Laminate film

Abstract

To provide a laminate film capable of securing adhesiveness of an inorganic material layer to a substrate film while suppressing the production cost.SOLUTION: There is provided a laminate film X comprising a substrate film 10 and an inorganic material layer 20 on the substrate film 10. In the C1s spectrum at an analysis depth in a carbon element ratio of 25 atom% of the X-ray photoelectron spectroscopy in the thickness direction H from the opposite side from the substrate film 10 to the side of the substrate film 10 in the inorganic material layer 20, the peak intensity Icc at 285 eV derived from a C-C bond, the peak intensity Ico at 286.5 eV derived from a C-O bond and the peak intensity Icoo at 289 eV derived from an O=C-O bond satisfy (Ico+Icoo) / Icc≥0.5.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated film. [Background technology]

[0002] In order to reduce the weight and improve the functionality of electronic products, various composite materials that combine organic and inorganic materials have been developed. One known example of such composite materials is a laminate film that includes an organic substrate film and an inorganic layer on the substrate film. During the manufacturing process of such a laminate film, for example, before the inorganic layer is formed on the substrate film, the surface of the substrate film is plasma-treated to remove dirt and moisture from the surface. Removing dirt and moisture from the surface of the substrate film helps to improve the adhesion of the inorganic layer formed on the surface to the substrate film. Technology related to such laminate films is described, for example, in Patent Document 1 listed below. [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] Patent Document 1 describes a laminated film as an anti-reflection film. This laminated film includes an inorganic layer as an anti-reflection layer and a substrate film that supports the inorganic layer. The substrate film includes a resin film and an HC layer on the resin film. The HC layer contains nanosilica particles. This gives the HC layer a surface irregularity on the inorganic layer side. According to Patent Document 1, the surface irregularity of the HC layer enhances the adhesion of the inorganic layer to the substrate film.

[0005] However, nanosilica particles are relatively expensive and increase the manufacturing cost of the laminated film.

[0006] The present invention provides a laminated film that can ensure adhesion of an inorganic layer to a substrate film while suppressing production costs. [Means for solving the problem]

[0007] The present invention [1] is a laminated film comprising a substrate film and an inorganic layer on the substrate film, wherein in a C1s spectrum at an analysis depth with a carbon element ratio of 25 atom % in an X-ray photoelectron spectroscopy analysis of the inorganic layer in the thickness direction from the side opposite to the substrate film toward the substrate film, the intensity Icc of the peak at 285 eV derived from a C-C bond, the intensity Ico of the peak at 286.5 eV derived from a C-O bond, and the intensity Icoo of the peak at 289 eV derived from an O=C-O bond satisfy (Ico+Icoo) / Icc≧0.50.

[0008] The present invention [2] includes the laminated film according to the above [1], in which the intensity Ioc of the peak at 288 eV derived from the C=O bond in the C1s spectrum, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy Ioc / (Icc+Ico+Icoo)≦0.01.

[0009] The present invention [3] includes the laminated film according to the above [1] or [2], wherein in the C1s spectrum of the X-ray photoelectron spectroscopy analysis at an analysis depth with a carbon element ratio of 55 atom%, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy (Ico+Icoo) / Icc≧0.80.

[0010] The present invention [4] includes the laminated film according to any one of the above [1] to [3], wherein in the C1s spectrum of the X-ray photoelectron spectroscopy at an analysis depth with a carbon element ratio of 55 atom%, the intensity Ioc of the peak at 288 eV derived from a C=O bond, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy Ioc / (Icc+Ico+Icoo)≦0.01.

[0011] The present invention [5] includes the laminate film according to any one of the above [1] to [4], wherein the inorganic layer contains at least one element selected from the group consisting of In, Si, Cr, and Nb. [Effects of the Invention]

[0012] In the laminate film of the present invention, as described above, in the C1s spectrum at an analysis depth of a carbon element ratio of 25 atom% in X-ray photoelectron spectroscopy analysis of the inorganic layer in the thickness direction from the side opposite to the substrate film toward the substrate film, the intensity Icc of the peak (285 eV) derived from the C-C bond, the intensity Ico of the peak (286.5 eV) derived from the C-O bond, and the intensity Icoo of the peak (289 eV) derived from the O=C-O bond satisfy the relationship (Ico+Icoo) / Icc≧0.5, which indicates a strong chemical interaction between the substrate film and the inorganic layer. Specifically, this indicates that a relatively large number of chemical bonds are formed between the substrate film and the inorganic layer via CO- and O=CO- moieties contained in components derived from the substrate film in the boundary region between the substrate film and the inorganic layer (at and near the interface). (The more such chemical bonds there are, the higher the adhesion of the inorganic layer to the substrate film.) This allows the content of particles such as nanosilica particles in the surface layer on the inorganic layer side of the substrate film to be reduced. This reduces the manufacturing cost of the laminate film. Therefore, the laminate film of the present invention can ensure the adhesion of the inorganic layer to the substrate film while suppressing manufacturing costs. [Brief explanation of the drawings]

[0013] [Figure 1]1 is a cross-sectional view of one embodiment of a laminated film of the present invention. [Figure 2] FIG. 1 shows a case where the laminated film has a laminated structure of an adhesive layer and an anti-reflection layer as inorganic layers. [Figure 3] 3 shows an example of a method for producing the laminated film shown in Fig. 1. Fig. 3A shows a cured resin layer forming step, Fig. 3B shows a plasma treatment step, and Fig. 3C shows an inorganic layer forming step. [Figure 4] 2 is a schematic diagram of an apparatus for carrying out a plasma treatment step and a film formation step in the example of the method for producing the laminated film shown in FIG. 1. FIG. [Figure 5] 5 is a perspective view showing the positional relationship between a low inductance antenna and a base film in the plasma processing chamber shown in FIG. [Figure 6] 5 is a cross-sectional view showing the positional relationship between the low inductance antenna and the base film in the plasma processing chamber shown in FIG. [Figure 7] 1 shows a C1s spectrum at an analysis depth of an X-ray photoelectron spectroscopy analysis with a carbon element ratio of 25 atom % in Example 1. [Figure 8] 1 shows a C1s spectrum of Comparative Example 1 at an analysis depth of an X-ray photoelectron spectroscopy analysis where the carbon element ratio is 25 atom %. DETAILED DESCRIPTION OF THE INVENTION

[0014] As shown in Fig. 1, a laminate film X according to one embodiment of the present invention includes a base film 10 and an inorganic layer 20 on the base film 10. Specifically, the inorganic layer 20 is disposed on one surface of the base film 10 in the thickness direction H. The base film 10 and the inorganic layer 20 are in contact with each other. The laminate film X extends in a direction (plane direction D) perpendicular to the thickness direction H.

[0015] The base film 10 has a first surface 10a on the inorganic layer 20 side and a second surface 10b opposite to the first surface 10a. In this embodiment, the base film 10 includes a resin film 11 and a cured resin layer 12, which are arranged in this order in the thickness direction H. In this embodiment, the resin film 11 and the cured resin layer 12 are in contact with each other. In the base film 10, the cured resin layer 12 forms the first surface 10a, and the resin film 11 forms the second surface 10b.

[0016] The resin film 11 is an element that ensures the strength of the laminated film X. The resin film 11 is, for example, a flexible, transparent resin film. Examples of materials for the resin film 11 include polyester resin, polyolefin resin, cellulose resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, and polystyrene resin. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of cellulose resins include triacetyl cellulose (TAC). These materials may be used alone or in combination. From the viewpoints of transparency and strength, the material for the resin film 11 is preferably at least one selected from the group consisting of polyester resin, polyolefin resin, and cellulose resin, and more preferably at least one selected from the group consisting of PET, COP, and TAC. In addition, in this embodiment, the resin film 11 does not contain particles.

