Laminated film and method for manufacturing laminated film

Abstract

The present invention provides a laminated film and a method for manufacturing a laminated film that have good optical properties while improving adhesion. [Solution] The laminated film 1 of the present invention comprises a base film 2, a cured resin layer 3 disposed on one side of the base film 2 in the thickness direction, and an inorganic layer 4 disposed on one side of the cured resin layer 3 in the thickness direction. On one side of the cured resin layer 3 in the thickness direction, C3H3O2 is measured by time-of-flight secondary ion mass spectrometry. - HSi2O5 as a function of the ionic strength of the fragment - The ratio of the ionic intensities of the fragments is 1.0 × 10⁻⁶ -1 That concludes the report. Furthermore, the total reflectance of the light irradiated from one side of the inorganic layer 4 in the thickness direction with respect to the laminated film 1, using a standard light source D65 with wavelengths from 380 nm to 780 nm, is 0.40% or less.

Description

[Technical Field]

[0001] This invention relates to a laminated film and a method for manufacturing a laminated film. [Background technology]

[0002] An anti-reflective film is placed on the outer surface of the display screen in display devices such as liquid crystal displays and organic EL displays, in order to improve the visibility of the displayed image. As an example of such an anti-reflective film, one is known that comprises, in the thickness direction, a film substrate, a hard coat layer, an inorganic oxide primer layer, and an anti-reflective layer in that order (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-65437 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the anti-reflective film described in Patent Document 1, the hard coat layer contains inorganic oxide particles (silica particles). As a result, the surface of the hard coat layer on the inorganic oxide primer layer side has surface irregularities. The anchoring effect based on these surface irregularities suppresses the peeling of the anti-reflective layer.

[0005] However, in the anti-reflective film of Patent Document 1, the surface of the anti-reflective layer opposite to the inorganic oxide primer layer also has surface irregularities that follow the surface irregularities of the hard coat layer. Such surface irregularities in an anti-reflective layer scatter some of the light incident on the anti-reflective film. Furthermore, silica particles within the hard coat layer also scatter some of the light incident on the anti-reflective film. In other words, such an anti-reflective film has defects in its optical properties.

[0006] The present invention aims to provide a laminated film and a method for manufacturing a laminated film that have good optical properties while improving adhesion. [Means for solving the problem]

[0007] The present invention [1] is a laminated film comprising a base film, a cured resin layer disposed on one side of the base film in the thickness direction, and an inorganic layer disposed on one side of the cured resin layer in the thickness direction, wherein on one side of the cured resin layer in the thickness direction, C3H3O2 is measured by time-of-flight secondary ion mass spectrometry. - HSi2O5 as a function of the ionic strength of the fragment - The ratio of the ionic intensities of the fragments is 1.0 × 10⁻⁶ -1 The present invention includes a laminated film in which the total reflectance of light irradiated onto the laminated film from one side in the thickness direction of the inorganic layer using a standard light source D65 with wavelengths from 380 nm to 780 nm is 0.40% or less.

[0008] The present invention [2] is a laminated film comprising a base film, a cured resin layer disposed on one side of the base film in the thickness direction, and an inorganic layer disposed on one side of the cured resin layer in the thickness direction, wherein on one side of the cured resin layer in the thickness direction, C3H9Si is measured by time-of-flight secondary ion mass spectrometry. + HSiO + The ratio of the ionic intensities of the fragments is 1.0 × 10⁻⁶ -1 The present invention includes a laminated film in which the total reflectance of light irradiated onto the laminated film from one side in the thickness direction of the inorganic layer using a standard light source D65 with wavelengths from 380 nm to 780 nm is 0.40% or less.

[0009] The present invention [3] comprises the laminated film described in [1] or [2] above, wherein the cured resin layer contains a silicone compound.

[0010] The present invention [4] further comprises the laminated film described in [3] above, wherein the cured resin layer further contains an acrylate resin.

[0011] The present invention [5] includes the laminated film described in [4] above, wherein the amount of the silicone compound blended with 100 parts by mass of the acrylate resin is 0.0025 parts by mass or more.

[0012] The present invention [6] includes a laminated film according to any one of the above [1] to [5], wherein one surface in the thickness direction of the cured resin layer is a plasma-treated surface.

[0013] The present invention [7] includes a laminated film according to any one of the above [1] to [6], wherein the inorganic layer comprises an anti-reflective layer.

[0014] The present invention [8] includes a laminated film according to any one of the above [1] to [7], wherein the laminated film further comprises an antifouling layer disposed on one side in the thickness direction of the inorganic layer.

[0015] The present invention [9] is a method for manufacturing a laminated film according to any one of the above [1] to [7], comprising a preparation step of preparing a base film with a cured resin layer, which comprises a long base film and a cured resin layer disposed on one side of the base film in the thickness direction; a plasma treatment step of plasma treatment of one side of the base film with the cured resin layer in the thickness direction; and an inorganic layer formation step of forming the inorganic layer on one side of the base film with the cured resin layer in the thickness direction.

[0016] The present invention

[10] includes a method for manufacturing a laminated film according to claim 9, wherein the plasma treatment is a treatment with inductively coupled plasma of an oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna, and a method for manufacturing a laminated film according to [9] above. [Effects of the Invention]

[0017] In the laminated film of the present invention, as described above, the total reflectance of irradiation light with a wavelength of 380 nm to 780 nm from a standard light source D65 applied to the laminated film from one side in the thickness direction of the inorganic layer is 0.40% or less. That is, it has excellent optical properties. Further, measured by time-of-flight secondary ion mass spectrometry on one surface in the thickness direction of the cured resin layer, C3H3O2 - with respect to the ion intensity of the fragment, HSi2O5 - the ratio of the ion intensity of the fragment is 1.0×10 -1 or more. Therefore, adhesion can be improved.

[0018] In addition, in the laminated film of the present invention, as described above, the total reflectance of irradiation light with a wavelength of 380 nm to 780 nm from a standard light source D65 applied to the laminated film from one side in the thickness direction of the inorganic layer is 0.40% or less. That is, it has excellent optical properties. Further, measured by time-of-flight secondary ion mass spectrometry on one surface in the thickness direction of the cured resin layer, C3H9Si + with respect to the ion intensity of the fragment, HSiO + the ratio of the ion intensity of the fragment is 1.0×10 -1 or more. Therefore, adhesion can be improved.

[0019] The method for producing a laminated film of the present invention is a method for producing the laminated film of the present invention as described above, comprising a plasma treatment step of performing plasma treatment on one surface in the thickness direction of a base film with a cured resin layer. Therefore, a laminated film having excellent optical properties and improved adhesion can be produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] [Figure 1] Fig. 1 is a cross-sectional view of an embodiment of the laminated film of the present invention. [Figure 2]Figures 2A to 2D show one embodiment of the method for manufacturing a laminated film according to the present invention. Figure 2A shows the process of preparing a substrate film with a cured resin layer, Figure 2B shows the process of plasma treatment of one side in the thickness direction of the substrate film with the cured resin layer, Figure 2C shows the process of forming an inorganic layer, and Figure 2D shows the process of forming an antifouling layer. [Figure 3] Figure 3 is a schematic diagram of the apparatus for carrying out the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process in the manufacturing method of a laminated film. [Figure 4] Figure 4 is a perspective view showing the positional relationship between the low-inductance antenna and the substrate film with a cured resin layer in the plasma processing chamber. [Figure 5] Figure 5 is 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. [Modes for carrying out the invention]

[0021] 1. Laminated film An embodiment of the laminated film 1 of the present invention will be described with reference to Figure 1.

[0022] As shown in Figure 1, the laminated film 1 comprises a base film 2, a cured resin layer 3 disposed on one side of the base film 2 in the thickness direction, and an inorganic layer 4 disposed on one side of the cured resin layer 3 in the thickness direction. The laminated film 1 optionally includes an antifouling layer 5 disposed on one side of the inorganic layer 4 in the thickness direction. In this embodiment, the laminated film 1 comprises the base film 2, the cured resin layer 3, the inorganic layer 4, and the antifouling layer 5 in order toward one side in the thickness direction.

[0023] The laminated film 1 extends in a planar direction perpendicular to the thickness direction.

[0024] <Base film> The base film 2 is the bottom layer of the laminated film 1 and is a support film that ensures the strength of the laminated film 1.

[0025] The base film 2 has a film shape (including a sheet shape). The base film 2 is, for example, a flexible, transparent resin film.

[0026] Examples of materials for the base 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 cycloolefin polymer (COP). Examples of cellulose resins include triacetylcellulose (TAC).

[0027] The materials of the base film 2 can be used individually or in combination of two or more types.

[0028] The base film 2 is preferably at least one selected from the group consisting of polyester resin film, polyolefin resin film, and cellulose resin film, from the viewpoint of transparency and strength. 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.

[0029] The base film 2 preferably does not contain particles (for example, metal oxide particles described later).

[0030] The thickness of the base film 2 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 30 μm or more, and also, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, from the viewpoint of strength and handling.

[0031] The total light transmittance of the base film 2 (JIS K 7375:2008) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and also, for example, 100% or less.

[0032] If the total light transmittance of the base film 2 is equal to or greater than the above lower limit, good transparency can be ensured in the laminated film 1.

[0033] Furthermore, if the cured resin layer 3, described later, is placed on only one side of the base film 2 in the thickness direction or the other side in the thickness direction, a carrier film (not shown) may be laminated to the side of the base film 2 opposite to the side on which the cured resin layer 3 is placed, in order to ensure the transportability and handling of the base film 2 in a roll-to-roll process.

[0034] <Cured resin layer> 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 base film 2 in the thickness direction. The cured resin layer 3 may also be placed on the other side of the base film 2 in the thickness direction as needed.

[0035] In this embodiment, one surface in the thickness direction of the cured resin layer 3 is a plasma-treated surface 3a. The plasma-treated surface 3a is a surface that has been plasma-treated. The plasma treatment will be described in detail later, but from the viewpoint of controlling the surface state of the plasma-treated surface 3a, it is preferably a treatment using inductively coupled plasma with an oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna (LIA) (oxygen-plasma treatment). In other words, one surface in the thickness direction of the cured resin layer 3 is a plasma-treated surface 3a using inductively coupled plasma with an oxygen-containing gas. The oxygen-plasma treatment will be described in detail in the method for manufacturing the laminated film. Note that one surface in the thickness direction of the cured resin layer 3 before plasma treatment is an untreated surface 3a'.

