Laminated film, method for producing laminated film, and substrate film with cured resin layer

Abstract

To provide a laminated film improved in adhesion while having good optical characteristics, and a method for manufacturing the laminated film.SOLUTION: The laminated film 1 of the present invention includes a base film 2, a cured resin layer 3 disposed on one surface in the thickness direction of the base film 2, and an inorganic material layer 4 disposed on one surface in the thickness direction of the cured resin layer 3. The ratio of the ion intensity of the C3H3O2 fragment to the ion intensity of the HSi2O5 fragment measured by time-of-flight secondary ion mass spectrometry is 1.0 * 10 - 1 or more. In addition, the total reflectance of the laminated film 1 from one side in the thickness direction of the inorganic material layer 4 with respect to irradiated light of wavelengths 380nm to 780nm of a standard illuminant D65 is 0.40% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated film and a method for producing the laminated film. [Background technology]

[0002] In order to improve the visibility of displayed images, an anti-reflection film is disposed on the outer surface of the display screen of a display device such as a liquid crystal display or an organic electroluminescence display. For example, an anti-reflection film having a film substrate, a hard coat layer, an inorganic oxide primer layer, and an anti-reflection layer in that order in the thickness direction is known (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-65437 Summary of the Invention [Problem to be solved by the invention]

[0004] In the antireflection 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 surface irregularities have an anchoring effect that prevents the antireflection layer from peeling off.

[0005] However, in the antireflection film of Patent Document 1, the surface of the antireflection layer opposite the inorganic oxide primer layer also has surface irregularities that follow the surface irregularities of the hard coat layer. Such surface irregularities of the antireflection layer scatter a portion of the light incident on the antireflection film. Furthermore, silica particles in the hard coat layer also scatter a portion of the light incident on the antireflection film. In other words, such an antireflection film has poor optical properties.

[0006] The present invention provides a laminated film and a method for producing the laminated film, which have good optical properties and improved 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 surface in the thickness direction of the base film, and an inorganic layer disposed on one surface in the thickness direction of the cured resin layer, wherein the cured resin layer has a C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments is 1.0 × 10 -1 The present invention includes a laminate film having a total reflectance of 0.40% or less for light of standard illuminant D65 having a wavelength of 380 nm to 780 nm irradiated from one side of the inorganic material layer in the thickness direction of the laminate film.

[0008] The present invention [2] is a laminated film comprising a base film, a cured resin layer disposed on one surface of the base film in the thickness direction, and an inorganic layer disposed on one surface of the cured resin layer in the thickness direction, wherein the cured resin layer has a C3H9Si + HSiO versus ionic strength of fragments + The ratio of the ion intensities of the fragments is 1.0 × 10 -1 The present invention includes a laminate film having a total reflectance of 0.40% or less for light of standard illuminant D65 having a wavelength of 380 nm to 780 nm irradiated from one side of the inorganic material layer in the thickness direction of the laminate film.

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

[0010] The present invention [4] includes the laminated film according to the above [3], in which the cured resin layer further contains an acrylate resin.

[0011] The present invention [5] includes the laminated film according to the above [4], in which the blending amount of the silicone compound is 0.0025 parts by mass or more relative to 100 parts by mass of the acrylate resin.

[0012] The present invention [6] includes the 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 the laminate film according to any one of the above [1] to [6], wherein the inorganic layer comprises an anti-reflection layer.

[0014] The present invention [8] includes the laminate film according to any one of the above [1] to [7], further comprising an antifouling layer disposed on one surface in the thickness direction of the inorganic layer.

[0015] The present invention [9] is a method for producing the laminate film according to any one of the above [1] to [7], and includes the method for producing a laminate film, comprising: a preparation step of preparing a cured resin layer-attached substrate film, the substrate film including a long length and the cured resin layer disposed on one surface of the substrate film in the thickness direction; a plasma treatment step of subjecting the one surface of the cured resin layer-attached substrate film in the thickness direction to plasma treatment; and an inorganic layer formation step of forming the inorganic layer on one surface of the cured resin layer-attached substrate film in the thickness direction.

[0016] The present invention

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

[0017] As described above, the laminate film of the present invention has a total reflectance of 0.40% or less for light irradiated from one side of the inorganic layer in the thickness direction of the laminate film with standard illuminant D65 at a wavelength of 380 nm to 780 nm. In other words, it has good optical properties. Furthermore, on one side of the cured resin layer in the thickness direction, the total reflectance of C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments is 1.0 × 10 -1 As a result, the adhesion can be improved.

[0018] Furthermore, as described above, the laminate film of the present invention has a total reflectance of 0.40% or less for light irradiated from one side of the inorganic layer in the thickness direction of the laminate film with standard illuminant D65 at a wavelength of 380 nm to 780 nm. In other words, it has good optical properties. Furthermore, on one side of the cured resin layer in the thickness direction, the total reflectance of C3H9Si + HSiO versus ionic strength of fragments + The ratio of the ion intensities of the fragments is 1.0 × 10 -1 As a result, the adhesion can be improved.

[0019] As described above, the method for producing a laminate film of the present invention is a method for producing a laminate film of the present invention, and includes a plasma treatment step of subjecting one surface in the thickness direction of a substrate film having a cured resin layer to plasma treatment, thereby producing a laminate film having good optical properties and improved adhesion. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a cross-sectional view of one embodiment of the laminated film of the present invention. [Figure 2]2A to 2D show one embodiment of the method for producing a laminated film of the present invention. Fig. 2A shows a step of preparing a substrate film with a cured resin layer, Fig. 2B shows a step of plasma treating one surface in the thickness direction of the substrate film with a cured resin layer, Fig. 2C shows a step of forming an inorganic layer, and Fig. 2D shows a step of forming an antifouling layer. [Figure 3] FIG. 3 is a schematic diagram of an apparatus for carrying out the plasma treatment step, the inorganic layer forming step, and the antifouling layer forming step in the method for producing a laminated film. [Figure 4] 5 is a perspective view illustrating the positional relationship between a low inductance antenna and a substrate film with a cured resin layer in the plasma processing chamber shown in FIG. [Figure 5] 6 is a cross-sectional view illustrating the positional relationship between a low inductance antenna and a substrate film with a cured resin layer in the plasma processing chamber shown in FIG. 5. DETAILED DESCRIPTION OF THE INVENTION

[0021] 1. Laminated film Referring to FIG. 1, one embodiment of the laminated film 1 of the present invention will be described.

[0022] 1, the laminate film 1 includes a base film 2, a cured resin layer 3 disposed on one thickness-wise surface of the base film 2, and an inorganic layer 4 disposed on one thickness-wise surface of the cured resin layer 3. The laminate film 1 optionally includes an antifouling layer 5 disposed on one thickness-wise surface of the inorganic layer 4. In this embodiment, the laminate film 1 includes the base film 2, the cured resin layer 3, the inorganic layer 4, and the antifouling layer 5, in that order toward one thickness-wise side.

[0023] The laminated film 1 extends in a plane 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 supporting film that ensures the strength of the laminated film 1.

[0025] The base film 2 has a film shape (including a sheet shape) and 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 resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of cellulose resin include triacetyl cellulose (TAC).

[0027] The material for the base film 2 can be used alone or in combination of two or more kinds.

[0028] From the viewpoints of transparency and strength, 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, more preferably at least one selected from the group consisting of PET film, COP film, and TAC film, and even more preferably a TAC film.

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

[0030] From the viewpoints of strength and ease of handling, 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 for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

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

[0032] When 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 laminate film 1.

[0033] In addition, when the cured resin layer 3 described later is arranged on only one thickness-wise surface or the other thickness-wise surface of the base film 2, a carrier film (not shown) may be attached to the surface of the base film 2 opposite to the surface on which the cured resin layer 3 is arranged, in order to ensure the transportability and handleability 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 surface in the thickness direction of the base film 2. If necessary, a further cured resin layer 3 may be disposed on the other surface in the thickness direction of the base film 2.

[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 by inductively coupled plasma using an oxygen-containing gas (oxygen-plasma treatment) generated by applying high-frequency power to a low-inductance antenna (LIA). In other words, one surface in the thickness direction of the cured resin layer 3 is a plasma-treated surface 3a by inductively coupled plasma using an oxygen-containing gas. The oxygen-plasma treatment will be described in detail in the method for producing a laminated film. Note that, before the plasma treatment, one surface in the thickness direction of the cured resin layer 3 is a plasma-untreated surface 3a'.

