Laminate film

Abstract

To provide a laminate film capable of securing an adhesion of an inorganic layer to a base material film having a curable resin layer while suppressing a production cost.SOLUTION: A laminate film X includes a base material film 11, a curable resin layer 12 on the base material film 11 and an inorganic layer 20 on the curable resin layer 12. In a Raman spectrum by a Raman spectroscopic analysis to an inorganic layer 20 side of the laminate film X, a ratio of an intensity I2 of a peak within a range of 1625 to 1635 cm-1 derived from C=C coupling to an intensity I1 of a peak within a range of 1455 to 1465 cm-1 derived from C-H coupling is 1.66 or lower.SELECTED DRAWING: Figure 1

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 combined have been developed. As a 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 such a laminated film, for example, before the inorganic layer is formed on the base film, the surface of the base film is plasma-treated to remove dirt and moisture on the surface of the base film. Removal of dirt 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. Technologies related to such laminated films are described, for example, in Patent Document 1 below.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 describes a laminated film as an antireflection film. This 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 nanosilica particles. Thereby, 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.

[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 the adhesion of an inorganic layer to a base film with a cured resin layer while suppressing the manufacturing cost.

Means for Solving the Problems

[0007] The present invention [1] is a laminated film including a base film, a cured resin layer on the base film, and an inorganic layer on the cured resin layer, wherein in the Raman spectrum of Raman spectroscopic analysis with respect to the inorganic layer side in the laminated film, the intensity I1 of the peak in the range of 1455 to 1465 cm -1 derived from the C-H bond, and the ratio of the intensity I2 of the peak in the range of 1625 to 1635 cm -1 derived from the C=C bond is 1.66 or less.

[0008] The present invention [2] includes the laminated film according to the above [1], wherein the ratio is 1.20 or more.

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

[0010] The present invention [4] includes the laminated film according to any one of the above [1] to [3], further including an antifouling layer on the inorganic layer.

Advantages of the Invention

[0011] In the laminated film of the present invention, as described above, in the Raman spectrum of Raman spectroscopic analysis with respect to the inorganic layer side, the intensity I1 of the peak in the range of 1455 to 1465 cm -1 derived from the C-H bond, and the intensity I2 of the peak in the range of 1625 to 1635 cm -1The ratio (I2 / I1) of the intensity I2 of the peak within the range is 1.66 or less. This indicates that the chemical interaction between the cured resin layer and the inorganic layer on the base film is strong. Specifically, it shows that there are relatively many chemical bonds formed between the cured resin layer and the inorganic layer through the part where a bond is generated from the C=C bond part that the resin in the cured resin layer had (the part where one bond of the carbon-carbon double bond is broken and a bond is generated). The greater the number of such chemical bonds, the higher the adhesion of the inorganic layer to the cured resin layer. Therefore, the content of particles such as nanosilica 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, while suppressing the manufacturing cost, the adhesion of the inorganic layer to the base film with the cured resin layer can be ensured.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

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Figure 7

Figure 8

Mode for Carrying Out the Invention

[0013] As shown in FIG. 1, the laminated film X of one embodiment of the present invention includes 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. The cured resin layer 12 is in contact with the base 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.

[0014] The base film 11 and the cured resin layer 12 form a base film 10 with a cured resin layer. The base film 10 with a cured resin layer has a first surface 10a on the inorganic layer 20 side 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 base film 11 forms the second surface 10b. The inorganic layer 20 is disposed on one surface in the thickness direction H of the base film 10 with a cured resin layer.

[0015] 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 resin, polyolefin resin, cellulose resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, and polystyrene resin. 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 may 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 resin, polyolefin resin, and cellulose resin, and more preferably at least one selected from the group consisting of PET, COP, and TAC. Further, the base film 11 does not contain particles in the present embodiment.