[0036] Examples of the cured resin layer 3 include a hard coat layer, an optical adjustment layer, and an antiblocking layer. The hard coat layer is, for example, a layer that makes it difficult for scratches to form on the exposed surface of the base film 2. The optical adjustment layer adjusts the optical properties (e.g., refractive index) of the laminated film 1. The antiblocking layer is, for example, a layer that provides antiblocking properties to the surfaces of multiple laminated films 1 that come into contact with each other, such as when the laminated films 1 are laminated in the thickness direction.

[0037] Preferably, the cured resin layer 3 is a hard coat layer. If the cured resin layer 3 is a hard coat layer, it is possible to suppress the formation of scratches on one side in the thickness direction (exposed surface) of the inorganic layer 4 formed on one side in the thickness direction (plasma-treated surface 3a) of the cured resin layer 3, or on one side in the thickness direction (exposed surface) of the anti-fouling layer 5 formed on one side in the thickness direction of the inorganic layer 4.

[0038] The cured resin layer 3 is a cured product of a curable resin composition. Specifically, the cured resin layer 3 can be formed by applying a curable resin composition to one side in the thickness direction of the base film 2, drying it as necessary, and then curing it.

[0039] Examples of curable resin compositions include compositions containing ultraviolet-curable resins (ultraviolet-curable resin compositions) and compositions containing thermosetting resins. From the viewpoint of manufacturing efficiency, ultraviolet-curable resin compositions are preferred as curable resin compositions. In other words, the cured resin layer 3 is a cured product layer of the ultraviolet-curable resin composition.

[0040] Examples of UV-curable resins include (meth)acrylate resins. Preferably, acrylate resins are used. Examples of acrylate resins include acrylic urethane resins and acrylic resins (excluding acrylic urethane resins). Preferably, acrylic urethane resins are used. Alternatively, a copolymer of acrylic urethane resin and polyfunctional acrylate may be used. UV-curable resins can be used alone or in combination of two or more types. Note that (meth)acrylate resin refers to methacrylate resin and / or acrylate resin.

[0041] In other words, the cured resin layer 3 preferably contains an acrylate resin. More preferably, it contains an acrylic urethane resin. The cured resin layer 3 may also contain a copolymer of acrylic urethane resin and polyfunctional acrylate.

[0042] When the cured resin layer 3 contains an acrylate resin and a leveling agent containing a silicone compound (described later), plasma treatment of the untreated surface 3a' of the cured resin layer 3 forms -Si-O- 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, adhesion can be improved by bonding between the -Si-O- on the plasma-treated surface 3a of the cured resin layer 3 and the inorganic atoms of the inorganic layer 4.

[0043] The cured resin layer 3 may also contain other UV-curable resins.

[0044] Other UV-curable resins include, for example, polyester resins, urethane resins (excluding acrylic urethane resins), amide resins, epoxy resins, and melamine resins. These other UV-curable resins can be used individually or in combination of two or more types.

[0045] The UV-curable resin composition may contain particles. Preferably, it does not contain particles. In other words, the cured resin layer 3 preferably does not contain particles.

[0046] If the cured resin layer 3 does not contain particles, the total reflectance (visible reflectance) can be improved. In other words, the laminated film 1 has excellent optical properties.

[0047] Examples of particles include organic particles and inorganic particles.

[0048] Examples of materials for organic particles include polymethyl methacrylate, polystyrene, acrylic-styrene copolymer, and polycarbonate.

[0049] Examples of inorganic particles include inorganic oxide particles. Examples of materials for inorganic oxide particles include metal oxides and metalloid oxides, specifically silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Furthermore, the material for inorganic oxide particles may also be a metal composite oxide, which is a composite of the above-mentioned metal oxides. Additionally, functional groups such as acrylic groups and epoxy groups may be introduced to the surface of the inorganic oxide particles to enhance adhesion and affinity with the resin.

[0050] The average particle diameter of the particles is not particularly limited, but is, for example, 500 nm or less, preferably 300 nm or less, and more preferably 100 nm or less.

[0051] The average particle diameter can be measured using the specific surface area (BET) method.

[0052] The particle content in the UV-curable resin composition (solids) 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 particularly preferably 0% by mass.

[0053] If the particle content in the UV-curable resin composition (solids) is below the above upper limit, scattering of light incident on the laminated film 1 due to particles within the laminated film 1 can be suppressed.

[0054] Furthermore, the curable resin composition includes, 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 leveling agents containing silicone compounds.

[0055] In other words, the cured resin layer 3 preferably contains a silicone compound.

[0056] Examples of silicone compounds include compounds having a siloxane structure. Preferably, compounds having a dimethylsiloxane structure are included.

[0057] Examples of compounds having a siloxane structure include compounds having a methylalkylsiloxane structure. Preferably, compounds having a dimethylsiloxane structure are included. Examples of compounds having a dimethylsiloxane structure include polydimethylsiloxane, (meth)acrylic acid ester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified (meth)acrylic group-containing polydimethylsiloxane, and polyester-modified (meth)acrylic group-containing polydimethylsiloxane. Preferably, methacrylic acid ester-modified polydimethylsiloxane is included. (Meth)acrylic means acrylic and / or methacrylic.

[0058] The leveling agent may also contain other components (e.g., (meth)acrylate esters).

[0059] When the cured resin layer 3 contains a silicone compound, plasma treatment of the untreated surface 3a' of the cured resin layer 3 forms -Si-O- 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, adhesion can be improved by bonding between the -Si-O- on the plasma-treated surface 3a of the cured resin layer 3 and the inorganic atoms of the inorganic layer 4.

[0060] When the cured resin layer 3 contains an ultraviolet-curable resin and a leveling agent, the amount of leveling agent blended with 100 parts by mass of ultraviolet-curable resin is, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, and also, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, even more preferably 0.08 parts by mass or less, and particularly preferably 0.06 parts by mass or less.

[0061] If the amount of leveling agent added to 100 parts by mass of UV-curable resin is less than or equal to the above upper limit, the total reflectance (visible reflectance) of the laminated film 1 can be further improved.

[0062] When the cured resin layer 3 contains an acrylate resin and a silicone compound, the amount of silicone compound blended with 100 parts by mass of acrylate resin is, for example, 0.0025 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.0075 parts by mass or more, and also, for example, 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less.

[0063] When the cured resin layer 3 contains an acrylate resin and a silicone compound, the amount of silicone compound blended with 100 parts by mass of acrylate resin is, for example, 0.0025 parts by mass to 10 parts by mass, preferably 0.005 parts by mass to 8 parts by mass, and more preferably 0.0075 parts by mass to 6 parts by mass.

[0064] If the amount of silicone compound blended with 100 parts by mass of acrylate resin is equal to or greater than the above lower limit, then plasma treatment of the untreated surface 3a' of the cured resin layer 3 will reliably form -Si-O- on the plasma-treated surface 3a of the cured resin layer 3.

[0065] Furthermore, if the curable resin composition is an ultraviolet-curable resin composition, it preferably contains a photopolymerization initiator.

[0066] Furthermore, the curable resin composition may contain additives such as solvents, thixotropic agents, and antistatic agents.

[0067] 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 also, for example, 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less.

[0068] If the thickness of the cured resin layer 3 is greater than or equal to the lower limit, the cured resin layer 3 can be easily formed, and the functions of the cured resin layer 3 can be fully expressed. Also, if the thickness of the cured resin layer 3 is less than or equal to the upper limit, the laminated film 1 can be made thinner.

[0069] Note that the thickness of the cured resin layer 3 described above refers to the thickness of the cured resin layer 3 on one side of the base film 2 in the thickness direction, when the cured resin layer 3 is arranged on both sides of the base film 2 in the thickness direction, and is not the total thickness of the cured resin layer 3.

[0070] The surface roughness Sa (arithmetic mean height based on ISO 25178-2:2012) of one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a) is, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1.0 nm or more, even more preferably 1.5 nm or more, and also, for example, 5.0 nm or less, preferably 4.0 nm or less, and more preferably 3.00 nm or less.

[0071] If the surface roughness Sa of one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a) is greater than or equal to the lower limit, the adhesion of the inorganic layer 4 to the inorganic layer 4 formed on one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a) can be improved by the anchoring effect of the fine irregularities of the plasma-treated surface 3a. If the surface roughness Sa of one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a) is less than or equal to the upper limit, excessive irregularities on the plasma-treated surface 3a can be suppressed, improving the total reflectance (visible reflectance). In other words, the laminated film 1 has excellent optical properties.

[0072] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H3O2 - HSi2O5 as a function of the ionic strength of the fragment - Ratio of ionic strengths of fragments (HSi2O5) - / C3H3O2 - ) is 1.0 × 10 -1 Preferably, 1.1 × 10 -1 The above is more 1.2 × 10 -1 In addition, for example, 10 x 10 -1 Preferably, 5.0 × 10 -1 More preferably, 3.0 × 10 -1 The following applies:

[0073] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H3O2 - HSi2O5 as a function of the ionic strength of the fragment - Ratio of ionic strengths of fragments (HSi2O5) - / C3H3O2 - ) For example, 1.0 × 10 -1 ~10×10 -1 Preferably, 1.1 × 10 -1 ~5.0×10 -1 , more comfortably, 1.2 × 10 -1 ~3.0×10 -1 That is the case.

[0074] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H3O2 - HSi2O5 as a function of the ionic strength of the fragment - Ratio of ionic strengths of fragments (HSi2O5) - / C3H3O2 - If the value is above the lower limit mentioned above, then -Si-O- can be formed on the plasma-treated surface 3a, thus improving adhesion.

[0075] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H9Si + HSiO +Ratio of ionic strengths of fragments (HSiO + / C3H9Si + ) is 1.0 × 10 -1 Preferably, 2.0 × 10 -1 More preferably, 3.0 × 10 -1 In addition, for example, 30 x 10 -1 Preferably, 20 × 10 -1 For a more comfortable experience, 15 × 10 -1 The following applies:

[0076] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H9Si + HSiO + Ratio of ionic strengths of fragments (HSiO + / C3H9Si + ) For example, 1.0 × 10 -1 ~30×10 -1 Preferably, 2.0 × 10 -1 ~20×10 -1 , more preferably, 3.0 × 10 -1 ~15×10 -1 That is the case.

