Laminated film

Abstract

The invention relates to a laminated film. This laminated film (X) is provided with a base film (11), a cured resin layer (12) on the base film (11), and an inorganic layer (20) on the cured resin layer (12). In a Raman spectrum obtained by Raman spectrum analysis on the inorganic material layer (20) side of the laminated film (X), the ratio of the peak intensity I2 in the range of 1625-1635 cm <-1 > derived from a C = C bond to the peak intensity I1 in the range of 1455-1465 cm <-1 > derived from a C-H bond is 1.66 or less.

Description

Technical Field

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

[0002] From the viewpoints of weight reduction and high functionality of electronic products, various composite materials in which an organic material and an inorganic material are compounded have been developed. As the composite material, for example, a laminated film including a base film made of an organic material and an inorganic layer on the base film is known. In the manufacturing process of the above laminated film, for example, before forming the inorganic layer on the base film, the surface of the base film is subjected to plasma treatment in order to remove stains and moisture on the surface of the base film. Removing stains and moisture from the surface of the base film helps to improve the adhesion of the inorganic layer formed on the surface to the base film. Techniques related to such laminated films are described, for example, in Patent Document 1 below.

[0003] Patent Document 1 describes a laminated film as an antireflection film. The laminated film includes a base film, a hard coat (HC) layer on the base film, and an antireflection layer as an inorganic layer on the HC layer. The HC layer contains nano-silica particles. Accordingly, the HC layer has surface irregularities on the antireflection layer side. According to Patent Document 1, the surface irregularities of the HC layer improve the adhesion of the antireflection layer to the base film.

[0004] However, the price of nano-silica particles is high, and the manufacturing cost of the laminated film increases.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022-65437 Summary of the Invention

[0008] The present invention provides a laminated film that can suppress the manufacturing cost and ensure the adhesion of the inorganic layer to the base film with a cured resin layer.

[0009] The present invention [1] includes a laminated film including a base film, a cured resin layer on the base film, and an inorganic layer on the cured resin layer. In a Raman spectrum obtained by performing Raman spectroscopy on the inorganic layer side in the laminated film, the ratio of the peak intensity I2 in the range of 1625 to 1635 cm －1 derived from the C═C bond to the peak intensity I1 in the range of 1455 to 1465 cm －1 derived from the C−H bond is 1.66 or less.

[0010] The present invention [2] includes the laminated film according to the above [1], wherein the ratio is 1.20 or more.

[0011] The present invention [3] includes the laminated film according to [1] or [2] above, wherein the cured resin layer contains a silicone-based compound.

[0012] The present invention [4] includes the laminated film according to any one of [1] to [3] above, wherein an antifouling layer is further provided on the inorganic layer.

[0013] Advantages of the Invention

[0014] In the laminated film of the present invention, as described above, in the Raman spectrum obtained by performing Raman spectroscopic analysis on the inorganic layer side, the peak intensity I2 in the range of 1625 - 1635 cm －1 derived from the C═C bond and the ratio (I2 / I1) of the peak intensity I1 in the range of 1455 - 1465 cm －1 derived from the C−H bond are 1.66 or less. This indicates a strong chemical interaction between the cured resin layer on the substrate film and the inorganic layer. Specifically, it indicates that there are many chemical bonds formed between the cured resin layer and the inorganic layer through the part where a bonding bond is generated by the C═C bond portion of the resin in the cured resin layer (the part where one bond in the carbon-carbon double bond is cut to generate a bonding bond). The more the above-mentioned chemical bonds, the higher the adhesion of the inorganic layer to the cured resin layer. Therefore, the content of particles such as nano-silica particles in the cured resin layer can be reduced. Thereby, the manufacturing cost of the laminated film can be reduced. Therefore, according to the laminated film of the present invention, the manufacturing cost can be suppressed and the adhesion of the inorganic layer to the substrate film with the cured resin layer can be ensured. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is a schematic cross-sectional view of an embodiment of the laminated film of the present invention.

[0016] Figure 2 represents Figure 1 the case where the laminated film shown has a laminated structure of a bonding layer and an antireflection layer as the inorganic layer.

[0017] Figure 3 represents Figure 2 the case where the laminated film shown further has an antifouling layer on the inorganic layer.

[0018] Figures 4A to 4C represents Figure 3 an example of the manufacturing method of the laminated film shown. Figure 4A represents the cured resin layer forming step, Figure 4B represents the plasma treatment step, Figure 4C represents the film forming step.

[0019] Figure 5 is for implementing Figure 1Schematic configuration diagram of the apparatus for the plasma treatment step and the film formation step in an example of the method for manufacturing the laminated film shown.

[0020] Figure 6 It shows Figure 5 A perspective view showing the positional relationship between the low inductance antenna and the substrate film in the plasma treatment chamber shown.

[0021] Figure 7 It shows Figure 5 A cross-sectional view showing the positional relationship between the low inductance antenna and the substrate film in the plasma treatment chamber shown.

[0022] Figure 8 It shows the Raman spectra obtained by measuring the Raman spectra of the laminated films of Example 1 and Comparative Example 1.

[0023] Explanation of reference numerals

[0024] X: laminated film; H: thickness direction; D: plane direction; 10: substrate film with a cured resin layer; 10a: first surface; 10b: second surface; 11: substrate film; 12: cured resin layer; 20: inorganic layer; 21: adhesion layer; 22: antireflection layer; 22a, 22c: high refractive index layers; 22b, 22d: low refractive index layers; 30: antifouling layer. Detailed description of the invention

[0025] The laminated film X of an embodiment of the present invention is as Figure 1 shown, and includes a substrate film 11, a cured resin layer 12 on the substrate film 11, and an inorganic layer 20 on the cured resin layer 12. The cured resin layer 12 is in contact with the substrate film 11. The inorganic layer 20 is in contact with the cured resin layer 11. The laminated film X extends in a direction (plane direction D) orthogonal to the thickness direction H.

[0026] The substrate film 11 and the cured resin layer 12 form a substrate film 10 with a cured resin layer. The substrate film 10 with a cured resin layer has a first surface 10a on the side of the inorganic layer 20 and a second surface 10b on the side opposite to the first surface 10a. The cured resin layer 12 forms the first surface 10a, and the substrate film 11 forms the second surface 10b. The inorganic layer 20 is disposed on one surface in the thickness direction H of the substrate film 10 with a cured resin layer.

[0027] The base film 11 is an element for ensuring the strength of the laminated film X. The base film 11 is, for example, a flexible transparent resin film. Examples of the material of the base film 11 include polyester resins, polyolefin resins, cellulose resins, acrylic resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, and polystyrene resins. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of the cellulose resin include triacetyl cellulose (TAC). These materials can be used alone or in combination of two or more. From the viewpoints of transparency and strength, the material of the base film 11 is preferably at least one selected from the group consisting of polyester resins, polyolefin resins, and cellulose resins, and more preferably at least one selected from the group consisting of PET, COP, and TAC. In addition, the base film 11 does not contain particles in the present embodiment.

[0028] From the viewpoint of ensuring the strength of the laminated film X, the thickness of the base film 11 is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. From the viewpoint of ensuring the operability of the base film 10 with the cured resin layer in the process described later in the roll-to-roll method, the thickness of the base film 11 is preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less. From the viewpoint of balancing the above-mentioned strength and operability in the laminated film X, the thickness of the laminated film X is preferably 10 to 200 μm, more preferably 20 to 150 μm, and further preferably 30 to 100 μm. In addition, in order to ensure the transportability and operability in the process of the roll-to-roll method, a carrier film (not shown) can be adhered to the second surface 10b of the base film 11.

[0029] From the viewpoint of ensuring good transparency in the laminated film X, the total light transmittance (JIS K7375: 2008) of the base film 11 is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more. The total light transmittance of the base film 11 is, for example, 100% or less.

[0030] 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. As the functional layer, for example, a hard coat can be mentioned. The hard coat is a layer that is not easily scratched on the exposed surface ( Figure 1 the upper surface) of the inorganic layer 20.

[0031] 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 can 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.

[0032] Examples of the curable resin include ultraviolet curable resin and thermosetting resin. The curable resin is preferably ultraviolet curable resin. When the curable resin is ultraviolet curable resin, the curable resin can be cured without high-temperature heating, so that the manufacturing efficiency of the laminated film X can be improved.