[0017] The thickness of the resin film 11 is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, and is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less. When the thickness of the resin film 11 is equal to or greater than the above-mentioned lower limit, the strength of the laminated film X can be ensured. When the thickness of the resin film 11 is equal to or less than the above-mentioned upper limit, the handleability of the base film 10 in the roll-to-roll process described below can be ensured. Furthermore, a carrier film (not shown) may be attached to the second surface 10b of the resin film 11 to ensure the transportability and handleability of the base film 10 in the roll-to-roll process.

[0018] The total light transmittance (JIS K 7375:2008) of the resin film 11 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, and is, for example, 100% or less. When the total light transmittance of the resin film 11 is the above-mentioned lower limit or more, good transparency can be ensured in the laminate film X.

[0019] The cured resin layer 12 is a functional layer containing a resin. Specifically, the cured resin layer 12 is a cured product of a curable resin composition containing a curable resin. An example of the functional layer is a hard coat layer. The hard coat layer is a layer that makes it difficult for scratches to form on the exposed surface (the upper surface in FIG. 1 ) of the inorganic layer 20.

[0020] Examples of the curable resin include polyester resin, acrylic urethane resin, acrylic resin (excluding acrylic urethane resin), urethane resin (excluding acrylic urethane resin), amide resin, silicone resin, epoxy resin, and melamine resin. These curable resins may be used alone or in combination of two or more. From the viewpoint of ensuring the hardness of the cured resin layer 12, the curable resin is preferably at least one selected from the group consisting of acrylic urethane resin and acrylic resin.

[0021] Examples of the curable resin include ultraviolet-curable resins and thermosetting resins. The curable resin is preferably an ultraviolet-curable resin. When the curable resin is an ultraviolet-curable resin, the curable resin can be cured without high-temperature heating, which can improve the production efficiency of the laminated film X.

[0022] When the substrate film 10 has a cured resin layer 12, it is preferable that the cured resin layer 12 contain fewer inorganic oxide particles. The fewer inorganic oxide particles in the cured resin layer 12, the more effectively the scattering of light incident on the laminate film X caused by particles in the substrate film 10 can be suppressed, and the manufacturing cost of the laminate film X can be reduced. Examples of inorganic oxide particle materials include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. The inorganic oxide particle content of the cured resin layer 12 is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, still more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.0% by mass.

[0023] The thickness of the cured resin layer 12 is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and is preferably 30 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less. When the thickness of the cured resin layer 12 is equal to or greater than the above-mentioned lower limit, the functionality of the cured resin layer 12 can be ensured. Specifically, when the cured resin layer 12 is a hard coat layer, the scratch resistance of the inorganic layer 20 can be ensured. When the thickness of the cured resin layer 12 is equal to or less than the above-mentioned upper limit, the transparency of the cured resin layer 12 can be ensured.

[0024] The total light transmittance (JIS K 7375:2008) of the base film 10 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, and is, for example, 100% or less. When the total light transmittance of the base film 10 is the above-mentioned lower limit or more, good transparency can be ensured in the laminate film X.

[0025] The surface roughness Sa (arithmetic mean height according to ISO 25178-2:2012) of the first surface 10a of the substrate film 10 is preferably 1.0 nm or more, more preferably 1.2 nm or more, even more preferably 1.3 nm or more, and is preferably 10.0 nm or less, more preferably 7.0 nm or less, even more preferably 4.5 nm or less. When the surface roughness Sa of the first surface 10a is equal to or greater than the above-mentioned lower limit, the fine irregularities on the first surface 10a act as an anchor for the inorganic layer 20, thereby enhancing adhesion of the inorganic layer 20 to the substrate film 10. When the surface roughness Sa of the first surface 10a is equal to or less than the above-mentioned upper limit, excessive irregularities at the interface within the inorganic layer 20, which will be described later, can be suppressed.

[0026] In this embodiment, the first surface 10a is a plasma-treated surface. The plasma treatment is a treatment using inductively coupled plasma (oxygen-LAICP treatment) using an oxygen-containing gas, which is generated by applying high-frequency power to a low-inductance antenna, in order to increase the value of the first ratio equation described below. The oxygen-LAICP treatment of the first surface 10a will be specifically described later in relation to the manufacturing method of the laminated film X.

[0027] The total light transmittance (JIS K 7375:2008) of the laminate film X is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, and is, for example, 100% or less. When the total light transmittance of the laminate film X is the above-mentioned lower limit or more, the laminate film X can ensure good transparency.

[0028] Examples of the inorganic layer 20 include an anti-reflection layer and a conductive layer. An anti-reflection layer is a layer with anti-reflection properties that suppress the reflection intensity of external light. A conductive layer is a layer with conductivity. The inorganic layer 20 may be another layer. The inorganic layer 20 may also be a composite layer including an anti-reflection layer and another layer. The inorganic layer 20 may also be a composite layer including a conductive layer and another layer. Figure 2 shows a case where the inorganic layer 20 has a laminated structure of an adhesive layer 21 and an anti-reflection layer 22.

[0029] The adhesion layer 21 is disposed on the first surface 10a of the base film 10. Specifically, the adhesion layer 21 is disposed on the cured resin layer 12 of the base film 10. The adhesion layer 21 is in contact with the cured resin layer 12. The adhesion layer 21 is a layer that enhances adhesion of the inorganic layer 20 to the laminate film X. Examples of materials for the adhesion layer 21 include metals such as In, Si, 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. From the viewpoint of achieving both adhesion to both the laminate film X and the antireflection layer 22 and transparency of the adhesion layer 21, the adhesion layer 21 is preferably an inorganic oxide film containing at least one element selected from the group consisting of In, Si, Cr, and Nb. That is, the inorganic layer 20 preferably contains at least one element selected from the group consisting of In, Si, Cr, and Nb. From the viewpoint of achieving both adhesion to both the laminated film X and the antireflection layer 22 and transparency of the adhesion layer 21, indium tin composite oxide (ITO) or silicon oxide (SiOx) is more preferred as the material for the adhesion layer 21. The silicon oxide used as the material for the adhesion layer 21 is preferably SiOx having a lower oxygen content than the stoichiometric composition, and more preferably SiOx where x is 1.2 or more and 1.9 or less.

[0030] The thickness of the adhesive layer 21 is preferably 1 nm or more, more preferably 2 nm or more, even more preferably 3 nm or more, and is preferably 50 nm or less, more preferably 30 nm or less, even more preferably 10 nm or less, and even more preferably 5 nm or less. When the thickness of the adhesive layer 21 is equal to or greater than the above-mentioned lower limit, the adhesive strength between the laminated film X and the antireflection layer 22 can be ensured. When the thickness of the adhesive layer 21 is equal to or less than the above-mentioned upper limit, the transparency of the adhesive layer 21 can be ensured.

[0031] The antireflection layer 22 is disposed on one surface of the adhesive layer 21 in the thickness direction H. The antireflection layer 22 preferably includes a plurality of transparent inorganic oxide films stacked in the thickness direction H. FIG. 2 shows an example of such an antireflection layer 22. The antireflection layer 22 in FIG. 2 includes a high-refractive-index layer 22a, a low-refractive-index layer 22b, a high-refractive-index layer 22c, and a low-refractive-index layer 22d, in this order from the adhesive layer 21 side in the thickness direction H. The high-refractive-index layer 22a is in contact with the adhesive layer 21. The high-refractive-index layer 22a is in contact with the low-refractive-index layer 22b. The low-refractive-index layer 22b is in contact with the high-refractive-index layer 22c. The high-refractive-index layer 22c is in contact with the low-refractive-index layer 22d. The high-refractive-index layers 22a and 22c have relatively high refractive indices, and the low-refractive-index layers 22b and 22d have relatively low refractive indices. In this laminated structure, the intensity of reflected light is attenuated by interference between reflected light at multiple interfaces in the high-refractive-index layers 22 a, 22 c and the low-refractive-index layers 22 b, 22 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 22.

[0032] The high refractive index layer 22a (first high refractive index layer) is made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm. Examples of high refractive index materials include niobium oxide (Nb2O5), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO). From the viewpoint of 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). The optical film thickness of the high refractive index layer 22a is, for example, 20 nm or more and, for example, 55 nm or less.