[0077] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H9Si + HSiO + Ratio of ionic strengths of fragments (HSiO + / C3H9Si + If the value is above the lower limit mentioned above, then -Si-O- can be formed on the plasma-treated surface 3a, thus improving adhesion.

[0078] Note: C3H3O2 - The fragment originates from the acrylate resin in the UV-curable resin, and HSi2O5 - The fragments originate from the acrylate resin in the UV-curable resin and the silicone compound in the leveling agent that have been modified by plasma treatment. Also, C3H9Si + The fragments originate from the silicone compound in the leveling agent, HSiO+ The fragments originate from acrylate resins in UV-curable resins and silicone compounds in leveling agents that have been modified by plasma treatment.

[0079] On one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H3O2 - HSi2O5 as a function of the ionic strength of the fragment - Ratio of ionic strengths of fragments (HSi2O5) - / C3H3O2 - ), and on one side in the thickness direction of the cured resin layer 3 (plasma-treated surface 3a), C3H9Si + HSiO + Ratio of ionic strengths of fragments (HSiO + / C3H9Si + This can be calculated by time-of-flight secondary ion mass spectrometry.

[0080] In time-of-flight secondary ion mass spectrometry, C3H3O2 - Fragments and HSi2O5 - Spectra for multiple negative ion fragments containing fragments, and C3H9Si + Fragments and HSiO + Spectra can be obtained for multiple positive ion fragments containing the fragment. Therefore, the ionic intensity ratio of the positive ions (HSi2O5) can be obtained. - / C3H3O2 - ) and the ionic intensity ratio of negative ions (HSi2O5 - / C3H3O2 - The following values ​​are calculated for each. This allows us to show the plasma-treated surface 3a state. More details will be described in the examples below.

[0081] <Inorganic layer> Examples of inorganic layers 4 include an adhesion layer, an anti-reflective layer, and a conductive layer. The adhesion layer is placed between the cured resin layer and other inorganic layers (e.g., an anti-reflective layer and a conductive layer) to improve the adhesion between the cured resin layer and the other inorganic layers. The anti-reflective layer is a layer that has anti-reflective properties to suppress the reflection intensity of external light. The conductive layer is a layer that has conductivity.

[0082] Furthermore, if the inorganic layer 4 includes an anti-reflective layer, the laminated film 1 is an anti-reflective film. Also, if the inorganic layer 4 includes a conductive layer, the laminated film 1 is a conductive film.

[0083] The inorganic layer 4 may consist of only one layer having a single function, or it may be a composite layer consisting of multiple layers having different functions. Examples of composite layers include an inorganic layer 4 comprising an adhesion layer and an anti-reflective layer, and an inorganic layer 4 comprising an adhesion layer and a conductive layer. As shown in Figure 1, the inorganic layer 4 preferably comprises an adhesion layer 41 and an anti-reflective layer 42.

[0084] 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 deposition, and CVD. Sputtering is preferred. In other words, the inorganic layer 4 is preferably a dry coating layer. More preferably, it is a sputtered layer.

[0085] [Close-knit group] The adhesion layer 41 is positioned on one side of the cured resin layer 3 in the thickness direction (plasma-treated surface 3a). In other words, the adhesion layer 41 is in contact with the cured resin layer 3.

[0086] Examples of materials for the adhesion layer 41 include 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. Si and its oxides are also examples of materials for the adhesion layer 41. From the viewpoint of achieving both adhesion to both the cured resin layer 3 and the anti-reflective layer 42 or conductive layer laminated on the adhesion layer 41, and transparency of the adhesion layer 41, the material for the adhesion layer 41 is preferably an inorganic oxide containing at least one element selected from the group consisting of Si, In, Al, Sn, Ti, and Zr. More preferably, indium tin composite oxide (ITO) and silicon oxide (SiOx) are used. Even more preferably, ITO is used.

[0087] The silicon oxide used as the material for the adhesion layer 41 is, for example, SiOx with a lower oxygen content than the stoichiometric composition, and preferably x is 1.2 or more and 1.9 or less.

[0088] When ITO is used as the material for the adhesion layer 41, the tin oxide content 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, even more preferably 15% by mass or more, and also, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.

[0089] The thickness of the adhesion layer 41 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.

[0090] If the thickness of the adhesion layer 41 is greater than or equal to the lower limit value, adhesion between the cured resin layer 3 and the anti-reflective layer 42 or conductive layer laminated on the adhesion layer 41 can be ensured. If the thickness of the adhesion layer 41 is less than or equal to the upper limit value, the transparency of the adhesion layer 41 can be ensured.

[0091] [Anti-reflection layer] The anti-reflective layer 42 is disposed, for example, on one side in the thickness direction of the adhesion layer 41. The anti-reflective layer 42 includes, for example, multiple transparent inorganic oxide films stacked in the thickness direction.

[0092] The anti-reflective layer 42 is, for example, an alternating laminate of high-refractive-index layers and low-refractive-index layers. The number of layers in the alternating laminate is not particularly limited, and is, for example, four layers.

[0093] Specifically, the anti-reflective layer 42 shown in Figure 3 comprises a high refractive index layer 42a, a low refractive index layer 42b, a high refractive index layer 42c, and a low refractive index layer 42d, arranged in order toward one side in the thickness direction.

[0094] The high refractive index layer 42a is in contact with the adhesion layer 41. The high refractive index layer 42a and the low refractive index layer 42b are in contact. The low refractive index layer 42b and the high refractive index layer 42c are in contact. The high refractive index layer 42c and the low refractive index layer 42d are in contact.

[0095] The high refractive index layers 42a and 42c are layers with a relatively high refractive index, while the low refractive index layers 42b and 42d are layers with a relatively low refractive index.

[0096] In such a laminated configuration, the reflected light intensity is attenuated by interference between reflected light at multiple interfaces in the high refractive index layers 42a and 42c and the low refractive index layers 42b and 42d. Such interference can be brought about by adjusting the optical film thickness (product of refractive index and thickness) of each layer of the anti-reflective layer 42.

[0097] The high refractive index layer 42a (first high refractive index layer) is made of a high refractive index material having a refractive index of 1.9 or higher at a wavelength of 550 nm, for example. Examples of high refractive index materials include niobium oxide (Nb2O5), titanium oxide, zirconium oxide, indium tin composite oxide (ITO), and antimony tin composite oxide (ATO). From the viewpoint of achieving both a high refractive index and low absorption of visible light, the high refractive index material is preferably niobium oxide (refractive index 2.33).

[0098] The thickness of the high refractive index layer 42a is, for example, 1 nm or more, preferably 5 nm or more, and also, for example, 50 nm or less, preferably 30 nm or less. The optical film thickness of the high refractive index layer 42a is, for example, 20 nm or more, and also, for example, 55 nm or less.

[0099] The low refractive index layer 42b (first low refractive index layer) is made of a low refractive index material having a refractive index of 1.6 or less at a wavelength of 550 nm, for example. Examples of low refractive index materials include silicon dioxide (SiO2) and magnesium fluoride. From the viewpoint of achieving both a low refractive index and low absorption of visible light, silicon dioxide (refractive index 1.46) is preferred as the low refractive index material.

[0100] The thickness of the low refractive index layer 42b is, for example, 5 nm or more, preferably 10 nm or more, and also, for example, 80 nm or less, preferably 50 nm or less. The optical film thickness of the low refractive index layer 42b is, for example, 15 nm or more, and also, for example, 70 nm or less.

[0101] The high refractive index layer 42c (second high refractive index layer) is made of a high refractive index material having a refractive index of 1.9 or higher at a wavelength of 550 nm, for example. Examples of high refractive index materials include the above-mentioned materials for the high refractive index layer 42a, and niobium oxide is preferred.

[0102] The thickness of the high refractive index layer 42c is, for example, 30 nm or more, preferably 50 nm or more, and also, for example, 200 nm or less, preferably 150 nm or less. The optical film thickness of the high refractive index layer 42c is, for example, 60 nm or more, and also, for example, 330 nm or less.

[0103] The low refractive index layer 42d (second low refractive index layer) is made of a low refractive index material having a refractive index of 1.6 or less at a wavelength of 550 nm, for example. Examples of low refractive index materials include the materials mentioned above for the low refractive index layer 42b, and silicon dioxide is preferably used.

[0104] The thickness of the low refractive index layer 42d is, for example, 20 nm or more, preferably 40 nm or more, and also, for example, 200 nm or less, preferably 120 nm or less. The optical film thickness of the low refractive index layer 42b is, for example, 100 nm or more, and also, for example, 160 nm or less.

[0105] The total thickness of the anti-reflective layer 42 is, for example, 100 nm or more, preferably 150 nm or more, more preferably 200 nm or more, and also, 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 anti-reflective layer 42 is the sum of the thicknesses of the high refractive index layers 42a, 42c and the low refractive index layers 42b, 42d.

[0106] If the total thickness of the anti-reflective layer 42 is greater than or equal to the lower limit value, the function of attenuating reflected light intensity can be ensured in the anti-reflective layer 42. If the total thickness of the anti-reflective layer 42 is less than or equal to the upper limit value, cracking of the anti-reflective layer 42 can be suppressed.

[0107] [Conductive layer] The conductive layer, although not shown in the figures, is arranged on one side in the thickness direction of the adhesion layer 41. The conductive layer is, for example, a layer formed from a conductive material. Examples of conductive materials include metals and metal oxides.

[0108] 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 composite oxide (ITO), indium-zinc composite oxide (IZO), indium-gallium composite oxide (IGO), and indium-gallium-zinc composite oxide (IGZO). An example of an antimony-containing conductive oxide is antimony-tin composite oxide (ATO). An example of a zinc-containing conductive oxide is zinc-aluminum composite oxide (AZO).

[0109] 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 also, 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.

[0110] <Stain-resistant layer> The antifouling layer 5 is a layer that prevents contamination from the external environment and facilitates the removal of adhering contaminants. Furthermore, the antifouling layer 5 also possesses water vapor barrier properties.

[0111] The antifouling layer 5 is arranged on one side in the thickness direction of the inorganic layer 4, if necessary. In this embodiment, the laminated film 1 includes the antifouling layer 5.