[0016] 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 still more preferably 30 μm or more. From the viewpoint of ensuring the handleability of the base film 10 with a cured resin layer in the roll-to-roll process described later, the thickness of the base film 11 is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less. From the viewpoint of achieving both the above strength and handleability 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 still more preferably 30 to 100 μm. Further, a carrier film (not shown) may be attached to the second surface 10b of the base film 11 to ensure the transportability and handleability in the roll-to-roll process.

[0017] The total light transmittance (JIS K 7375:2008) of the base film 11 is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more, from the viewpoint of ensuring good transparency in the laminated film X. The total light transmittance of the base film 11 is, for example, 100% or less.

[0018] 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. Examples of the functional layer include a hard coat layer. The hard coat layer is a layer that makes it difficult for scratches to be formed on the exposed surface (the upper surface in FIG. 1) of the inorganic layer 20.

[0019] 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.

[0020] Examples of the curable resin include ultraviolet curable resin and thermosetting resin. 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, so the production efficiency of the laminated film X can be improved.

[0021] 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) of the LAICP treatment described later on the surface of the cured resin layer 12 can be effectively enhanced. The silicone-based compound has a tendency to segregate on the surface of the cured resin layer 12 in the same layer. Therefore, the effect of the LAICP treatment on the surface of the cured resin layer 12 is effectively enhanced.

[0022] 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. Commercially available products of silicone-based leveling agents include, for example, "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. Commercially available products of silicone-based leveling agents also include "Megafac S-333" manufactured by DIC. Commercially available products of silicone-based leveling agents also include "KP-323", "KP-326", "KP-341", "KP-104", and "KP-110" manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available products of silicone-based leveling agents also include "LP-7001", "LP-7002", "8032 ADDITIVE", and "57 ADDITIVE" manufactured by Toray Dow Corning.

[0023] From the viewpoint of ensuring the above effects of the 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, still more preferably 0.02 parts by mass or more, even 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 due to an excessive content of the same 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, still more preferably 0.12 parts by mass or less, even 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 effects of the LAICP treatment and suppressing the above 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, still more preferably 0.02 to 0.12 parts by mass, even 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.

[0024] It is preferable that the amount of inorganic oxide particles in the cured resin layer 12 is small. The smaller the amount of inorganic oxide particles in the cured resin layer 12, the more the scattering of light incident on the laminated film X due to the particles in the cured resin layer 12 can be suppressed, and the more the manufacturing cost of the laminated film X can be reduced. Examples of the material of the inorganic oxide particles include silica, alumina, titania, 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, still more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.0% by mass.

[0025] From the viewpoint of ensuring the function 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. Also, from the viewpoint of suppressing cracking of 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 cracking of the cured resin layer 12 helps to achieve good transportability of the base film 10 with the cured resin layer in the roll-to-roll process described later. From the viewpoint of achieving both ensuring the function of the cured resin layer 12 and suppressing cracking, 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.

[0026] From the viewpoint of ensuring good transparency in the laminated film X, the total light transmittance (JIS K 7375:2008) of the base 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 base film 10 with the cured resin layer is, for example, 100% or less.

[0027] The first surface 10a is, for example, a plasma-treated surface. The plasma treatment is preferably a treatment by inductively coupled plasma using an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to a low-inductance antenna. The oxygen-LAICP treatment for the first surface 10a will be specifically described later in relation to the method for manufacturing the laminated film X.

[0028] Examples of the inorganic layer 20 include an antireflection layer and a conductive layer. The antireflection layer is a layer having antireflection properties for suppressing the reflection intensity of external light. The conductive layer is a layer having conductivity. The inorganic layer 20 may be other layers. Also, 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 FIG. 2.

[0029] The adhesion layer 21 is disposed on one surface in the thickness direction H of the base film 10 with a cured resin layer. Specifically, the adhesion layer 21 is disposed on the first surface 10a of the base film 10 with a cured resin layer. The adhesion layer 21 is in contact with the base film 10 with a cured resin layer. The adhesion layer 21 is a layer that enhances the adhesion of the antireflection layer 22 to the base film 10 with a cured resin layer. Examples of the material of the adhesion layer 21 include 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. From the viewpoint of achieving both the adhesion to both the base film 10 with a 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.