[0033] The cured resin layer 12 preferably contains a silicone-based compound. That is, the curable resin composition preferably contains a silicone-based compound. When the cured resin layer 12 contains a silicone-based compound, the effect (effect of improving the adhesion of the inorganic layer 20) achieved by performing the following-described LAICP treatment on the surface of the cured resin layer 12 can be effectively improved. The silicone-based compound has a tendency to segregate on the surface of the cured resin layer 12 in the cured resin layer 12. Therefore, the effect of performing the LAICP treatment on the surface of the cured resin layer 12 is effectively improved.

[0034] Examples of the silicone-based compound include silicone-based leveling agents. Examples of the silicone-based leveling agents include alkyl-modified silicone, polyether-modified silicone, polyester-modified silicone, and dimethylpolysiloxane. Examples of commercially available products of the silicone-based leveling agents include "Polyflow LE-303", "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", and "Polyflow KL-404" manufactured by Kyoeisha Chemical Co., Ltd. Examples of commercially available products of the silicone-based leveling agents also include "MEGAFAC S-333" manufactured by DIC Corporation. Examples of commercially available products of the silicone-based leveling agents also include "KP-323", "KP-326", "KP-341", "KP-104", and "KP-110" manufactured by Shin-Etsu Chemical Co., Ltd. Examples of commercially available products of the silicone-based leveling agents also include "LP-7001", "LP-7002", "8032ADDITIVE", and "57ADDITIVE" manufactured by Toray DowCorning.

[0035] From the viewpoint of ensuring the above-described effects of LAICP treatment, the content of the silicone-based compound in the cured resin layer 12 is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.02 parts by mass or more, still more preferably 0.03 parts by mass or more, and even more preferably 0.04 parts by mass or more, based on 100 parts by mass of the curable resin. From the viewpoint of suppressing a decrease in the adhesion of the inorganic layer 20 caused by an excessive content of the silicone-based compound in the cured resin layer 12, the content of the silicone-based compound in the cured resin layer 12 is preferably 0.2 parts by mass or less, more preferably 0.15 parts by mass or less, further preferably 0.12 parts by mass or less, still more preferably 0.1 parts by mass or less, and even more preferably 0.08 parts by mass or less, based on 100 parts by mass of the curable resin. From the viewpoint of achieving both ensuring the above-described effects of LAICP treatment and suppressing the above-described decrease in the adhesion of the inorganic layer 20, the content of the silicone-based compound in the cured resin layer 12 is preferably 0.005 to 0.2 parts by mass, more preferably 0.01 to 0.15 parts by mass, further preferably 0.02 to 0.12 parts by mass, still more preferably 0.03 to 0.1 parts by mass, and even more preferably 0.04 to 0.08 parts by mass, based on 100 parts by mass of the curable resin.

[0036] The inorganic oxide particles in the cured resin layer 12 are preferably fewer. The fewer the inorganic oxide particles in the cured resin layer 12, the more the scattering of light incident on the laminated film X caused by the particles in the cured resin layer 12 can be suppressed, and in addition, the manufacturing cost of the laminated film X can be reduced. Examples of the material of the inorganic oxide particles include silica, alumina, titanium dioxide, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. The content of the inorganic oxide particles in the cured resin layer 12 is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, still more preferably 1% by mass or less, even more preferably 0.5% by mass or less, further preferably 0.2% by mass or less, particularly preferably 0.1% by mass or less, and particularly preferably 0.0% by mass.

[0037] From the viewpoint of ensuring the functions of the cured resin layer 12, the thickness of the cured resin layer 12 is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. Further, from the viewpoint of suppressing cracks in the cured resin layer 12, the thickness of the cured resin layer 12 is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less. Suppressing cracks in the cured resin layer 12 contributes to achieving good transportability of the substrate film 10 with the cured resin layer in the roll-to-roll process described later. From the viewpoint of achieving both ensuring the functions of the cured resin layer 12 and suppressing cracks, the thickness of the cured resin layer 12 is preferably 1 to 30 μm, more preferably 3 to 25 μm, and still more preferably 5 to 20 μm.

[0038] From the viewpoint of ensuring good transparency of the laminated film X, the total light transmittance (JIS K 7375: 2008) of the substrate film 10 with the cured resin layer is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. The total light transmittance of the substrate film 10 with the cured resin layer is, for example, 100% or less.

[0039] The first surface 10a is, for example, a surface treated with plasma. The plasma treatment is preferably a treatment (oxygen-LAICP treatment) using an oxygen-containing gas and realized by inductively coupled plasma generated by applying high-frequency power to a low-inductance antenna. Specifically, the oxygen-LAICP treatment performed on the first surface 10a is described in the manufacturing method of the laminated film X below.

[0040] Examples of the inorganic layer 20 include an antireflection layer and a conductive layer. The antireflection layer is a layer having antireflectivity for suppressing the reflection intensity of external light. The conductive layer is a layer having conductivity. The inorganic layer 20 may be other layers. Further, the inorganic layer 20 may be a composite layer including an antireflection layer and other layers. The inorganic layer 20 may be a composite layer including a conductive layer and other layers. The case where the inorganic layer 20 has a laminated structure of an adhesion layer 21 and an antireflection layer 22 is shown in Figure 2 .

[0041] The adhesion layer 21 is disposed on one surface of the base film 10 with the cured resin layer in the thickness direction H. Specifically, the adhesion layer 21 is disposed on the first surface 10a of the base film 10 with the cured resin layer. The adhesion layer 21 is in contact with the base film 10 with the cured resin layer. The adhesion layer 21 is a layer that improves the adhesion of the antireflection layer 22 to the base film 10 with the cured resin layer. As the material of the adhesion layer 21, for example, metals such as silicon, indium, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, palladium, niobium, etc., alloys of two or more of these metals, and oxides of these metals can be cited. From the viewpoint of balancing the adhesion to both the base film 10 with the cured resin layer and the antireflection layer 22, and the transparency of the adhesion layer 21, the material of the adhesion layer 21 is preferably indium tin composite oxide (ITO) or silicon oxide (SiOx). The silicon oxide as the material of the adhesion layer 21 is preferably SiOx with an oxygen content less than the stoichiometric composition, and more preferably SiOx with x being 1.2 or more and 1.95 or less.

[0042] From the viewpoint of ensuring the adhesion force between the base film 10 with the cured resin layer and the antireflection layer 22, the thickness of the adhesion layer 21 is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 3 nm or more. From the viewpoint of ensuring the transparency of the adhesion layer 21, the thickness of the adhesion layer 21 is preferably 10 nm or less, more preferably 7 nm or less, and further preferably 5 nm or less. From the viewpoint of balancing the above adhesion force and transparency, the thickness of the adhesion layer 21 is preferably 1 to 10 nm, more preferably 2 to 7 nm, and further preferably 3 to 5 nm.

[0043] The antireflection layer 22 is disposed on one surface of the adhesion layer 21 in the thickness direction H. The antireflection layer 22 is in contact with the adhesion layer 21. The antireflection layer 22 is a layer that suppresses the reflection intensity of external light (antireflection property).

[0044] In the present embodiment, the antireflection layer 22 sequentially 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 the thickness direction H from the adhesion layer 21 side. The high refractive index layer 22a is in contact with the adhesion 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 are layers with relatively large refractive indices, and the low refractive index layers 22b and 22d are layers with relatively small refractive indices. In the antireflection layer 22, for example, the intensity of the reflected light is attenuated by the interference between the reflected lights at multiple interfaces of the high refractive index layers 22a and 22c and the low refractive index layers 22b and 22d. The above interference effect can be exhibited by adjusting the optical film thickness (the product of the refractive index and thickness of the film) of each layer of the antireflection layer 22.

[0045] The high refractive index layer 22a (the first high refractive index layer) is formed 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 niobium oxide (Nb2O5), titanium oxide, zirconium oxide, indium tin composite oxide (ITO), and antimony tin composite oxide (ATO). From the viewpoint of achieving both high refractive index and low absorbance 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 further, for example, 55 nm or less.

[0046] The low refractive index layer 22b (the first low refractive index layer) is formed 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 silicon dioxide (SiO2) and magnesium fluoride. From the viewpoint of achieving both low refractive index and low absorbance 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 further, for example, 70 nm or less.

[0047] The high refractive index layer 22c (the second high refractive index layer) is formed 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 film thickness of the high refractive index layer 22c is, for example, 60 nm or more, and further, for example, 330 nm or less.

[0048] The low refractive index layer 22d (the second low refractive index layer) is formed 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, and silicon dioxide is preferred. The optical film thickness of the low refractive index layer 22d is, for example, 100 nm or more, and further, for example, 160 nm or less.