[0112] The antifouling layer 5 is in contact with one side of the inorganic layer 4 in the thickness direction. The antifouling layer 5 is the uppermost layer of the laminated film 1.

[0113] Examples of materials for the antifouling layer 5 include organofluorine compounds. Preferably, an alkoxysilane compound having a perfluoropolyether group is used as the organofluorine compound. Examples of alkoxysilane compounds having a perfluoropolyether group include compounds represented by the following general formula (1).

[0114] R1-R2-X-(CH2)m-Si(OR3)3(1)

[0115] In general formula (1), R1 represents a linear or branched alkyl fluoride (with, for example, 1 to 20 carbon atoms) in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms. Preferably, it represents a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0116] R2 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 linear PFPE groups and repeating branched PFPE groups. Examples of repeating linear PFPE groups include -(OC n F 2n ) p Examples of structures represented by - (where n is an integer between 1 and 20, and p is an integer between 1 and 50; the same applies hereafter) include -(OC(CF3)2) p -A structure represented by -(OCF2CF(CF3)CF2) p Examples of structures represented by - include a repeating structure of a linear PFPE group, and more preferably a repeating structure of -(OCF2) p -and-(OC2F4) p - are listed.

[0117] R3 represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

[0118] X represents an ether group, a carbonyl group, an amino group, or an amide group. Preferably, it represents an ether group.

[0119] m represents an integer greater than or equal to 1. Preferably, m represents an integer less than or equal to 20, more preferably less than or equal to 10, and even more preferably less than or equal to 5.

[0120] Among such alkoxysilane compounds having a perfluoropolyether group, the compound shown in the following general formula (2) is preferably used.

[0121] CF3-(OCF2) q -(OC2F4) r -O-(CH2)3-Si(OCH3)3(2)

[0122] In general formula (2), q represents an integer of 1 or more and 50 or less, and r represents an integer of 1 or more and 50 or less.

[0123] Further, the alkoxysilane compound having a perfluoropolyether group may be used alone or in combination of two or more kinds thereof.

[0124] In the present embodiment, the antifouling layer 5 is a layer formed by a dry coating method (dry coating layer). Examples of the dry coating method include a sputtering method, a vacuum deposition method, and CVD. A vacuum deposition method is preferable. That is, the antifouling layer 5 is preferably a dry coating layer, and more preferably a vacuum deposition layer.

[0125] 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 is, for example, 25 nm or less, preferably 20 nm or less, more preferably 15 nm or less.

[0126] The thickness of the laminated film 1 is, for example, 5 µm or more, preferably 10 µm or more, more preferably 30 µm or more, and is, for example, 300 µm or less, preferably 200 µm or less, more preferably 150 µm or less.

[0127] The total reflectance (luminosity reflectance) of irradiation light with a wavelength of 380 nm to 780 nm from a standard light source D65 applied to the laminated film 1 from one side in the thickness direction of the inorganic layer 4 (one side in the thickness direction of the laminated film 1) is 0.40% or less, preferably 0.37% or less, more preferably 0.35% or less, still more preferably 0.33% or less, and particularly preferably 0.31% or less.

[0128] (Actions and Effects) As described above, the laminated film 1 includes a base film, a cured resin layer, and an inorganic layer sequentially arranged toward one side in the thickness direction. In such a laminated film 1, C3H3O2 measured by time-of-flight secondary ion mass spectrometry on one surface of the cured resin layer in the thickness direction -HSi2O5 as a function of the ionic strength of the fragment - The ratio of the ionic intensities of the fragments is 1.0 × 10⁻⁶ -1 The above conditions are met. Alternatively, C3H9Si is measured by time-of-flight secondary ion mass spectrometry on one side in the thickness direction of the cured resin layer 3. + HSiO + The ratio of the ionic intensities of the fragments is 1.0 × 10⁻⁶ -1 The above conditions are met. Therefore, the adhesion between the cured resin layer 3 and the inorganic layer 4 in the laminated film 1 can be improved.

[0129] Furthermore, the total reflectance of light irradiated from one side of the inorganic layer 4 in the thickness direction with respect to the laminated film 1, using a standard light source D65 with wavelengths from 380 nm to 780 nm, is 0.40% or less. In other words, the laminated film 1 has excellent optical properties.

[0130] Therefore, the laminated film 1 described above can have good optical properties while also improving adhesion.

[0131] 2. Method for manufacturing laminated film Referring to Figures 2A to 2D, one embodiment of a method for manufacturing a laminated film, which produces the laminated film 1 described above, will be explained.

[0132] The method for manufacturing a laminated film includes, for example, a preparation step (Figure 2A) to prepare a base film 10' with a cured resin layer, which comprises a long base film 2 and a cured resin layer 3 disposed on one side of the base film 2 in the thickness direction; a plasma treatment step (Figure 2B) to perform plasma treatment on one side of the base film 10' with the cured resin layer in the thickness direction; and an inorganic layer formation step (Figure 2C) to form an inorganic layer 4 on one side of the base film 10 with the cured resin layer in the thickness direction. In this embodiment, the method for manufacturing a laminated film further includes an antifouling layer formation step (Figure 2D) to form an antifouling layer 5 on one side of the inorganic layer 4 in the thickness direction. The plasma treatment step, the inorganic layer formation step, and the antifouling layer formation step are carried out sequentially using an apparatus Z as shown in Figure 3.

[0133] (Preparation Step) In the preparation step, as shown in FIG. 2A, a long base film 10' with a cured resin layer is prepared, which comprises a flexible base film 2 and a cured resin layer 3 disposed on one surface in the thickness direction of the base film 2. In the long base film 10' with a cured resin layer, one surface in the thickness direction of the cured resin layer 3 is not subjected to plasma treatment. That is, the long base film 10' with a cured resin layer has a plasma-untreated surface 3a', and one surface in the thickness direction of the long base film 10' with a cured resin layer is the plasma-untreated surface 3a'.

[0134] Specifically, in the preparation step, the base film 10' with a cured resin layer is prepared by providing a flexible base film 2, applying the above ultraviolet-curable resin composition onto one surface in the thickness direction of the base film 2 to form a coating film, and then curing the coating film to form the cured resin layer 3.

[0135] From the viewpoint of manufacturability, the ultraviolet-curable resin composition preferably contains a solvent. Examples of the solvent include butyl acetate, ethyl acetate, toluene and cyclopentanone. Butyl acetate and cyclopentanone are preferable.

[0136] When the ultraviolet-curable resin composition contains a solvent, the coating film on the base film 2 is dried after application of the ultraviolet-curable resin composition.

[0137] The drying temperature is, for example, 50°C or higher and, for example, 120°C or lower. The drying time is, for example, 10 seconds or more and, for example, 10 minutes or less.

[0138] The coating film on one surface in the thickness direction of the base film 2 is cured by ultraviolet irradiation. Examples of light sources for ultraviolet irradiation include high-pressure mercury lamps and LED lights. The cumulative irradiation amount of ultraviolet light is, for example, 100 mJ / cm 2 or more, and for example, 500 mJ / cm 2 or less.

[0139] As described above, a long base film 10' with a cured resin layer is prepared. In this embodiment, a roll of the long base film 10' with a cured resin layer is prepared. Specifically, the long base film 10' with a cured resin layer is wound so that one side in the thickness direction of the base film 10 (the untreated surface 3a') faces inward in the diameter direction of the roll.

[0140] [Device Z] In the method for manufacturing the laminated film, the substrate film 10' with the cured resin layer is then conveyed as a work film W using a roll-to-roll method under a reduced-pressure atmosphere, while sequentially performing the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process. Referring to Figure 3, an example of apparatus Z for performing the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process will be described.

[0141] Furthermore, the work film W before the plasma treatment process is a base film 10' with a cured resin layer, the work film W after the plasma treatment process and before the inorganic layer formation process is a base film 10 with a cured resin layer, and the work film W after the inorganic layer formation process is a laminated film 1.

[0142] Apparatus Z comprises a feeding chamber R1, a winding chamber R2, a connection chamber P1, a plasma processing chamber P2, a connection chamber P3, a first film deposition chamber P4, a connection chamber P5, a second film deposition chamber P6, a connection chamber P7, and a PEM device (not shown).

[0143] The dispensing chamber R1 is equipped with a dispensing roller 51 for dispensing the work film W. A roll of long cured resin-coated base film 10' is attached to the dispensing roller 51 as the work film W. In addition, a predetermined number of guide rollers G for guiding the work film W are provided inside the dispensing chamber R1.

[0144] The winding chamber R2 is equipped with a winding roller 52 for winding the work film W. A predetermined number of guide rollers G for guiding the work film W are provided inside the winding chamber R2.

[0145] The connection chamber P1 is located between the feed chamber R1 and the plasma processing chamber P2 in the direction of travel of the work film W. A predetermined number of guide rollers G are provided inside the connection chamber P1 to guide the work film W. The connection chamber P1 is connected to a vacuum pump (not shown) and is configured to allow adjustment of the chamber pressure. When the apparatus Z is operated, the pressure inside the connection chamber P1 is maintained at a predetermined pressure between the pressure inside the feed chamber R1 and the pressure inside the plasma processing chamber P2. This ensures a differential pressure between the feed chamber R1 and the plasma processing chamber P2.

[0146] Plasma processing chamber P2 is located between connection chamber P1 and connection chamber P3 in the direction of travel of the work film W. Plasma processing is performed in plasma processing chamber P2.

[0147] The plasma processing chamber P2 is equipped with multiple LIAs 71. An LIA is an antenna having a low inductance of 7.5 μH or less and capable of generating inductively coupled plasma by the application of high-frequency power. In this embodiment, as shown in Figures 4 and 5, the LIAs 71 are supported by mounting fixtures 72 and covered by cover blocks 73 (omitted in Figure 4), and are arranged inside the plasma processing chamber P2 (Figure 4 shows the case where there are four LIAs 71).

[0148] Multiple LIA71 are arranged in alignment so as to be aligned in the direction of travel of the work film W and in a direction perpendicular to the direction of travel (the width direction of the work film W). The mounting fixture 72 is a vacuum flange. As shown in Figure 5, the LIA71 is fixed to the mounting fixture 72 via a field-through 74. As shown in Figure 3, the mounting fixture 72 is assembled into an opening 75 provided in the wall of the plasma processing chamber P2. Specifically, the mounting fixture 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 fixture 72. Although not shown, the LIA71 is electrically connected to a high-frequency power supply (RF power supply) outside the plasma processing chamber P2 via an impedance matching device.