[0030] From the viewpoint of ensuring the adhesive force between the base film 10 with a 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 still more 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 still more preferably 5 nm or less. From the viewpoint of achieving both the above-mentioned adhesive force and transparency, the thickness of the adhesion layer 21 is preferably 1 to 10 nm, more preferably 2 to 7 nm, and still more preferably 3 to 5 nm.

[0031] The antireflection layer 22 is disposed on one surface in the thickness direction H of the adhesion layer 21. 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).

[0032] In this embodiment, the antireflection layer 22 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 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 and the low refractive index layer 22b are in contact with each other. The low refractive index layer 22b and the high refractive index layer 22c are in contact with each other. The high refractive index layer 22c and the low refractive index layer 22d are in contact with each other. The high refractive index layers 22a and 22c are layers with relatively high refractive indices, and the low refractive index layers 22b and 22d are layers with relatively low refractive indices. In the antireflection layer 22, for example, the intensity of the reflected light is attenuated by the interference effect between the reflected lights at a plurality of interfaces in the high refractive index layers 22a and 22c and the low refractive index layers 22b and 22d. Such an interference effect can be achieved 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.

[0033] The high refractive index layer 22a (the first high refractive index layer) is preferably made of a high refractive index material having a refractive index of 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 a high refractive index and low absorbability 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.

[0034] The low refractive index layer 22b (the first low refractive index layer) is preferably made of a low refractive index material having a refractive index of 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 a low refractive index and low absorbability 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.

[0035] 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 preferable. The optical film thickness of the high refractive index layer 22c is, for example, 60 nm or more and, for example, 330 nm or less.

[0036] 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, and silicon dioxide is preferable. The optical film thickness of the low refractive index layer 22d is, for example, 100 nm or more and, for example, 160 nm or less.

[0037] The total thickness from the high refractive index layer 22a to the low refractive index layer 22d in the antireflection layer 22 is preferably 180 nm or more, more preferably 200 nm or more, still more preferably 220 nm or more, and is 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 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 lower limit value, the function of attenuating the reflected light intensity 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, cracking of the antireflection layer 22 can be suppressed.

[0038] 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).

[0039] In the Raman spectrum of Raman spectroscopic analysis with respect to the inorganic layer 20 side in the laminated film X, 1455 to 1465 cm -1 within the range is defined as the intensity I1 of the peak derived from the C-H bond, and 1625 to 1635 cm -1 within the range is defined as the intensity I2 of the peak derived from the C═C bond. The method of Raman spectroscopic analysis is specifically as described later in the examples.

[0040] The ratio (I2 / I1) of the intensity I2 to the intensity I1 in the Raman spectrum of the laminated film X is 1.66 or less, preferably 1.63 or less, more preferably 1.60 or less. When the ratio (I2 / I1) is equal to or less than the above upper limit value, sufficient adhesion of the inorganic layer 20 to the cured resin layer 12 can be ensured. The ratio (I2 / I1) is preferably 1.20 or more, more preferably 1.30 or more, and still more preferably 1.40 or more. The fact that the ratio (I2 / I1) is equal to or more than the above lower limit value is preferable from the viewpoint of ensuring the functions and properties (such as high hardness) of the cured resin layer 12. The ratio (I2 / I1) is preferably 1.20 to 1.66, more preferably 1.30 to 1.63, and still more preferably 1.40 to 1.60 from the viewpoint of achieving both the adhesion of the inorganic layer 20 and the functions and properties of the cured resin layer 12.

[0041] Figure 3 shows an example in the case where the laminated film X further includes an antifouling layer 30 on the inorganic layer 20. Specifically, the laminated film X in Figure 3 has an inorganic layer 20 including an adhesion layer 21 and an antireflection layer 22, and an antifouling layer 30 on the inorganic layer 20, on a base film 10 with a cured resin layer.