[0036] Examples of the cured resin layer 3 include a hard coat layer, an optical adjustment layer, and an anti-blocking layer. The hard coat layer is, for example, a layer that makes the exposed surface of the base film 2 less susceptible to scratches. The optical adjustment layer is, for example, a layer that adjusts the optical properties (e.g., refractive index) of the laminate film 1. The anti-blocking layer is a layer that imparts anti-blocking properties to the surfaces of multiple laminate films 1 that come into contact with each other, for example, when the laminate films 1 are stacked in the thickness direction.

[0037] A hard coat layer is preferably used as the cured resin layer 3. When the cured resin layer 3 is a hard coat layer, it is possible to prevent scratches from being formed on one surface (exposed surface) in the thickness direction of the inorganic layer 4 formed on one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3 or on one surface (exposed surface) in the thickness direction of the antifouling layer 5 formed on one surface (exposed surface) 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 surface in the thickness direction of the base film 2, drying it as necessary, and then curing it.

[0039] Examples of the curable resin composition include a composition containing an ultraviolet-curable resin (an ultraviolet-curable resin composition) and a composition containing a thermosetting resin. From the viewpoint of production efficiency, the curable resin composition is preferably an ultraviolet-curable resin composition. In other words, the cured resin layer 3 is a cured product layer of the ultraviolet-curable resin composition.

[0040] Examples of ultraviolet 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. The ultraviolet curable resins may also be copolymers of acrylic urethane resins and polyfunctional acrylates. The ultraviolet curable resins can be used alone or in combination of two or more. The (meth)acrylate resin is a methacrylate resin and / or an acrylate resin.

[0041] That is, the cured resin layer 3 preferably contains an acrylate resin, more preferably an acryl urethane resin, or may contain a copolymer of an acryl urethane resin and a polyfunctional acrylate.

[0042] When the cured resin layer 3 contains an acrylate resin and a leveling agent containing a silicone compound, which will be described later, plasma treatment of the plasma-untreated surface 3a' of the cured resin layer 3 results in the formation of -Si-O- on the plasma-treated surface 3a of the cured resin layer 3. When an inorganic layer 4 is laminated on the plasma-treated surface 3a of the cured resin layer 3, the -Si-O- on the plasma-treated surface 3a of the cured resin layer 3 bonds with inorganic atoms in the inorganic layer 4, thereby improving adhesion.

[0043] The cured resin layer 3 may contain other ultraviolet curable resins.

[0044] Examples of other ultraviolet curable resins include polyester resins, urethane resins (excluding acrylic urethane resins), amide resins, epoxy resins, and melamine resins. The other ultraviolet curable resins can be used alone or in combination of two or more.

[0045] The ultraviolet 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 (luminous reflectance) can be improved, that is, the laminated film 1 has excellent optical properties.

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

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

[0049] Examples of inorganic particles include inorganic oxide particles. Materials for inorganic oxide particles include metal oxides and semi-metal oxides, specifically silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. The inorganic oxide particle material may also be a metal composite oxide in which the above-mentioned metal oxides are combined. Furthermore, functional groups such as acrylic groups and epoxy groups may be introduced onto the surface of the inorganic oxide particles in order to enhance adhesion and affinity with resins.

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

[0051] The average particle size of the particles can be measured by the specific surface area measurement (BET) method.

[0052] The particle content in the ultraviolet-curable resin composition (solid content) 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] When the content of particles in the ultraviolet-curable resin composition (solid content) is equal to or less than the above upper limit, scattering of light incident on the laminate film 1 due to particles in the laminate film 1 can be suppressed.

[0054] The curable resin composition also contains, for example, a leveling agent. The leveling agent is used to modify the surface shape of the cured resin layer 3. Examples of the leveling agent include a leveling agent containing a silicone compound.

[0055] That is, the cured resin layer 3 preferably contains a silicone compound.

[0056] Examples of silicone compounds include compounds having a siloxane structure, and preferably compounds having a dimethylsiloxane structure.

[0057] Examples of compounds having a siloxane structure include compounds having a methylalkylsiloxane structure. Preferably, compounds having a dimethylsiloxane structure are used. 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 used. Note that (meth)acrylic means acrylic and / or methacrylic.

[0058] The leveling agent may contain other components (for example, a (meth)acrylic acid ester).

[0059] When the cured resin layer 3 contains a silicone compound, plasma treatment of the unplasma-treated surface 3a' of the cured resin layer 3 results in the formation of -Si-O- on the plasma-treated surface 3a of the cured resin layer 3. When the inorganic layer 4 is laminated on the plasma-treated surface 3a of the cured resin layer 3, bonding occurs between the -Si-O- on the plasma-treated surface 3a of the cured resin layer 3 and inorganic atoms in the inorganic layer 4, thereby improving adhesion.

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

[0061] If the blending amount of the leveling agent relative to 100 parts by mass of the ultraviolet curable resin is equal to or less than the above upper limit, the total reflectance (luminous reflectance) of the laminate film 1 can be further improved.

[0062] When the cured resin layer 3 contains an acrylate resin and a silicone compound, the amount of the silicone compound relative to 100 parts by mass of the 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 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 the silicone compound relative to 100 parts by mass of the 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 per 100 parts by mass of acrylate resin is equal to or greater than the above lower limit, then by plasma treating the plasma-untreated surface 3a' of the cured resin layer 3, -Si-O- can be reliably formed on the plasma-treated surface 3a of the cured resin layer 3.

[0065] When 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 a solvent, a thixotropic agent, and an antistatic agent.

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

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

[0069] In addition, when the cured resin layer 3 is arranged on both sides of the base film 2 in the thickness direction, the thickness of the cured resin layer 3 mentioned above is the thickness of the cured resin layer 3 arranged on one side 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 surface 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 for example, 5.0 nm or less, preferably 4.0 nm or less, more preferably 3.00 nm or less.

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

[0072] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments (HSi2O5 - / C3H3O2 - ) is 1.0 × 10 -1 or more, preferably 1.1 x 10 -1 More preferably, 1.2 × 10 -1 or more, for example, 10 x 10 -1 Preferably, 5.0 x 10 or less -1 or less, more preferably 3.0 × 10 -1 The following is the result.

[0073] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments (HSi2O5 - / C3H3O2 - ) is, for example, 1.0×10 -1 ~10×10 -1 , preferably 1.1 x 10 -1 ~5.0×10 -1 , more preferably 1.2 × 10 -1 ~3.0×10 -1 is.

[0074] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments (HSi2O5 - / C3H3O2 - ) is equal to or greater than the lower limit, -Si-O- can be formed on the plasma-treated surface 3a, thereby improving adhesion.

[0075] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H9Si + HSiO versus ionic strength of fragments +Ratio of ion intensities of fragments (HSiO + / C3H9Si + ) is 1.0 × 10 -1 More than 2.0 × 10 -1 More preferably, 3.0 × 10 -1 or more, for example, 30 x 10 -1 Less than 20 × 10, preferably -1 or less, more preferably 15 × 10 -1 The following is the result.

[0076] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H9Si + HSiO versus ionic strength of fragments + Ratio of ion intensities of fragments (HSiO + / C3H9Si + ) is, for example, 1.0×10 -1 ~30×10 -1 , preferably 2.0 x 10 -1 ~20×10 -1 , more preferably 3.0 × 10 -1 ~15×10 -1 is.

[0077] On one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3, C3H9Si + HSiO versus ionic strength of fragments + Ratio of ion intensities of fragments (HSiO + / C3H9Si + ) is equal to or greater than the lower limit, -Si-O- can be formed on the plasma-treated surface 3a, thereby improving adhesion.

[0078] In addition, C3H3O2 - The fragments are derived from the acrylate resin in the UV-curable resin and are HSi2O5 - The fragments are derived from the acrylate resin in the UV-curable resin and the silicone compound in the leveling agent, which are modified by plasma treatment. + The fragments are derived from the silicone compounds in the leveling agent and are HSiO+ The fragments are derived from the acrylate resin in the ultraviolet curable resin and the silicone compound in the leveling agent that are modified by the plasma treatment.