[0149] LIA71 is formed of a conductor. Examples of conductors include copper and silver, with copper being preferred. LIA71 may be covered with an insulator (e.g., glass and quartz).

[0150] The cover block 73 comprises a block body 73A and a plurality of partition plates 73B. The block body 73A has a plurality of storage spaces 73a. One LIA 71 is housed in each storage space 73a. The partition plates 73B are arranged to close off the storage spaces 73a. The inside of the storage spaces 73a is a sealed space. In the cover block 73, the block body 73A is formed of, for example, aluminum. The partition plates 73B are made of insulating material (for example, quartz and glass).

[0151] The separation distance d' (shown in Figure 3) between the work film W traveling within the plasma processing chamber P2 and the cover block 73 is, for example, 50 to 200 mm.

[0152] The cover block 73 helps to avoid damage and contamination of the LIA 71 due to plasma treatment without excessively reducing the plasma conversion efficiency due to the power applied to the LIA 71, and also helps to suppress damage to the work film W (base film 10' with cured resin layer) being plasma treated.

[0153] The plasma processing chamber P2 may further include a transport roller 53. The transport roller 53 is the main guide roller for transporting the work film W within the plasma processing chamber P2. The transport roller 53 has a temperature control function that allows heating or cooling of the work film W. In other words, the transport roller 53 is a roller with a temperature control function. The transport roller 53 transports the base film 10' with the cured resin layer while contacting the other surface of the base film 10' with the cured resin layer in the thickness direction. LIA 71 is positioned opposite the transport roller 53. By including the transport roller 53, the plasma processing can be performed on one surface of the base film 10' with the cured resin layer in the thickness direction (untreated surface 3a') while cooling or heating the work film W (base film 10' with cured resin layer) during the plasma processing process. Therefore, thermal deformation of the base film 10' with the cured resin layer can be suppressed, and consequently, the influence of thermal deformation on the transport of the work film W can be suppressed.

[0154] In this embodiment, as shown in Figure 4, the LIA71 has an open-loop shape. Having an open-loop shape in the LIA71 allows for a lower inductance of the LIA71. Therefore, with an open-loop LIA71, the increase in voltage due to an increase in the power applied to the LIA71 can be suppressed. This suppresses abnormal discharge during the plasma processing process. By suppressing abnormal discharge, damage to the substrate film 10' with the cured resin layer due to plasma processing can be suppressed. Specifically, the LIA71 has a U-shape with two free ends. Each LIA71 has two free ends fixed to a mounting fixture 72 so as to be aligned in the width direction of the work film W. In this embodiment, the LIA71 also has an extension 71a on the opposite side from the two free ends. The extension 71a extends parallel to the work film W as it passes through the plasma processing chamber P2. Each extension 71a extends in the width direction of the work film W. Each extension 71a may also extend in the direction of travel of the work film W (four LIA71 may be arranged in this way). The length of the extension 71a is, for example, 50 to 150 mm (Figure 4 shows the case where the length of the extension 71a is the same as the maximum length d2 of the LIA71 described below). The LIA71 may have a coil shape.

[0155] The LIA71 extends from the mounting fixture 72 toward the work film W. Preferably, the LIA71 extends perpendicular to the mounting fixture 72. The extension length d1 of the LIA71 from the mounting fixture 72 is, for example, 30 to 150 mm. The maximum length d2 of the LIA71 in the planar direction of the work film W is, for example, 50 to 200 mm. The separation distance d3 between the LIA71 and the work film W is, for example, 50 to 200 mm. The ratio of the separation distance d3 to the extension length d1 (d3 / d1) is, for example, 0.5 to 3.5. The number of LIA71 (number of rows) arranged spaced apart in the direction of travel of the work film W can be appropriately adjusted according to the travel speed of the work film W (i.e., plasma processing time), and may be, for example, 1 to 4 or 4 or more. In the direction of travel of the work film W, the distance d4 between the centers of adjacent LIA71 is, for example, 100 to 500 mm. In the width direction of the work film W, the distance d5 between the centers of adjacent LIA71 is, for example, 200 to 500 mm. By adjusting the distance d5 between centers, the uniformity of the plasma density in the width direction of the work film W, as described later, can be controlled. The ratio of the distance d5 to the distance d4 (d5 / d4) is, for example, 0.5 to 2.0. With such a set of LIA71, a high-density plasma can be generated. As the LIA71, for example, a high-frequency antenna for plasma generation described in Japanese Patent Application Publication No. 2013-258153 may be used.

[0156] The PEM apparatus is a device for performing plasma emission monitoring (PEM) during plasma processing, and comprises the apparatus body and an optical fiber for light collection. One end of the optical fiber is positioned between the work film W and LIA71 in the plasma processing chamber P2. The other end of the optical fiber is connected to the apparatus body. In addition, a first line L1 with a flow control valve for introducing gas into the plasma processing chamber P2 is connected to the plasma processing chamber P2.

[0157] The connection chamber P3 is located between the plasma processing chamber P2 and the first film deposition chamber P4 in the direction of travel of the work film W. A predetermined number of guide rollers G for guiding the work film W are provided inside the connection chamber P3. The connection chamber P3 is connected to a vacuum pump (not shown) and is configured to allow adjustment of the chamber pressure. When the apparatus Z is in operation, the pressure inside the connection chamber P3 is maintained at a predetermined pressure between the pressure inside the plasma processing chamber P2 and the pressure inside the first film deposition chamber P4. This ensures a differential pressure between the plasma processing chamber P2 and the first film deposition chamber P4.

[0158] The first deposition chamber P4 is located next to the connection chamber P3 in the direction of travel of the work film W. The first deposition chamber P4 is also connected to a vacuum pump (not shown) and is configured to allow adjustment of the vacuum level inside the chamber. In the first deposition chamber P4, the inorganic layer formation process is carried out as described later.

[0159] In this embodiment, the first deposition chamber P4 is a sputter deposition chamber. The first deposition chamber P4 comprises a deposition roller 54 and a plurality of sputter chambers 60 (sputter chambers 60a to 60e) (Figure 3 shows the case where there are 5 sputter chambers 60). The deposition roller 54 is the main guide roller for transporting the work film W within the first deposition chamber P4. The deposition roller 54 has a temperature control function that allows heating or cooling of the work film W. The sputter chambers 60 are partitioned spaces within the first deposition chamber P4. The plurality of sputter chambers 60 are arranged along the circumferential direction of the deposition roller 54. Each sputter chamber 60 opens toward the deposition roller 54. A cathode 61 is provided inside the sputter chamber 60. A target (not shown) as a deposition material supply is placed on the cathode 61. The target is placed on the target so as to face the deposition roller 54. Each sputtering chamber 60 is equipped with a power supply (not shown) for applying voltage to the target to generate a glow discharge. Examples of power supplies include DP power supplies, AC power supplies, MF power supplies, RF power supplies, and MF-AC power supplies. An 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 second line (not shown) with the necessary number of flow control valves for introducing gas into the chamber. In addition, a predetermined number of guide rollers G for guiding the work film W are provided inside the first deposition chamber P4.

[0160] The connection chamber P5 is located between the first deposition chamber P4 and the second deposition chamber P6 in the direction of travel of the work film W. A predetermined number of guide rollers G for guiding the work film W are provided inside the connection chamber P3. The connection chamber P5 is connected to a vacuum pump (not shown) and is configured to allow adjustment of the chamber pressure. When the apparatus Z is in operation, the pressure inside the connection chamber P3 is maintained at a predetermined pressure between the pressure inside the first deposition chamber P4 and the pressure inside the second deposition chamber P6. This ensures a differential pressure between the first deposition chamber P4 and the second deposition chamber P6.

[0161] The second film deposition chamber P6 is located next to the connection chamber P5 in the direction of travel of the work film W. The second film deposition chamber P6 is also connected to a vacuum pump (not shown) and is configured to allow adjustment of the vacuum level inside the chamber. In the second film deposition chamber P6, the antifouling layer formation process is carried out as described later.

[0162] In this embodiment, the second deposition chamber P6 is a vacuum deposition chamber. The second deposition chamber P6 includes a material holding section 81, a vacuum pump (not shown), and a deposition amount adjustment valve (not shown) whose opening degree can be controlled. In addition, a predetermined number of guide rollers G for guiding the work film W are provided inside the second deposition chamber P6 as needed. A deposition material supply material (not shown) is arranged in the material holding section 81 so as to face the work film W being transported inside the second deposition chamber P6. The material holding section 81 may have a built-in resistance heating means, a built-in high-frequency induction heating means, or an electron beam heating means as means for heating the deposition material supply material.

[0163] The connection chamber P7 is located between the second deposition chamber P6 and the winding chamber R2 in the direction of travel of the work film W. A predetermined number of guide rollers G for guiding the work film W are provided inside the connection chamber P7. The connection chamber P7 is connected to a vacuum pump (not shown) and is configured to allow adjustment of the chamber pressure. When the apparatus Z is in operation, the pressure inside the connection chamber P7 is maintained at a predetermined pressure between the pressure inside the second deposition chamber P6 and the pressure inside the winding chamber R2. This ensures a differential pressure between the second deposition chamber P6 and the winding chamber R2.

[0164] The apparatus Z described above sequentially performs the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process. Specifically, it is as follows.

[0165] (Plasma treatment process) The work film W is unfurled from the unfurling chamber R1. After being unfurled from the unfurling chamber R1, the work film W sequentially passes through the connection chamber P1, the plasma processing chamber P2, the connection chamber P3, the first deposition chamber P4, the connection chamber P5, the second deposition chamber P6, and the connection chamber P7, and is wound up in the winding chamber R2. The travel speed of the work film W is, for example, 0.1 m / min to 10 m / min, preferably 0.5 m / min to 8 m / min. Furthermore, the entire line from the unfurling chamber R1 to the winding chamber R2 is not opened to the atmosphere along the way, and the process is carried out under a reduced pressure atmosphere. The reduced pressure atmosphere is preferably a vacuum. A vacuum preferably means a reduced pressure atmosphere of 7 Pa or less.