[0033] The low refractive index layer 22b (first low refractive index layer) is made of a low refractive index material having a refractive index of preferably 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). The optical film thickness of the low refractive index layer 22b is, for example, 15 nm or more and, for example, 70 nm or less.

[0034] The high-refractive-index layer 22c (second high-refractive-index layer) is made of a high-refractive-index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm. Examples of the high-refractive-index material include the materials described above for the high-refractive-index layer 22a, and niobium oxide is preferred. The optical thickness of the high-refractive-index layer 22c is, for example, 60 nm or more and, for example, 330 nm or less.

[0035] The low-refractive-index layer 22d (second low-refractive-index layer) is made of a low-refractive-index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm. Examples of the low-refractive-index material include the materials described above for the low-refractive-index layer 22b, with silicon dioxide being preferred. The optical thickness of the low-refractive-index layer 22d is, for example, 100 nm or more and, for example, 160 nm or less.

[0036] The total thickness of the antireflection layer 22 is preferably 180 nm or more, more preferably 200 nm or more, and even more preferably 220 nm or more, and is preferably 320 nm or less, more preferably 280 nm or less, and even more preferably 250 nm or less. In this embodiment, the total thickness of the antireflection layer 22 is the sum of the thicknesses of the high-refractive-index layers 22a and 22c and the low-refractive-index layers 22b and 22d. When the total thickness of the antireflection layer 22 is equal to or greater than the above-mentioned lower limit, the antireflection layer 22 can ensure its function of attenuating the intensity of reflected light. When the total thickness of the antireflection layer 22 is equal to or less than the above-mentioned upper limit, cracking of the antireflection layer 22 can be suppressed.

[0037] When the inorganic layer 20 includes a conductive layer, the conductive layer is formed from a conductive material. Examples of conductive materials include metals and metal oxides. Examples of metals include copper, silver, gold, nickel, chromium, and alloys thereof. Examples of metal oxides include indium-containing conductive oxides and antimony-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).

[0038] In the C1s spectrum at a predetermined analysis depth in X-ray photoelectron spectroscopy (XPS) in the thickness direction H of the inorganic layer 20 from the opposite side to the base film 10 toward the base film 10, the intensity of the peak at 285 eV derived from C-C bonds is defined as Icc, the intensity of the peak at 286.5 eV derived from C-O bonds (excluding C-O bonds in carboxy groups) is defined as Ico, the intensity of the peak at 288 eV derived from C=O bonds (excluding C=O bonds in carboxy groups) is defined as Ioc, and the intensity of the peak at 289 eV derived from O=C-O bonds is defined as Icoo. Specific methods for X-ray photoelectron spectroscopy are as described below in the examples.

[0039] In the XPS C1s spectrum (first C1s spectrum) of the laminate film X at an analysis depth where the carbon element ratio is 25 atom %, the intensities Icc, Ico, and Icoo of the laminate film X satisfy the following formula (1).

[0040] (Ico+Icoo) / Icc≧0.50 (1)

[0041] The numerator of the left-hand side of Equation (1) (first ratio equation) specifically represents the total ratio of carbon atoms contained in C-O bonds (excluding C-O bonds in carboxy groups) and O=C-O bonds among the carbon atoms present at the analysis depth of the carbon atom ratio of 25 atom% in the XPS analysis. The larger the value V1 of the first ratio equation, the more C-O bonds and O=C-O bonds there are in the resin component derived from the base film 10 at the position (first depth position) of the carbon atom ratio of 25 atom% in the thickness direction H of the inorganic layer 20. Therefore, the larger the value V1, the more chemical bonds there are formed between the base film 10 and the inorganic layer 20 at the first depth position via the C-O moieties and O=C-O moieties of the resin component derived from the base film 10. The more such chemical bonds there are, the stronger the adhesion of the inorganic layer 20 to the base film 10. In the XPS analysis of the inorganic layer 20, the analysis depth of the carbon atom ratio of 25 atom% is farther from the base film 10 than the analysis depth of the carbon atom ratio of 55 atom%, as described below. The high value V1 of the first ratio equation at such an analysis depth better reflects the strength of the chemical interaction between the substrate film 10 and the inorganic layer 20 compared to the high value V3 of the third ratio equation described below at an analysis depth with a carbon element ratio of 55 atom % described below.

[0042] In the laminate film X, the value V1 of the first ratio formula is 0.50 or more, preferably 0.60 or more, and more preferably 0.70 or more. The value V1 is preferably 1.00 or less, more preferably 1.50 or less, and even more preferably 2.00 or less. When the value V1 is equal to or greater than the above-mentioned lower limit, the adhesion of the inorganic layer 20 to the base film 10 can be sufficiently ensured. When the value V1 is equal to or less than the above-mentioned upper limit, it means that the number of C-C bonds in the organic material at the first depth position is greater than a certain level, and therefore the cohesive strength of the organic components derived from the base film 10 is sufficiently maintained. Such a value V1 equal to or less than the above-mentioned upper limit is preferable for preventing cohesive failure between the base film 10 and the inorganic layer 20.

[0043] In the laminated film X, the intensities Ioc, Icc, Ico, and Icoo in the first C1s spectrum preferably satisfy the following formula (2):

[0044] Ioc / (Icc+Ico+Icoo)≦0.01 (2)

[0045] The denominator of the left-hand side of Equation (2) (the second ratio equation) specifically represents the total ratio of carbon atoms contained in C-C bonds, carbon atoms contained in C-O bonds (excluding C-O bonds in carboxy groups), and carbon atoms contained in O=C-O bonds, among the carbon atoms present at the analysis depth where the carbon element ratio in the XPS is 25 atom%. The smaller the value V2 of the second ratio equation, the fewer C=O bonds there are in the resin component derived from the base film 10 at the first depth position in the inorganic layer 20. Therefore, a value V2 of 0.01 or less means that the number of oxygen atoms located at the molecular chain terminals in the organic component derived from the base film 10 at the first depth position is less than a certain level, and therefore means that the ratio of oxygen atoms bonded to inorganic atoms in the organic component derived from the base film 10 is greater than a certain level. The value V2 is, for example, 0.00 or greater.

[0046] In the above XPS C1s spectrum (second C1s spectrum) of laminate film X at an analysis depth where the carbon element ratio is 55 atom %, the intensities Icc, Ico, and Icoo of laminate film X satisfy the following formula (3).

[0047] (Ico+Icoo) / Icc≧0.80 (3)

[0048] The numerator of the left-hand side of Equation (3) (third ratio equation) specifically represents the total ratio of carbon atoms contained in C-O bonds (excluding C-O bonds in carboxy groups) to carbon atoms contained in O=C-O bonds among the carbon atoms present at the analysis depth where the carbon atom ratio is 55 atom% in the XPS analysis. The larger the value V3 of the third ratio equation, the more C-O bonds and O=C-O bonds there are in the resin component derived from the base film 10 at the position where the carbon atom ratio is 55 atom% (second depth position) in the thickness direction H of the inorganic layer 20. Therefore, the larger the value V3, the more chemical bonds there are formed between the base film 10 and the inorganic layer 20 at the second depth position via the C-O moieties and O=C-O moieties of the resin component derived from the base film 10. The more such chemical bonds there are, the stronger the adhesion of the inorganic layer 20 to the base film 10.

[0049] In the laminate film X, the value V3 of the third ratio is preferably 0.80 or more, more preferably 0.85 or more, and even more preferably 0.90 or more. The value of the third ratio is preferably 1.20 or less, more preferably 1.70 or less, and even more preferably 2.20 or less. When the value V3 is equal to or greater than the above-mentioned lower limit, the adhesion of the inorganic layer 20 to the base film 10 can be sufficiently ensured. When the value V3 is equal to or less than the above-mentioned upper limit, it means that the number of C-C bonds in the organic material at the second depth position is greater than a certain level, and therefore the cohesive strength of the organic components derived from the base film 10 is sufficiently maintained. When the value V3 is equal to or less than the above-mentioned upper limit, it is preferable to prevent cohesive failure between the base film 10 and the inorganic layer 20.