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

[0080] Time-of-flight secondary ion mass spectrometry (TOFMS) revealed that C3H3O2 - Fragments and HSi2O5 - Spectra for fragments of several negative ions, including the C3H9Si fragment + Fragments and HSiO + The spectra of the fragments of multiple positive ions containing the fragments can be obtained. Therefore, the ion intensity ratio between the positive ions (HSi2O5 - / C3H3O2 - ) and the ionic strength ratio between negative ions (HSi2O5 - / C3H3O2 - ) are calculated, respectively. This makes it possible to indicate the state of the plasma-treated surface 3a. More details will be described in the Examples below.

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

[0082] When the inorganic layer 4 includes an anti-reflection layer, the laminate film 1 is an anti-reflection film. When the inorganic layer 4 includes a conductive layer, the laminate film 1 is a conductive film.

[0083] The inorganic layer 4 may be composed of a single layer having one function, or may be a composite layer composed of multiple layers having different functions. Examples of composite layers include an inorganic layer 4 comprising an adhesive layer and an anti-reflection layer, and an inorganic layer 4 comprising an adhesive layer and a conductive layer. As shown in FIG. 1, the inorganic layer 4 preferably comprises an adhesive layer 41 and an anti-reflection layer 42.

[0084] In this embodiment, the inorganic layer 4 is a layer (dry coating layer) formed by a dry coating method. Examples of dry coating methods include sputtering, vacuum deposition, and CVD. Preferably, sputtering is used. That is, the inorganic layer 4 is preferably a dry coating layer. More preferably, it is a sputtered layer.

[0085] [Adhesion layer] The adhesive layer 41 is disposed on one surface (plasma-treated surface 3a) in the thickness direction of the cured resin layer 3. That is, the adhesive 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. Examples of materials for the adhesion layer 41 also include Si and its oxides. From the viewpoint of achieving both adhesion to both the cured resin layer 3 and the anti-reflection layer 42 or conductive layer laminated on the adhesion layer 41, and transparency of the adhesion layer 41, preferred materials for the adhesion layer 41 include inorganic oxides containing at least one element selected from the group consisting of Si, In, Al, Sn, Ti, and Zr. More preferred materials include indium tin oxide (ITO) and silicon oxide (SiOx). Even more preferred is ITO.

[0087] The silicon oxide used as the material of the adhesion layer 41 is, for example, SiOx, which has a smaller amount of oxygen 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 of 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 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, and for example, 50 mass% or less, preferably 40 mass% or less, more preferably 35 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 for example, 30 nm or less, preferably 15 nm or less, more preferably 10 nm or less.

[0090] If the thickness of the adhesive layer 41 is equal to or greater than the above-mentioned lower limit, it is possible to ensure adhesion between the cured resin layer 3 and the antireflection layer 42 or conductive layer laminated on the adhesive layer 41. If the thickness of the adhesive layer 41 is equal to or less than the above-mentioned upper limit, it is possible to ensure the transparency of the adhesive layer 41.

[0091] [Anti-reflection layer] The antireflection layer 42 is disposed, for example, on one surface in the thickness direction of the adhesive layer 41. The antireflection layer 42 includes, for example, a plurality of transparent inorganic oxide films stacked in the thickness direction.

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

[0093] Specifically, the antireflection layer 42 shown in FIG. 3 includes 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 in this order toward one side in the thickness direction.

[0094] The high refractive index layer 42a contacts the adhesive layer 41. The high refractive index layer 42a and the low refractive index layer 42b contact each other. The low refractive index layer 42b and the high refractive index layer 42c contact each other. The high refractive index layer 42c and the low refractive index layer 42d contact each other.

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

[0096] In such a layered structure, the intensity of reflected light is attenuated by interference between reflected light at multiple interfaces in the high-refractive-index layers 42 a, 42 c and the low-refractive-index layers 42 b, 42 d. Such interference can be achieved by adjusting the optical film thickness (product of the refractive index and thickness of the film) of each layer in the antireflection 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 more at a wavelength of 550 nm, for example. Examples of high refractive index materials include niobium oxide (NbO), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin 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 high refractive index layer 42a has a thickness of, for example, 1 nm or more, or preferably 5 nm or more, and for example, 50 nm or less, or preferably 30 nm or less. The high refractive index layer 42a has an optical film thickness of, for example, 20 nm or more, or 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. 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, the low-refractive-index material is preferably silicon dioxide (refractive index 1.46).

[0100] The low refractive index layer 42b has a thickness of, for example, 5 nm or more, or preferably 10 nm or more, and an optical thickness of, for example, 15 nm or more, or preferably 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 more at a wavelength of 550 nm, for example. Examples of the high refractive index material include the materials described above for the high refractive index layer 42a, and preferably niobium oxide.

[0102] The high refractive index layer 42c has a thickness of, for example, 30 nm or more, preferably 50 nm or more, and for example, 200 nm or less, preferably 150 nm or less. The high refractive index layer 42c has an optical film thickness of, for example, 60 nm or more, and 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 the low refractive index material include the materials described above for the low refractive index layer 42b, and preferably silicon dioxide.

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

[0105] The total thickness of the antireflection layer 42 is, for example, 100 nm or more, preferably 150 nm or more, more preferably 200 nm or more, and 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 antireflection 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 antireflection layer 42 is equal to or greater than the above-mentioned lower limit, the function of attenuating the reflected light intensity can be ensured in the antireflection layer 42. If the total thickness of the antireflection layer 42 is equal to or less than the above-mentioned upper limit, cracking of the antireflection layer 42 can be suppressed.

[0107] [Conductive layer] Although not shown, the conductive layer is disposed, for example, on one surface in the thickness direction of the adhesive layer 41. The conductive layer is, for example, a layer formed from a conductive material. Examples of the conductive material include metals and metal oxides.

[0108] Examples of metals include copper, silver, gold, aluminum, and alloys thereof. 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). Examples of antimony-containing conductive oxides include antimony tin composite oxide (ATO). Examples of zinc-containing conductive oxides include 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 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] <Anti-fouling layer> The antifouling layer 5 is a layer that prevents contamination from the external environment and facilitates the removal of adhered contaminants. The antifouling layer 5 also has water vapor barrier properties.

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

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

[0113] Examples of materials for the antifouling layer 5 include organic fluorine compounds. As the organic fluorine compound, an alkoxysilane compound having a perfluoropolyether group is preferably used. Examples of the alkoxysilane compound 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 fluorinated alkyl group (having, for example, 1 to 20 carbon atoms) in which one or more hydrogen atoms in the alkyl group have been substituted with fluorine atoms. Preferably, R1 represents a perfluoroalkyl group in which all of the hydrogen atoms in the alkyl group have been substituted with fluorine atoms.

[0116] R2 represents a structure containing at least one repeating unit of a perfluoropolyether (PFPE) group. Preferably, it represents a structure containing two repeating units of a PFPE group. Examples of the repeating unit of a PFPE group include a repeating unit of a linear PFPE group and a repeating unit of a branched PFPE group. Examples of the repeating unit of a linear PFPE group include -(OC n F 2n ) p (n represents an integer of 1 or more and 20 or less, and p represents an integer of 1 or more and 50 or less; the same applies hereinafter). Examples of the repeating structure of the branched PFPE group include a structure represented by -(OC(CF3)2) p - and -(OCF2CF(CF3)CF2) p The repeating structure of the PFPE group is preferably a repeating structure of a linear PFPE group, more preferably -(OCF2) p -and-(OC2F4) p - are some examples.

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

[0118] X represents an ether group, a carbonyl group, an amino group, or an amide group, and preferably represents an ether group.

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

[0120] Of such alkoxysilane compounds having a perfluoropolyether group, the compound represented by the following general formula (2) is preferably used.

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

[0122] In the 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] The alkoxysilane compounds having a perfluoropolyether group can be used alone or in combination of two or more kinds.

[0124] In this embodiment, the antifouling layer 5 is a layer (dry coating layer) formed by a dry coating method. Examples of dry coating methods include sputtering, vacuum deposition, and CVD. Preferably, the vacuum deposition method is used. That is, the antifouling layer 5 is preferably a dry coating layer. More preferably, it is a vacuum deposition layer.

[0125] The antifouling layer 5 has a thickness of, for example, 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and for example, 25 nm or less, preferably 20 nm or less, more preferably 15 nm or less.

[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 for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

[0127] The total reflectance (luminous reflectance) of light irradiated with standard illuminant D65 at a wavelength of 380 nm to 780 nm from one thickness-wise side of the inorganic layer 4 (one thickness-wise side of the laminate film 1) on the laminate film 1 is 0.40% or less, preferably 0.37% or less, more preferably 0.35% or less, even more preferably 0.33% or less, and particularly preferably 0.31% or less.