[0166] In the plasma treatment chamber P2, the plasma treatment process is carried out. In the plasma treatment process, under a reduced-pressure atmosphere in the plasma treatment chamber P2 (chamber), plasma treatment is performed on one side in the thickness direction (untreated surface 3a') of the substrate film 10' (work film W) with a cured resin layer, while detecting the plasma emission intensity. In this embodiment, the plasma treatment is performed by inductively coupled plasma of an oxygen-containing gas generated by applying high-frequency power to the LIA71 (oxygen-plasma treatment). Specifically, it is as follows.

[0167] During plasma processing, oxygen is supplied to the plasma processing chamber P2 via the first line L1. In addition to oxygen, an inert gas may 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 the inert gas 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, even more preferably 90% by volume or more, and particularly preferably 100% by volume. If the oxygen concentration is above the above lower limit, a high-density oxygen plasma can be generated. This has an effect on nanometer-order fine unevenness on the plasma-untreated surface 3a' of the substrate film 10' with the cured resin layer, and on chemical bond changes near the surface of the plasma-untreated surface 3a' of the substrate film 10' with the cured resin layer.

[0168] The pressure inside the plasma processing chamber P2 during plasma processing (first pressure) is, for example, 0.1 Pa or more, preferably 0.3 Pa or more, and for example, 7 Pa or less, preferably 3 Pa or less. If the first pressure is above the lower limit, a plasma environment with sufficient density for surface modification treatment of the work film W can be formed inside the plasma processing chamber P2 during plasma processing. If the first pressure is below the upper limit, damage to the work film W caused by excessively high-density plasma can be suppressed during plasma processing. The first pressure can be adjusted by the amount of oxygen gas supplied into the plasma processing chamber P2.

[0169] The temperature of the work film W (base film 10' with cured resin layer) which is temperature-controlled by the conveyor roller 53 is, for example, -20°C to 150°C.

[0170] The frequency of the high-frequency power applied to the LIA71 during plasma processing is, for example, 1 MHz or higher, preferably 5 MHz or higher, and for example, 100 MHz or lower, preferably 60 MHz or lower. If the frequency of the high-frequency power is above the lower limit, the plasma discharge can be stabilized while increasing the plasma current density during plasma processing. If the frequency of the high-frequency power is below the upper limit, the antenna potential can be suppressed, and therefore, damage to the workpiece film W by the plasma can be suppressed.

[0171] The high-frequency power applied to LIA71 during plasma processing is, for example, 1 kW or more, preferably 2.0 kW or more, more preferably 3.0 kW or more, and also, for example, 15 kW or less, preferably 10 kW or less, more preferably 8.0 kW or less, and even more preferably 5 kW or less. If the high-frequency power is above the lower limit, a high-density plasma environment can be formed in the plasma processing chamber P2 during plasma processing by inductively coupled plasma. If the high-frequency power is below the upper limit, excessive damage to the workpiece film W by the plasma can be suppressed. Furthermore, if the high-frequency power is below the upper limit, the total reflectance (visible reflectance) can be improved.

[0172] In the plasma treatment process, preferably, the plasma emission intensity during plasma treatment is monitored by a PEM device. Based on the monitoring results, the amount of oxygen gas introduced, the high-frequency power, and the travel speed are controlled.

[0173] In the plasma treatment process, the plasma current density at the intermediate position between LIA71 and the work film W (substrate film 2' with cured resin layer) is, for example, 0.1 mA / cm². 3 Preferably, 0.5 mA / cm² 3 In addition, for example, 8mA / cm 3 Preferably, 5 mA / cm 3The following applies: Inductively coupled plasma processing using LIA can achieve a higher plasma current density than capacitively coupled plasma processing (for example, a plasma density approximately 100 times higher can be achieved). If the plasma current density is above the lower limit, sufficient plasma-induced oxygen particles can be secured in the plasma processing chamber P2 during plasma processing, and the surface of the work film W can be appropriately surface-modified. If the plasma current density is below the upper limit, damage to the work film W due to excessively high density of plasma-induced oxygen particles can be suppressed during plasma processing. Methods for adjusting the plasma current density include, for example, adjusting the amount of oxygen gas introduced into the plasma processing chamber P2, adjusting the frequency of the high-frequency power applied to the high-frequency power supply, and adjusting the magnitude of the applied power. The plasma current density can be measured using a Langmuir probe for plasma measurement.

[0174] As shown in Figure 2B, the substrate film 10' with the cured resin layer is manufactured by the plasma treatment described above. The substrate film 10 with the cured resin layer has a plasma-treated surface 3a. In other words, one side of the substrate film 10 with the cured resin layer in the thickness direction is the plasma-treated surface 3a.

[0175] The adhesion to the substrate film 10' with the cured resin layer can be improved by the plasma treatment described above.

[0176] (Inorganic layer formation process) In the inorganic layer formation process, following the plasma treatment process, an inorganic layer 4 is formed on one side (plasma-treated surface 3a) in the thickness direction of the cured resin layer-attached substrate film 10 (work film W) under a reduced pressure atmosphere by sputtering, vapor deposition, or chemical vapor deposition. In the inorganic layer formation process, the inorganic layer 4 is preferably formed by sputtering. The reduced pressure atmosphere is preferably a vacuum.

[0177] In the sputtering method, a sputtering gas (inert gas) is introduced into each sputtering chamber 60 via a second line, while a negative voltage is applied to the target (film deposition material) placed on the cathode 61 in the sputtering chamber 60. This generates a glow discharge, ionizing the gas atoms, which then collide with the target surface at high speed, ejecting the target material from the target surface and depositing it onto the work film W. Examples of sputtering gases include argon, krypton, and xenon.

[0178] Furthermore, the sputtering method may be a reactive sputtering method. In the reactive sputtering method, oxygen (reactive gas) is introduced into the sputtering chamber 60 in addition to the sputtering gas. The oxygen is introduced into the sputtering chamber 60 via another second line. In the reactive sputtering method, the amount of reactive gas introduced relative to 100 parts by volume of sputtering gas is, for example, 1 to 50 parts by volume. In the reactive sputtering method, if the target is a metal or Si, the formed inorganic layer 4 contains an oxide of the target (i.e., an oxide of the metal or an oxide of Si).

[0179] In the sputtering method, the pressure in the sputtering chamber 60 (second pressure) is adjusted appropriately according to the type of layer to be formed, for example, from 0.1 to 5.0 Pa. The film deposition temperature (temperature of the work film W, which is controlled by the film deposition roller 54) is, for example, from -20°C to 150°C. The discharge power is, for example, from 1 kW to 50 kW.

[0180] In the inorganic layer formation process, an 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, an adhesion layer 41 is formed on one side in the thickness direction of the cured resin layer 3 in sputtering chamber 60a, a high refractive index layer 42a is formed on one side in the thickness direction of the adhesion layer 41 in sputtering chamber 60b, a low refractive index layer 42b is formed on one side in the thickness direction of the high refractive index layer 42a in sputtering chamber 60c, a high refractive index layer 42c is formed on one side in the thickness direction of the low refractive index layer 42b in sputtering chamber 60d, and a low refractive index layer 42d is formed on one side in the thickness direction of the high refractive index layer 42c in sputtering chamber 60e.

[0181] (Anti-fouling layer formation process) In the antifouling layer formation step, following the inorganic layer formation step, an antifouling layer 5 is formed on one side in the thickness direction of the inorganic layer 4 of the work film W (laminated film 1) after the inorganic layer formation step, under a reduced pressure atmosphere by sputtering, vapor deposition, or chemical vapor deposition. In the antifouling layer formation step, the antifouling layer 5 is preferably formed by vapor deposition. The reduced pressure atmosphere is preferably a vacuum. In other words, in the antifouling layer formation step, the antifouling layer 5 is more preferably formed by vacuum vapor deposition.

[0182] In the vacuum deposition method, the second deposition chamber P6 is reduced to a vacuum by operating a vacuum pump, and the deposition source located in the material holding section 81 is heated to a predetermined temperature, causing the antifouling layer 5 material to evaporate and deposit onto the work film W.

[0183] In vacuum deposition, the pressure in the second deposition chamber P6 (third pressure) is, for example, 0.1 Pa or less, preferably 0.05 Pa or less, and also, for example, 1 × 10⁻⁶ -5 It is Pa or higher.

[0184] In vacuum deposition, the heating temperature of the deposition source is, for example, 200°C or higher, and for example, 400°C or lower.

[0185] In apparatus Z, after the plasma treatment process, the inorganic layer formation process, and the antifouling layer formation process, the laminated film 1, which is the work film W, travels through the connection chamber P7 to the winding chamber R2 and is wound up by the winding roller 52.

[0186] In this manner, a long laminated film 1 is manufactured.

[0187] (Effects and Benefits) The above-described method for manufacturing a laminated film is a method for manufacturing a laminated film 1, and includes a plasma treatment step of plasma treatment applied to one surface in the thickness direction of a base film 10' with a cured resin layer. Therefore, it is possible to manufacture a laminated film that has good optical properties while improving adhesion. [Examples]

[0188] The present invention will be further described below with reference to examples and comparative examples. However, the present invention is not limited in any way to the examples and comparative examples. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical properties, and parameters used in the following description may be replaced with the upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the corresponding blending ratios (content ratios), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0189] Example 1 (Preparation steps) A hard coat layer, acting as a cured resin layer, was formed on one side in the thickness direction of a triacetylcellulose (TAC) film used as a base film.

[0190] Specifically, 80 parts by mass (solid content equivalent) of UV-curable acrylic urethane resin (product name "UT-7314", manufactured by Mitsubishi Chemical Corporation), 20 parts by mass (solid content equivalent) of polyfunctional acrylate mainly composed of pentaerythritol triacrylate (product name "Viscote #300", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.5 parts by mass of photopolymerization initiator (product name "Omnirad127D", manufactured by BASF), and 0.06 parts by mass of leveling agent (product name "Polyflow LE-303", leveling agent containing a silicone compound, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixture. Next, a mixed solvent of butyl acetate and cyclopentanone (CPN) (mass ratio of butyl acetate to CPN is 70:30) was added to the mixture as a solvent to prepare a cured resin composition with a solid content concentration of 40% by mass.