[0049] The total thickness of the antireflection layer 22 from the high refractive index layer 22a to the low refractive index layer 22d is preferably 180 nm or more, more preferably 200 nm or more, still more preferably 220 nm or more, and further, preferably 320 nm or less, more preferably 280 nm or less, still more preferably 250 nm or less. In the present embodiment, the total thickness of the antireflection layer 22 means 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 more than the above lower limit value, the function of attenuating the intensity of reflected light can be ensured in the antireflection layer 22. When the total thickness of the antireflection layer 22 is equal to or less than the above upper limit value, cracks in the antireflection layer 22 can be suppressed.

[0050] When the inorganic layer 20 includes a conductive layer, the conductive layer is formed of a conductive material. Examples of the conductive material include metals and metal oxides. Examples of the metal include copper, silver, gold, nickel, chromium, and alloys thereof. Examples of the metal oxide include indium-containing conductive oxides and antimony-containing conductive oxides. Examples of the indium-containing conductive oxide 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 the antimony-containing conductive oxide include antimony tin composite oxide (ATO).

[0051] In the Raman spectrum obtained by performing Raman spectroscopic analysis on the inorganic layer 20 side of the laminate film X, the peak intensity in the range of 1455 to 1465 cm －1 derived from the C−H bond is defined as I1, and the peak intensity in the range of 1625 to 1635 cm －1 derived from the C═C bond is defined as I2. The method of Raman spectroscopic analysis is specifically described in the examples below.

[0052] The ratio (I2 / I1) of the intensity I2 to the intensity I1 in the above Raman spectrum of the laminate film X is 1.66 or less, preferably 1.63 or less, and more preferably 1.60 or less. When the ratio (I2 / I1) is equal to or less than the above upper limit value, the adhesion of the inorganic layer 20 to the cured resin layer 12 can be sufficiently ensured. The ratio (I2 / I1) is preferably 1.20 or more, more preferably 1.30 or more, and further preferably 1.40 or more. From the viewpoint of ensuring the functions and properties (such as high hardness) of the cured resin layer 12, it is preferable that the ratio (I2 / I1) is equal to or more than the above lower limit value. Considering both the adhesion of the inorganic layer 20 and the functions and properties of the cured resin layer 12 as described above, the ratio (I2 / I1) is preferably 1.20 to 1.66, more preferably 1.30 to 1.63, and further preferably 1.40 to 1.60.

[0053] Figure 3 An example in which the laminate film X further includes an antifouling layer 30 on the inorganic layer 20 is shown. Specifically, Figure 3 the laminate film X has an inorganic layer 20 including an adhesion layer 21 and an antireflection layer 22 on a base film 10 with a cured resin layer, and an antifouling layer 30 on the inorganic layer 20.

[0054] The antifouling layer 30 is a layer having an antifouling function. The antifouling layer 30 is disposed on the low refractive index layer 22d. The antifouling layer 30 has a surface 31 on the side opposite to the antireflection layer 22. The antifouling function of the antifouling layer 30 includes the function of suppressing the adhesion of contaminants such as finger grease to the film exposed surface when using the laminate film X, and the function of easily removing the adhered contaminants.

[0055] As the material of the antifouling layer 30, for example, an organic fluorine compound can be cited. As the organic fluorine compound, an alkoxysilane compound having a perfluoropolyether group is preferably used. As the alkoxysilane compound having a perfluoropolyether group, for example, a compound represented by the following general formula (1) can be cited.

[0056] R 1 -R 2 -X-(CH2) m -Si(OR 3 )3……(1)

[0057] In the general formula (1), R 1 represents a linear or branched fluorinated alkyl group (the number of carbon atoms is, for example, 1 or more and 20 or less) in which one or more hydrogen atoms in the alkyl group are replaced by fluorine atoms, and preferably represents a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0058] R 2 represents a structure having a repeating structure containing at least one perfluoropolyether (PFPE) group, and preferably represents a structure having a repeating structure containing two PFPE groups. As the repeating structure of the PFPE group, for example, a repeating structure of a linear PFPE group and a repeating structure of a branched PFPE group can be cited. As the repeating structure of the linear PFPE group, for example, a structure represented by -(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). As the repeating structure of the branched PFPE group, for example, a structure represented by -(OC(CF3)2) p - and a structure represented by -(OCF2CF(CF3)CF2) p - can be cited. As the repeating structure of the PFPE group, a repeating structure of a linear PFPE group is preferably cited, and more preferably, -(OCF2) p - and -(OC2F4) p - are cited.

[0059] R 3 represents an alkyl group having 1 or more and 4 or less carbon atoms, and preferably represents a methyl group.

[0060] X represents an ether group, a carbonyl group, an amino group, or an amide group, and preferably represents an ether group.

[0061] m represents an integer of 1 or more. In addition, m preferably represents an integer of 20 or less, more preferably represents an integer of 10 or less, and further preferably represents an integer of 5 or less.

[0062] Among such alkoxysilane compounds having a perfluoropolyether group, the compound represented by the following general formula (2) is preferably used.

[0063] CF3-(OCF2) q -(OC2F4) r -O-(CH2)3-Si(OCH3)3……(2)

[0064] 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.

[0065] In addition, the alkoxysilane compound having a perfluoropolyether group can be used alone or in combination of two or more.

[0066] In the present embodiment, the antifouling layer 30 is a film (dry coating film) formed by a dry coating method. Examples of the dry coating method include sputtering, vacuum evaporation, and CVD. The antifouling layer 30 is preferably a dry coating film, more preferably a vacuum evaporation film.

[0067] The material of the antifouling layer 30 contains an alkoxysilane compound having a perfluoropolyether group, and the constitution in which the antifouling layer 30 is a dry coating film (preferably a vacuum evaporation film) is suitable for ensuring a high bonding strength of the antifouling layer 30 to the substrate of the antifouling layer 30, and thus is suitable for ensuring the peel resistance of the antifouling layer 30. The high peel resistance of the antifouling layer 30 contributes to maintaining the antifouling function of the antifouling layer 30.

[0068] From the viewpoint of ensuring the peel resistance of the antifouling layer 30, the thickness of the antifouling layer 30 is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, particularly preferably 7 nm or more. In addition, it is preferably 25 nm or less, more preferably 20 nm or less, further preferably 18 nm or less.

[0069] Figures 4A to 4C An example of the manufacturing method of the laminated film X is shown. This manufacturing method includes a cured resin layer forming step ( Figure 4A ), a plasma treatment step ( Figure 4B ), and a film forming step ( Figure 4C ).

[0070] In the cured resin layer forming step, as Figure 4AAs shown, a cured resin layer 12 is formed on a long strip-shaped base material film 11. Thus, a base material film 10 with a cured resin layer is obtained. The cured resin layer 12 can be formed by applying the above-mentioned curable resin composition on the base material film 11 to form a coating film and then curing the coating film. The curable resin composition may contain other components other than the above-mentioned curable resin as needed. As other components, for example, solvents can be cited. As solvents, for example, butyl acetate, ethyl acetate, toluene, and cyclopentanone can be cited. When the curable resin composition contains an ultraviolet curable resin as the curable resin, the curable resin composition preferably contains a photoinitiator. When the curable resin composition contains a thermosetting resin as the curable resin, the curable resin composition preferably contains a thermal polymerization initiator.

[0071] When the curable resin composition contains a solvent, after applying the curable resin composition, the coating film on the base material film 11 is dried. The drying temperature is, for example, 50°C or higher, and further, for example, 120°C or lower. The drying time is, for example, 10 seconds or longer, and further, for example, 10 minutes or shorter.

[0072] When the curable resin composition contains an ultraviolet curable resin, the coating film on the base material film 11 is cured by ultraviolet irradiation. As the light source for ultraviolet irradiation, for example, a high-pressure mercury lamp and an LED lamp can be cited. The cumulative irradiation light amount of ultraviolet rays is, for example, 100 mJ / cm 2 above, and further, for example, 500 mJ / cm 2 or less.

[0073] When the curable resin composition contains a thermosetting resin, the coating film on the base material film 11 is cured by heating. The heating temperature is, for example, 100°C or higher, and further, for example, 150°C or lower. The heating time is, for example, 10 seconds or longer, and further, for example, 10 minutes or shorter.

