIA71s are arranged neatly in the direction of travel of the working membrane W and in a direction orthogonal to the direction of travel (the width direction of the working membrane W). The mounting component 72 is a vacuum flange. (The text abruptly ends here.) Figure 7 As shown, LIA71 is fixed to mounting member 72 via feedthrough 74. (As indicated...) Figure 5 As shown, the mounting component 72 is assembled to the opening 75 located in the wall of the plasma processing chamber P2. Specifically, the mounting component 72 is assembled to the opening 75 with a sealing member (not shown) sandwiched between the wall of the plasma processing chamber P2 and the mounting component 72. Although not shown, LIA71 is electrically connected to a high-frequency power supply (RF power supply) outside the plasma processing chamber P2 via an impedance matching device.

[0168] LIA71 is formed of a conductor. Examples of conductors include copper and silver, with copper being preferred. LIA71 may also be covered with an insulator (e.g., glass and quartz).

[0169] The cover block 73 comprises a block body 73A and a plurality of partition plates 73B. The block body 73A has a plurality of receiving spaces 73a. Each receiving space 73a receives one LIA 71. The partition plates 73B are configured to enclose the receiving spaces 73a. The receiving spaces 73a are sealed spaces. In the cover block 73, the block body 73A is formed, for example, of aluminum. The partition plates 73B are made of insulating materials (e.g., quartz and glass).

[0170] The isolation distance d' between the working membrane W traveling within the plasma processing chamber P2 and the cover block 73. Figure 5 (As shown) For example, 50-200mm.

[0171] The cover block 73 prevents the plasma conversion efficiency achieved by applying power to LIA71 from being excessively reduced, and plays a role in avoiding damage and contamination of LIA71 caused by plasma treatment. In addition, it plays a role in suppressing damage to the working film W (substrate film 10' with cured resin layer) that has undergone plasma treatment.

[0172] The plasma treatment chamber P2 may further include a conveyor roller 53. The conveyor roller 53 is a main guide roller for conveying the working film W within the plasma treatment chamber P2. The conveyor roller 53 has a temperature regulating function that can heat or cool the working film W. That is, the conveyor roller 53 is a roller with a temperature regulating function. The conveyor roller 53 contacts the surface of the substrate film 10' with the cured resin layer in the thickness direction opposite to the surface of the substrate film 10' with the cured resin layer, and conveys the substrate film 10' with the cured resin layer. LIA71 is arranged opposite to the conveyor roller 53. When the conveyor roller 53 is included, in the plasma treatment process, the working film W (the substrate film 10' with the cured resin layer) can be cooled or heated, and the surface of the substrate film 10' with the cured resin layer in the thickness direction (the untreated plasma surface 3a') can be plasma treated. Therefore, thermal deformation of the substrate film 10' with the cured resin layer can be suppressed, and consequently, the effect of thermal deformation on the conveying of the working film W can be suppressed.

[0173] In this embodiment, such as Figure 6 As shown, LIA71 has an open-loop shape. The open-loop shape of LIA71 reduces its inductance. Therefore, the open-loop shape of LIA71 suppresses voltage increases caused by increased applied power to LIA71. This suppresses abnormal discharges during the plasma treatment process. Suppressing abnormal discharges helps prevent damage to the substrate film 10' with the cured resin layer caused by plasma treatment. Specifically, LIA71 has a U-shape with two movable ends. The two movable ends of each LIA71 are fixed to the mounting member 72 in a manner arranged in the width direction of the working film W. Furthermore, in this embodiment, LIA71 has an extension 71a on the side opposite to the two movable ends. The extension 71a extends parallel to the working film W passing through the plasma treatment chamber P2. Each extension 71a extends in the width direction of the working film W. Each extension 71a may also extend in the travel direction of the working film W (or four LIA71s may be configured in this way). The length of the extension 71a is, for example, 50 to 150 mm. Figure 6 This refers to the case where the length of the extension 71a is the same as the maximum length d2 of LIA71 (described later). LIA71 can also have a coil shape.

[0174] LIA71 extends from the mounting member 72 toward the working membrane W. LIA71 preferably extends in a direction perpendicular to the mounting member 72. The extension length d1 of LIA71 from the mounting member 72 is, for example, 30 to 150 mm. The maximum length d2 of LIA71 in the surface direction of the working membrane W is, for example, 50 to 200 mm. The isolation distance d3 between LIA71 and the working membrane W is, for example, 50 to 200 mm. The ratio of the isolation distance d3 to the extension length d1 (d3 / d1) is, for example, 0.5 to 3.5. The number (rows) of LIA71 arranged in isolation in the travel direction of the working membrane W can be appropriately adjusted according to the travel speed of the working membrane W (i.e., plasma processing time), for example, from 1 to 4, or more than 4. In the travel direction of the working membrane W, the center-to-center distance d4 between adjacent LIA71 is, for example, 100 to 500 mm. In the width direction of the working membrane W, the center-to-center distance d5 between adjacent LIA71 is, for example, 200 to 500 mm. By adjusting the center-to-center distance d5, the uniformity of the plasma density (described later) in the width direction of the working membrane W can be controlled. The ratio (d5 / d4) of the center-to-center distance d5 is, for example, 0.5 to 2.0. With such a set of LIA71s, high-density plasma can be generated. As LIA71, for example, a high-frequency antenna for plasma generation described in Japanese Patent Application Publication No. 2013-258153 can be used.

[0175] The PEM device is used for plasma emission monitoring (PEM) in plasma processing. It consists of a main body and an optical fiber for light collection. One end of the optical fiber is positioned between the working membrane W and LIA71 within the plasma processing chamber P2. The other end of the optical fiber is connected to the main body of the device. Furthermore, a first pipeline L1 with a flow control valve is connected to the plasma processing chamber P2 for introducing gas into the chamber.