[0050] The ratio (V1 / V3) of the value V1 in the first ratio formula to the value V3 in the third ratio formula is preferably 0.60 or more, more preferably 0.70 or more, and even more preferably 0.75 or more, and is, for example, 1.00 or less. When the ratio (V1 / V3) is equal to or greater than the above lower limit, the adhesion of the inorganic layer 20 to the base film 10 can be sufficiently ensured.

[0051] In the laminated film X, the intensities Ioc, Icc, Ico, and Icoo in the second C1s spectrum preferably satisfy the following formula (4):

[0052] Ioc / (Icc+Ico+Icoo)≦0.01 (4)

[0053] The denominator of the left-hand side of equation (4) (fourth ratio) specifically represents the total ratio of carbon atoms contained in C—C bonds, carbon atoms contained in C—O bonds (excluding C—O bonds in carboxy groups), and carbon atoms contained in O═C—O bonds, among the carbon atoms present at the analysis depth where the carbon element ratio in the XPS is 55 atom %. The smaller the value of the fourth ratio, the fewer C═O bonds there are in the resin component derived from the base film 10 at the second depth position in the inorganic layer 20. Therefore, a value of 0.01 or less in the fourth ratio means that the number of oxygen atoms located at the molecular chain terminals in the organic component derived from the base film 10 at the second depth position is less than a certain level, and therefore means that the ratio of oxygen atoms bonded to inorganic atoms in the organic component derived from the base film 10 is greater than a certain level. The value of the fourth ratio is, for example, 0.00 or greater.

[0054] The peeling rate of the inorganic layer 20 of the laminated film X in the second test described below after the first test (accelerated weather resistance test) described below is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less, from the viewpoint of ensuring the adhesion of the inorganic layer 20. The methods of the first and second tests are more specifically as described below in the examples. When the peeling rate of the inorganic layer 20 is equal to or less than the above upper limit, it is possible to suppress a substantial decrease in the functionality of the inorganic layer 20 due to peeling of the inorganic layer 20.

[0055] First test: First, the substrate film 10 side of the laminated film X is fixed to a glass plate. Next, the inorganic layer 20 of the laminated film X on the glass plate is irradiated with light at a temperature of 85°C, a relative humidity of 45%, and an irradiation intensity (integrated illuminance from 290 nm to 450 nm) of 150 mW / cm. 2 The light was irradiated for 32.5 hours under the above conditions.

[0056] 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 in the inorganic layer 20 of the laminate film X on the glass plate after the first test, forming 100 grids. Next, isopropyl alcohol was continuously dripped at 2 mL / min on the 100 grid areas of the laminate film X, while a polyester wiper was slid over the wiper contact surface of 20 mm x 20 mm, with a load of 1.5 kg / 20 mm square, a sliding speed of 50 mm / sec, and 1000 reciprocations. Next, 0.25 mm of the 100 grids were removed. 2 The number of squares where the above peeling occurred is counted, and then the count is divided by 100 to calculate the peeling rate (%).

[0057] 3A to 3C show an example of a method for producing the laminated film X. This production method includes a cured resin layer forming step (FIG. 3A), a plasma treatment step (FIG. 3B), and a film forming step (FIG. 3C).

[0058] In the cured resin layer forming step, as shown in FIG. 3A, a cured resin layer 12′ is formed on a long resin film 11. The cured resin layer 12′ can be formed by applying the above-described curable resin composition to a substrate film 11 to form a coating film, and then curing the coating film. The curable resin composition may contain other components besides the above-described curable resin, as necessary. Examples of other components include a solvent and a leveling agent. Examples of solvents include butyl acetate, ethyl acetate, toluene, and cyclopentanone. When the curable resin composition contains an ultraviolet-curable resin as the curable resin, the curable resin composition preferably contains a photopolymerization initiator. When the curable resin composition contains a thermosetting resin as the curable resin, the curable resin composition preferably contains a thermal polymerization initiator.

[0059] When the curable resin composition contains a solvent, the coating film on the resin film 11 is dried after the curable resin composition is applied. 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 longer and, for example, 10 minutes or shorter.

[0060] When the curable resin composition contains an ultraviolet-curable resin, the coating on the resin film 11 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, and for example, 500 mJ / cm 2 The following is the result.

[0061] When the curable resin composition contains a thermosetting resin, the coating on the resin film 11 is cured by heating. The heating temperature is, for example, 100° C. or higher and, for example, 150° C. or lower. The heating time is, for example, 10 seconds or higher and, for example, 10 minutes or shorter.

[0062] In this manner, a long substrate film 10' is obtained. The first surface 10a' of the substrate film 10' on the side of the cured resin layer 12' is the surface before the plasma treatment described below. In this embodiment, a roll of the long substrate film 10' is prepared. Specifically, the substrate film 10' is wound so that the first surface 10a' of the substrate film 10' faces inward in the radial direction of the roll.

[0063] In this manufacturing method, a plasma treatment process and a film formation process are then carried out sequentially while the base film 10' is transported as a workpiece film W by a roll-to-roll method under a reduced pressure atmosphere. The apparatus Y shown in Figure 4 is an example of an apparatus for carrying out the plasma treatment process and the film formation process. The apparatus Y includes a feed chamber R1, a winding chamber R2, a connecting chamber C1, a plasma treatment chamber C2, a connecting chamber C3, a film formation chamber C4, a connecting chamber C5, a connecting chamber C6, and a PEM device (not shown).

[0064] The unwinding chamber R1 is equipped with a unwinding roller 51 for unwinding the workpiece film W. A roll of a long base film 10' 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.

[0065] 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.

[0066] The connecting chamber C1 is located next to the unwinding chamber R1 in the running direction of the workpiece film W and before the plasma processing chamber C2. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber C1. The connecting chamber C1 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Y is in operation, the pressure within the connecting chamber C1 is maintained at a predetermined pressure between the pressure within the unwinding chamber R1 and the pressure within the plasma processing chamber C2. This ensures a pressure difference between the unwinding chamber R1 and the plasma processing chamber C2.

[0067] The plasma processing chamber C2 is disposed between the connecting chamber C1 and the connecting chamber C3 in the running direction of the workpiece film W. In the plasma processing chamber C2, a plasma processing step is carried out as described below.

[0068] In this embodiment, the plasma processing chamber C2 is equipped with a plurality of low inductance antennas (LA) 71. A low inductance antenna means 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, the LA71 is supported by a mounting fixture 72 and covered by a cover block 73 (omitted in FIG. 5) as shown in FIGS. 5 and 6, and is placed inside the plasma processing chamber C2 (an example in which the number of LA71 is four is shown).

[0069] The multiple LAs 71 are aligned in the running direction of the base film 10 and in a direction perpendicular to the running direction (the width direction of the base film 10). The fixture 72 is a vacuum flange. As shown in FIG. 6, the LAs 71 are fixed to the fixture 72 via feedthroughs 74. As shown in FIG. 4, the fixture 72 is attached to an opening 75 provided in the wall of the plasma processing chamber C2. 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 C2 and the fixture 72. The LAs 71 are electrically connected to a high-frequency power source (RF power source) outside the plasma processing chamber C2 via an impedance matching box. The LAs 71 are formed of a conductor. Examples of conductors include copper and silver, with copper being preferred. The LAs 71 may be covered with an insulator. Examples of insulators include glass and quartz.

[0070] 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 LA 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. Examples of aluminum include aluminum A5052. The partition plates 73B are made of an insulating material. Examples of insulating materials include quartz and glass. The separation distance d' (shown in FIG. 6) between the base film 10 traveling in the plasma processing chamber C2 and the cover block 73 is, for example, 50 to 200 mm. Such a cover block 73 helps to avoid damage and contamination of the LA71 due to plasma processing without excessively reducing the plasma conversion efficiency due to the power applied to the LA71, and also helps to suppress damage to the substrate film 10 being plasma processed.