[0042] 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 a function of suppressing the adhesion of contaminants such as fingerprints to the film exposed surface during the use of the laminated film X, and a function of making it easy to remove the adhered contaminants.

[0043] Examples of the material of the antifouling layer 30 include organic fluorine compounds. As the organic fluorine compound, an alkoxysilane compound having a perfluoropolyether group is preferably used. Examples of the alkoxysilane compound having a perfluoropolyether group include compounds represented by the following general formula (1).

[0044] R 1 -R 2 -X-(CH2) m -Si(OR 3 )3(1)

[0045] In the general formula (1), R 1 represents a linear or branched fluorinated alkyl group (carbon number is, for example, 1 or more and 20 or less) in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms, and preferably represents a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0046] R 2represents a structure containing at least one repeating structure of perfluoropolyether (PFPE) group, preferably represents a structure containing two repeating structures of PFPE group. Examples of the repeating structure of PFPE group include a repeating structure of linear PFPE group and a repeating structure of branched PFPE group. Examples of the repeating structure of linear PFPE group include, for example, a structure represented by -(OC n F 2n ) p - (where n represents an integer of 1 or more and 20 or less, and p represents an integer of 1 or more and 50 or less. The same applies hereinafter). Examples of the repeating structure of branched PFPE group include, for example, a structure represented by -(OC(CF3)2) p - and a structure represented by -(OCF2CF(CF3)CF2) p -. As the repeating structure of PFPE group, preferably, a repeating structure of linear PFPE group is included, and more preferably, -(OCF2) p - and -(OC2F4) p - are included.

[0047] R 3 represents an alkyl group having 1 to 4 carbon atoms, preferably represents a methyl group.

[0048] X represents an ether group, a carbonyl group, an amino group, or an amide group, preferably represents an ether group.

[0049] m represents an integer of 1 or more. Also, m preferably represents an integer of 20 or less, more preferably 10 or less, and still more preferably 5 or less.

[0050] Among such alkoxysilane compounds having a perfluoropolyether group, preferably, a compound represented by the following general formula (2) is used.

[0051] CF3-(OCF2) q -(OC2F4) r -O-(CH2)3-Si(OCH3)3(2)

[0052] In general formula (2), q represents an integer of 1 or more and 50 or less, and r represents an integer of 1 or more and 50 or less.

[0053] In addition, the alkoxysilane compound having a perfluoropolyether group may be used alone or two or more thereof may be used in combination.

[0054] In this embodiment, the antifouling layer 30 is a film (dry coating film) formed by a dry coating method. Examples of the dry coating method include a sputtering method, a vacuum evaporation method, and CVD. The antifouling layer 30 is preferably a dry coating film, more preferably a vacuum evaporation film.

[0055] The configuration in which the material of the antifouling layer 30 contains an alkoxysilane compound having a perfluoropolyether group and 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 base of the antifouling layer 30. Therefore, it is suitable for ensuring the peel resistance of the antifouling layer 30. A high peel resistance of the antifouling layer 30 helps to maintain the antifouling function of the antifouling layer 30.

[0056] 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, still more preferably 5 nm or more, particularly preferably 7 nm or more, and is preferably 25 nm or less, more preferably 20 nm or less, still more preferably 18 nm or less.

[0057] Figures 4A to 4C show an example of a method for manufacturing the laminated film X. 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).

[0058] In the step of forming the cured resin layer, as shown in FIG. 4A, a cured resin layer 12 is formed on a long base film 11. Thereby, a base film 10 with a cured resin layer is obtained. The cured resin layer 12 can be formed by applying the above-described curable resin composition on the base film 11 to form a coating film and then curing this coating film. The curable resin composition may contain other components in addition to the above-described curable resin as necessary. Examples of other components include a solvent. Examples of the solvent 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 photoinitiator. 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 base film 11 is dried after the application of the curable resin composition. 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 film on the base 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 integrated irradiation light amount of ultraviolet rays is, for example, 100 mJ / cm 2 or more and, for example, 500 mJ / cm 2 or less.