[0074] As described above, a long strip-shaped base material film 10 with a cured resin layer can be produced. In the present embodiment, a roll of a long strip-shaped base material film 10 with a cured resin layer is prepared. Specifically, the first surface 10a of the base material film 10 with a cured resin layer is curled so as to face the radially inner side of the roll.

[0075] In this manufacturing method, then, in a reduced-pressure atmosphere, while conveying the base material film 10 with a cured resin layer as a workpiece film W in a roll-to-roll manner, a plasma treatment process and a film-forming process are sequentially performed. Figure 5The device Y shown is an example of a device for performing a plasma processing step and a film forming step. The device Y includes an extraction chamber R1, a winding chamber R2, a connection chamber C1, a plasma processing chamber C2, a connection chamber C3, a film forming chamber C4 (first film forming chamber), a connection chamber C5, and a film forming chamber C6 (second film forming chamber).

[0076] The extraction chamber R1 includes an extraction roll 51 for extracting the workpiece film W. The extraction roll 51 is equipped with a roll of a long strip-shaped base film 10 with a cured resin layer as the workpiece film W. In addition, a prescribed number of guide rolls G for guiding the workpiece film W are provided in the extraction chamber R1.

[0077] The winding chamber R2 includes a winding roll 52 for winding the workpiece film W. A prescribed number of guide rolls G for guiding the workpiece film W are provided in the winding chamber R2.

[0078] The connection chamber C1 is arranged following the extraction chamber R1 in the traveling direction of the workpiece film W and is arranged before the plasma processing chamber C2. A prescribed number of guide rolls G for guiding the workpiece film W are provided in the connection chamber C1. The connection chamber C1 is connected to a vacuum pump (not shown) and is configured to be able to adjust the chamber pressure. When the device Y is operating, the pressure in the connection chamber C1 is maintained at a prescribed pressure between the pressure in the extraction chamber R1 and the pressure in the plasma processing chamber C2. Thereby, the pressure difference between the extraction chamber R1 and the plasma processing chamber C2 is ensured.

[0079] The plasma processing chamber C2 is arranged between the connection chamber C1 and the connection chamber C3 in the traveling direction of the workpiece film W. In the plasma processing chamber C2, a plasma processing step is performed as described later. In addition, the plasma processing chamber C2 is connected to a first pipeline L1 with a flow rate regulating valve for introducing gas into the chamber.

[0080] In the present embodiment, the plasma processing chamber C2 includes a plurality of low inductance antennas (LA) 71. A low inductance antenna refers to an antenna having a low inductance of 7.5 μH or less and capable of generating inductively coupled plasma by applying high-frequency power. In the present embodiment, as Figure 6 and Figure 7 shown, the LA71 are arranged in the interior of the plasma processing chamber C2 in a state of being supported by a holder 72 and covered by a cover block 73 ( Figure 6 omitted in the figure).

[0081] The plurality of LA71 are arranged in a manner of being arranged in the traveling direction of the base film 10 with a cured resin layer and in a direction orthogonal to the traveling direction (the width direction of the base film 10 with a cured resin layer). The holder 72 is a vacuum flange. As Figure 7As shown, LA71 is fixed to the holder 72 through the field through 74. As Figure 5 shown, the holder 72 is installed in the opening 75 provided in the wall portion of the plasma processing chamber C2. Specifically, the holder 72 is installed in the opening 75 in a state where a sealing member (not shown) is sandwiched between the wall portion of the plasma processing chamber C2 and the holder 72. Outside the plasma processing chamber C2, LA71 is electrically connected to a high-frequency power supply (RF power supply) through an impedance matcher. Such LA71 is formed of a conductor. Examples of the conductor include copper and silver. The conductor is preferably copper. LA71 may be covered with an insulator. Examples of the insulator include glass and quartz.

[0082] The cover block 73 includes a block main body 73A and a plurality of partition plates 73B. The block main body 73A has a plurality of accommodation spaces 73a. Each accommodation space 73a accommodates one LA71. The partition plates 73B are arranged so as to enclose the accommodation spaces 73a. The inside of the accommodation space 73a is a sealed space. In the cover block 73, the block main body 73A is made of, for example, aluminum. Examples of the aluminum include aluminum A5052. The partition plates 73B are formed of an insulating material. Examples of the insulating material include quartz and glass. In addition, the separation distance d' (shown in Figure 7 ) between the base film 10 with the cured resin layer traveling in the plasma processing chamber C2 and the cover block 73 is, for example, 50 to 200 mm. Such a cover block 73 does not excessively reduce the plasma conversion efficiency generated by applying power to LA71, helps to avoid damage and contamination of LA71 caused by plasma processing, and in addition, helps to suppress damage to the base film 10 with the cured resin layer that has been plasma processed.

[0083] As Figure 6As shown, LA71 has an open-loop shape in this embodiment. The open-loop shape of LA71 is beneficial to reducing the inductance of LA71. Therefore, based on the open-loop shaped LA71, it is possible to suppress the increase in voltage caused by the increase in the power applied to LA71. Thus, it is possible to suppress abnormal discharges during the plasma treatment described later. By suppressing abnormal discharges, damage to the substrate film 10 with a cured resin layer that has undergone plasma treatment can be suppressed. Specifically, LA71 has a U shape with two free ends. Each LA71 is fixed to the holder 72 in such a way that the two free ends are arranged along the width direction of the substrate film 10 with a cured resin layer. In addition, in this embodiment, LA71 has an extension portion 71a on the side opposite to the two free ends. The extension portion 71a extends parallel to the substrate film 10 with a cured resin layer passing through the plasma treatment chamber C2. The extension portion 71a extends along the width direction of the substrate film 10 with a cured resin layer. Each extension portion 71a may also extend along the traveling direction of the substrate film 10 with a cured resin layer (four LA71s can be arranged in this way). The length of the extension portion 71a is, for example, 50 to 150 mm ( Figure 6 An example is shown where the length of the extension portion 71a is the same as the maximum length d2 of LA71 described later). LA71 may have a coil shape instead of an open-loop shape.

[0084] LA71 extends from the holder 72 toward the substrate film 10 with a cured resin layer. LA71 preferably extends in a direction perpendicular to the holder 72. The protruding length d1 of LA71 protruding from the holder 72 is, for example, 30 to 150 mm. The maximum length d2 of LA71 in the plane direction of the substrate film 10 with a cured resin layer is, for example, 50 to 150 mm. The separation distance d3 between LA71 and the substrate film 10 with a cured resin layer (shown in Figure 7)For example, it is 50 to 200 mm. The protruding length d1 and the separation distance d3 are preferably the same. The ratio of the separation distance d3 to the protruding length d1 (d3 / d1) is, for example, 0.5 to 3.5. The number (number of columns) of LA71s arranged separately in the traveling direction of the base material film 10 with the cured resin layer can be 1, 2, or 3 according to the traveling speed of the base material film 10 with the cured resin layer (i.e., the plasma treatment time), and can be 4 or more if necessary. The center-to-center distance d4 between adjacent LA71s in the traveling direction of the base material film 10 with the cured resin layer is, for example, 100 to 500 mm. The center-to-center distance d5 between adjacent LA71s in the width direction of the base material film 10 with the cured resin layer 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 base material film 10 with the cured resin layer can be controlled. 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 center points of the extending portions 71a of the four LA71s preferably form a square as vertices. According to such a group of LA71s, high-density plasma can be generated. As the LA71, for example, a high-frequency antenna for plasma generation described in Japanese Patent Laid-Open No. 2013-258153 can be used.

[0085] In this embodiment, the plasma processing chamber C2 further includes a conveying roller 53. The conveying roller 53 is a main guiding roller for conveying the workpiece film W in the plasma processing chamber C2. The conveying roller 53 has a temperature adjustment function capable of heating or cooling the workpiece film W. That is, the conveying roller 53 is a conveying roller with a temperature adjustment function. When the device Y is operating, the conveying roller 53 contacts the second surface 10b of the base material film 10 with the cured resin layer as the workpiece film W and conveys the base material film 10 with the cured resin layer. The above-mentioned LA71 is arranged opposite to the conveying roller 53. According to the device Y having such a plasma processing chamber C2, in the plasma processing step S2, the base material film 10 with the cured resin layer is cooled or heated by the conveying roller 53 with a temperature adjustment function that contacts the base material film 10 with the cured resin layer, and the plasma treatment can be performed on the base material film 10 with the cured resin layer. By controlling the temperature of the base material film 10 with the cured resin layer, the thermal deformation of the base material film 10 with the cured resin layer can be suppressed, and in addition, the influence of the thermal deformation on the conveyance of the base material film 10 with the cured resin layer can be suppressed.