[0128] (Action and effect) As described above, the laminate film 1 includes the substrate film 2, the cured resin layer 3, and the inorganic layer 4 in this order toward one side in the thickness direction. In such a laminate film 1, the cured resin layer 3 has a C3H3O2 -Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments is 1.0 × 10 -1 Alternatively, the cured resin layer 3 has a thickness on one side thereof, and the thickness on one side thereof is determined by time-of-flight secondary ion mass spectrometry to satisfy the above. + HSiO versus ionic strength of fragments + The ratio of the ion intensities of the fragments is 1.0 × 10 -1 The above conditions are satisfied. Therefore, in the laminated film 1, the adhesion between the cured resin layer 3 and the inorganic layer 4 can be improved.

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

[0130] Therefore, the laminated film 1 can have good optical properties and improved adhesion.

[0131] 2.Laminated film manufacturing method An embodiment of a method for producing the laminated film, which produces the laminated film 1, will be described with reference to FIGS. 2A to 2D.

[0132] The method for producing a laminated film includes, for example, a preparation step (FIG. 2A) of preparing a cured resin layer-attached substrate film 10' comprising a long substrate film 2 and a cured resin layer 3 disposed on one thickness-wise surface of the substrate film 2, a plasma treatment step (FIG. 2B) of plasma-treating one thickness-wise surface of the cured resin layer-attached substrate film 10', and an inorganic layer formation step (FIG. 2C) of forming an inorganic layer 4 on one thickness-wise surface of the cured resin layer-attached substrate film 10. In this embodiment, the method for producing a laminated film further includes an antifouling layer formation step (FIG. 2D) of forming an antifouling layer 5 on one thickness-wise surface of the inorganic layer 4. The plasma treatment step, the inorganic layer formation step, and the antifouling layer formation step are performed sequentially using an apparatus Z as shown in FIG. 3.

[0133] (Preparation process) 2A , a long substrate film 10′ with a cured resin layer is prepared, which includes a flexible substrate film 2 and a cured resin layer 3 disposed on one thickness-wise surface of the substrate film 2. In the long substrate film 10′ with a cured resin layer, one thickness-wise surface of the cured resin layer 3 is not plasma-treated. In other words, the long substrate film 10′ with a cured resin layer has a plasma-untreated surface 3a′, and one thickness-wise surface of the long substrate film 10′ with a cured resin layer is the plasma-untreated surface 3a′.

[0134] Specifically, in the preparation process, a flexible substrate film 2 is prepared, and the above-mentioned ultraviolet-curable resin composition is applied to one thickness-wise surface of the substrate film 2 to form a coating film, and then the coating film is cured to form a cured resin layer 3, thereby preparing a substrate film 10' with a cured resin layer.

[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. Preferred examples include butyl acetate and cyclopentanone.

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

[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 higher and, for example, 10 minutes or lower.

[0138] The coating film on one side of the substrate film 2 in the thickness direction is cured by ultraviolet irradiation. Examples of the light source for ultraviolet irradiation include a high-pressure mercury lamp and an LED light. The cumulative irradiation amount of ultraviolet light is, for example, 100 mJ / cm. 2 or more, for example, 500 mJ / cm 2 The following is the result.

[0139] In this manner, a long substrate film 10' with a cured resin layer is prepared. In this embodiment, a roll of the long substrate film 10' with a cured resin layer is prepared. Specifically, the long substrate film 10' with a cured resin layer is wound so that one surface in the thickness direction of the substrate film 10 with a cured resin layer (the plasma-untreated surface 3a') faces inward in the radial direction of the roll.

[0140] [Device Z] In the laminated film manufacturing method, a plasma treatment step, an inorganic layer formation step, and an antifouling layer formation step are then carried out in sequence in a reduced pressure atmosphere while the cured resin layer-attached substrate film 10' is transported as a workpiece film W by a roll-to-roll method. Referring to Figure 3, an apparatus Z, which is an example of an apparatus for carrying out the plasma treatment step, the inorganic layer formation step, and the antifouling layer formation step, will be described.

[0141] In addition, 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] The device Z includes a feed chamber R1, a winding chamber R2, a connection chamber P1, a plasma treatment chamber P2, a connection chamber P3, a first film formation chamber P4, a connection chamber P5, a second film formation chamber P6, a connection chamber P7, and a PEM device (not shown).

[0143] The unwinding chamber R1 is equipped with a unwinding roller 51 for unwinding the workpiece film W. A roll of a long substrate film 10' with a cured resin layer is attached to the unwinding roller 51 as the workpiece film W. In addition, a predetermined number of guide rollers G for guiding the workpiece film W are provided within the unwinding chamber R1.

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

[0145] The connecting chamber P1 is located between the payout chamber R1 and the plasma processing chamber P2 in the running direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber P1. The connecting chamber P1 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operated, the pressure within the connecting chamber P1 is maintained at a predetermined pressure between the pressure within the payout chamber R1 and the pressure within the plasma processing chamber P2. This ensures a pressure difference between the payout chamber R1 and the plasma processing chamber P2.

[0146] The plasma processing chamber P2 is disposed between the connecting chamber P1 and the connecting chamber P3 in the running direction of the workpiece film W. In the plasma processing chamber P2, a plasma processing step is carried out.

[0147] The plasma processing chamber P2 is equipped with multiple LIAs 71. An LIA is an antenna that has a low inductance of 7.5 μH or less and can generate inductively coupled plasma by applying high-frequency power. In this embodiment, as shown in FIGS. 4 and 5, the LIAs 71 are supported by fixtures 72 and covered by cover blocks 73 (not shown in FIG. 4), and are disposed inside the plasma processing chamber P2 (FIG. 4 shows a case where the number of LIAs 71 is four).

[0148] The multiple LIAs 71 are aligned in the travel direction of the workpiece film W and in a direction perpendicular to the travel direction (the width direction of the workpiece film W). The fixture 72 is a vacuum flange. As shown in FIG. 5, the LIAs 71 are fixed to the fixture 72 via feedthroughs 74. As shown in FIG. 3, the fixture 72 is attached to an opening 75 provided in the wall of the plasma processing chamber P2. Specifically, the fixture 72 is attached to the opening 75 with a seal member (not shown) sandwiched between the wall of the plasma processing chamber P2 and the fixture 72. Although not shown, the LIAs 71 are electrically connected to a high-frequency power source (RF power source) outside the plasma processing chamber P2 via an impedance matching box.

[0149] The LIA 71 is formed of a conductor, such as copper or silver, preferably copper, and may be covered with an insulator, such as glass or quartz.

[0150] The cover block 73 includes a block body 73A and multiple partition plates 73B. The block body 73A has multiple storage spaces 73a. Each storage space 73a stores one LIA 71. The partition plates 73B are arranged to close the storage spaces 73a. The storage spaces 73a are sealed spaces. In the cover block 73, the block body 73A is made of, for example, aluminum. The partition plates 73B are made of an insulating material (for example, quartz or glass).

[0151] The separation distance d' (shown in FIG. 3) between the workpiece film W traveling in 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 processing 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 (substrate film 10' with a cured resin layer) being plasma processed.

[0153] The plasma processing chamber P2 may further include a transport roller 53. The transport roller 53 is a main guide roller for transporting the workpiece film W within the plasma processing chamber P2. The transport roller 53 has a temperature control function that allows it to heat or cool the workpiece film W. In other words, the transport roller 53 is a roller with a temperature control function. The transport roller 53 transports the cured resin layer-formed substrate film 10' while contacting the other thickness-wise surface of the cured resin layer-formed substrate film 10'. The LIA 71 is disposed opposite the transport roller 53. By including the transport roller 53, in the plasma processing step, plasma processing can be performed on one thickness-wise surface (plasma untreated surface 3a') of the cured resin layer-formed substrate film 10' while cooling or heating the workpiece film W (cured resin layer-formed substrate film 10'). This suppresses thermal deformation of the cured resin layer-formed substrate film 10', thereby suppressing the effect of thermal deformation on the transport of the workpiece film W.