[0061] When the curable resin composition contains a thermosetting resin, the coating film on the base 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 longer and, for example, 10 minutes or shorter.

[0062] In this way, the long base material film 10 with a cured resin layer can be produced. In this embodiment, a roll of the long base material film 10 with a cured resin layer is prepared. Specifically, the base material film 10 with a cured resin layer is wound so that the first surface 10a of the base material film 10 with a cured resin layer faces the inner side in the roll diameter direction.

[0063] In this manufacturing method, next, while transporting the base material film 10 with a cured resin layer as the work film W in a roll-to-roll manner under a reduced pressure atmosphere, the plasma treatment step and the film forming step are sequentially carried out. The apparatus Y shown in FIG. 5 is an example of an apparatus for carrying out the plasma treatment step and the film forming step. The apparatus Y includes a pay-out chamber R1, a take-up chamber R2, a connection chamber C1, a plasma treatment chamber C2, a connection chamber C3, a film forming chamber C4 (the first film forming chamber), a connection chamber C5, and a film forming chamber C6 (the second film forming chamber).

[0064] The pay-out chamber R1 is provided with a pay-out roller 51 for paying out the work film W. A roll of the long base material film 10 with a cured resin layer is attached as the work film W to the pay-out roller 51. Also, a predetermined number of guide rollers G for guiding the work film W are provided in the pay-out chamber R1.

[0065] The take-up chamber R2 is provided with a take-up roller 52 for taking up the work film W. A predetermined number of guide rollers G for guiding the work film W are provided in the take-up chamber R2.

[0066] The connection chamber C1 is arranged next to the pay-out chamber R1 and in front of the plasma treatment chamber C2 in the running direction of the work film W. A predetermined number of guide rollers G for guiding the work 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 internal pressure. When the apparatus Y is in operation, the pressure in the connection chamber C1 is maintained at a predetermined pressure between the pressure in the pay-out chamber R1 and the pressure in the plasma treatment chamber C2. Thereby, a differential pressure between the pay-out chamber R1 and the plasma treatment chamber C2 is ensured.

[0067] The plasma processing chamber C2 is disposed between the connection chamber C1 and the connection chamber C3 in the traveling direction of the work film W. In the plasma processing chamber C2, a plasma processing step is performed as described later. Also, a first line L1 with a flow rate adjustment valve for introducing gas into the chamber is connected to the plasma processing chamber C2.

[0068] In this embodiment, the plasma processing chamber C2 is provided 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, as shown in FIGS. 6 and 7, the LA71 is disposed in the plasma processing chamber C2 while being supported by a fixture 72 and covered with a cover block 73 (omitted in FIG. 6) (the case where the number of LA71 is 4 is illustratively shown).

[0069] The plurality of LA71 are arranged in alignment so as to be aligned in the traveling direction of the base material film 10 with a cured resin layer and in a direction orthogonal to the traveling direction (the width direction of the base material film 10 with a cured resin layer). The fixture 72 is a vacuum flange. As shown in FIG. 7, the LA71 is fixed to the fixture 72 via a field through 74. As shown in FIG. 5, the fixture 72 is assembled to an opening 75 provided in the wall portion of the plasma processing chamber C2. Specifically, the fixture 72 is assembled to the opening 75 with a seal member (not shown) sandwiched between the wall portion of the plasma processing chamber C2 and the fixture 72. The LA71 is electrically connected to a high frequency power source (RF power source) via an impedance matcher outside the plasma processing chamber C2. Such LA71 is formed of a conductor. Examples of the conductor include copper and silver. The conductor is preferably copper. The LA71 may be covered with an insulator. Examples of the insulator include glass and quartz.