[0086] The connection chamber C3 is arranged immediately following the plasma processing chamber C2 in the traveling direction of the workpiece film W, and is arranged before the film forming chamber C4. A predetermined number of guide rollers G for guiding the workpiece film W are provided in the connection chamber C3. The connection chamber C3 is connected to a vacuum pump (not shown) and is configured to be able to adjust the chamber pressure. When the apparatus Y is operating, the pressure in the connection chamber C3 is maintained at a predetermined pressure between the pressure in the plasma processing chamber C2 and the pressure in the film forming chamber C4. Thereby, the pressure difference between the plasma processing chamber C2 and the film forming chamber C4 is ensured.

[0087] The film forming chamber C4 is arranged immediately following the connection chamber C3 in the traveling direction of the workpiece film W. In addition, the film forming chamber C4 is connected to a vacuum pump (not shown) and is configured to be able to adjust the interior to a predetermined degree of vacuum. In the film forming chamber C4, as will be described later, a film forming process from the high refractive index layer 22a to the low refractive index layer 22d is performed.

[0088] In the present embodiment, the film forming chamber C4 is a sputtering film forming chamber. The film forming chamber C4 includes a film forming roller 54 and a plurality of sputtering chambers 60 (sputtering chambers 60a to 60e) (the case where the number of sputtering chambers 60 is exemplarily shown as 5). The film forming roller 54 is the main guide roller for conveying the workpiece film W in the film forming chamber C4. The film forming roller 54 has a temperature adjustment function capable of heating or cooling the workpiece film W. The sputtering chamber 60 is a space partitioned in the film forming chamber C4. The plurality of sputtering chambers 60 are arranged along the circumferential direction of the film forming roller 54. Each sputtering chamber 60 opens toward the film forming roller 54. A cathode 61 is provided in the sputtering chamber 60. A target (not shown), which is a film forming material supply member, is arranged on the cathode 61. The target is arranged on the cathode so as to face the film forming roller 54. Each sputtering chamber 60 is provided with a power source (not shown) for applying a voltage to the target to generate glow discharge. As the power source, for example, a DC power source, an AC power source, an MF power source, an RF power source, and an MF-AC power source can be cited. The MF-AC power source refers to an AC power source with a frequency band of several kHz to several MHz. Each sputtering chamber 60 is connected to a second pipeline (not shown) with a flow rate regulating valve for introducing a required amount of gas into the chamber. In addition, a predetermined number of guide rollers G for guiding the workpiece film W are provided in the film forming chamber C4.

[0089] The connection chamber C5 is arranged between the connection chamber C4 and the film forming chamber C6 in the traveling direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided in the connection chamber C5.

[0090] The film forming chamber C6 is disposed between the connection chamber C5 and the winding chamber R2 in the traveling direction of the workpiece film W. In the present embodiment, the film forming chamber C6 is a vacuum evaporation chamber. The film forming chamber C6 includes a material holding portion 62 and a valve (not shown) capable of controlling the opening degree for adjusting the evaporation amount. The film forming chamber C6 is connected to a vacuum pump (not shown) and is configured to be able to adjust the indoor pressure. A predetermined number of guide rollers G for guiding the workpiece film W are provided in the film forming chamber C6. In such a film forming chamber C6, the film forming process of the antifouling layer 30 is carried out.

[0091] A film forming material supply member (not shown) is disposed in the material holding portion 62 so as to face the workpiece film W conveyed in the film forming chamber C6. In the material holding portion 62, as a unit for heating the film forming material supply member, a resistance heating unit may be built in, a high-frequency induction heating unit may be built in, or an electron beam heating unit may be provided.

[0092] Through the above device Y, the plasma treatment process and the film forming process are carried out in sequence. Specifically, as described below.

[0093] The workpiece film W is drawn out from the extraction chamber R1. After the workpiece film W is drawn out from the extraction chamber R1, it passes through the connection chamber C1, the plasma treatment chamber C2, the connection chamber C3, the film forming chamber C4, the connection chamber C5, and the film forming chamber C6 in sequence, and is wound in the winding chamber R2. The traveling speed of the workpiece film W is, for example, 0.5 m / minute or more, and further, for example, 5 m / minute or less. In addition, a series of pipelines from the extraction chamber R1 to the winding chamber R2 are not opened to the atmosphere in the middle, and the processes under a reduced pressure atmosphere are carried out in this pipeline. The reduced pressure atmosphere is preferably under vacuum. Vacuum means preferably under a reduced pressure atmosphere of 7 Pa or less.

[0094] As Figure 4B As shown, the plasma treatment process is carried out in the plasma treatment chamber C2. In the plasma treatment process, the first surface 10a of the base film 10 with the cured resin layer is subjected to plasma treatment in a reduced pressure atmosphere in the plasma treatment chamber C2 (chamber). In the present embodiment, the plasma treatment is a treatment (oxygen-LAICP treatment) realized by inductively coupled plasma of an oxygen-containing gas generated by applying high-frequency power to LA71. Specifically, as described below.

[0095] Oxygen is supplied to the inside of the plasma treatment chamber C2 during plasma treatment via the first pipeline L1. In addition to oxygen, an inert gas may also be supplied to the inside of the plasma treatment chamber C2. As the inert gas, for example, argon, krypton, and xenon can be cited. In addition, the gas in the plasma treatment chamber C2 may contain other gases other than the inert gas. As the other gas, for example, nitrogen, hydrogen, and water vapor can be cited.

[0096] 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, further preferably 80% by volume or more, still 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 at the above lower limit value or more, high-density oxygen plasma can be generated. Thereby, the first surface 10a of the substrate film 10 with the cured resin layer can be effectively highly activated. According to such oxygen-LAICP treatment, specifically, on the surface (the first surface 10a) of the cured resin layer 12, the high-density oxygen plasma acts on the C═C bond portion of the resin, and a portion (hanging bond site) where one bond of the double bond between carbons is cut off to generate a bonding bond is efficiently formed.

[0097] The pressure (the first pressure) in the plasma processing chamber C2 during plasma processing is preferably 0.1 Pa or more, more preferably 0.2 Pa or more, further preferably 0.3 Pa or more. In addition, it is preferably 7 Pa or less, more preferably 5 Pa or less, further preferably 3 Pa or less. When the first pressure is at the above lower limit value or more, during plasma processing, a plasma environment with a density sufficient to perform surface modification treatment on the first surface 10a of the substrate film 10 with the cured resin layer can be formed in the plasma processing chamber C2. When the first pressure is at the above upper limit value or less, during plasma processing, thermal damage to the first surface 10a caused by overly high-density plasma can be suppressed, and in addition, excessive roughening of the first surface 10a can be suppressed. Suppressing excessive roughening helps to suppress a decrease in the mechanical strength of the first surface 10a. The first pressure can be adjusted by the supply amount of oxygen into the plasma processing chamber C2.

[0098] In plasma treatment, the frequency of the high-frequency power applied to LA71 is preferably 1 MHz or more, more preferably 5 MHz or more, and further preferably 10 MHz or more. In addition, it is preferably 100 MHz or less, more preferably 80 MHz or less, and further preferably 60 MHz or less. When the frequency is above the lower limit value, in plasma treatment, the plasma current density can be increased and the plasma discharge can be stabilized. When the frequency is below the upper limit value, the antenna potential can be suppressed, and thus, damage to the substrate film 10 with the cured resin layer by the plasma can be suppressed. In addition, the high-frequency power is preferably 0.1 kW or more, more preferably 0.3 kW or more, and further preferably 1.0 kW or more. In addition, it is preferably 10 kW or less, more preferably 8 kW or less, and further preferably 6 kW or less. When the high-frequency power is above the lower limit value, in plasma treatment based on inductively coupled plasma, a high-density plasma environment can be formed in the plasma treatment chamber C2. When the high-frequency power is below the upper limit value, excessive damage to the substrate film 10 with the cured resin layer by the plasma can be suppressed.