[0176] A connecting chamber P3 is positioned between the plasma processing chamber P2 and the first film-forming chamber P4 in the direction of travel of the working film W. A predetermined number of guide rollers G are provided within the connecting chamber P3 to guide the working film W. The connecting chamber P3 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operated, the pressure within the connecting chamber P3 is maintained at a predetermined pressure between the pressure in the plasma processing chamber P2 and the pressure in the first film-forming chamber P4. This ensures the pressure difference between the plasma processing chamber P2 and the first film-forming chamber P4.

[0177] The first film-forming chamber P4 is positioned after the connecting chamber P3 in the direction of travel of the working film W. Furthermore, the first film-forming chamber P4 is connected to a vacuum pump (not shown) and is configured to adjust the vacuum level within the chamber to a predetermined degree. The inorganic layer formation process is performed in the first film-forming chamber P4 as described later.

[0178] In this embodiment, the first film-forming chamber P4 is a sputtering film-forming chamber. The first film-forming chamber P4 includes a film-forming roller 54 and a plurality of sputtering chambers 60 (sputtering chambers 60a to 60e) (in Figure 5 (This indicates the case where the number of sputtering chambers 60 is 5). The film-forming roller 54 is the main guide roller for conveying the working film W within the first film-forming chamber P4. The film-forming roller 54 has a temperature regulation function that can heat or cool the working film W. The sputtering chambers 60 are spaces divided within the first film-forming chamber P4. Multiple sputtering chambers 60 are arranged circumferentially along the film-forming roller 54. Each sputtering chamber 60 opens toward the film-forming roller 54. A cathode 61 is provided within the sputtering chamber 60. A target (not shown) serving as the film-forming material supply is disposed on the cathode 61. The target is disposed on the cathode 61 opposite to the film-forming roller 54. Each sputtering chamber 60 is provided with a power supply (not shown) for applying a voltage to the target to generate a glow discharge. Examples of power supplies include: DP power supply, AC power supply, MF power supply, RF power supply, and MF-AC power supply. MF-AC power supply refers to an AC power supply with a frequency band of several kHz to several MHz. Each sputtering chamber 60 is connected to a required number of second pipelines with flow control valves for introducing gas into the chamber (illustration omitted). Furthermore, a predetermined number of guide rollers G are provided in the first film-forming chamber P4 for guiding the working film W.

[0179] A connecting chamber P5 is positioned between the first film-forming chamber P4 and the second film-forming chamber P6 in the direction of travel of the working film W. A predetermined number of guide rollers G are provided within the connecting chamber P5 to guide the working film W. The connecting chamber P5 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operated, the pressure within the connecting chamber P5 is maintained at a predetermined pressure between the pressure in the first film-forming chamber P4 and the pressure in the second film-forming chamber P6. This ensures the pressure difference between the first film-forming chamber P4 and the second film-forming chamber P6.

[0180] The second film-forming chamber P6 is positioned after the connecting chamber P5 in the direction of travel of the working film W. Furthermore, the second film-forming chamber P6 is connected to a vacuum pump (not shown), configured to adjust the vacuum level within the chamber to a predetermined degree. The antifouling layer formation process is performed in the second film-forming chamber P6 as described later.

[0181] In this embodiment, the second film-forming chamber P6 is a vacuum evaporation chamber. The second film-forming chamber P6 includes a material holding section 81, a vacuum pump (not shown), and a evaporation amount adjustment valve (not shown) that controls the opening degree. Furthermore, a predetermined number of guide rollers G for guiding the working film W are provided in the second film-forming chamber P6 as needed. Film-forming material supply material (not shown) is arranged in the material holding section 81 opposite to the working film W transported in the second film-forming chamber P6. The material holding section 81 may contain a resistance heating unit, a high-frequency induction heating unit, or an electron beam heating unit to heat the film-forming material supply material.

[0182] A connecting chamber P7 is positioned between the second film-forming chamber P6 and the winding chamber R2 in the direction of travel of the working film W. A predetermined number of guide rollers G are provided within the connecting chamber P7 to guide the working film W. The connecting chamber P7 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operated, the pressure within the connecting chamber P7 is maintained at a predetermined pressure between the pressure in the second film-forming chamber P6 and the pressure in the winding chamber R2. This ensures the pressure difference between the second film-forming chamber P6 and the winding chamber R2.

[0183] Using the apparatus Z described above, a plasma treatment process, an inorganic layer formation process, and an antifouling layer formation process are performed sequentially. Specifically, as follows.

[0184] (Plasma treatment process)

[0185] The working membrane W is extracted from the extraction chamber R1. After being extracted from the extraction chamber R1, the working membrane W sequentially passes through the connecting chamber P1, the plasma treatment chamber P2, the connecting chamber P3, the first film-forming chamber P4, the connecting chamber P5, the second film-forming chamber P6, and the connecting chamber P7, and is then wound up in the winding chamber R2. The traveling speed of the working membrane W is, for example, 0.1 m / min to 10 m / min, preferably 0.5 m / min to 8 m / min. Furthermore, the series of pipelines from the extraction chamber R1 to the winding chamber R2 are not open to the atmosphere midway, but rather the process is carried out under a reduced pressure atmosphere. The reduced pressure atmosphere is preferably under vacuum. Vacuum preferably refers to a reduced pressure atmosphere of 7 Pa or less.

[0186] In the plasma treatment chamber P2, a plasma treatment process is performed. During this process, under a reduced pressure atmosphere within the plasma treatment chamber P2, the plasma luminescence intensity is sensed on one side of the substrate film 10' (working film W) with the cured resin layer (the untreated surface 3a'), and plasma treatment is performed. In this embodiment, the plasma treatment utilizes an inductively coupled plasma (oxygen LIA treatment) generated by applying high-frequency power to the LIA71 using oxygen-containing gas. Specifically, as described below.