[0071] As shown in FIG. 5, in this embodiment, the LA71 has an open loop shape. Having an open loop shape for the LA71 is advantageous for reducing the inductance of the LA71. Therefore, the open loop shape of the LA71 can suppress an increase in voltage due to an increase in power applied to the LA71. This suppresses abnormal discharge during plasma processing, as described below. Suppressing abnormal discharge can suppress damage to the workpiece film W being plasma processed. Specifically, the LA71 has a U-shape with two free ends. For each LA71, the two free ends are fixed to the fixture 72 so that they are aligned in the width direction of the workpiece film W. In this embodiment, the LA71 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 C2. Each extension 71a extends in the width direction of the workpiece film W. Each extension 71a may also extend in the running direction of the workpiece film W (four LA71 may be arranged in this manner). The length of the extension 71a is, for example, 50 to 150 mm (FIG. 5 exemplarily illustrates a case where the length of the extension 71a is the same as the maximum length d2 of the LA71, which will be described later). The LA71 may have a coil shape instead of an open loop shape.

[0072] The LA 71 extends from the fixture 72 toward the base film 10. The LA 71 preferably extends perpendicular to the fixture 72. The extension length d1 of the LA 71 from the fixture 72 is, for example, 30 to 150 mm. The maximum length d2 of the LA 71 in the surface direction of the base film 10 is, for example, 50 to 150 mm. The separation distance d3 (shown in FIG. 6) between the LA 71 and the base film 10 is, for example, 50 to 200 mm. The extension length d1 and the separation distance d3 are preferably the same. 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 LA 71 spaced apart in the running direction of the base film 10 may be 1, 2, or 3, or may be 4 or more if necessary, depending on the running speed of the base film 10 (i.e., the plasma treatment time). The center-to-center distance d4 between adjacent LAs 71 in the running direction of the base film 10 is, for example, 100 to 500 mm. The center-to-center distance d5 between adjacent LAs 71 in the width direction of the base film 10 is, for example, 200 to 500 mm. Adjusting the center-to-center distance d5 allows for control of the uniformity of the plasma density (described below) in the width direction of the base film 10. The center-to-center distance d4 and the center-to-center distance d5 are preferably the same. The ratio of the center-to-center distance d5 to the center-to-center distance d4 (d5 / d4) is, for example, 0.5 to 2.0. The centers of the extensions 71a of the four LAs 71 preferably form a square with the vertices at their vertices. Such a set of LAs 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 LAs 71.

[0073] In this embodiment, the plasma processing chamber C2 further includes a transport roller 53. The transport roller 53 is a main guide roller for transporting the workpiece film W within the plasma processing chamber C2. The transport roller 53 has a temperature adjustment function that allows the workpiece film W to be heated or cooled. In other words, the transport roller 53 is a transport roller with a temperature adjustment function. When the apparatus Y is in operation, the transport roller 53 transports the base film 10 while contacting the second surface 10b of the base film 10. The LA71 is disposed opposite the transport roller 53. With the apparatus Y equipped with such a plasma treatment chamber C2, in the plasma treatment step S2, the transport roller 53 with a temperature control function that contacts the base film 10 can perform plasma treatment on the base film 10 while cooling or heating the base film 10. Controlling the temperature of the base film 10 can suppress thermal deformation of the base film 10 and also suppress the effect of the thermal deformation on the transport of the base film 10.

[0074] 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 within the plasma processing chamber C2, between the workpiece film W and the LA71 in the direction of separation between them. 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 C2.

[0075] The connecting chamber C3 is located next to the plasma processing chamber C2 in the running direction of the workpiece film W and before the film forming chamber C4. A predetermined number of guide rollers G for guiding the workpiece film W are provided inside the connecting chamber C3. The connecting chamber C3 is connected to a vacuum pump (not shown) and is configured to adjust the pressure inside the chamber. When the device Y is in operation, the pressure inside the connecting chamber C3 is maintained at a predetermined pressure between the pressure inside the plasma processing chamber C2 and the pressure inside the film forming chamber C4. This ensures a pressure difference between the plasma processing chamber C2 and the film forming chamber C4.

[0076] The film-forming chamber C4 is located next to the connecting chamber C3 in the running direction of the workpiece film W. The film-forming chamber C4 is also connected to a vacuum pump (not shown) so that the chamber can be adjusted to a predetermined vacuum level. In the film-forming chamber C4, a film-forming process is carried out as described below.

[0077] In this embodiment, the film formation chamber C4 is a sputtering film formation chamber. The film formation chamber C4 includes a film formation roller 54 and multiple sputtering chambers 60 (sputtering chambers 60a to 60e) (five sputtering chambers 60 are illustrated as an example). The film formation roller 54 is a main guide roller for transporting the workpiece film W within the film formation chamber C4. The film formation roller 54 has a temperature control function that allows the workpiece film W to be heated or cooled. The sputtering chamber 60 is a partitioned space within the film formation chamber C4. The multiple sputtering chambers 60 are arranged along the circumferential direction of the film formation roller 54. Each sputtering chamber 60 opens 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 DC power supplies, AC power supplies, MF power supplies, RF power supplies, and MF-AC power supplies. MF-AC power supplies refer to AC power supplies 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 in the film formation chamber C4.

[0078] The connecting chamber C5 and the connecting chamber C6 are arranged in this order between the film forming chamber C4 and the winding chamber R2 in the running direction of the workpiece film W. A predetermined number of guide rollers G are provided in the connecting chamber C5 for guiding the workpiece film W. A predetermined number of guide rollers G are provided in the connecting chamber C6 for guiding the workpiece film W. The connecting chamber C5 is connected to a vacuum pump (not shown) and is configured so that the pressure inside the chamber can be adjusted. The connecting chamber C6 is connected to a vacuum pump (not shown) so that the pressure inside the chamber can be adjusted. When the apparatus Y is in operation, the pressure inside the connecting chambers C5 and C6 is maintained at a predetermined pressure between the pressure inside the film formation chamber C4 and the pressure inside the winding chamber R2. This ensures a pressure difference between the film formation chamber C4 and the winding chamber R2.

[0079] The plasma processing step and the film forming step are carried out in sequence by the above-described apparatus Y. Specifically, the steps are as follows.

[0080] 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 C1, the plasma treatment chamber C2, the connecting chamber C3, the film forming chamber C4, the connecting chamber C5, and the connecting chamber C6 in sequence, and is then wound up in the winding chamber R2. The running speed of the workpiece film W is, for example, 0.5 m / min or more, and, for example, 5 m / min or less. Furthermore, 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 this line under a reduced pressure atmosphere. The reduced pressure atmosphere is preferably under vacuum. Under vacuum preferably means a reduced pressure atmosphere of 7 Pa or less.

[0081] A plasma processing step is carried out in the plasma processing chamber C2. In the plasma processing step, the workpiece film W is plasma-processed in a reduced pressure atmosphere in the plasma processing chamber C2 (chamber) while the plasma emission intensity is being detected. In this embodiment, the plasma processing is a process using inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP process) generated by applying high-frequency power to the LA71. Specifically, the process is as follows.

[0082] During plasma processing, oxygen is supplied into the plasma processing chamber C2 via the first line L1. In addition to oxygen, an inert gas may be supplied into the plasma processing chamber C2. Examples of inert gases include argon, krypton, and xenon. The gas in the plasma processing chamber C2 may also contain gases other than the inert gas. Examples of other gases include oxygen, nitrogen, hydrogen, and water vapor. The oxygen concentration of the gas (oxygen-containing gas) in the plasma processing chamber C2 is preferably 30% by volume or more, more preferably 50% by volume or more, even more preferably 80% by volume or more, even more preferably 90% by volume or more, even more preferably 95% by volume or more, and particularly preferably 100% by volume. When the oxygen concentration is above the lower limit, high-density oxygen plasma can be generated. This is useful for creating nanometer-order micro-roughness on the surface of the workpiece film W and for highly activating the surface by cleaning it.