[0191] Meanwhile, a long sheet of TAC film (product name "KC8UAW", thickness 80 μm, manufactured by Konica Minolta) was prepared. Next, a curing resin composition was applied to one side in the thickness direction of the TAC film to form a coating. This coating was dried by heating and then cured by ultraviolet irradiation. As a result, a hard coat layer with a thickness of 5 μm was formed on one side in the thickness direction of the TAC film. The drying conditions were a heating temperature of 100°C and a heating time of 1 minute. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet light with a wavelength of 365 nm was irradiated onto the coating, with an integrated irradiation light intensity of 300 mJ / cm². 2 Thus, a roll of base film with a cured resin layer was prepared.

[0192] (Plasma treatment process) Under vacuum, a substrate film with a cured resin layer was transported using a roll-to-roll method, and plasma treatment was performed on one side of the substrate film in the thickness direction (one side in the thickness direction of the cured resin layer).

[0193] For plasma processing, a first apparatus capable of performing a roll-to-roll process on the work film was used. The first apparatus comprises a feeding chamber, a plasma processing chamber (first plasma processing chamber), a film deposition chamber (first film deposition chamber and second film deposition chamber), and a winding chamber. The feeding chamber, first plasma processing chamber, first film deposition chamber, second film deposition chamber, and winding chamber are arranged in this order and are also connected to each other. The feeding chamber is equipped with a feeding roller. A roll of the above-mentioned cured resin layer-coated substrate film is set on the feeding roller as the work film. The first plasma processing chamber comprises a transport roller with a temperature control function (transport roller 53 in Figure 3) and four LIAs (LIA71 in Figures 4 and 5) covered by cover blocks (cover block 73 in Figure 5), as shown in Figures 4 and 5. Each LIA has an extension portion (extension portion 71a in Figure 4) parallel to the substrate film. In 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 (see Figures 4 and 5). Each LIA is electrically connected to a high-frequency power supply (RF power supply, frequency 13.56 MHz) via an impedance matcher outside the first plasma processing chamber. The separation distance d' between the substrate film and the cover block running inside the first plasma processing chamber is 100 mm. The first deposition chamber is a sputter deposition chamber and is equipped with a deposition roller and a cathode positioned opposite the deposition roller. The second deposition chamber is a vacuum deposition chamber and is equipped with a deposition source. The winding chamber is equipped with a winding roller.

[0194] Specifically, using the first apparatus described above, a hard-coated substrate film was transported from the dispensing chamber to the winding chamber in a roll-to-roll manner, and plasma treatment was performed on one side in the thickness direction of the cured resin-coated substrate film in the first plasma treatment chamber. The travel speed of the cured resin-coated substrate film (work film travel speed) was set to 1.0 m / min. The temperature of the temperature-controlled transport roller was set to -8°C. The plasma treatment conditions were as follows:

[0195] The ultimate vacuum level in the first plasma processing chamber is 1.0 × 10⁻⁶ -4 After evacuating the apparatus to a vacuum of 1.5 Pa, oxygen gas was introduced into the first plasma processing chamber, and the atmospheric pressure inside the first plasma processing chamber was set to 1.5 Pa. By applying a high-frequency power of 5.0 kW to the four LIAs using a high-frequency power supply, an inductively coupled plasma of oxygen-containing gas was formed around the four LIAs. This plasma was used to plasma-treat one side in the thickness direction of the substrate film with a cured resin layer. The plasma current density at the intermediate position between the LIA and the work film was 1.3 mA / cm². 3 The plasma current density was measured using a Langmuir probe for plasma measurement.

[0196] As described above, one side in the thickness direction of the substrate film with the cured resin layer was plasma treated. In other words, one side in the thickness direction of this substrate film with the cured resin layer is the plasma treated surface. This plasma treatment is an inductively coupled plasma treatment using an oxygen-containing gas generated by applying high-frequency power to the LIA (oxygen LIA treatment).

[0197] (Inorganic layer formation process) Next, following the plasma treatment process, an inorganic layer was formed on the substrate film with the cured resin layer.

[0198] Specifically, using the first apparatus described above, which can perform sputter deposition using a roll-to-roll method, an adhesion layer, 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 were sequentially formed on one side in the thickness direction of the substrate film with a cured resin layer after plasma treatment in the first deposition chamber.

[0199] The first deposition chamber comprises a deposition roller (deposition roller 54 in Figure 5) and a number of sputtering chambers. The sputtering chambers are partitioned spaces within the first deposition chamber. Each sputtering chamber is equipped with a cathode positioned opposite the deposition roller. The sputtering chambers are connected to a second line (not shown) with the necessary number of flow control valves for introducing gas into the chamber.

[0200] While the substrate film with the cured resin layer was being transported and cooled by the deposition roller in the first deposition chamber, an adhesion layer was formed on one side in the thickness direction of the substrate film with the cured resin layer in the first sputtering chamber, a first high refractive index layer was formed on the adhesion layer in the second sputtering chamber, a first low refractive index layer was formed on the first high refractive index layer in the third sputtering chamber, a second high refractive index layer was formed on the first low refractive index layer in the fourth sputtering chamber, and a second low refractive index layer was formed on the second high refractive index layer in the fifth sputtering chamber (the adhesion layer, first high refractive index layer, first low refractive index layer, second high refractive index layer, and second low refractive index layer are inorganic layers). The deposition temperature (temperature of the deposition roll) was -8°C. The deposition conditions were as follows.

[0201] In the first sputtering chamber, a 4 nm thick ITO layer was formed as an adhesion layer using reactive sputtering. Specifically, the vacuum level achieved in the first deposition chamber was 1.0 × 10⁻⁶. -4 After evacuating to a vacuum of Pa, argon as an inert gas and oxygen as a reactive gas were introduced into the first sputtering chamber, and the pressure inside the first sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 volumes of argon into the first sputtering chamber was 10 volumes. A sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 30 mass%) was used as the target. An MF-AC power supply was used to apply voltage to the target (the same was used in the second to fifth sputtering chambers described later). The discharge power was set to 4.3 kW.

[0202] In the second sputtering chamber, a 14 nm thick Nb2O5 layer (refractive index 2.33) was formed as the first high refractive index layer using reactive sputtering. Specifically, after the first deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the second sputtering chamber, and the pressure in the second sputtering chamber was set to 0.5 Pa. The amount of oxygen introduced per 100 volumes of argon into the second sputtering chamber was 5 volumes. An Nb target was used as the target. The discharge power was 13 kW.

[0203] In the third sputtering chamber, a 28 nm thick SiO2 layer (refractive index 1.46) was formed as the first low refractive index layer using reactive sputtering. Specifically, after the first deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the third sputtering chamber, and the pressure in the third sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 volumes of argon into the third sputtering chamber was 30 volumes. A Si target was used as the target. The discharge power was set to 25 kW.

[0204] In the fourth sputtering chamber, a 105 nm thick Nb2O5 layer (refractive index 2.33) was formed as the second high refractive index layer using reactive sputtering. Specifically, after the first deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fourth sputtering chamber, and the pressure in the fourth sputtering chamber was set to 0.5 Pa. The amount of oxygen introduced per 100 volumes of argon into the fourth sputtering chamber was 13 volumes. An Nb target was used as the target. The discharge power was 27.5 kW.

[0205] In the fifth sputtering chamber, a SiO2 layer with a thickness of 84 nm (refractive index 1.46) was formed as the second low refractive index layer using reactive sputtering. Specifically, after the first deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fifth sputtering chamber, and the pressure inside the fifth sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 volumes of argon into the fifth sputtering chamber was 30 volumes. A Si target was used as the target. The discharge power was set to 20.5 kW.

[0206] (Anti-fouling layer formation process) Next, following the inorganic layer process, an antifouling layer was formed on one side in the thickness direction of the inorganic layer (specifically, one side in the thickness direction of the second low refractive index layer).

[0207] Specifically, using the first apparatus described above, an 8 nm thick antifouling layer was formed on one side of the inorganic layer in the thickness direction by vacuum deposition in the second deposition chamber, using a perfluoropolyether group-containing alkoxysilane compound as the deposition source. The deposition source was the solid content obtained by drying "KY1903-1" (a perfluoropolyether group-containing alkoxysilane compound represented by the above general formula (2), solid content concentration 20% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. The heating temperature of the deposition source in the vacuum deposition method was set to 260°C.

[0208] The laminated film of Example 1 was prepared as described above. The laminated film of Example 1 comprises a base film, a cured resin layer, an inorganic layer (adhesion layer, first high refractive index layer, first low refractive index layer, second high refractive index layer, second low refractive index layer), and an anti-fouling layer, arranged in order toward one side in the thickness direction.

[0209] Example 2 The laminated film of Example 2 was prepared in the same manner as in Example 1, except that the leveling agent used in the curable resin composition (product name "Polyflow LE-303", a leveling agent containing a silicone compound, manufactured by Kyoeisha Chemical Co., Ltd.) in the preparation step was changed to a leveling agent (product name "Megafac S-333", a leveling agent containing a silicone compound, manufactured by DIC Corporation).

[0210] Example 3 The laminated film of Example 3 was prepared in the same manner as in Example 1, except that the amount of leveling agent used in the curable resin composition was changed to 0.03 parts by mass during the preparation process.

[0211] Example 4 The laminated film of Example 4 was prepared in the same manner as in Example 1, except that the amount of leveling agent used in the curable resin composition was changed to 0.09 parts by mass during the preparation process.

[0212] Example 5 The laminated film of Example 5 was fabricated in the same manner as in Example 1, except that the high-frequency power applied to the four LIAs by the high-frequency power supply was changed to 2.5 kW during the plasma treatment process.

[0213] Example 6 The laminated film of Example 6 was fabricated in the same manner as in Example 1, except that the high-frequency power applied to the four LIAs by the high-frequency power supply was changed to 10.0 kW during the plasma treatment process.

[0214] Comparative Example 1 A laminated film of Comparative Example 1 was prepared in the same manner as in Example 1, except that the plasma treatment process was not performed.

[0215] Comparative Example 2 A laminated film of Comparative Example 2 was prepared in the same manner as in Example 2, except that the plasma treatment process was not performed.

[0216] Comparative Example 3 In the preparation step, 150 parts by mass (in terms of solid content) of silica particles with a particle size of 40-50 nm (product name "PGM-AC-4130Y", manufactured by Nissan Chemical Corporation) dispersed in propylene glycol monomethyl ether were added to the mixture, and the plasma treatment step was omitted. The laminated film of Comparative Example 3 was then prepared in the same manner as in Example 1.