[0099] In the plasma treatment step, the plasma current density at an intermediate position between LA71 and the substrate film 10 with the cured resin layer is preferably 0.5 mA / cm 3 or more, more preferably 0.8 mA / cm 3 or more, and further preferably 1.2 mA / cm 3 or more. In addition, it is preferably 10 mA / cm 3 or less, more preferably 5 mA / cm 3 or less, and further preferably 2 mA / cm 3 or less. Plasma treatment based on the inductively coupled method using a low-inductance antenna can achieve a higher plasma current density than plasma treatment using the capacitively coupled method (for example, a plasma density about 100 times higher can be achieved). When the plasma current density is above the lower limit value, in plasma treatment, sufficient plasma-oxidized particles can be ensured in the plasma treatment chamber C2, and the first surface 10a of the substrate film 10 with the cured resin layer can be appropriately surface-modified. When the plasma current density is below the upper limit value, damage to the first surface 10a by overly dense plasma-oxidized particles can be suppressed in plasma treatment. As a method for adjusting the plasma current density, for example, adjusting the introduction amount of oxygen into the plasma treatment chamber C2, adjusting the frequency of the high-frequency power in the high-frequency power supply, and adjusting the magnitude of the applied power can be cited.

[0100] In the film-forming step ( Figure 4C)In [the above process], first in the film formation chamber C4, and then in the plasma treatment process, an adhesion layer 21 and an antireflection layer 22 are sequentially formed on the first surface 10a of the substrate film 10 with a cured resin layer under a reduced pressure atmosphere. The reduced pressure atmosphere is preferably under vacuum.

[0101] In the sputtering method, a sputtering gas (inert gas) is introduced into each sputtering chamber 60 via a second pipeline, and a negative voltage is applied to the target (film forming material) disposed on the cathode 61 in the sputtering chamber 60. Thereby, glow discharge is generated to ionize gas atoms, and the gas ions are made 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. As the sputtering gas, for example, argon, krypton, and xenon can be cited.

[0102] When the film forming material is a metal oxide, the sputtering method can be a reactive sputtering method. In the reactive sputtering method, in addition to the sputtering gas, oxygen (reactive gas) is also introduced into the sputtering chamber 60. The oxygen is introduced into the sputtering chamber 60 via another second pipeline. In the reactive sputtering method, the target is formed of, for example, the metal in the metal oxides forming each layer.

[0103] In the sputtering method, the pressure (second pressure) in the sputtering chamber 60 is, for example, 0.1 to 5.0 Pa according to the type of the layer to be formed. The film forming temperature (the temperature of the workpiece film W adjusted by the film forming roller 54) is, for example, -10°C to 150°C.

[0104] In the film forming process, first, an adhesion layer 21 is formed on the substrate film 10 with a cured resin layer by the sputtering method in the sputtering chamber 60a. When forming an ITO layer as the adhesion layer 21, an ITO target is used as the target disposed on the cathode 61 in the sputtering chamber 60a. Moreover, reactive sputtering is carried out while introducing argon and oxygen into the sputtering chamber 60a (reactive sputtering is also carried out in the following sputtering methods in the sputtering chambers 60b to 60e). In this process, the material of the adhesion layer 21, which is the first layer of the inorganic layer 20, is formed on the first surface 10a including many dangling bond sites formed in the above plasma treatment process. Therefore, the adhesion layer 21 is formed on the first surface 10a with good adhesion.

[0105] Next, a high refractive index layer 22a is formed on the adhesion layer 21 by the sputtering method in the sputtering chamber 60b. When forming a Nb2O5 layer as the high refractive index layer 22a, an Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60b.

[0106] Next, a low refractive index layer 22b is formed on the high refractive index layer 22a by the sputtering method in the sputtering chamber 60c. When forming a SiO2 layer as the low refractive index layer 22b, a Si target is used as the target disposed on the cathode 61 in the sputtering chamber 60c.

[0107] Next, a high refractive index layer 22c is formed on the low refractive index layer 22b by sputtering in the sputtering chamber 60d. When forming an Nb2O5 layer as the high refractive index layer 22c, an Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60d.

[0108] Next, a low refractive index layer 22d is formed on the high refractive index layer 22c by sputtering in the sputtering chamber 60e. When forming an SiO2 layer as the low refractive index layer 22d, a Si target is used as the target disposed on the cathode 61 in the sputtering chamber 60e.

[0109] Film formation process ( Figure 4C ) In this process, an antifouling layer 30 is further formed in the film formation chamber C6. In this step, in the film formation chamber C6, the antifouling layer 30 is formed on the low refractive index layer 22d in the workpiece film W by vacuum evaporation as a dry coating method. Specifically, in a state where the inside of the film formation chamber C6 is decompressed to a vacuum by the operation of a vacuum pump, a film formation material supply member (not shown) disposed in the material holding portion 62 is heated to a predetermined temperature, and vacuum evaporation is performed.

[0110] In the apparatus Y, after the plasma treatment process and the film formation process, the laminated film X as the workpiece film W reaches the winding chamber R2 and is wound by the winding roller 52.

[0111] As described above, a long laminated film X can be manufactured. In the case where the laminated film X does not have the antifouling layer 30, the above-mentioned laminated film X can be manufactured by not performing the step in the film formation chamber C6 in the above manufacturing process.

[0112] In the laminated film X, as described above, in the Raman spectrum obtained by performing Raman spectroscopy on the inorganic layer 20 side, the peak intensity I2 in the range of 1625 - 1635 cm －1 derived from the C═C bond and the peak intensity I1 in the range of 1455 - 1465 cm －1 derived from the C−H bond have a ratio (I2 / I1) of 1.66 or less. This indicates a strong chemical interaction between the cured resin layer 12 and the inorganic layer 20 on the base material film 11. Specifically, it indicates that there are more chemical bonds formed between the cured resin layer 12 and the inorganic layer 20 through the part where a bonding bond is generated by the C═C bond portion of the resin in the cured resin layer 12 (the part where one bond in the carbon-carbon double bond is cut to generate a bonding bond). The more of the above chemical bonds, the higher the adhesion of the inorganic layer 20 to the cured resin layer 12. Therefore, the content of particles such as nano-silica particles in the cured resin layer 12 can be reduced. As a result, the manufacturing cost of the laminated film X can be reduced.

[0113] Therefore, according to the laminated film X, the manufacturing cost can be suppressed and the adhesion of the inorganic layer 20 to the base film 10 with the cured resin layer can be ensured.

[0114] [Examples]

[0115] The following examples specifically illustrate the present invention. However, the present invention is not limited to the examples. In addition, the specific numerical values such as the compounding amounts (contents), physical property values, parameters, etc. described below can be replaced with the upper limits (values defined as "below", "less than") or lower limits (values defined as "above", "exceeding") of the corresponding compounding amounts (contents), physical property values, parameters, etc. described in the above "Detailed Embodiments".

[0116] [Example 1]

[0117] The following steps were sequentially performed to produce the laminated film of Example 1.

[0118] First, a hard coat as a cured resin layer was formed on one side of a triacetyl cellulose (TAC) film as a base film (cured resin layer forming step). Specifically, first, 80 parts by mass (in terms of solid content) of a UV-curable urethane acrylate resin (trade name "UT-7314", manufactured by Mitsubishi Chemical Corporation), 20 parts by mass (in terms of solid content) of a polyfunctional acrylate mainly composed of pentaerythritol triacrylate (trade name "Viscoat #300", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.5 parts by mass of a photoinitiator (trade name "Omnirad127D", manufactured by BASF Corporation), and 0.06 parts by mass of a leveling agent (trade name "Polyflow LE-303", a silicone-based leveling agent, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixed solution. Then, by adding a mixed solvent of butyl acetate and cyclopentanone (CPN) (mass ratio of butyl acetate to CPN was 70:30), the solid content concentration of the mixed solution was adjusted to 40 mass%. Thus, a first resin composition was prepared. On the other hand, a long strip of TAC film (trade name "KC8UAW", thickness 80 μm, manufactured by Konica Minolta) was prepared. Then, the first resin composition was coated on one side of the TAC film to form a coating film. Then, the coating film was dried by heating and then cured by UV irradiation. Thus, a hard coat (HC) layer with a thickness of 12 μm was formed on the TAC film. The heating temperature was set at 80°C and the heating time was set at 1 minute. During UV irradiation, a high-pressure mercury lamp was used as the light source, and UV light with a wavelength of 365 nm was irradiated on the coating film, and the cumulative irradiation light amount was set at 300 mJ / cm 2 . As described above, a TAC film with an HC layer was produced as a base film with a cured resin layer.