[0070] 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. One LA 71 is accommodated in each accommodation space 73a. The partition plates 73B are arranged to close 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 made of an insulating material. Examples of the insulating material include quartz and glass. Further, the separation distance d’ (shown in FIG. 7) between the base film 10 with a cured resin layer that travels in the plasma treatment 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 LA 71 by plasma treatment without excessively reducing the plasma conversion efficiency due to the applied power to the LA 71, and also helps to suppress damage to the base film 10 with a cured resin layer to be plasma-treated.

[0071] As shown in FIG. 6, in this embodiment, LA71 has an open-loop shape. The fact that LA71 has an open-loop shape is advantageous for reducing the inductance of LA71. Therefore, according to the open-loop-shaped LA71, an increase in voltage due to an increase in the applied power to LA71 can be suppressed. As a result, abnormal discharge during plasma processing described later can be suppressed. By suppressing abnormal discharge, damage to the substrate film 10 with the cured resin layer to be plasma-processed can be suppressed. Specifically, LA71 has a U shape with two free ends. For each LA71, the two free ends are fixed to the fixture 72 so as to be arranged in the width direction of the substrate film 10 with the cured resin layer. Further, 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 the cured resin layer passing through the plasma processing chamber C2. The extension portion 71a extends in the width direction of the substrate film 10 with the cured resin layer. Each extension portion 71a may extend in the running direction of the substrate film 10 with the cured resin layer (four LA71s may be arranged in this way). The length of the extension portion 71a is, for example, 50 to 150 mm (FIG. 6 exemplarily shows the case 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 the open-loop shape.

[0072] LA71 extends from the fixture 72 toward the base film 10 with a cured resin layer. LA71 preferably extends in a direction perpendicular to the fixture 72. The extension length d1 of LA71 from the fixture 72 is, for example, 30 to 150 mm. The maximum length d2 of LA71 in the plane direction of the base film 10 with a cured resin layer is, for example, 50 to 150 mm. The separation distance d3 (shown in FIG. 7) between LA71 and the base film 10 with a cured resin layer 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 LA71 arranged at intervals in the running direction of the base film 10 with a cured resin layer may be 1, or may be 2 or 3, or may be 4 or more if necessary, depending on the same running speed (i.e., plasma treatment time). In the running direction of the base film 10 with a cured resin layer, the center-to-center distance d4 between adjacent LA71 is, for example, 100 to 500 mm. In the width direction of the base film 10 with a cured resin layer, the center-to-center distance d5 between adjacent LA71 is, for example, 200 to 500 mm. By adjusting the center-to-center distance d5, the uniformity of the plasma density in the width direction of the base film 10 with a cured resin layer described below can be controlled. The center-to-center distance d4 and the center-to-center distance d5 are preferably the same. The ratio (d5 / d4) of the center-to-center distance d5 to the center-to-center distance d4 is, for example, 0.5 to 2.0. The center points of the extension portions 71a of the four LA71 preferably form a square as vertices. With such a set of LA71, high-density plasma can be generated. As LA71, for example, a high-frequency antenna for plasma generation described in JP-A-2013-258153 may be used.

[0073] In this embodiment, the plasma processing chamber C2 further includes a transfer roller 53. The transfer roller 53 is a main guide roller for transferring the work film W within the plasma processing chamber C2. The transfer roller 53 has a temperature adjustment function capable of heating or cooling the work film W. That is, the transfer roller 53 is a transfer roller with a temperature adjustment function. During the operation of the apparatus Y, the transfer roller 53 contacts the second surface 10b of the base film 10 with the cured resin layer as the work film W and transfers the base film 10 with the cured resin layer. The above LA71 is disposed opposite to the transfer roller 53. According to the apparatus Y provided with such a plasma processing chamber C2, in the plasma processing step S2, the base film 10 with the cured resin layer can be cooled or heated by the transfer roller 53 with a temperature adjustment function that contacts the base film 10 with the cured resin layer, and plasma processing can be performed on the base film 10 with the cured resin layer. By controlling the temperature of the base film 10 with the cured resin layer, thermal deformation of the base film 10 with the cured resin layer can be suppressed, and the influence of such thermal deformation on the transfer of the base film 10 with the cured resin layer can be suppressed.