[0187] Oxygen is supplied to the plasma processing chamber P2 via the first pipeline L1. In addition to oxygen, an inert gas may also be supplied to the plasma processing chamber P2. Examples of inert gases include argon, krypton, and xenon. Furthermore, the gas in the plasma processing chamber P2 may contain other gases besides inert gases and oxygen. Examples of other gases include nitrogen and hydrogen. The oxygen concentration of the gas (oxygen-containing gas) in the plasma processing chamber P2 is, for example, 30% by volume or more, preferably 50% by volume or more, more preferably 80% by volume or more, further preferably 90% by volume or more, and particularly preferably 100% by volume. If the oxygen concentration is above the aforementioned lower limit, a high-density oxygen plasma can be generated. This has an effect on the nanoscale micro-texturation of the untreated surface 3a' of the substrate film 10' with the cured resin layer and on the changes in chemical bonds near the surface of the untreated surface 3a' of the substrate film 10' with the cured resin layer.

[0188] The pressure (first pressure) within the plasma processing chamber P2 during plasma treatment is, for example, 0.1 Pa or more, preferably 0.3 Pa or more, and further, for example, 7 Pa or less, preferably 3 Pa or less. If the first pressure is above the aforementioned lower limit, a plasma environment with a density sufficient to perform surface modification treatment on the working film W can be formed within the plasma processing chamber P2 during plasma treatment. If the first pressure is below the aforementioned upper limit, damage to the working film W caused by excessively high-density plasma can be suppressed during plasma treatment. The first pressure can be adjusted by the amount of oxygen supplied to the plasma processing chamber P2.

[0189] The temperature of the working film W (substrate film 10' with a cured resin layer) whose temperature is adjusted by the conveying roller 53 is, for example, -20°C to 150°C.

[0190] In plasma processing, the frequency of the high-frequency power applied to LIA71 is, for example, 1 MHz or more, preferably 5 MHz or more, and further, for example, 100 MHz or less, preferably 60 MHz or less. If the frequency of the high-frequency power is above or below the aforementioned lower limit, the plasma current density can be increased and the plasma discharge can be stabilized during plasma processing. If the frequency of the high-frequency power is below or below the aforementioned upper limit, the antenna potential can be suppressed, and therefore, damage to the working film W caused by the plasma can be suppressed.

[0191] In plasma processing, the high-frequency power applied to LIA71 is, for example, 1.0 kW or more, preferably 2.0 kW or more, more preferably 3.0 kW or more, and further preferably 15 kW or less, preferably 10 kW or less, more preferably 8.0 kW or less, and even more preferably 6.0 kW or less. If the high-frequency power is above or below the aforementioned lower limit, a high-density plasma environment can be formed in the plasma processing chamber P2 in plasma processing using inductively coupled plasma. If the high-frequency power is below the aforementioned upper limit, excessive damage to the working film W caused by the plasma can be suppressed. Furthermore, if the high-frequency power is below the aforementioned upper limit, the total reflectivity (light reflectance ratio) can be improved.

[0192] In the plasma processing procedure, it is preferable to use a PEM device to monitor the plasma luminescence intensity during plasma processing. Furthermore, based on the monitoring results, the oxygen introduction amount, the high-frequency power, and the travel speed are controlled.

[0193] In the plasma treatment process, the plasma current density at the midpoint between LIA71 and the working film W (the substrate film 10' with the cured resin layer) is, for example, 0.1 mA / cm². 3 The above is preferably 0.5 mA / cm. 3 In addition, for example, 8mA / cm 3 The preferred value is 5mA / cm. 3 The following describes how plasma treatment using inductive coupling (LIA) can achieve a higher plasma current density than plasma treatment using capacitive coupling (e.g., approximately 100 times higher). If the plasma current density is above the lower limit mentioned above, sufficient plasma-enhanced oxygen particles can be ensured within the plasma treatment chamber P2 during plasma treatment, allowing for appropriate surface modification of the working film W. If the plasma current density is below the upper limit mentioned above, damage to the working film W caused by excessively high-density plasma-enhanced oxygen particles can be suppressed during plasma treatment. Methods for adjusting the plasma current density include, for example, adjusting the amount of oxygen introduced into the plasma treatment chamber P2, adjusting the frequency of the high-frequency power applied by the high-frequency power supply, and adjusting the magnitude of the applied power. It should be noted that the plasma current density can be measured using a Langmuir probe for plasma measurement.

[0194] By performing plasma treatment on the substrate film 10' with the cured resin layer as described above, one or more protrusions B are formed, thereby... Figure 3BAs shown, a laminated film 1 is manufactured. The laminated film 1 has a plasma treatment surface 3a having one or more protrusions B. In other words, one side of the laminated film 1 in the thickness direction is a plasma treatment surface 3a having one or more protrusions B.

[0195] By performing plasma treatment on the substrate film 10' with the cured resin layer as described above, one or more protrusions B are formed, and a laminated film 1 is made, thereby improving the adhesion.

[0196] (Inorganic layer formation process)

[0197] In the inorganic layer formation process, immediately following the plasma treatment process, an inorganic layer 4 is formed on one side (plasma-treated surface 3a) of the laminated film 1 (working film W) in the thickness direction by sputtering, evaporation, or chemical vapor deposition under a reduced pressure atmosphere. In the inorganic layer formation process, sputtering is preferably used to form the inorganic layer 4. It should be noted that the reduced pressure atmosphere is preferably under vacuum.

[0198] In sputtering, a sputtering gas (inert gas) is introduced into each sputtering chamber 60 via a second conduit, and a negative voltage is applied to the target (film-forming material) disposed on the cathode 61 within the sputtering chamber 60. This generates a glow discharge, ionizing the gas atoms. These gas ions collide with the target surface at high speed, ejecting the target material from the target surface, which is then deposited onto the working film W. Examples of sputtering gases include argon, krypton, and xenon.

[0199] Furthermore, the sputtering method can be reactive sputtering. In reactive sputtering, sputtering gas and oxygen (reactive gas) are introduced into the sputtering chamber 60. Oxygen is introduced into the sputtering chamber 60 via a second conduit. In reactive sputtering, the amount of reactive gas introduced is, for example, 1 to 50 parts by volume relative to 100 parts by volume of sputtering gas. In reactive sputtering, when the target is a metal or Si, the formed inorganic layer 4 contains an oxide of the target (that is, an oxide of the metal or an oxide of Si).