[0119] Next, in a roll-to-roll manner under vacuum, while conveying a substrate film with a cured resin layer as a workpiece film, a plasma treatment process for the film and a subsequent film formation process (roll-to-roll process) were carried out. In the plasma treatment process and the film formation process, a device (first device) capable of performing a roll-to-roll process on the workpiece film was used. The first device includes an extraction chamber, a plasma treatment chamber (first plasma treatment), a first film formation chamber, a second film formation chamber, and a winding chamber. The extraction chamber, the plasma treatment chamber, the first film formation chamber, the second film formation chamber, and the winding chamber are arranged and connected in sequence. The extraction chamber is provided with an extraction roller. A roll of the above-mentioned substrate film with a cured resin layer is installed on the extraction roller as a workpiece film. The plasma treatment chamber is provided with a conveying roller with a temperature adjustment function ( Figure 5 the conveying roller 53 in Figure 6 and Figure 7 the covered block shown in Figure 7 the cover block 73 in Figure 6 and Figure 7 covers four low-inductance antennas ( Figure 6 the extension part 71a in Figure 6 and Figure 7 ). Each low-inductance antenna has an extension part ( Figure 5 the extension part 71a in Figure 5 parallel to the workpiece film. Among the four low-inductance antennas, the protruding length d1 is 88 mm, the maximum length d2 (the length of the extension part) 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 ( Figure 5 the material holding part 62 in

[0120] ). Each low-inductance antenna is electrically connected to a high-frequency power supply (RF power supply, frequency 13.56 MHz) through an impedance matcher outside the plasma treatment chamber. The separation distance d' between the workpiece film and the cover block traveling in the plasma treatment chamber is 100 mm. The first film formation chamber is a sputtering film formation chamber and is provided with a film formation roller (

[0121] The inside of the apparatus is evacuated to a vacuum until the ultimate vacuum of the plasma processing chamber reaches 1.0×10 －4 Pa, and then oxygen is introduced into the plasma processing chamber, and the pressure in the plasma processing chamber is set to 1.5 Pa. High-frequency power of 2 kW is applied to four low-inductance antennas by a high-frequency power supply, thereby forming an inductively coupled plasma of oxygen-containing gas around the antennas (the surface of the cured resin layer of the workpiece film is processed by this plasma). The plasma current density at the intermediate position between the low-inductance antenna and the workpiece film is 1.3 mA / cm 3 . The plasma current density was measured by a Langmuir probe for plasma measurement.

[0122] In the first film formation chamber, a bonding 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 are sequentially formed on the workpiece film (substrate film with a cured resin layer) after plasma treatment. Specifically, the workpiece film is conveyed while being cooled by a film formation roller in the first film formation chamber, and a bonding layer is formed on the cured resin layer of the workpiece film in the first sputtering chamber, a first high refractive index layer is formed on the bonding layer in the second sputtering chamber, a first low refractive index layer is formed on the first high refractive index layer in the third sputtering chamber, a second high refractive index layer is formed on the first low refractive index layer in the fourth sputtering chamber, and a second low refractive index layer is formed on the second high refractive index layer in the fifth sputtering chamber (these layers form an inorganic layer). The film formation temperature (the temperature of the film formation roller) is set to -8°C. More specifically, as described below.

[0123] In the first sputtering chamber, an ITO layer with a thickness of 4 nm is formed as a bonding layer by reactive sputtering (bonding layer formation process). In this process, the inside of the first film formation chamber is evacuated to a vacuum until the ultimate vacuum reaches 1.0×10 －4 Pa, and then argon as an inert gas and oxygen as a reactive gas are introduced into the first sputtering chamber, and the pressure in the first sputtering chamber is set to 0.2 Pa. The oxygen introduction amount is set to 10 volume parts with respect to 100 volume parts of argon introduced into the first sputtering chamber. As the target, a sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 30 mass%) is used. As the power supply for applying voltage to the target, an MF-AC power supply is used (the same applies to the second to fifth sputtering chambers described later). The discharge power is set to 4.3 kW.

[0124] In the second sputtering chamber, a Nb2O5 layer (refractive index 2.33) with a thickness of 14 nm was formed as the first high refractive index layer by reactive sputtering. In this process, after the first film-forming 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. With respect to 100 volume parts of argon introduced into the second sputtering chamber, the oxygen introduction amount was set to 5 volume parts. As the target, a Nb target was used. The discharge power was set to 13 kW.

[0125] In the third sputtering chamber, a SiO2 layer (refractive index 1.46) with a thickness of 28 nm was formed as the first low refractive index layer by reactive sputtering. In this process, after the first film-forming 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. With respect to 100 volume parts of argon introduced into the third sputtering chamber, the oxygen introduction amount was set to 30 volume parts. As the target, a Si target was used. The discharge power was set to 25 kW.

[0126] In the fourth sputtering chamber, a Nb2O5 layer (refractive index 2.33) with a thickness of 105 nm was formed as the second high refractive index layer by reactive sputtering. In this process, after the first film-forming 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. With respect to 100 volume parts of argon introduced into the fourth sputtering chamber, the oxygen introduction amount was set to 13 volume parts. As the target, a Nb target was used. The discharge power was set to 27.5 kW.

[0127] In the fifth sputtering chamber, a SiO2 layer (refractive index 1.46) with a thickness of 84 nm was formed as the second low refractive index layer by reactive sputtering. In this process, after the first film-forming 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. With respect to 100 volume parts of argon introduced into the fifth sputtering chamber, the oxygen introduction amount was set to 30 volume parts. As the target, a Si target was used. The discharge power was set to 20.5 kW.

[0128] In the second film-forming chamber, an antifouling layer was formed on the second low refractive index layer. Specifically, by vacuum evaporation using a perfluoropolyether group-containing alkoxysilane compound as the evaporation source, an antifouling layer with a thickness of 8 nm was formed on the second low refractive index layer. The evaporation source was the solid component obtained from "KY1903-1" manufactured by Shin-Etsu Chemical Co., Ltd. (perfluoropolyether group-containing alkoxysilane compound represented by the above general formula (2), solid component concentration 20 mass%). In addition, the heating temperature of the evaporation source in the vacuum evaporation method was set to 260 °C.

[0129] The laminated film of Example 1 was produced as described above. The laminated film of Example 1 includes a substrate film with an HC layer, an inorganic layer (adhesion layer / antireflection layer) on the HC layer, and an antifouling layer on the inorganic layer. In the substrate film with an HC layer in the laminated film of Example 1, the surface of the HC layer was subjected to plasma treatment. This plasma treatment was achieved by inductively coupled plasma using an oxygen-containing gas generated by applying high-frequency power to a low-inductance antenna (oxygen-LAICP treatment). In addition, an adhesion layer, an antireflection layer, and an antifouling layer on the substrate film with an HC layer form a multilayer film.

[0130] 〔Examples 2 to 5 and Comparative Examples 1 and 2〕

[0131] In the curable resin layer forming step, the amount and type of the leveling agent used were changed as shown in Table 1. Except for this, the laminated films of Examples 2 to 5 and Comparative Examples 1 and 2 were produced in the same manner as the laminated film of Example 1. The leveling agent used in Example 3 was "MEGAFACS-333" (silicone-based leveling agent) manufactured by DIC Corporation. The leveling agent used in Comparative Example 2 was "MEGAFACF-556" (fluorine-based leveling agent) manufactured by DIC Corporation.

[0132] 〔Comparative Example 3〕

[0133] First, an HC layer was formed on one side of a TAC film in the same manner as in the curable resin layer forming step of Example 1 to obtain a substrate film with a curable resin layer (TAC film with an HC layer).

[0134] Next, in a roll-to-roll manner under vacuum, while conveying the substrate film with a curable resin layer as a workpiece film, a plasma treatment step for this film and a subsequent film forming step (roll-to-roll process) were performed. In the plasma treatment step and the film forming step, a second apparatus capable of performing a roll-to-roll process on the workpiece film was used. The second apparatus includes a second plasma treatment chamber instead of the first plasma treatment, and has the same configuration as the first apparatus except for this. The second plasma treatment chamber includes a cathode electrode and an anode electrode as a pair of planar electrodes for generating plasma (both are rectangular electrodes made of SUS304). The pair of planar electrodes are spaced 50 mm apart and are arranged parallel to the workpiece film passing through the second plasma treatment chamber. The anode electrode is arranged at a position 35 mm away from the workpiece film passing through the plasma treatment chamber and is grounded outside the plasma treatment chamber. The cathode electrode is arranged opposite to the surface of the HC layer of the workpiece film and is electrically connected to a high-frequency power supply (RF power supply, 13.56 MHz) through an impedance matcher. The length of each electrode opposite to the workpiece film in the film traveling direction is 110 mm, and the length in the width direction is 430 mm.