[0074] The connection chamber C3 is disposed next to the plasma processing chamber C2 and in front of the film forming chamber C4 in the traveling direction of the work film W. A predetermined number of guide rollers G for guiding the work 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 indoor pressure. During the operation of the apparatus Y, 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, a differential pressure between the plasma processing chamber C2 and the film forming chamber C4 is ensured.

[0075] The film forming chamber C4 is disposed next to the connection chamber C3 in the traveling direction of the work film W. The film forming chamber C4 is also 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.

[0076] 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 a plurality of sputtering chambers 60 (sputtering chambers 60a to 60e) (the case where the number of sputtering chambers 60 is 5 is exemplarily illustrated). The film formation roller 54 is a main guide roller for conveying the work film W within the film formation chamber C4. The film formation roller 54 has a temperature adjustment function capable of heating or cooling the work film W. The sputtering chamber 60 is a space partitioned within the film formation chamber C4. The plurality of 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), which is a film formation material supply member, is disposed on the cathode 61. The target is disposed on the target so as to face the film formation roller 54. Each sputtering chamber 60 is provided with a power source (not shown) for applying a voltage to the target to generate a glow discharge. Examples of the power source include a DC power source, an AC power source, an MF power source, an RF power source, and an MF-AC power source. The MF-AC power source means an AC power source having a frequency band of several kHz to several MHz. Each sputtering chamber 60 is connected to a required number of second lines (not shown) with flow rate adjustment valves for introducing gas into the chamber. Also, a required number of guide rollers G for guiding the work film W are provided within the film formation chamber C4.

[0077] The connection chamber C5 is disposed between the connection chamber C4 and the film formation chamber C6 in the traveling direction of the work film W. A required number of guide rollers G for guiding the work film W are provided within the connection chamber C5.

[0078] The film forming chamber C6 is arranged between the connection chamber C5 and the winding chamber R2 in the running direction of the work film W. The film forming chamber C6 is a vacuum evaporation chamber in this embodiment. The film forming chamber C6 includes a material holding part 62 and a vapor deposition amount adjusting valve (not shown) with adjustable opening degree. The film forming chamber C6 is connected to a vacuum pump (not shown) and is configured to be able to adjust the internal pressure. A predetermined number of guide rollers G for guiding the work 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.

[0079] A film forming material supply (not shown) is arranged in the material holding part 62 so as to face the work film W conveyed in the film forming chamber C6. The material holding part 62 may incorporate resistance heating means, high-frequency induction heating means, or electron beam heating means as means for heating the film forming material supply.

[0080] With the apparatus Y as described above, the plasma treatment process and the film forming process are sequentially carried out. Specifically, it is as follows.

[0081] The work film W is fed out from the feeding chamber R1. After being fed out from the feeding chamber R1, the work film W sequentially 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, and is wound up in the winding chamber R2. The running speed of the work film W is, for example, 0.5 m / min or more and, for example, 5 m / min or less. Also, the series of lines from the feeding chamber R1 to the winding chamber R2 are not opened to the atmosphere midway, and in this line, the process under a reduced pressure atmosphere is carried out. The reduced pressure atmosphere is preferably under vacuum. Under vacuum preferably means under a reduced pressure atmosphere of 7 Pa or less.

[0082] In the plasma processing chamber C2, as shown in FIG. 4B, a plasma processing step is performed. In the plasma processing step, plasma processing is performed on the first surface 10a of the base material film 10 with a cured resin layer in a reduced-pressure atmosphere in the plasma processing chamber C2 (chamber). In this embodiment, the plasma processing is a process by inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP processing) generated by applying high-frequency power to LA71. Specifically, it is as follows.