[0200] In the sputtering method, the pressure (second pressure) inside the sputtering chamber 60 is appropriately adjusted according to the type of layer to be formed, for example, from 0.1 to 5.0 Pa. The film-forming temperature (the temperature of the working film W, which is adjusted by the film-forming roller 54) is, for example, from -20°C to 150°C. Furthermore, the discharge power is, for example, from 1 kW to 50 kW.

[0201] In the inorganic layer formation process, the inorganic layer 4 is then formed on the plasma-treated surface 3a of the cured resin layer 3 by sputtering in at least one sputtering chamber selected from sputtering chambers 60a to 60e. In this embodiment, a high refractive index layer 41a is formed on one side of the cured resin layer 3 in the thickness direction in sputtering chamber 60b, a low refractive index layer 41b is formed on one side of the high refractive index layer 41a in the thickness direction in sputtering chamber 60c, a high refractive index layer 41c is formed on one side of the low refractive index layer 41b in the thickness direction in sputtering chamber 60d, and a low refractive index layer 41d is formed on one side of the high refractive index layer 41c in the thickness direction in sputtering chamber 60e.

[0202] (Antifouling layer formation process)

[0203] In the antifouling layer formation process, immediately following the inorganic layer formation process, under reduced pressure, the antifouling layer 5 is formed on one side of the inorganic layer 4 of the working film W (laminated film 1) after the inorganic layer formation process by sputtering, vapor deposition, or chemical vapor deposition. In the antifouling layer formation process, vapor deposition is preferably used to form the antifouling layer 5. It should be noted that the reduced pressure atmosphere is preferably under vacuum. That is, in the antifouling layer formation process, vacuum vapor deposition is more preferably used to form the antifouling layer 5.

[0204] In the vacuum evaporation method, the second film-forming chamber P6 is depressurized to a vacuum state by operating a vacuum pump, and the evaporation source arranged in the material holding part 81 is heated to a specified temperature, so that the material of the anti-fouling layer 5 evaporates and is deposited on the working film W.

[0205] In the vacuum evaporation method, the pressure (third pressure) inside the second film-forming chamber P6 is, for example, 0.1 Pa or less, preferably 0.05 Pa or less, and also, for example, 1 × 10⁻⁶ Pa. －5 Pa or above.

[0206] In vacuum evaporation, the heating temperature of the evaporation source is, for example, above 200°C, or below 400°C.

[0207] In apparatus Z, after the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process, the laminated film 1, which serves as the working film W, travels through the connecting chamber P7 to the winding chamber R2 and is wound up by the winding roller 52.

[0208] The long strip of laminated film 1a is manufactured as described above.

[0209] (Effects)

[0210] The method for manufacturing the aforementioned laminated film includes a plasma treatment step, wherein one or more protrusions B are formed by plasma treatment of one side of the cured resin layer 3 in the thickness direction. Therefore, a laminated film with good optical properties and improved adhesion can be manufactured.

[0211] 3. Variations

[0212] like Figure 4 As shown, in the laminated film of the first modified example, an adhesive layer 42, which is an inorganic layer 4, is further provided between the cured resin layer 3 and the antireflective layer 41 in the laminated film of the first embodiment. In this case, the inorganic layer 4 is a composite layer of the adhesive layer 42 and the antireflective layer 41. The adhesive layer 42 is disposed between the cured resin layer 3 and other inorganic layers (e.g., the antireflective layer or the conductive layer) to improve the adhesion between the cured resin layer 3 and other inorganic layers. As a result, the adhesion of the laminated film can be further improved. In the first modified example, the structure other than the adhesive layer is the same as in the first and second embodiments. The adhesive layer 42 will be specifically described below.

[0213] The adhesive layer 42 is disposed on one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a). That is, the adhesive layer 42 is in contact with the cured resin layer 3. Furthermore, the adhesive layer 42 is disposed on the other side of the anti-reflective layer 41 in the thickness direction. That is, the adhesive layer 42 is in contact with the anti-reflective layer 41.

[0214] Materials for the adhesive layer 42 include, for example, metals such as In, Ni, Cr, Ar, Sn, Au, Ag, Pt, Zn, Ti, W, Zr, Pd, and Nb, alloys of two or more of these metals, and oxides of these metals. Furthermore, materials for the adhesive layer 42 may include, for example, Si and its oxides. From the viewpoint of balancing the adhesion between the cured resin layer 3 and the antireflective layer 41 or conductive layer stacked on the adhesive layer 42, as well as the transparency of the adhesive layer 42, inorganic oxides containing at least one element selected from the group consisting of Si, In, Al, Sn, Ti, and Zr are preferred materials for the adhesive layer 42. Indium tin oxide (ITO) and silicon oxide (SiOx) are more preferred. ITO is even more preferred.

[0215] The silicon dioxide used as the material of the sealing layer 42 is, for example, SiOx with less oxygen content than the stoichiometric composition, preferably x is 1.2 or more and 1.9 or less.

[0216] When ITO is used as the material of the sealing layer 42, the content of tin oxide relative to the total amount of tin oxide (SnO2) and indium oxide (In2O3) is, for example, 0.5% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and in addition, for example, 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less.

[0217] The thickness of the sealing layer 42 is, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1.0 nm or more, and also, for example, 30 nm or less, preferably 15 nm or less, more preferably 10 nm or less.

[0218] If the thickness of the adhesive layer 42 is above the lower limit mentioned above, the adhesion between the cured resin layer 3 and the antireflective layer 41 or conductive layer laminated on the adhesive layer 42 can be improved. If the thickness of the adhesive layer 42 is below the upper limit mentioned above, the optical properties of the adhesive layer 42 can be improved.

[0219] Following the plasma treatment step in the aforementioned method for manufacturing the laminated film 1a, as part of the inorganic layer formation step, an adhesive layer 42 is formed under the same conditions as in the inorganic layer formation step. Next to the plasma treatment step, under reduced pressure, the adhesive layer 42 is formed on one side of the laminated film 1 (plasma-treated surface 3a) by sputtering, evaporation, or chemical vapor deposition. In forming the adhesive layer 42, sputtering is preferred. It should be noted that the reduced pressure atmosphere is preferably under vacuum.