[0217] Comparative Example 4 (Preparation steps) A roll of substrate film with a cured resin layer was prepared in the same manner as in Example 1, except that 150 parts by mass (solid content equivalent) of silica particles with a particle size of 40-50 nm (product name "PGM-AC-4130Y", manufactured by Nissan Chemical Corporation) dispersed in propylene glycol monomethyl ether was added to the mixture.

[0218] (Plasma treatment process) Under vacuum, a substrate film with a cured resin layer was transported using a roll-to-roll method, and plasma treatment was performed on one side of the substrate film in the thickness direction (one side in the thickness direction of the cured resin layer).

[0219] For plasma processing, a second apparatus capable of performing a roll-to-roll process on the work film was used. The second apparatus has the same configuration as the first apparatus, except that it has a second plasma processing chamber instead of the first plasma processing chamber. The second plasma processing chamber is equipped with a pair of planar electrodes for plasma generation: a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304). The pair of planar electrodes are spaced 50 mm apart and are positioned parallel to the substrate film with the cured resin layer passing through the second plasma processing chamber. The anode electrode is positioned 35 mm away from the substrate film with the cured resin layer passing through the second plasma processing chamber and is grounded outside the second plasma processing chamber. The cathode electrode is positioned facing one side in the thickness direction of the substrate film with the cured resin layer 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 facing the substrate film with the cured resin layer in the film travel direction is 110 mm, and the length in the width direction is 430 mm.

[0220] Specifically, using the second apparatus described above, the substrate film with the cured resin layer was transported from the dispensing chamber to the winding chamber in a roll-to-roll manner, and then plasma-treated (bombarded treatment) was performed on one side in the thickness direction of the substrate film with the cured resin layer in the second plasma treatment chamber. The travel speed of the substrate film with the cured resin layer (film travel speed) was set to 1.0 m / min. The conditions for plasma treatment are as follows:

[0221] The ultimate vacuum level in the second plasma processing chamber is 1.0 × 10⁻⁶ -4 After evacuating the apparatus to a vacuum of 0.5 Pa, argon was introduced into the second plasma processing chamber, and the pressure inside the second plasma processing chamber was set to 0.5 Pa. By applying 500 W of power from a high-frequency power supply between the planar electrodes, a capacitively coupled plasma (CCP) was generated. Under this plasma environment, bombardment (BB treatment) with argon ions was performed on one side in the thickness direction of the substrate film with a cured resin layer.

[0222] As described above, one side of the substrate film with the cured resin layer in the thickness direction was plasma-treated. In other words, this one side of the substrate film with the cured resin layer in the thickness direction is the plasma-treated surface. This plasma treatment is ion bombardment (Ar-BB) using capacitively coupled plasma with argon gas.

[0223] The inorganic layer formation process and the antifouling layer formation process were carried out in the same manner as in Example 1 to produce the laminated film of Comparative Example 3.

[0224] <Rating> [Ionic intensity ratio] In each example and Comparative Example 4, a sample of the substrate film with the cured resin layer was taken after the plasma treatment step and before the inorganic layer formation step. In Comparative Examples 1 to 3, a sample of the substrate film with the cured resin layer was taken after the preparation step and before the inorganic layer formation step. Each substrate film with the cured resin layer was cut to a size of 10 mm x 10 mm to be used as a sample for analysis. One side of the sample in the thickness direction (the exposed surface of the cured resin layer) was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). The analysis conditions are shown below. A neutralization gun was used to correct the charge of the sample during analysis.

[0225] {Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis conditions} Time-of-flight secondary ion mass spectrometer: Product name "TOF-SIMS5", manufactured by ION-TOF. Primary irradiated ions: Double-charged ions of bismuth clusters (Bi 3++ ) Primary ion acceleration voltage: 25kV Sample measurement range: 300 μm × 300 μm Analysis mass range (m / z): 0~300

[0226] Analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS) revealed that HSiO + Fragment, C3H9Si + Fragment, HSiO3 - Fragments, and C3H3O2 -The ionic strength of each of the plurality of fragments including the fragment was obtained by TOF-SIMS analysis, and HSiO + fragment has a ratio of secondary ion mass (m) to secondary ion charge number (z) (m / z) of 45, and C3H9Si + fragment has said ratio (m / z) of 73, and HSiO3 - fragment has said ratio (m / z) of 77, and C3H3O2 - fragment has said ratio (m / z) of 71.

[0227] From the obtained ionic strengths, C3H3O2 - fragment with respect to the ionic strength of HSi2O5 - fragment ionic strength ratio (HSi2O5 - / C3H3O2 - ) and the ratio of the ionic strength of HSiO + fragment to the ionic strength of C3H9Si + fragment (HSiO + / C3H9Si + ) were obtained. The results are shown in Table 1.

[0228] [Adhesion] The following first test and second test were performed on the laminated films of each example and each comparative example.

[0229] First test: First, the other surface in the thickness direction of the laminated film (exposed surface of the base film) was fixed to a glass plate. Next, from one side in the thickness direction of the laminated film on the glass plate, light was irradiated by a metal halide lamp using a weather resistance tester (Eye Super UV Tester SUV-W161, manufactured by Iwasaki Electric Co., Ltd.) (accelerated weather resistance test). Note that other conditions were set as and . The conditions of the accelerated weather resistance test are shown below.

[0230] {Conditions for accelerated weather resistance test} Light irradiation time: 32.5 hours Temperature and humidity in the weather resistance tester: temperature 85°C, relative humidity 45%RH Irradiance (integrated irradiance at 300 to 700 nm): 1500 W / m 2

[0231] Second Test: First, on the antifouling layer and inorganic layer of the laminated film on the glass plate after the first test, 11 parallel first cuts (1 mm intervals) linearly extending in a first direction and 11 parallel second cuts (1 mm intervals) linearly extending in a second direction orthogonal to the first direction were formed with a utility knife, and 100 grids were formed by the first cuts and the second cuts. Next, while continuously dropping isopropyl alcohol at a rate of 2 mL / min onto the region of the 100 grids in the laminated film, a polyester wiper (product name "Anticon Gold", manufactured by Sampler Tech Co., Ltd.) was slid. The sliding conditions were set as follows: wiper contact surface 20 mm × 20 mm, load 1.5 kg / 20 mm, and 1000 reciprocations. Then, among the 100 grids, 0.25 mm 2 The number of grids where peeling of 1 / 4 or more of the grid area occurred was counted, the number of remaining grids was calculated, and evaluation was performed according to the following criteria. The results are shown in Table 1.

[0232] {Criteria} A: The number of remaining grids is 90 or more B: The number of remaining grids is 70 or more and less than 90 C: The number of remaining grids is 20 or more and less than 70 D: The number of remaining grids is less than 20

[0233] [Total Reflectance] The other side (exposed surface of the base film) of the laminated film in the thickness direction of each example and comparative example was bonded to a black acrylic plate (2 mm thick) via a predetermined transparent acrylic adhesive. This prepared a sample for measurement. Next, the spectrum of the total reflected light (including specular reflected light) of this sample was measured using a spectrophotometer (product name "UH4150", manufactured by Hitachi High-Tech Science Corporation). For the measurement, a standard light source D65 was used as the light source, and the sample was placed inside the spectrophotometer so that light shone on it from one side in the thickness direction of the inorganic layer of the sample. The measurement was performed in the integrating sphere measurement mode of the spectrophotometer. The reflectance measured is the total reflectance (visible reflectance) of the light irradiated from one side in the thickness direction of the inorganic layer of the sample (laminated film) by the standard light source D65 at wavelengths of 380 nm to 780 nm. The results are shown in Table 1.

[0234] [Table 1] [Explanation of Symbols]

[0235] 1. Laminated film 2. Base film 3 Cured resin layer 4 Inorganic layer

Claims

1. A laminated film comprising a base film, a cured resin layer disposed on one side of the base film in the thickness direction, and an inorganic layer disposed on one side of the cured resin layer in the thickness direction, On one side in the thickness direction of the cured resin layer, C is measured by time-of-flight secondary ion mass spectrometry. ３ H ３ O ２ － HSi as a function of the ionic strength of the fragment ２ O ５ － The ratio of the ionic strengths of the fragments is 1.0 × 10⁻⁶. －１ That's all. A laminated film wherein the total reflectance of light irradiated onto the laminated film from one side in the thickness direction of the inorganic layer using a standard light source D65 with wavelengths from 380 nm to 780 nm is 0.40% or less.

2. A laminated film comprising a base film, a cured resin layer disposed on one side of the base film in the thickness direction, and an inorganic layer disposed on one side of the cured resin layer in the thickness direction, On one surface in the thickness direction of the cured resin layer, C measured by time-of-flight secondary ion mass spectrometry ３ H ９ Si ＋ The ratio of the ion intensity of the HSiO fragment to the ion intensity of the fragment ＋ is 1.0×10 －１ or more, A laminated film wherein the total reflectance of light irradiated onto the laminated film from one side in the thickness direction of the inorganic layer using a standard light source D65 with wavelengths from 380 nm to 780 nm is 0.40% or less.

3. The laminated film according to claim 1 or 2, wherein the cured resin layer contains a silicone compound.

4. The laminated film according to claim 3, wherein the cured resin layer further contains an acrylate resin.

5. The laminated film according to claim 4, wherein the amount of the silicone compound blended with 100 parts by mass of the acrylate resin is 0.0025 parts by mass or more.

6. The laminated film according to claim 1 or 2, wherein one surface in the thickness direction of the cured resin layer is a plasma-treated surface.

7. The laminated film according to claim 1 or 2, wherein the inorganic layer comprises an anti-reflective layer.

8. The laminated film according to claim 1 or 2, further comprising an antifouling layer disposed on one side in the thickness direction of the inorganic layer.

9. A method for producing a laminated film according to claim 1 or 2, A preparation step for preparing a base film with a cured resin layer, comprising a long base film and the cured resin layer disposed on one side of the base film in the thickness direction, A plasma treatment step is performed on one side in the thickness direction of the substrate film with the cured resin layer, An inorganic layer formation step in which the inorganic layer is formed on one side in the thickness direction of the substrate film with the cured resin layer, A method for manufacturing a laminated film, comprising the features described above.

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

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