[0083] The pressure (first pressure) within the plasma processing chamber C2 during plasma processing is preferably 0.1 Pa or more, more preferably 0.2 Pa or more, even more preferably 0.3 Pa or more, and is preferably 7 Pa or less, more preferably 5 Pa or less, and even more preferably 3 Pa or less. When 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 C2. When 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 C2.

[0084] The frequency of the high-frequency power applied to the LA71 during plasma processing is preferably 1 MHz or higher, more preferably 5 MHz or higher, even more preferably 10 MHz or higher, and preferably 100 MHz or lower, more preferably 80 MHz or lower, and even more preferably 60 MHz or lower. When the frequency is above the lower limit, plasma current density can be increased while stabilizing plasma discharge during plasma processing. When the frequency is below the upper limit, the antenna potential can be suppressed, thereby suppressing damage to the workpiece film W caused by the plasma. Furthermore, the high-frequency power is preferably 0.1 kW or higher, more preferably 0.3 kW or higher, even more preferably 1.0 kW or higher, and preferably 10 kW or lower, more preferably 8 kW or lower, and even more preferably 6 kW or lower. When the high-frequency power is above the lower limit, a high-density plasma environment can be formed in the plasma processing chamber C2 during inductively coupled plasma processing. When the high-frequency power is below the upper limit, excessive damage to the workpiece film W caused by the plasma can be suppressed.

[0085] 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.

[0086] In the plasma treatment process, the plasma current density at the intermediate position between the LA71 and the workpiece film W is preferably 1.0 mA / cm 3 More preferably, 2.0 mA / cm 3 More preferably, 3.0 mA / cm 3 or more, and preferably 10 mA / cm 3 Less than or equal to 8mA / cm 3 Less than 4 mA / cm, more preferably 3 The inductively coupled plasma processing using a low inductance antenna can achieve a higher plasma current density (for example, a plasma density about 100 times higher) than the capacitively coupled plasma processing. When the plasma current density is equal to or greater than the lower limit, sufficient plasma oxygen particles can be secured in the plasma processing chamber C2 during plasma processing, enabling proper surface modification of the workpiece film W. When the plasma current density is equal to or less than the upper limit, damage to the workpiece film W caused by excessively high density plasma 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 C2, adjusting the frequency of the high-frequency power in the high-frequency power supply, and adjusting the magnitude of the applied power.

[0087] By subjecting the substrate film 10' (FIG. 3A) to the above-described plasma treatment, a substrate film 10 having a cured resin layer 12 is obtained, as shown in FIG. 3B. The substrate film 10 has a first surface 10a that has been subjected to the oxygen-LAICP treatment described above. The oxygen-LAICP treatment enhances the activity of the surface of the cured resin layer 12. Specifically, the oxygen-LAICP treatment causes C-O bonds to be formed from some of the multiple C-C bonds on the surface of the cured resin layer 12, and O-C-O bonds to be formed from some of the multiple C=O bonds.

[0088] In the film formation process, following the plasma treatment process, an inorganic layer 20 is formed on the workpiece film W (substrate film 10) by sputtering in a reduced pressure atmosphere, as shown in Figure 3C. Specifically, the inorganic layer 20 is formed on the cured resin layer 12 whose surface has been highly activated as described above. The reduced pressure atmosphere is preferably a vacuum.

[0089] 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.

[0090] When the film forming material is a metal oxide, the sputtering method may be a reactive sputtering method. In the reactive sputtering method, oxygen (reactive gas) is introduced into the sputtering chamber 60 in addition to the sputtering gas. The oxygen is introduced into the sputtering chamber 60 through another second line. In the reactive sputtering method, the target is made of, for example, a metal in the metal oxide that forms each layer.

[0091] In the sputtering method, the pressure (second pressure) inside the sputtering chamber 60 is, for example, 0.1 to 5.0 Pa depending on the type of layer to be formed. The film formation temperature (the temperature of the workpiece film W adjusted by the film formation roller 54) is, for example, -10°C to 150°C.

[0092] Specifically, in the film formation step, an inorganic layer 20 is formed on the cured resin layer 12 by a sputtering method in at least one sputtering chamber selected from sputtering chambers 60a to 60e. For example, when producing the laminated film X shown in Fig. 2, an adhesive layer 21 is formed on the cured resin layer 12 in sputtering chamber 60a, a high refractive index layer 22a is formed on the adhesive layer 21 in sputtering chamber 60b, a low refractive index layer 22b is formed on the high refractive index layer 22a in sputtering chamber 60c, a high refractive index layer 22c is formed on the low refractive index layer 22b in sputtering chamber 60d, and a high refractive index layer 22d is formed on the high refractive index layer 22c in sputtering chamber 60e.

[0093] In the device Y, after the plasma treatment process and the film forming process, the laminated film X as the workpiece film W passes through the connecting chambers C5 and C6 and reaches the winding chamber R2, where it is wound up by the winding roller 52.

[0094] In this manner, a long laminate film X can be produced.

[0095] In laminate film X, as described above, in the C1s spectrum at an analysis depth of 25 atom% carbon element ratio in X-ray photoelectron spectroscopy in the thickness direction H of inorganic layer 20 from the side opposite to substrate film 10 toward substrate film 10, the intensity Icc of the peak derived from C--C bonds, the intensity Ico of the peak derived from C--O bonds, and the intensity Icoo of the peak derived from O=C--O bonds satisfy (Ico+Icoo) / Icc≧0.5. This indicates a strong chemical interaction between substrate film 10 and inorganic layer 20. Specifically, this indicates that a relatively large number of chemical bonds are formed between substrate film 10 and inorganic layer 20 at the boundary region (interface and its vicinity) between substrate film 10 and inorganic layer 20 via CO- and O=C-- moieties of the resin component derived from substrate film 10. By forming inorganic layer 20 after performing oxygen-LAICP treatment on the surface of substrate film 10 as described above, such a boundary region can be formed, thereby improving the adhesion of the inorganic layer to substrate film 10. This reduces the content of particles such as nanosilica particles in the surface layer of the base film 10 on the inorganic layer 20 side, thereby reducing the manufacturing cost of the laminated film X.

[0096] Therefore, the laminated film X can ensure adhesion of the inorganic layer 20 to the base film 10 while suppressing production costs. [Example]

[0097] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. The specific numerical values ​​of the blending amounts (contents), physical property values, parameters, etc. described below can be substituted for the upper limits (numerical values ​​defined as "equal to or less than") or lower limits (numerical values ​​defined as "equal to or more than") of the corresponding blending amounts (contents), physical property values, parameters, etc. described in the above-mentioned "Description of the Invention."

[0098] Example 1 The laminated film of Example 1 was produced by carrying out the following steps in order.

[0099] First, a hard coat layer was formed on one side of a triacetyl cellulose (TAC) film as a resin film to prepare a substrate film (cured resin layer formation process). Specifically, 100 parts by mass (solid content equivalent) of a butyl acetate solution of UV-curable acrylic urethane resin (product name "Luxidia 17-806", solid content concentration 80% by mass, manufactured by DIC Corporation), 5 parts by mass of a photopolymerization initiator (product name "Omnirad 907", manufactured by IGM Resins), 0.03 parts by mass of a leveling agent (product name "GRANDIC PC4100", manufactured by DIC Corporation), and butyl acetate as a solvent were mixed to prepare a first resin composition with a solid content concentration of 75% by mass. Next, cyclopentanone was added as an additional solvent to the first resin composition to prepare a second resin composition with a solid content concentration of 50% by mass. Meanwhile, a long TAC film (length 100 m, width 340 mm, thickness 40 μm) was prepared. Next, a second resin composition was applied to one side of the TAC film to form a coating film. Next, this coating film was dried by heating and then cured by ultraviolet irradiation. This resulted in a 5 μm-thick hard coat (HC) layer being formed on the TAC film. The heating temperature was 100°C, and the heating time was 60 seconds. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. 2 In this manner, a TAC film with an HC layer was prepared as a substrate film.