[0220] When forming an adhesive layer using the aforementioned apparatus Z via sputtering as part of an inorganic layer formation process, following the plasma treatment process in the plasma treatment chamber P2, an adhesive layer 42 is formed on the plasma-treated surface 3a of the cured resin layer 3 via sputtering in the sputtering chamber 60a of the first film formation chamber P4. Then, following the formation of the adhesive layer 42 in the sputtering chamber 60a, a high refractive index layer 41a is formed on one side of the adhesive layer 42 in the thickness direction in the sputtering chamber 60b; a low refractive index layer 41b is formed on one side of the high refractive index layer 41a in the thickness direction in the sputtering chamber 60c; a high refractive index layer 41c is formed on one side of the low refractive index layer 41b in the thickness direction in the sputtering chamber 60d; and a low refractive index layer 41d is formed on one side of the high refractive index layer 41c in the thickness direction in the sputtering chamber 60e. Finally, an antifouling layer 5 is formed, thereby manufacturing the laminated film 1b of the first modified example.

[0221] Example

[0222] The following examples and comparative examples further illustrate the present invention in detail. It should be noted that the present invention is not limited to any particular example or comparative example. Furthermore, the specific values ​​of proportions (including proportions), physical property values, parameters, etc., used in the following description can be replaced by the upper limits (defined as values ​​"below" or "less than") or lower limits (defined as values ​​"above" or "greater than") of the corresponding proportions (including proportions), physical property values, parameters, etc., described in the above-described "Specific Embodiments".

[0223] <Example 1>

[0224] As shown in Table 1, the laminated film of Example 1 was produced in the following order according to the manufacturing conditions outlined in Table 1.

[0225] (Preparation process)

[0226] A hard coating layer, serving as a curing resin layer, is formed on one side of the triacetic acid cellulose (TAC) film, which serves as the substrate film, in the thickness direction.

[0227] Specifically, 80 parts by weight (converted solids content) of UV-curable urethane acrylate resin (product name "UT-7314", manufactured by Mitsubishi Chemical Co., Ltd.), 20 parts by weight (converted solids content) of polyfunctional acrylate with pentaerythritol triacrylate as the main component (product name "Viscoat#300", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.5 parts by weight of photopolymerization initiator (product name "Omnirad127D", manufactured by BASF Co., Ltd.), and 0.06 parts by weight of leveling agent (product name "POLYFLOWLE-303", a leveling agent containing organosilicon compounds, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixture. Next, a mixed solvent of butyl acetate and cyclopentanone (CPN) (butyl acetate to CPN mass ratio of 70:30) was added to the mixture to prepare a cured resin composition with a solids content of 40% by weight.

[0228] On the other hand, a long strip of TAC film (product name "KC8UAW", thickness 80μm, manufactured by KONICA MINOLTA) was prepared. Next, a curing resin composition was coated onto the thickness-direction side of the TAC film to form a coating. This coating was dried by heating and then cured by ultraviolet (UV) irradiation. This resulted in a 9μm thick hard coating layer on the thickness-direction side of the TAC film. It should be noted that, as drying conditions, the heating temperature was set to 80°C and the heating time to 1 minute. For UV irradiation, a high-pressure mercury lamp was used as the light source, and the coating was irradiated with UV light at a wavelength of 365nm, with a cumulative irradiation dose set to 300mJ / cm². 2 Prepare a roll of substrate film with a cured resin layer as described above.

[0229] (Plasma treatment process)

[0230] While conveying a substrate film with a cured resin layer in a roll-to-roll manner under vacuum, plasma treatment is performed on one side of the substrate film with the cured resin layer in the thickness direction (the side with the cured resin layer in the thickness direction).

[0231] In plasma processing, a first apparatus is used to perform a roll-to-roll process on a working film. The first apparatus includes: an extraction chamber, a plasma processing chamber (first plasma processing chamber), a film forming chamber (first film forming chamber and second film forming chamber), and a winding chamber. The extraction chamber, first plasma processing chamber, first film forming chamber, second film forming chamber, and winding chamber are arranged sequentially and connected. The extraction chamber includes an extraction roller. A roll of the aforementioned substrate film with a cured resin layer, serving as the working film, is disposed on the extraction roller. The first plasma processing chamber includes: a conveyor roller with a temperature regulating function (in... Figure 5 The middle part is the conveyor roller 53) and such Figure 6 and Figure 7 The covered block shown (in) Figure 7 The four LIAs covered by the cover block 73 are located in the middle. Figure 6 and Figure 7 (LIA71 is shown in the middle). Each LIA has an extension parallel to the substrate film (in...). Figure 6 The middle part is extension 71a). Among the four LIAs, the extension length d1 is 88 mm, the maximum length d2 (length of the extension) is 100 mm, the separation distance d3 is 112 mm, the center-to-center distance d4 is 290 mm, and the center-to-center distance d5 is 280 mm (refer to...). Figure 6 and Figure 7 Each LIA is electrically connected to a high-frequency power supply (RF power supply, frequency 13.56MHz) outside the first plasma treatment chamber via an impedance matching device. The isolation distance d' between the substrate film and the cover block traveling within the first plasma treatment chamber is 100mm. Furthermore, the first film deposition chamber is a sputtering film deposition chamber, equipped with a film deposition roller and a cathode arranged opposite to the film deposition roller. The second film deposition chamber is a vacuum evaporation chamber, equipped with an evaporation source. The winding chamber is equipped with a winding roller.

[0232] Using the first apparatus described above, specifically, while conveying a substrate film with a cured resin layer from the extraction chamber to the winding chamber via a roll-to-roll method, plasma treatment is performed on one side of the substrate film with the cured resin layer in the thickness direction within a first plasma treatment chamber. The travel speed of the substrate film with the cured resin layer (the travel speed of the working film) is set to 1.0 m / min. The temperature of the conveyor roller with temperature control function is set to -8°C. It should be noted that the plasma treatment conditions are as follows.