[0154] In this embodiment, as shown in FIG. 4, the LIA 71 has an open loop shape. The open loop shape of the LIA 71 allows for a low inductance of the LIA 71. Therefore, the open loop LIA 71 can suppress an increase in voltage due to an increase in power applied to the LIA 71. This suppresses abnormal discharge during the plasma processing process. Suppressing abnormal discharge also suppresses damage to the cured resin layer-attached substrate film 10' due to plasma processing. Specifically, the LIA 71 has a U-shape with two free ends. For each LIA 71, the two free ends are fixed to the fixture 72 so as to be aligned in the width direction of the workpiece film W. In this embodiment, the LIA 71 also has an extension 71a on the side opposite the two free ends. The extension 71a extends parallel to the workpiece film W passing through the plasma processing chamber P2. Each extension 71a extends in the width direction of the workpiece film W. Each extension 71a may extend in the running direction of the workpiece film W (four LIAs 71 may be arranged in this manner). The length of the extension 71a is, for example, 50 to 150 mm (FIG. 4 shows a case where the length of the extension 71a is the same as the maximum length d2 of the LIA 71, which will be described later). The LIA 71 may have a coil shape.

[0155] The LIA 71 extends from the fixture 72 toward the workpiece film W. It is preferable that the LIA 71 extend perpendicular to the fixture 72. The extension length d1 of the LIA 71 from the fixture 72 is, for example, 30 to 150 mm. The maximum length d2 of the LIA 71 in the plane direction of the workpiece film W is, for example, 50 to 200 mm. The separation distance d3 between the LIA 71 and the workpiece film W is, for example, 50 to 200 mm. The ratio (d3 / d1) of the separation distance d3 to the extension length d1 is, for example, 0.5 to 3.5. The number (number of rows) of the LIA 71 spaced apart in the running direction of the workpiece film W can be adjusted appropriately depending on the running speed of the workpiece film W (i.e., the plasma processing time), and may be, for example, 1 to 4, or may be 4 or more. In the running direction of the workpiece film W, the center-to-center distance d4 between adjacent LIAs 71 is, for example, 100 to 500 mm. In the width direction of the workpiece film W, the center-to-center distance d5 between adjacent LIAs 71 is, for example, 200 to 500 mm. By adjusting the center-to-center distance d5, the uniformity of the plasma density (described later) in the width direction of the workpiece film W can be controlled. The ratio (d5 / d4) of the center-to-center distance d5 to the center-to-center distance d4 is, for example, 0.5 to 2.0. Such a set of LIAs 71 can generate high-density plasma. For example, the high-frequency antenna for plasma generation described in JP 2013-258153 A may be used as the LIA 71.

[0156] The PEM device is used to perform plasma emission monitoring (PEM) during plasma processing, and includes a device body and an optical fiber for collecting light. One end of the optical fiber is positioned in the plasma processing chamber P2, between the workpiece film W and the LIA 71. The other end of the optical fiber is connected to the device body. A first line L1 equipped with a flow control valve for introducing gas into the chamber is also connected to the plasma processing chamber P2.

[0157] The connecting chamber P3 is located between the plasma processing chamber P2 and the first film deposition chamber P4 in the travel direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber P3. The connecting chamber P3 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operating, the pressure within the connecting chamber P3 is maintained at a predetermined pressure between the pressure within the plasma processing chamber P2 and the pressure within the first film deposition chamber P4. This ensures a pressure difference between the plasma processing chamber P2 and the first film deposition chamber P4.

[0158] The first film forming chamber P4 is disposed next to the connecting chamber P3 in the running direction of the workpiece film W. The first film forming chamber P4 is also connected to a vacuum pump (not shown) so that the chamber can be adjusted to a predetermined vacuum level. In the first film forming chamber P4, an inorganic layer forming process is carried out as described below.

[0159] In this embodiment, the first film formation chamber P4 is a sputtering film formation chamber. The first film formation chamber P4 includes a film formation roller 54 and multiple sputtering chambers 60 (sputtering chambers 60a to 60e) (FIG. 3 shows a case where the number of sputtering chambers 60 is five). The film formation roller 54 is a main guide roller for transporting the workpiece film W within the first film formation chamber P4. The film formation roller 54 has a temperature adjustment function that allows the workpiece film W to be heated or cooled. The sputtering chamber 60 is a partitioned space within the first film formation chamber P4. The multiple sputtering chambers 60 are arranged along the circumferential direction of the film formation roller 54. Each sputtering chamber 60 is open toward the film formation roller 54. A cathode 61 is provided within the sputtering chamber 60. A target (not shown) is arranged on the cathode 61 as a film formation material supply material. The target is arranged on the target so as to face the film formation roller 54. Each sputtering chamber 60 is provided with a power supply (not shown) for applying a voltage to the target to generate a glow discharge. Examples of power supplies include a DP power supply, an AC power supply, an MF power supply, an RF power supply, and an MF-AC power supply. 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 required number of second lines (not shown) equipped with flow rate control valves for introducing gas into the chamber. In addition, a predetermined number of guide rollers G for guiding the workpiece film W are provided within the first film formation chamber P4.

[0160] The connecting chamber P5 is located between the first film forming chamber P4 and the second film forming chamber P6 in the running direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber P3. The connecting chamber P5 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is operating, the pressure within the connecting chamber P3 is maintained at a predetermined pressure between the pressure within the first film forming chamber P4 and the pressure within the second film forming chamber P6. This ensures a pressure difference between the first film forming chamber P4 and the second film forming chamber P6.

[0161] The second film-forming chamber P6 is disposed next to the connecting chamber P5 in the running direction of the workpiece film W. The second film-forming chamber P6 is also connected to a vacuum pump (not shown) so that the chamber can be adjusted to a predetermined vacuum level. In the second film-forming chamber P6, the antifouling layer forming process is carried out as described below.

[0162] In this embodiment, the second film formation chamber P6 is a vacuum deposition chamber. The second film formation chamber P6 is equipped with a material holding unit 81, a vacuum pump (not shown), and a deposition amount adjustment valve (not shown) whose opening is controllable. Furthermore, a predetermined number of guide rollers G for guiding the workpiece film W are provided within the second film formation chamber P6 as necessary. A film formation material supply (not shown) is disposed within the material holding unit 81 so as to face the workpiece film W being transported within the second film formation chamber P6. The material holding unit 81 may be provided with a built-in resistance heating means, a built-in high-frequency induction heating means, or an electron beam heating means as a means for heating the film formation material supply.

[0163] The connecting chamber P7 is disposed between the second film forming chamber P6 and the winding chamber R2 in the running direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber P7. The connecting chamber P7 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Z is in operation, the pressure within the connecting chamber P7 is maintained at a predetermined pressure between the pressure within the second film forming chamber P6 and the pressure within the winding chamber R2. This ensures a pressure difference between the second film forming chamber P6 and the winding chamber R2.

[0164] The plasma treatment step, the inorganic layer forming step, and the antifouling layer forming step are carried out in this order by the above-described apparatus Z. Specifically, the steps are as follows.

[0165] (Plasma treatment process) The workpiece film W is unwound from the unwinding chamber R1. After being unwound from the unwinding chamber R1, the workpiece film W passes through the connecting chamber P1, the plasma processing chamber P2, the connecting chamber P3, the first film forming chamber P4, the connecting chamber P5, the second film forming chamber P6, and the connecting chamber P7 in sequence, and is then wound up in the winding chamber R2. The running speed of the workpiece film W is, for example, 0.1 m / min to 10 m / min, preferably 0.5 m / min to 8 m / min. The entire line from the unwinding chamber R1 to the winding chamber R2 is not open to the atmosphere along the way, and the process is carried out in a reduced pressure atmosphere. The reduced pressure atmosphere is preferably a vacuum. "Vacuum" preferably means a reduced pressure atmosphere of 7 Pa or less.

[0166] A plasma treatment process is carried out in the plasma treatment chamber P2. In the plasma treatment process, one thickness-wise surface (plasma untreated surface 3a') of the substrate film 10' (workpiece film W) with a cured resin layer is plasma-treated in a reduced pressure atmosphere in the plasma treatment chamber P2 (chamber) while detecting the plasma emission intensity. In this embodiment, the plasma treatment is a treatment using inductively coupled plasma of an oxygen-containing gas (oxygen-plasma treatment) generated by applying high-frequency power to the LIA 71. Specifically, the process is as follows.