[0100] Next, a plasma treatment process and a subsequent film-forming process were performed on the base film while the base film was transported in a vacuum using a roll-to-roll method (roll-to-roll process). An apparatus (first apparatus) capable of performing roll-to-roll processes on a workpiece film was used for the plasma treatment process and film-forming process. The first apparatus includes a payout chamber, a plasma treatment chamber, a film-forming chamber, and a winding chamber. The payout chamber, plasma treatment chamber (first plasma treatment), film-forming chamber, and winding chamber are arranged in this order and are connected to each other. The payout chamber includes a payout roller. A roll of the base film was set on the payout roller as the workpiece film. The plasma treatment chamber includes a temperature-adjustable transport roller (transport roller 53 in FIG. 4) and four low-inductance antennas (LA71 in FIG. 5 and FIG. 6) covered by cover blocks (cover block 73 in FIG. 6), as shown in FIG. 5 and FIG. 6. Each low-inductance antenna has an extension (extension 71a in FIG. 5) parallel to the substrate film. The four low-inductance antennas have an extension length d1 of 88 mm, a maximum length d2 (length of the extension) of 100 mm, a separation distance d3 of 112 mm, a center-to-center distance d4 of 290 mm, and a center-to-center distance d5 of 280 mm (FIGS. 5 and 6). Each low-inductance antenna is electrically connected to a high-frequency power source (RF power source, frequency 13.56 MHz) via an impedance matcher outside the plasma processing chamber. The separation distance d' between the substrate film traveling within the plasma processing chamber and the cover block is 100 mm. The deposition chamber is a sputtering deposition chamber and includes a deposition roller (deposition roller 54 in FIG. 4) and first and second sputtering chambers (sputtering chambers 60a and 60b in FIG. 4). Each sputtering chamber is a partitioned space within the deposition chamber. The first and second sputtering chambers are arranged in this order along the circumferential direction of the deposition roller and in the running direction of the substrate film. Each sputtering chamber is equipped with a cathode arranged opposite the deposition roller. Each sputtering chamber is connected to a required number of second lines (not shown) equipped with flow rate control valves for introducing gas into the chamber. The winding chamber is equipped with a winding roller.

[0101] In the roll-to-roll process, the HC surface (first side) of the base film was plasma treated in the plasma treatment chamber (plasma treatment step). The running speed of the base film (film running speed) was 1.0 m / min. The temperature of the temperature-controlled transport roller was -8°C. The plasma treatment conditions were as follows:

[0102] The ultimate vacuum level of the plasma processing chamber is 1.0 x 10 -4 After evacuating the inside of the apparatus until the pressure reached 0.5 Pa, oxygen gas was introduced into the plasma treatment chamber, and the pressure inside the plasma treatment chamber was adjusted to 0.5 Pa. By applying high frequency power of 5.0 kW to the four low inductance antennas using a high frequency power supply, inductively coupled plasma of the oxygen-containing gas was formed around the antennas (the surface of the HC layer of the base film was treated with this plasma).

[0103] In the film-forming chamber, an ITO layer and an SiO2 layer were sequentially formed on the substrate film after plasma treatment (film-forming process). Specifically, while the substrate film was cooled and transported by the film-forming roll in the film-forming chamber, an ITO layer was formed on the HC layer of the substrate film in the first sputtering chamber, and an SiO2 layer was formed on the ITO in the second sputtering chamber. The film-forming temperature (temperature of the film-forming roll) was set to -8°C. More specifically, the process is as follows.

[0104] In the first sputtering chamber, a 5 nm thick ITO layer was formed as the first inorganic layer by sputtering (ITO layer formation step). In this step, the film formation chamber was maintained at a vacuum level of 1.0×10 -4 After the first sputtering chamber was evacuated to a vacuum of 0.3 Pa, argon was introduced as an inert gas into the first sputtering chamber, and the pressure inside the first sputtering chamber was set to 0.3 Pa. A sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 10 mass %) was used as the target. A DC power supply was used as the power source for applying voltage to the target, and the discharge power was set to 1.0 kW.

[0105] In the second sputtering chamber, a 20 nm thick SiO2 layer was formed as the second inorganic layer by reactive sputtering (SiO2 layer formation process). In this process, after the 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 0.3 Pa. The amount of oxygen introduced per 100 volume parts of argon introduced into the second sputtering chamber was 30 volume parts. A Si target was used as the target. A MF-AC power supply (60 kHz) was used as the power source for applying voltage to the target. The discharge power was 3.0 kW.

[0106] In this manner, a laminated film was produced in Example 1. The laminated film in Example 1 includes a substrate film with an HC layer, and an inorganic layer (ITO layer / SiO2 layer) on the HC layer. The surface of the HC layer of the substrate film of the laminated film of Example 1 was plasma-treated. This plasma treatment was a treatment by inductively coupled plasma using an oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna (oxygen-LAICP treatment).

[0107] Comparative Example 1 First, an HC layer was formed on one surface of a TAC film in the same manner as in the cured resin layer forming step in Example 1. This gave a base film (TCA film / HC layer).

[0108] Next, a plasma treatment process and a subsequent film formation process were performed on the substrate film while the substrate film was transported in a vacuum using a roll-to-roll method (roll-to-roll process). A second device capable of performing roll-to-roll processes on workpiece films was used for the plasma treatment and film formation processes. The second device had the same configuration as the first device, except that it had a second plasma treatment chamber instead of the first plasma treatment chamber. The second plasma treatment chamber had a pair of flat electrodes for generating plasma: a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304). The pair of flat electrodes were spaced 50 mm apart and arranged parallel to the substrate film passing through the second plasma treatment chamber. The anode electrode was located 35 mm away from the substrate film passing through the plasma treatment chamber and was grounded outside the plasma treatment chamber. The cathode electrode was positioned facing the HC layer surface of the substrate film and was electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. Each electrode facing the base film has a length of 110 mm in the film running direction and a length of 430 mm in the width direction.

[0109] In the roll-to-roll process, the HC surface (first side) of the substrate film was plasma treated (bombardment treatment) in the second plasma treatment chamber. The running speed of the substrate film (film running speed) was 1.0 m / min. The plasma treatment conditions were as follows:

[0110] The ultimate vacuum of the second plasma processing chamber is 1.0 x 10 -4 After evacuating the chamber to a vacuum of 0.5 Pa, argon was introduced into the second plasma treatment chamber, and the pressure inside the plasma treatment chamber was set to 0.5 Pa. A capacitively coupled plasma (CCP) was generated by applying 700 W of power between the planar electrodes using a high-frequency power supply. In this plasma environment, the surface of the HC layer of the substrate film was bombarded with argon ions (Ar-BB treatment).

[0111] In the film formation chamber, an ITO layer and an SiO2 layer were formed in sequence on the plasma-treated substrate film in the same manner as described above in relation to Example 1.

[0112] In this way, a laminated film of Comparative Example 1 was produced. The laminated film of Comparative Example 1 includes a substrate film with an HC layer, and an inorganic layer (ITO layer / SiO2 layer) on the HC layer. The surface of the HC layer of the base film of the laminated film of Comparative Example 1 was plasma-treated. This plasma treatment was an ion bombardment treatment (Ar-BB treatment) using capacitively coupled plasma with argon-containing gas.

[0113] <X-ray photoelectron spectroscopy analysis> The depth profile of element composition ratio (atom %) (element composition ratio according to depth) was measured by X-ray photoelectron spectroscopy for the inorganic layers in each of the laminate films of Example 1 and Comparative Example 1. Specifically, the results are as follows.