[0233] The device was evacuated until the ultimate vacuum level of the first plasma processing chamber reached 1.0 × 10⁻⁶. －4 After Pa, oxygen is introduced into the first plasma treatment chamber, and the pressure inside the chamber is set to 1.5 Pa. A high-frequency power of 5.0 kW is applied to the four LIAs using a high-frequency power supply, thereby forming an oxygen-containing inductively coupled plasma around the four LIAs. This plasma is then used to treat one side of the substrate film with the cured resin layer along its thickness direction. The plasma current density at the midpoint between the LIA and the working film is 1.3 mA / cm². 3 The plasma current density was measured using a Langmuir probe, a standard instrument for plasma measurement.

[0234] As described above, plasma treatment is performed on one side of the substrate film with the cured resin layer in the thickness direction. That is, the side of the substrate film with the cured resin layer in the thickness direction is the plasma-treated surface. The plasma treatment is a treatment using plasma that utilizes inductively coupled plasma (oxygen LIA treatment) generated by applying high-frequency power to the LIA and using oxygen-containing gas.

[0235] (Inorganic layer formation process)

[0236] Next, in conjunction with the plasma treatment process, an inorganic layer is formed on the substrate film with the cured resin layer.

[0237] Specifically, using the aforementioned first apparatus capable of sputtering film formation in a roll-to-roll manner, a first high refractive index layer, a first low refractive index layer, a second high refractive index layer, and a second low refractive index layer are sequentially formed on one side of the substrate film with a cured resin layer after plasma treatment in the thickness direction in the first film formation chamber.

[0238] The first film-forming chamber is equipped with film-forming rollers (in... Figure 7 The first film-forming roller (54) and multiple sputtering chambers are located in the middle. Each sputtering chamber is a space partitioned within the first film-forming roller. Each sputtering chamber has a cathode positioned opposite the film-forming roller. A number of second pipelines (not shown) with flow control valves are connected to each sputtering chamber for introducing gas into the chamber.

[0239] The substrate film with a cured resin layer is cooled and conveyed simultaneously using a film-forming roller in the first film-forming chamber. A first high-refractive-index layer is formed on the substrate film with the cured resin layer in the second sputtering chamber. A first low-refractive-index layer is formed on the first high-refractive-index layer in the third sputtering chamber. A second high-refractive-index layer is formed on the first low-refractive-index layer in the fourth sputtering chamber. A second low-refractive-index layer is formed on the second high-refractive-index layer in the fifth sputtering chamber (the first high-refractive-index layer, the first low-refractive-index layer, the second high-refractive-index layer, and the second low-refractive-index layer are inorganic layers). The film-forming temperature (temperature of the film-forming roll) is set to -8°C. It should be noted that the film-forming conditions are as follows.

[0240] In the second sputtering chamber, a 14 nm thick Nb₂O₅ layer (refractive index 2.33) is formed as the first high-refractive-index layer using reactive sputtering. Specifically, after evacuating the first film-forming chamber as described above, argon as an inert gas and oxygen as a reactive gas are introduced into the second sputtering chamber, and the pressure in the second sputtering chamber is set to 0.5 Pa. The amount of oxygen introduced into the second sputtering chamber is set to 5 parts per 100 parts per volume of argon. An Nb target is used as the target. The discharge power is set to 13 kW.

[0241] In the third sputtering chamber, a 28 nm thick SiO2 layer (refractive index 1.46) is formed as the first low-refractive-index layer using reactive sputtering. Specifically, after evacuating the first film-forming chamber as described above, argon as an inert gas and oxygen as a reactive gas are introduced into the third sputtering chamber, and the pressure in the third sputtering chamber is set to 0.2 Pa. The amount of oxygen introduced into the third sputtering chamber is set to 30 parts per 100 parts per volume of argon. A Si target is used as the target. The discharge power is set to 25 kW.

[0242] In the fourth sputtering chamber, a 105 nm thick Nb₂O₅ layer (refractive index 2.33) is formed as a second high-refractive-index layer using reactive sputtering. Specifically, after evacuating the first film-forming chamber as described above, argon as an inert gas and oxygen as a reactive gas are introduced into the fourth sputtering chamber, and the pressure in the fourth sputtering chamber is set to 0.5 Pa. The amount of oxygen introduced into the fourth sputtering chamber is set to 13 parts per 100 parts per volume of argon. An Nb target is used as the target. The discharge power is set to 27.5 kW.

[0243] In the fifth sputtering chamber, a SiO2 layer with a thickness of 84 nm (refractive index 1.46) is formed as a second low-refractive-index layer using reactive sputtering. Specifically, after vacuum venting of the first film-forming chamber as described above, argon as an inert gas and oxygen as a reactive gas are introduced into the fifth sputtering chamber, and the pressure in the fifth sputtering chamber is set to 0.2 Pa. The amount of oxygen introduced into the fifth sputtering chamber is set to 30 parts per 100 parts per volume of argon. A Si target is used as the target. The discharge power is set to 20.5 kW.

[0244] (Antifouling layer formation process)

[0245] Next, in continuous with the inorganic layer formation process, an antifouling layer is formed on one side of the inorganic layer in the thickness direction (specifically, on one side of the second low-refractive-index layer in the thickness direction).

[0246] Specifically, using the first apparatus described above, an antifouling layer with a thickness of 8 nm is formed on one side of the inorganic layer in the thickness direction by vacuum evaporation in the second film-forming chamber using a perfluoropolyether-containing alkoxysilane compound as the evaporation source. The evaporation source is a solid component obtained by drying "KY1903-1" (a perfluoropolyether-containing alkoxysilane compound represented by the above general formula (2), with a solid component concentration of 20% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Furthermore, the heating temperature of the evaporation source in the vacuum evaporation method is set to 260°C.

[0247] The laminated film of Example 1 was fabricated as described above. The laminated film of Example 1 comprises, sequentially on the thickness-direction side: a substrate film, a cured resin layer, inorganic layers (a first high-refractive-index layer, a first low-refractive-index layer, a second high-refractive-index layer, and a second low-refractive-index layer), and an antifouling layer. It should be noted that a summary of the manufacturing conditions is shown in Table 1.