[0167] During plasma treatment, oxygen is supplied into the plasma treatment chamber P2 via the first line L1. In addition to oxygen, an inert gas may be supplied into the plasma treatment chamber P2. Examples of inert gas include argon, krypton, and xenon. The gas in the plasma treatment chamber P2 may contain gases other than 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 treatment 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. When the oxygen concentration is equal to or greater than the above-mentioned lower limit, high-density oxygen plasma can be generated. This is effective in forming nanometer-order fine irregularities on the plasma-untreated surface 3a' of the cured resin layer-formed substrate film 10' and in changing chemical bonds near the surface of the plasma-untreated surface 3a' of the cured resin layer-formed substrate film 10'.

[0168] The pressure (first pressure) within the plasma processing chamber P2 during plasma processing 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 equal to or greater than the above-mentioned lower limit, a plasma environment of sufficient density for surface modification of the workpiece film W can be formed within the plasma processing chamber P2 during plasma processing. If the first pressure is equal to or less than the above-mentioned upper limit, damage to the workpiece 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 workpiece film W (substrate film 10' with a cured resin layer) adjusted by the transport rollers 53 is, for example, -20°C to 150°C.

[0170] The frequency of the high-frequency power applied to the LIA 71 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 above-mentioned lower limit, the plasma current density can be increased and the plasma discharge can be stabilized during plasma processing. If the frequency of the high-frequency power is below the above-mentioned upper limit, the antenna potential can be suppressed, thereby suppressing damage to the workpiece film W by the plasma.

[0171] The high-frequency power applied to the LIA 71 during plasma processing is, for example, 1 kW or more, preferably 2.0 kW or more, more preferably 3.0 kW or more, and 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 equal to or greater than the above-mentioned lower limit, a high-density plasma environment can be formed in the plasma processing chamber P2 during plasma processing using inductively coupled plasma. If the high-frequency power is equal to or less than the above-mentioned upper limit, excessive damage to the workpiece film W by the plasma can be suppressed. Furthermore, if the high-frequency power is equal to or less than the above-mentioned upper limit, the total reflectance (luminous reflectance) can be improved.

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

[0173] In the plasma treatment process, the plasma current density at the intermediate position between the LIA 71 and the workpiece film W (the substrate film 2' with the cured resin layer) is, for example, 0.1 mA / cm 3 More than 0.5mA / cm 3 or more, for example, 8mA / cm 3 Preferably, 5 mA / cm or less 3The following is true. Inductively coupled plasma processing using an LIA can achieve a higher plasma current density than capacitively coupled plasma processing (for example, a plasma density approximately 100 times higher). If the plasma current density is equal to or greater than the lower limit, sufficient plasma-converted oxygen particles can be secured in the plasma processing chamber P2 during plasma processing, allowing for appropriate surface modification of the workpiece film W surface. If the plasma current density is equal to or less than the upper limit, damage to the workpiece film W due to excessively high density plasma-converted 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 source, and adjusting the magnitude of the applied power. The plasma current density can be measured using a Langmuir probe for plasma measurement.

[0174] By subjecting the cured resin layer-containing substrate film 10' to the above-described plasma treatment, a cured resin layer-containing substrate film 10 is produced, as shown in Fig. 2B. The cured resin layer-containing substrate film 10 has a plasma-treated surface 3a. In other words, one surface in the thickness direction of the cured resin layer-containing substrate film 10 is the plasma-treated surface 3a.

[0175] By subjecting the substrate film 10' with a cured resin layer to the plasma treatment as described above, adhesion can be improved.

[0176] (Inorganic layer formation process) In the inorganic layer forming step, following the plasma treatment step, an inorganic layer 4 is formed on one surface in the thickness direction (plasma-treated surface 3a) of the substrate film 10 (workpiece film W) with a cured resin layer by sputtering, vapor deposition, or chemical vapor deposition in a reduced pressure atmosphere. In the inorganic layer forming step, 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 a target (film forming material) placed on a cathode 61 in the sputtering chamber 60. This generates a glow discharge, ionizing the gas atoms, causing the gas ions to collide with the target surface at high speed, ejecting the target material from the target surface and depositing the ejected target material on the workpiece film W. Examples of sputtering gases include argon, krypton, and xenon.

[0178] The sputtering method may also 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 the sputtering gas is, for example, 1 part by volume to 50 parts by volume. In the reactive sputtering method, when 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 (second pressure) inside the sputtering chamber 60 is adjusted appropriately depending on the type of layer to be formed, and is, for example, 0.1 to 5.0 Pa. The film formation temperature (the temperature of the workpiece film W adjusted by the film formation roller 54) is, for example, -20°C to 150°C. The discharge power is, for example, 1 kW to 50 kW.

[0180] In the inorganic layer forming step, next, by sputtering in at least one sputtering chamber selected from sputtering chambers 60a to 60e, an inorganic layer 4 is formed on the plasma-treated surface 3a of the cured resin layer 3. In this embodiment, an adhesive layer 41 is formed on one thickness-wise surface of the cured resin layer 3 in sputtering chamber 60a, a high-refractive index layer 42a is formed on one thickness-wise surface of the adhesive layer 41 in sputtering chamber 60b, a low-refractive index layer 42b is formed on one thickness-wise surface of the high-refractive index layer 42a in sputtering chamber 60c, a high-refractive index layer 42c is formed on one thickness-wise surface of the low-refractive index layer 42b in sputtering chamber 60d, and a low-refractive index layer 42d is formed on one thickness-wise surface of the high-refractive index layer 42c in sputtering chamber 60e.

[0181] (Anti-fouling layer formation process) In the antifouling layer forming process, following the inorganic layer forming process, the antifouling layer 5 is formed on one thickness-wise surface of the inorganic layer 4 of the workpiece film W (laminated film 1) after the inorganic layer forming process by sputtering, vapor deposition, or chemical vapor deposition in a reduced pressure atmosphere. In the antifouling layer forming process, the antifouling layer 5 is preferably formed by vapor deposition. Note that the reduced pressure atmosphere is preferably a vacuum. That is, in the antifouling layer forming process, the antifouling layer 5 is more preferably formed by vacuum vapor deposition.

[0182] In the vacuum deposition method, the vacuum pump is operated to reduce the pressure inside the second film forming chamber P6, and the deposition source placed in the material holding section 81 is heated to a predetermined temperature, evaporating the material of the anti-fouling layer 5 and depositing it on the work film W.

[0183] In the vacuum deposition method, the pressure in the second film formation chamber P6 (third pressure) is, for example, 0.1 Pa or less, preferably 0.05 Pa or less, and, for example, 1×10 -5 Pa or more.

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

[0185] In the device Z, after the plasma treatment process, the inorganic layer forming process, and the antifouling layer forming process, the laminated film 1 as the workpiece film W passes through the connecting chamber P7 and travels to the winding chamber R2, where it is wound up by the winding roller 52.

[0186] In this manner, a long laminate film 1 is produced.

[0187] (Action and effect) The method for producing the laminated film described above is a method for producing the laminated film 1, and includes a plasma treatment step of subjecting one surface in the thickness direction of the cured resin layer-attached substrate film 10' to plasma treatment. As a result, a laminated film having good optical properties and improved adhesion can be produced. [Example]

[0188] The present invention will be described in more detail below with reference to examples and comparative examples. It should be noted that the present invention is not limited to these examples and comparative examples. The specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be substituted with the upper limit (a numerical value defined as "equal to or less than") or lower limit (a numerical value defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the "Description of the Invention" above.

[0189] Example 1 (Preparation process) A hard coat layer as a cured resin layer was formed on one surface in the thickness direction of a triacetyl cellulose (TAC) film as a substrate film.

[0190] Specifically, 80 parts by mass (solids equivalent) of an ultraviolet-curable acrylic urethane resin (product name "UT-7314" manufactured by Mitsubishi Chemical Corporation), 20 parts by mass (solids equivalent) of a multifunctional acrylate (product name "Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd.) whose main component is pentaerythritol triacrylate, 1.5 parts by mass of a photopolymerization initiator (product name "Omnirad127D" manufactured by BASF), and 0.06 parts by mass of a leveling agent (product name "Polyflow LE-303" manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixed solution. Next, a mixed solvent of butyl acetate and cyclopentanone (CPN) (mass ratio of butyl acetate to CPN was 70:30) was added to the mixed solution as a solvent to prepare a cured resin composition with a solids concentration of 40% by mass.