[0114] The sample for analysis was prepared by cutting out a piece of 10 mm x 10 mm from the center of the width direction of the laminated film. An X-ray photoelectron spectrometer (product name "KRATOS ULTRA2", manufactured by Shimadzu Corporation) was used for the analysis. In the analysis, ion etching of the inorganic layer from the side opposite the substrate film and X-ray photoelectron spectroscopy (XPS) under the following conditions were repeated alternately. For ion etching, Ar gas cluster ions (Ar n + ) was used. In this analysis, the carbon element ratio gradually increased as the analysis position in the thickness direction of the inorganic layer increased. In this analysis, narrow scan analysis of the C1s spectrum was performed at a depth position (first depth position) where the carbon element ratio was 25 atom %, and narrow scan analysis of the C1s spectrum was performed at a depth position (second depth position) where the carbon element ratio was 55 atom %.

[0115] [XPS conditions] Excitation X-ray source: Monochrome AI Kα X-ray Setting:700μm×300μm(5mA,75W) Photoelectron take-off angle: 90° to the sample surface Neutralization conditions: Use of a neutralization gun and an Ar ion gun (neutralization mode) Bond energy correction: The peak due to the CC bond in the C1s spectrum is corrected to 285.0 eV

[0116] Based on the results of the narrow-scan analysis, the intensity of the peak at 285 eV (Icc) due to the C-C bond, the intensity of the peak at 286.5 eV (Ico) due to the C=O bond, the intensity of the peak at 288 eV (Ioc) due to the C=O bond, and the intensity of the peak at 289 eV (Icoo) due to the O=C-O bond were calculated for each depth position. The intensities Icc, Ico, Ioc, and Icoo at the first depth position, the value V1 of (Ico + Icoo) / Icc as the first ratio, and the value Ioc / (Icc + Ico + Icoo) are shown in Table 1. The intensities Icc, Ico, Ioc, and Icoo at the second depth position, the value V3 of (Ico + Icoo) / Icc as the third ratio, and the value Ioc / (Icc + Ico + Icoo) are also shown in Table 1. The ratio (V1 / V3) of the value V1 of the first ratio equation to the value V3 of the third ratio equation is also shown in Table 1. FIG. 7 shows the C1s spectrum at a depth position where the carbon element ratio is 25 atom % in the inorganic layer of the laminate film of Example 1. FIG. 8 shows the C1s spectrum at a depth position where the carbon element ratio is 25 atom % in the inorganic layer of the laminate film of Comparative Example 1. In each spectrum, the horizontal axis represents the binding energy (eV) of the photoelectrons observed by XPS, and the vertical axis represents the normalized emission intensity (normalized intensity). In FIGS. 7 and 8, the positions where the binding energies are 285 eV, 286.5 eV, 288 eV, and 289 eV are indicated by dashed lines.

[0117] <Adhesion> The laminated films of Example 1 and Comparative Example 1 were subjected to the following first and second tests to examine the adhesion of the inorganic layer.

[0118] First test: First, the substrate film side of the laminated film was fixed to a glass plate. Next, the inorganic layer of the laminated film on the glass plate was irradiated with light at a temperature of 85°C, a relative humidity of 45%, and an irradiation intensity (integrated illuminance from 290 nm to 450 nm) of 150 mW / cm. 2 The test was carried out using an Iwasaki Electric Co., Ltd. "Eye Super UV Tester SUV-W161" and was conducted under the conditions of (1) above for 32.5 hours.

[0119] Second test: First, 11 parallel first incisions (1 mm apart) extending linearly in a first direction and 11 parallel second incisions (1 mm apart) extending linearly in a second direction perpendicular to the first direction were made with a cutter knife in the inorganic layer and adhesive layer of the laminate film on the glass plate after the first test, forming 100 grids. Next, isopropyl alcohol was continuously dripped at 2 mL / min over the 100 grid areas of the laminate film, while a polyester wiper (trade name "Anticon Gold", manufactured by Sanplatec Co., Ltd.) was slid over the area with a wiper contact surface of 20 mm x 20 mm, a load of 1.5 kg / 20 mm, a sliding speed of 50 mm / sec, and 1,000 reciprocations. Next, 0.25 mm of the 100 grids were removed. 2 The number of squares where the above peeling occurred was counted, and the counted number was then divided by 100 to calculate the peeling rate (%).

[0120] A peeling rate of 5% or less was evaluated as "good", and a peeling rate of more than 5% was evaluated as "poor". The results are shown in Table 1. The number of squares where peeling occurred in the laminated film of Example 1 was 0. The number of squares where peeling occurred in the laminated film of Comparative Example 1 was 82.

[0121] [evaluation] In the laminate film of Example 1, in the C1s spectrum of the inorganic layer at an analysis depth of a carbon element ratio of 25 atom% in X-ray photoelectron spectroscopy, the intensity Icc of the peak derived from C-O bonds, the intensity Ico of the peak derived from C-O bonds, and the intensity Icoo of the peak derived from O=C-O bonds satisfied the relationship (Ico + Icoo) / Icc ≥ 0.5, and the value of this formula was 0.72. This indicates that in the boundary region between the substrate film and the inorganic layer (the interface and its vicinity), a relatively large number of chemical bonds are formed between the substrate film and the inorganic layer via the C-O and O=C-O moieties of the resin component derived from the substrate film. Therefore, the laminate film of Example 1 ensured adhesion of the inorganic layer.

[0122] In contrast, in the laminate film of Comparative Example 1, in the C1s spectrum of the inorganic layer at an analysis depth of a carbon element ratio of 25 atom% in X-ray photoelectron spectroscopy, the peak intensity Icc derived from C-O bonds, the peak intensity Ico derived from C-O bonds, and the peak intensity Icoo derived from O=C-O bonds did not satisfy (Ico+Icoo) / Icc≧0.5, and the value of the same formula was 0.46. This indicates that the chemical bonds formed between the substrate film and the inorganic layer via the C-O moieties and O=C-O moieties of the resin component derived from the substrate film in the boundary region between the substrate film and the inorganic layer (the interface and its vicinity) were significantly fewer than in Example 1. Therefore, the laminate film of Comparative Example 1 could not ensure adhesion of the inorganic layer.

[0123] [Table 1] [Explanation of symbols]

[0124] X Laminated Film H thickness direction D plane direction 10 Base film 10a 1st page 10b 2nd side 11 Resin film 12 Cured resin layer 20 Inorganic layer 21 Adhesion layer 22a, 22c High refractive index layer 22b, 22d Low refractive index layer

Claims

1. A laminated film comprising a base film and an inorganic layer on the base film, A laminate film, wherein in a C1s spectrum at an analysis depth with a carbon element ratio of 25 atom %, obtained by X-ray photoelectron spectroscopy in a thickness direction of the inorganic layer from the opposite side to the base film toward the base film, the intensity Icc of a peak at 285 eV derived from a C—C bond, the intensity Ico of a peak at 286.5 eV derived from a C—O bond, and the intensity Icoo of a peak at 289 eV derived from an O═C—O bond satisfy (Ico+Icoo) / Icc≧0.

50.

2. 2. The laminate film according to claim 1, wherein in the C1s spectrum, the intensity Ioc of the peak at 288 eV derived from a C=O bond, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy Ioc / (Icc+Ico+Icoo)≦0.

01.

3. 2. The laminate film according to claim 1, wherein in a C1s spectrum obtained by X-ray photoelectron spectroscopy at an analysis depth with a carbon element ratio of 55 atom%, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy (Ico+Icoo) / Icc≧0.

80.

4. In the C1s spectrum of the X-ray photoelectron spectroscopy at an analysis depth with a carbon element ratio of 55 atom %, the intensity Ioc of a peak at 288 eV derived from a C═O bond, the intensity Icc, the intensity Ico, and the intensity Icoo satisfy Ioc / (Icc+Ico+Icoo)≦0.

01. The laminated film according to claim 1 .

5. The laminated film according to claim 1 , wherein the inorganic layer contains at least one element selected from the group consisting of In, Si, Cr, and Nb.

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