[0248] <Example 2>

[0249] As shown in Table 1, in the preparation process, the leveling agent used in the curable resin composition (product name "POLYFLOW LE-303", a leveling agent containing an organosilicon compound, manufactured by Kyoei Chemical Co., Ltd.) was changed to a leveling agent (product name "MEGAFACE S-333", a leveling agent containing an organosilicon compound, manufactured by DIC Corporation). Otherwise, the laminated film of Example 2 was produced in the same manner as in Example 1.

[0250] <Comparative Example 1>

[0251] As shown in Table 1, the manufacturing conditions are summarized, but the plasma treatment process is not performed. Otherwise, the laminated film of Comparative Example 1 is produced in the same manner as in Example 1.

[0252] <Comparative Example 2>

[0253] As shown in Table 1, the manufacturing conditions are summarized. In the preparation process, no leveling agent is added to the curable resin composition. Otherwise, the laminated film of Comparative Example 2 is produced in the same manner as in Example 1.

[0254] <Comparative Example 3>

[0255] As shown in Table 1, the laminated film of Comparative Example 3 was produced in the following order according to the manufacturing conditions outlined in Table 1.

[0256] (Preparation process)

[0257] Further, 150 parts by weight (converted solid content value) of silica particles with a particle size of 40-50 nm (product name "PGM-AC-4130Y", manufactured by Nissan Chemical Co., Ltd.) dispersed in propylene glycol monomethyl ether were mixed into the mixture. Otherwise, a roll of substrate film with a cured resin layer was prepared in the same manner as the preparation process in Example 1.

[0258] (Plasma treatment process)

[0259] While conveying a substrate film with a cured resin layer in a roll-to-roll manner under vacuum, plasma treatment is performed on one side of the substrate film with the cured resin layer in the thickness direction (the side with the cured resin layer in the thickness direction).

[0260] In plasma processing, a second apparatus is used that performs a roll-to-roll process on the working film. The second apparatus has a second plasma processing chamber instead of a first plasma processing chamber, but otherwise has the same configuration as the first apparatus. The second plasma processing chamber has a pair of planar electrodes, a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304), used for plasma generation. The pair of planar electrodes are spaced 50 mm apart and are arranged parallel to the substrate film with a cured resin layer passing through the second plasma processing chamber. The anode electrode is positioned 35 mm away from the substrate film with a cured resin layer passing through the second plasma processing chamber and is grounded outside the second plasma processing chamber. The cathode electrode is positioned opposite the substrate film with a cured resin layer in the thickness direction and is electrically connected to a high-frequency power supply (RF power supply, 13.56 MHz) via an impedance matching device. The length of each electrode opposite the substrate film with a cured resin layer in the film travel direction is 110 mm, and the length in the width direction is 430 mm.

[0261] Using the second apparatus described above, specifically, while conveying the substrate film with the cured resin layer from the extraction chamber to the winding chamber via a roll-to-roll method, plasma treatment (bombardment treatment) is performed on one side of the substrate film with the cured resin layer in the thickness direction in the second plasma treatment chamber. The travel speed (film travel speed) of the substrate film with the cured resin layer is set to 1.0 m / min. It should be noted that the plasma treatment conditions are as follows.

[0262] The device was evacuated until the ultimate vacuum level of the second plasma processing chamber reached 1.0 × 10⁻⁶. －4 After Pa, argon is introduced into the second plasma treatment chamber, and the pressure inside the second plasma treatment chamber is set to 0.5 Pa. A power of 500 W is applied between the planar electrodes using a high-frequency power supply, thereby generating capacitively coupled plasma (CCP). Under this plasma environment, the thickness-direction side of the substrate film with the cured resin layer is subjected to argon ion bombardment treatment (BB treatment).

[0263] As described above, plasma treatment is performed on one side of the substrate film with the cured resin layer in the thickness direction. That is, the side of the substrate film with the cured resin layer in the thickness direction is the plasma-treated surface. The plasma treatment is ion bombardment treatment using capacitively coupled plasma with argon gas (Ar-BB).

[0264] The inorganic layer formation process and the antifouling layer formation process were the same as those in Example 1 to produce the laminated film of Comparative Example 3.

[0265] [Table 1]

[0266]

[0267] <Measurement and Evaluation>

[0268] [Determination of surface properties of cured resin layers using SEM]

[0269] The thickness direction of the cured resin layer of the laminated films of each embodiment and each comparative example was observed using an electron microscope. The ratio (%) of the total area of ​​the protrusions to the measured area (total area), the average interface length (nm) of the protrusions, and the average area (nm) of the protrusions were determined. 2 Specifically, samples were taken from the substrate film during the manufacturing process of each laminated film, after plasma treatment and before the formation of the inorganic layer. A field emission electron microscope (FE-SEM, product name "Regulus 8230", manufactured by HITACHI HIGH TECH SCIENCE) was used at an accelerating voltage of 2kV and a magnification of 100,000x to measure 500 nm of one side of the cured resin layer in the thickness direction. 2The area was observed. Then, the obtained surface SEM image was binarized using image processing software (ImageJ) to determine the position and shape of the protrusions on one side of the thickness direction of the cured resin layer. Then, based on the binarized image, the ratio (%) of the total area of ​​the protrusions to the measured area (total area), the average interface length (nm) of the protrusions, and the average area (nm) of the protrusions were calculated. 2 It should be noted that the average area of ​​the convex portion (nm) 2 The area (nm) of the convex portion was measured. 2 The value is calculated by dividing by the number of protrusions. It should be noted that in Comparative Examples 1 and 2, the presence of protrusions could not be determined in the binarized images, making it impossible to calculate the above value; therefore, the data is not shown. The results are shown in Table 2. Furthermore, the surface SEM images and binarized images of Example 1, Comparative Example 1, and Comparative Example 3 are shown in Table 2. Figure 8 .