[0135] In the second plasma processing chamber, plasma processing (bombardment processing) was performed on the surface (the first surface) of the cured resin layer in the workpiece film. The traveling speed of the substrate film (film traveling speed) was set to 1.0 m / minute. The conditions for the plasma processing are as described below.

[0136] After evacuating the inside of the apparatus to a ultimate vacuum degree of 1.0×10 －4 Pa in the second plasma processing chamber, argon was introduced into the second plasma processing chamber, and the pressure in the plasma processing chamber was set to 0.5 Pa. Electric power of 500 W was applied between the planar electrodes by a high-frequency power supply, thereby generating capacitively coupled plasma (CCP). In this plasma environment, bombardment processing using argon ions (Ar-BB processing) was performed on the surface of the HC layer of the workpiece film.

[0137] In the first film-forming chamber, on the workpiece film (substrate film with a cured resin layer) after the plasma processing, a bonding layer to a second low refractive index layer were sequentially formed in the same manner as in the above process in Example 1. In the second film-forming chamber, an antifouling layer was formed on the second low refractive index layer in the same manner as in the above process in Example 1.

[0138] As described above, the laminated film of Comparative Example 3 was produced. The laminated film of Comparative Example 3 includes a substrate film with an HC layer, an inorganic layer (bonding layer / antireflection layer) on the HC layer, and an antifouling layer on the inorganic layer. In the substrate film with an HC layer in the laminated film of Comparative Example 3, the surface of the HC layer was subjected to bombardment processing using argon ions (Ar-BB processing).

[0139] 〈Raman spectroscopy analysis〉

[0140] For the inorganic layer in each of the laminated films of the examples and comparative examples, Raman spectra were obtained by Raman spectroscopy analysis. Specifically, as described below.

[0141] The specimen for analysis was prepared by cutting out a size of 10 mm×10 mm from the central portion in the width direction of the laminated film. Analysis was performed using a Raman spectroscopy apparatus (trade name “alpha300 RSA”, manufactured by WITec Corporation). The analysis was performed under the following conditions in a state where the irradiation light was focused on the hard coat surface of the laminated film. Regarding the obtained spectrum, a baseline was drawn so that the intensity I (intensity of Raman scattering) at a wave number of 2000 cm －1 was 0. Then, the peak intensity I2 in the range of 1625 - 1635 cm －1 derived from the C═C bond and the peak intensity I1 in the range of 1455 - 1465 cm －1 derived from the C-H bond were calculated. The values of the peak intensities I1, I2, and the ratio (I2 / I1) are shown in Table 1.

[0142] Figure 8 Shows the Raman spectra obtained for the laminated films of Example 1 and Comparative Example 1. Figure 8 In, the horizontal axis represents the Raman shift (cm －1 ), and the vertical axis represents the relative intensity (normalized intensity) normalized with respect to the intensity at 1460 cm －1 . The positions of the wavenumbers 1460 cm －1 and 1630 cm －1 are indicated by dashed lines. Further, Figure 8 in, the solid line spectrum is the Raman spectrum of Example 1, and the dashed line spectrum is the Raman spectrum of Comparative Example 1.

[0143] [Conditions for Raman spectroscopic analysis]

[0144] Excitation wavelength: 532 nm.

[0145] Measurement wavenumber range: 200 cm －1 to 2800 cm －1 .

[0146] Objective lens: 100×.

[0147] Detector: Electron multiplying CCD (EMCCD).

[0148] 〈Initial adhesion〉

[0149] Regarding each of the laminated films of the examples and comparative examples, the adhesion of the inorganic layer to the substrate film with the cured resin layer was investigated as follows (first adhesion test).

[0150] First, the substrate film side of the laminated film was fixed to a glass plate. Next, for the multilayer film (adhesion layer / antireflection layer / antifouling layer) in the laminated film on the glass plate, 11 parallel first cuts (2 mm interval) extending linearly in the first direction and 11 parallel second cuts (2 mm interval) extending linearly in the second direction orthogonal to the first direction were formed by a cutter, and 100 grids were formed from the first cuts and the second cuts. Next, isopropyl alcohol was continuously dropped at 2 mL / minute into the 100 grid regions in the laminated film, and a polyester wiper (trade name “ANTICON GOLD”, manufactured by SANPLATEC Co., Ltd.) was slid under the conditions of a wiper contact surface of 20 mm × 20 mm, a load of 1.5 kg / 20 mm, a sliding speed of 50 mm / second, and 1000 reciprocations. Next, the number of grids with peeling of 1 mm 2 or more in the 100 grids was counted. Next, the peeling rate (%) was calculated by dividing by 100.

[0151] Then, regarding the adhesion of the inorganic layer to the substrate film with the cured resin layer, a case where the peeling rate is 10% or less was evaluated as "excellent", a case where the peeling rate exceeded 10% and was 30% or less was evaluated as "good", a case where the peeling rate exceeded 30% and was 80% or less was evaluated as "poor", and a case where the peeling rate exceeded 80% was evaluated as "significantly poor". The evaluation results are shown in Table 1.

[0152] 〈Adhesion after weather resistance test〉

[0153] Regarding each laminated film of the examples and comparative examples, the adhesion of the inorganic layer to the substrate film with the cured resin layer was investigated as follows.

[0154] First, one side of the substrate film in the laminated film was fixed to a glass plate. Next, the multilayer film in the laminated film on the glass plate was irradiated with ultraviolet light at a temperature of 85 °C, a relative humidity of 45%, and an irradiation intensity (cumulative illuminance of 290 nm to 450 nm) of 1500 W / m 2 for 32.5 hours (to promote the weather resistance test). This test was carried out using "EYESUPER UVTESTER SUV-W161" manufactured by Iwasaki Electric Co., Ltd. After the promotion of the weather resistance test, the above-mentioned first adhesion test (second adhesion test) was carried out. Then, regarding the adhesion of the inorganic layer to the substrate film with the cured resin layer, evaluation was carried out based on the same criteria as the criteria described in the first adhesion test above. The evaluation results are shown in Table 1.

[0155] [Evaluation]

[0156] In each of the laminated films of Examples 1 to 5, in the Raman spectrum obtained by Raman spectroscopic analysis of the inorganic layer side, the peak intensity I2 in the range of 1625 to 1635 cm －1 derived from the C═C bond and the peak intensity I1 in the range of 1455 to 1465 cm －1 derived from the C−H bond had a ratio (I2 / I1) of 1.66 or less. This indicates that there are many chemical bonds formed between the cured resin layer and the inorganic layer through the part where a bonding bond is generated by the C═C bond portion of the resin in the cured resin layer in the laminated film (the part where one bond in the carbon-carbon double bond is cut to generate a bonding bond). Therefore, each of the laminated films of Examples 1 to 5 can ensure the adhesion of the inorganic layer to the substrate film with the cured resin layer.

[0157] In contrast, in each of the laminated films of Comparative Examples 1 to 3, the above ratio (I2 / I1) exceeded 1.66. This indicates that the chemical bonds formed between the cured resin layer and the inorganic layer due to the bonding bonds generated by the C═C bond portions of the resins in the cured resin layer derived from the laminated film are fewer than those in the laminated films of the Examples. Therefore, each of the laminated films of Comparative Examples 1 to 3 cannot ensure the adhesion of the inorganic layer to the base film with the cured resin layer.

[0158] [Table 1]

[0159]

[0160] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only an example and should not be construed in a limiting sense. Modifications of the present invention that are not in doubt to those skilled in the art are also included in the claims.

[0161] Industrial Applicability

[0162] The laminated film of the present invention is preferably used, for example, as an antireflection film disposed on the outer surface of an image display device such as a liquid crystal display and an organic EL display.

Claims

1. A laminated film comprising a substrate film, a cured resin layer on the substrate film, and an inorganic layer on the cured resin layer, In the Raman spectrum obtained by Raman spectroscopy analysis of the inorganic layer side in the laminated film, the wavelengths of 1625 to 1635 cm derived from the C=C bond are －1 The peak intensity I2 in the range of 1455 to 1465 cm-1 originates from the C-H bond. －1 The ratio of the peak intensity I1 within the range of is less than 1.

66.

2. The laminated film according to claim 1, wherein The ratio is 1.20 or more.

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

4. The laminated film according to any one of claims 1 to 3, wherein The inorganic layer is further provided with an antifouling layer.

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