[0191] On the other hand, a long TAC film (product name "KC8UAW", thickness 80 μm, manufactured by Konica Minolta) was prepared. Next, a curable resin composition was applied to one surface of the TAC film in the thickness direction to form a coating film. This coating film was dried by heating and then cured by ultraviolet light irradiation. As a result, a hard coat layer with a thickness of 5 μm was formed on one surface of the TAC film in the thickness direction. The drying conditions were a heating temperature of 100°C and a heating time of 1 minute. For ultraviolet light 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 film, with an integrated irradiation dose of 300 mJ / cm. 2 In this manner, a roll of the substrate film with a cured resin layer was prepared.

[0192] (Plasma treatment process) While the substrate film with the cured resin layer was transported by a roll-to-roll system under vacuum, plasma treatment was performed on one surface in the thickness direction of the substrate film with the cured resin layer (one surface in the thickness direction of the cured resin layer).

[0193] For the plasma treatment, a first device capable of performing a roll-to-roll process on the workpiece film was used. The first device includes a feed chamber, a plasma treatment chamber (first plasma treatment chamber), a film-forming chamber (first and second film-forming chambers), and a take-up chamber. The feed chamber, first plasma treatment chamber, first film-forming chamber, second film-forming chamber, and take-up chamber are arranged in this order and are connected to each other. The feed chamber includes a feed roller. A roll of the substrate film with the cured resin layer described above was set on the feed roller as the workpiece film. The first plasma treatment chamber includes a temperature-controlled transport roller (transport roller 53 in FIG. 3) and four LIAs (LIA 71 in FIG. 4 and FIG. 5) covered by cover blocks (cover block 73 in FIG. 5), as shown in FIG. 4 and FIG. 5. Each LIA has an extension (extension 71a in FIG. 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 portion) 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 source (RF power source, frequency 13.56 MHz) via an impedance matcher outside the first plasma processing chamber. The separation distance d' between the substrate film traveling in the first plasma processing chamber and the cover block is 100 mm. The first film formation chamber is a sputtering film formation chamber and is equipped with a film formation roller and a cathode arranged opposite the film formation roller. The second film formation chamber is a vacuum deposition chamber and is equipped with a deposition source. The winding chamber is equipped with a winding roller.

[0194] Using the first device described above, specifically, while the hard-coated substrate film was transported from the unwinding chamber to the winding chamber in a roll-to-roll manner, plasma treatment was performed on one side of the thickness direction of the substrate film with the cured resin layer in the first plasma treatment chamber. The running speed of the substrate film with the cured resin layer (running speed of the work film) was 1.0 m / min. The temperature of the temperature-adjustable transport roller was set to -8°C. The plasma treatment conditions were as follows:

[0195] The ultimate vacuum level of the first plasma processing chamber is 1.0 x 10 -4 After evacuating the inside of the device until the pressure reached 1.5 Pa, oxygen gas was introduced into the first plasma treatment chamber, and the pressure inside the first plasma treatment chamber was set to 1.5 Pa. An inductively coupled plasma of oxygen-containing gas was formed around the four LIAs by applying 5.0 kW of high-frequency power to the four LIAs using a high-frequency power supply. This plasma was used to plasma treat one side of the thickness direction of the substrate film with the cured resin layer. The plasma current density at the midpoint between the LIAs and the workpiece film was 1.3 mA / cm. 3 The plasma current density was measured by a Langmuir probe for plasma measurement.

[0196] In this way, one thickness-wise surface of the substrate film with a cured resin layer was plasma-treated. That is, this thickness-wise surface of the substrate film with a cured resin layer was the plasma-treated surface. This plasma treatment was a treatment by inductively coupled plasma using an oxygen-containing gas generated by applying high-frequency power to the LIA (oxygen LIA treatment).

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

[0198] Specifically, using the above-mentioned first device capable of sputtering deposition using a roll-to-roll method, an adhesive 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 formed in this order in the first deposition chamber on one thickness-wise surface of the substrate film with a cured resin layer after plasma treatment.

[0199] The first film formation chamber includes a film formation roller (film formation roller 54 in FIG. 5) and multiple sputtering chambers. The sputtering chambers are partitioned spaces within the first film formation chamber. The sputtering chambers include cathodes arranged opposite the film formation rollers. The sputtering chambers are connected to a required number of second lines (not shown) equipped with flow rate control valves for introducing gas into the chambers.

[0200] While the substrate film with the cured resin layer was transported while being cooled by the film-forming roller in the first film-forming chamber, an adhesive layer was formed on one surface 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 adhesive 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 adhesive layer, first high refractive index layer, first low refractive index layer, second high refractive index layer, and second low refractive index layer were inorganic layers). The film-forming temperature (temperature of the film-forming roll) was -8°C. The film-forming conditions were as follows:

[0201] In the first sputtering chamber, a 4 nm thick ITO layer was formed as an adhesive layer by reactive sputtering. Specifically, the first film formation chamber was maintained at a vacuum of 1.0 × 10 -4 After the chamber was evacuated to a vacuum of 0.2 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 was 10 parts by volume per 100 parts by volume of argon introduced into the first sputtering chamber. A sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 30% by mass) was used as the target. An MF-AC power supply was used as the power source for applying voltage to the target (the same applies to the second to fifth sputtering chambers described below). The discharge power was 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 by reactive sputtering. Specifically, after the first film formation 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 volume parts of argon introduced into the second sputtering chamber was 5 volume parts. A Nb target was used. 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 by reactive sputtering. Specifically, after the first film formation 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 volume parts of argon introduced into the third sputtering chamber was 30 volume parts. A Si target was used as the target. The discharge power was 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 by reactive sputtering. Specifically, after the first film formation 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 volume parts of argon introduced into the fourth sputtering chamber was 13 volume parts. A Nb target was used as the target. The discharge power was 27.5 kW.

[0205] In the fifth sputtering chamber, a 84 nm thick SiO2 layer (refractive index 1.46) was formed as the second low refractive index layer by reactive sputtering. Specifically, after the first film formation 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 in the fifth sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 volume parts of argon introduced into the fifth sputtering chamber was 30 volume parts. A Si target was used as the target. The discharge power was 20.5 kW.

[0206] (Anti-fouling layer formation process) Next, following the inorganic layer step, an antifouling layer was formed on one surface in the thickness direction of the inorganic layer (specifically, one surface 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 thickness-wise surface of the inorganic layer by vacuum deposition in the second film-forming chamber using a perfluoropolyether-containing alkoxysilane compound as the deposition source. The deposition source was a solid obtained by drying "KY1903-1" (a perfluoropolyether-containing alkoxysilane compound represented by the general formula (2) above, 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 260°C.

[0208] In this manner, a laminated film of Example 1 was produced. The laminated film of Example 1 includes, in order toward one side in the thickness direction, a base film, a cured resin layer, inorganic layers (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), and an antifouling layer.

[0209] Example 2 The laminated film of Example 2 was produced in the same manner as in Example 1, except that in the preparation process, 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.) 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 A laminated film of Example 3 was produced in the same manner as in Example 1, except that in the preparation step, the amount of the leveling agent used in the curable resin composition was changed to 0.03 parts by mass.

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

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

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

[0214] Comparative Example 1 A laminated film of Comparative Example 1 was produced in the same manner as in Example 1, except that the plasma treatment step was not carried out.

[0215] Comparative Example 2 A laminated film of Comparative Example 2 was produced in the same manner as in Example 2, except that the plasma treatment step was not carried out.

[0216] Comparative Example 3 In the preparation step, 150 parts by mass (solid content equivalent) of silica particles (product name "PGM-AC-4130Y", manufactured by Nissan Chemical Industries, Ltd.) having a particle size of 40 to 50 nm dispersed in propylene glycol monomethyl ether was further mixed into the mixed liquid, and the laminated film of Comparative Example 3 was produced in the same manner as in Example 1, except that the plasma treatment step was not performed.

[0217] Comparative Example 4 (Preparation process) 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 (trade name "PGM-AC-4130Y", manufactured by Nissan Chemical Industries, Ltd.) having a particle size of 40 to 50 nm dispersed in propylene glycol monomethyl ether was further mixed into the mixed solution.

[0218] (Plasma treatment process) While the substrate film with the cured resin layer was transported by a roll-to-roll system under vacuum, plasma treatment was performed on one surface in the thickness direction of the substrate film with the cured resin layer (one surface in the thickness direction of the cured resin layer).