[0270] [Determination of the arithmetic mean height Sa using AFM]

[0271] The arithmetic mean height Sa of the cured resin layer on one side of the laminated films in the thickness direction of each embodiment and comparative example was measured using atomic force microscopy (AFM). Specifically, a sample of the substrate film was taken during the manufacturing process of the laminated films of each example, after plasma treatment and before the formation of the inorganic layer, and the thickness direction side was observed using an atomic force microscope (product name "DimentionEdge SPC-160113-01", manufactured by Bruker). During the observation, the measurement mode was set to tapping mode, and an antimony-doped Si cantilever (product name "RTESP-300", manufactured by Bruker) was used as a probe. Then, the height Sa of the 1 μm thickness was measured. 2 The arithmetic mean height Sa of the observed images was calculated based on ISO 25178-2:2012. The results are shown in Table 2.

[0272] [Evaluation of fit]

[0273] The following first and second tests were performed on the laminated films of each embodiment and each comparative example.

[0274] First test: First, the side of the laminated film opposite to its thickness direction (the exposed side of the substrate film) is fixed to a glass plate. Next, using a weathering tester (EYE Super UV Tester SUV-W161, manufactured by Iwasaki Electric Co., Ltd.), light is irradiated from the side of the laminated film on the glass plate using a metal halide lamp (to accelerate the weathering test). It should be noted that the conditions for accelerating the weathering test are as follows.

[0275] {Conditions for promoting weather resistance testing}

[0276] Light exposure time: 32.5 hours.

[0277] Temperature and humidity inside the weathering test chamber: temperature 85℃, relative humidity 45%.

[0278] Radiance (cumulative irradiance from 300 to 700 nm): 1500 W / m 2 .

[0279] Second test: First, using a cutting tool, 11 parallel first cuts (1mm intervals) extending linearly in a first direction and 11 parallel second cuts (1mm intervals) extending linearly in a second direction orthogonal to the first direction were formed on the laminated film of the glass plate after the first test, creating 100 grids. Next, isopropyl alcohol was continuously added dropwise at 2 mL / min to the 100 grid areas of the laminated film, and a polyester wiper (product name "Anticon Gold", manufactured by Sanplatec) was slid. It should be noted that the sliding conditions were set as follows: wiper contact surface 20mm × 20mm, load 1.5kg / 20mm, and 1000 reciprocating cycles. Then, 0.25mm of the film was observed in the 100 grids. 2 The number of stripped cells (more than 1 / 4 of the cell area) was counted, and the number of remaining cells was calculated and evaluated according to the following criteria. The results are shown in Table 2.

[0280] {Benchmark}

[0281] A: There are more than 90 remaining grid cells.

[0282] B: The number of remaining squares is more than 70 but less than 90.

[0283] C: The number of remaining cells is more than 20 but less than 70.

[0284] D: The number of remaining squares is less than 20.

[0285] [Evaluation of Total Reflectivity]

[0286] The surfaces (exposed surfaces of the substrate film) of the laminated films of each embodiment and each comparative example were bonded to a black acrylic sheet (2 mm thick) with a specified transparent acrylic adhesive across them in the thickness direction. This produced a test sample. Next, the total internal reflection spectrum (including specular reflection) of the test sample was measured using a spectrophotometer (product name "UH4150", manufactured by HITACHI HIGH TECH SCIENCE). In the measurement, a standard light source D65 was used as the light source, and the test sample was placed inside the spectrophotometer such that light irradiated from the thickness direction side of the inorganic layer of the test sample. The measurement was performed in the integrating sphere mode of the spectrophotometer. The measured reflectance is the total reflectance (light reflectance ratio) of the light irradiated from the thickness direction side of the inorganic layer of the test sample (laminated film) by the standard light source D65 with wavelengths from 380 nm to 780 nm. The results are shown in Table 2.

[0287] [Table 2]

[0288]

[0289] It should be noted that the above-described invention is provided as an example of an embodiment of the present invention, but it is merely an example and not a limiting interpretation. Modifications of the invention that are apparent to those skilled in the art are included in the claims.

[0290] Industrial availability

[0291] The aforementioned laminated film 1 is preferably used as an anti-reflective film and a conductive film. Specifically, the aforementioned laminated film 1 is preferably used in display devices such as liquid crystal displays and organic EL displays.

Claims

1. A laminated film comprising: a substrate film; and a cured resin layer disposed on one side of the substrate film in the thickness direction. One or more protrusions are formed on one side of the cured resin layer in the thickness direction. The average area of ​​the protrusion is 80 nm. 2 Above and 500nm 2 the following, The arithmetic mean height Sa of one side of the cured resin layer in the thickness direction is 1.0 nm or more.

2. The laminated film according to claim 1, wherein, The average interface length of the protrusion divided by the average area of ​​the protrusion yields a value of 0.2 nm. －1 above.

3. The laminated film according to claim 1, wherein, The total area of ​​the protrusion is 15% to 40% of the total area of ​​the surface on one side of the thickness direction of the cured resin layer.

4. The laminated film according to claim 1, wherein, The cured resin layer contains organosilicon compounds.

5. The laminated film according to claim 1, wherein, One side of the cured resin layer in the thickness direction is the plasma-treated surface.

6. The laminated film according to any one of claims 1 to 5, wherein, The laminated film further comprises: an inorganic layer disposed on one side of the cured resin layer in the thickness direction.

7. The laminated film according to claim 6, wherein, The laminated film further comprises: an antifouling layer disposed on one side of the inorganic layer in the thickness direction.

8. A method for manufacturing a laminated film, comprising the steps described in claim 1: The preparation process involves preparing a substrate film with a cured resin layer. This substrate film comprises: a strip of the substrate film; and the cured resin layer disposed on one side of the substrate film in its thickness direction. The plasma treatment process involves plasma treating one or more protrusions on one side of the substrate film with the cured resin layer in the thickness direction to form a plasma treatment.

9. The method for manufacturing a laminated film according to claim 8, wherein, The plasma treatment utilizes an inductively coupled plasma of oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna.

10. The method for manufacturing a laminated film according to claim 8 or 9, wherein, The method further includes a forming step in which an inorganic layer is formed on one side of the substrate film with the cured resin layer in the thickness direction.

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