[0219] For plasma treatment, a second device capable of performing a roll-to-roll process on the workpiece film was used. The second device had the same configuration as the first device, except that it had a second plasma treatment chamber instead of the first. The second plasma treatment chamber had a pair of planar electrodes for generating plasma: a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304). The pair of planar electrodes were spaced 50 mm apart and arranged parallel to the substrate film with a cured resin layer passing through the second plasma treatment chamber. The anode electrode was located 35 mm away from the substrate film with a cured resin layer passing through the second plasma treatment chamber and was grounded outside the second plasma treatment chamber. The cathode electrode was positioned facing one side of the substrate film with a cured resin layer in the thickness direction and electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. The length of each electrode facing the substrate film with a cured resin layer in the film running direction was 110 mm and the length in the width direction was 430 mm.

[0220] Using the second device described above, specifically, while transporting the substrate film with the cured resin layer from the unwinding chamber to the winding chamber in a roll-to-roll manner, one side of the substrate film with the cured resin layer in the thickness direction was subjected to plasma treatment (bombardment treatment) in the second plasma treatment chamber. The running speed of the substrate film with the cured resin layer (film running speed) was 1.0 m / min. The plasma treatment conditions were as follows:

[0221] The ultimate vacuum of the second plasma processing chamber is 1.0 x 10 -4 After evacuating the inside of the apparatus until the pressure reached 0.5 Pa, argon was introduced into the second plasma treatment chamber, and the pressure inside the second plasma treatment chamber was set to 0.5 Pa. A capacitively coupled plasma (CCP) was generated by applying 500 W of power between the planar electrodes using a high-frequency power supply. In this plasma environment, argon ion bombardment treatment (BB treatment) was performed on one surface in the thickness direction of the substrate film with the cured resin layer.

[0222] In this way, one thickness-wise surface of the substrate film with the cured resin layer was plasma-treated. That is, this thickness-wise surface of the substrate film with the cured resin layer was the plasma-treated surface. This plasma treatment was ion bombardment treatment by capacitively coupled plasma using argon gas (Ar-BB).

[0223] The inorganic layer forming step and the antifouling layer forming step were carried out in the same manner as in Example 1, to prepare a laminated film of Comparative Example 3.

[0224] <Evaluation> [Ion intensity ratio] In each Example and Comparative Example 4, the substrate film with a cured resin layer was sampled after the plasma treatment step and before the inorganic layer formation step. Furthermore, in Comparative Examples 1 to 3, the substrate film with a cured resin layer was sampled after the preparation step and before the inorganic layer formation step. Each substrate film with a cured resin layer was cut into a size of 10 mm x 10 mm to prepare a sample for analysis. One surface in the thickness direction of each analytical sample (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 charging 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 Irradiated primary ions: Bismuth cluster doubly charged ions (Bi 3++ ) Primary ion acceleration voltage: 25 kV Sample measurement range: 300 μm x 300 μm Mass range (m / z): 0-300

[0226] Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis revealed that HSiO + Fragment, C3H9Si + Fragment, HSiO3 - Fragment, and C3H3O2 -The ion intensities of each of the fragments, including the HSiO fragment, were obtained. + The ratio of secondary ion mass (m) to secondary ion charge (z) of the fragment (m / z) is 45, which is C3H9Si + The fragment ratio (m / z) was 73, and HSiO3 - The fragment ratio (m / z) is 77, and C3H3O2 - The fragment isocratic ratio (m / z) is 71.

[0227] From the obtained ion intensities, C3H3O2 - Ionic strength of the fragments versus HSi2O5 - The ratio of the ion intensities of the fragments (HSi2O5 - / C3H3O2 - ) and C3H9Si + HSiO versus ionic strength of fragments + Ratio of ion intensities of fragments (HSiO + / C3H9Si + The results are shown in Table 1.

[0228] [Adhesion] The laminated films of each of the Examples and Comparative Examples were subjected to the following first and second tests.

[0229] First test: First, the other thickness-wise surface of the laminate film (the exposed surface of the substrate film) was fixed to a glass plate. Next, light was irradiated from one thickness-wise side of the laminate film on the glass plate using a weathering tester (Eye Super UV Tester SUV-W161, manufactured by Iwasaki Electric Co., Ltd.) using a metal halide lamp (accelerated weathering test). Other conditions were as follows: and The conditions for the accelerated weathering test are shown below.

[0230] {Accelerated weathering test conditions} Light exposure time: 32.5 hours Temperature and humidity inside the weather resistance test chamber: Temperature 85°C, relative humidity 45% Irradiance (300-700nm cumulative irradiance): 1500W / m 2

[0231] Second test: First, eleven parallel first incisions (1 mm apart) extending linearly in a first direction and eleven parallel second incisions (1 mm apart) extending linearly in a second direction perpendicular to the first direction were made with a cutter knife on the antifouling layer and inorganic layer of the laminate film on the glass plate after the first test. The first and second incisions formed 100 grids. Next, a polyester wiper (trade name "Anticon Gold" manufactured by Sanplatec Co., Ltd.) was slid across the 100 grid areas of the laminate film while continuously dripping isopropyl alcohol at a rate of 2 mL / min. The sliding conditions were a wiper contact surface of 20 mm x 20 mm, a load of 1.5 kg / 20 mm, and 1,000 reciprocations. Next, 0.25 mm of the 100 grids were removed. 2 The number of squares in which peeling of more than 1 / 4 of the square area occurred was counted, the number of remaining squares was calculated, and the results were evaluated according to the following criteria. The results are shown in Table 1.

[0232] {standard} A: The number of remaining squares is 90 or more. B: The number of remaining squares is 70 or more but less than 90. C: The number of remaining squares is 20 or more but less than 70. D: The number of remaining squares is less than 20 squares.

[0233] [Total reflectance] The other thickness-wise surface (exposed surface of the base film) of each laminate film of each example and comparative example was attached to a black acrylic plate (2 mm thick) via a specified transparent acrylic adhesive. This produced a measurement sample. The spectrum of the total reflected light (including specular reflected light) of this measurement sample was then measured using a spectrophotometer (product name "UH4150", manufactured by Hitachi High-Tech Science Corporation). Standard illuminant D65 was used as the light source, and the measurement sample was placed in the spectrophotometer so that light was incident on one side of the inorganic layer in the thickness direction of the measurement sample. The measurement was performed using the integrating sphere measurement mode of the spectrophotometer. The measured reflectance was the total reflectance (visual reflectance) of light irradiated from one side of the inorganic layer in the thickness direction of the measurement sample (laminate film) with standard illuminant 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 surface of the base film in a thickness direction, and an inorganic layer disposed on one surface of the cured resin layer in the thickness direction, C measured by time-of-flight secondary ion mass spectrometry on one surface in the thickness direction of the cured resin layer ３ H ３ O ２ － HSi versus ion intensity of fragments ２ O ５ － The ratio of the ion intensities of the fragments is 1.0 × 10 －１ That's all, A laminate film, wherein the total reflectance of light irradiated onto the laminate film from one side in the thickness direction of the inorganic layer and having a wavelength of 380 nm to 780 nm of standard light source D65 is 0.40% or less.

2. A laminated film comprising a base film, a cured resin layer disposed on one surface of the base film in a thickness direction, and an inorganic layer disposed on one surface of the cured resin layer in the thickness direction, C measured by time-of-flight secondary ion mass spectrometry on one surface in the thickness direction of the cured resin layer ３ H ９ Si ＋ HSiO versus ionic strength of fragments ＋ The ratio of the ion intensities of the fragments is 1.0 × 10 －１ That's all, A laminate film, wherein the total reflectance of light irradiated onto the laminate film from one side in the thickness direction of the inorganic layer and having a wavelength of 380 nm to 780 nm of standard light source D65 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 blending amount of the silicone compound is 0.0025 parts by mass or more relative to 100 parts by mass of the acrylate resin.

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 laminate film according to claim 1 or 2, wherein the inorganic layer comprises an anti-reflection layer.

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

9. A method for producing the laminated film according to claim 1 or 2, comprising: a preparation step of preparing a substrate film with a cured resin layer, the substrate film including the long substrate film and the cured resin layer disposed on one surface of the substrate film in a thickness direction; a plasma treatment step of subjecting one surface in a thickness direction of the cured resin layer-attached substrate film to plasma treatment; an inorganic layer forming step of forming the inorganic layer on one surface in the thickness direction of the cured resin layer-attached substrate film; A method for manufacturing a laminated film, comprising:

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

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