[0083] Oxygen is supplied into the plasma processing chamber C2 during plasma processing through the first line L1. An inert gas may be supplied into the plasma processing chamber C2 in addition to oxygen. Examples of the inert gas include argon, krypton, and xenon. Further, the gas in the plasma processing chamber C2 may contain other gases other than the inert gas. Examples of the other gas include nitrogen, hydrogen, and water vapor.

[0084] 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, still more preferably 80% by volume or more, even more preferably 90% by volume or more, still even more preferably 95% by volume or more, and particularly preferably 100% by volume. When the oxygen concentration is equal to or higher than the above lower limit value, high-density oxygen plasma can be generated. Thereby, the first surface 10a of the base material film 10 with a cured resin layer can be effectively highly activated. According to such oxygen-LAICP processing, specifically, on the surface (first surface 10a) of the cured resin layer 12, high-density oxygen plasma acts on the C=C bond portion of the resin, and one of the carbon-carbon double bonds is cleaved to form a portion with a bond (dangling bond site), which is efficiently formed.

[0085] The pressure (first pressure) inside the plasma processing chamber C2 during plasma processing is preferably 0.1 Pa or more, more preferably 0.2 Pa or more, still more preferably 0.3 Pa or more, and is preferably 7 Pa or less, more preferably 5 Pa or less, still more preferably 3 Pa or less. When the first pressure is equal to or higher than the above lower limit value, a plasma environment with a sufficient density can be formed inside the plasma processing chamber C2 for the surface modification treatment of the first surface 10a of the base material film 10 with a cured resin layer in plasma processing. When the first pressure is equal to or lower than the above upper limit value, in plasma processing, heat damage to the first surface 10a caused by an excessively high-density plasma can be suppressed, and 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 gas into the plasma processing chamber C2.

[0086] The frequency of the high-frequency power applied to LA71 during plasma processing is preferably 1 MHz or more, more preferably 5 MHz or more, still more preferably 10 MHz or more, and is preferably 100 MHz or less, more preferably 80 MHz or less, still more preferably 60 MHz or less. When the frequency is equal to or higher than the above lower limit value, in plasma processing, the plasma current density can be increased while stabilizing the plasma discharge. When the frequency is equal to or lower than the above upper limit value, the antenna potential can be suppressed, and thus damage to the base material film 10 with a cured resin layer by the plasma can be suppressed. Also, the high-frequency power is preferably 0.1 kW or more, more preferably 0.3 kW or more, still more preferably 1.0 kW or more, and is preferably 10 kW or less, more preferably 8 kW or less, still more preferably 6 kW or less. When the high-frequency power is equal to or higher than the above lower limit value, a high-density plasma environment can be formed inside the plasma processing chamber C2 in plasma processing by inductively coupled plasma. When the high-frequency power is equal to or lower than the above upper limit value, excessive damage to the base material film 10 with a cured resin layer by the plasma can be suppressed.

[0087] In the plasma processing step, the plasma current density at an intermediate position between LA71 and the base material film 10 with a cured resin layer is preferably 0.5 mA / cm 3More preferably, it is 0.8 mA / cm or more 3 Still more preferably, it is 1.2 mA / cm or more 3 Preferably, it is 10 mA / cm or less 3 More preferably, it is 5 mA / cm or less 3 Still more preferably, it is 2 mA / cm or less 3 It is as follows. In the inductively coupled plasma treatment using a low-inductance antenna, a higher plasma current density can be achieved than in the capacitively coupled plasma treatment (for example, a plasma density about 100 times higher can be achieved). When the plasma current density is equal to or higher than the above lower limit value, sufficient plasma oxygen particles can be ensured in the plasma treatment chamber C2 during the plasma treatment, 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 equal to or lower than the above upper limit value, damage to the first surface 10a caused by excessively high-density plasma oxygen particles can be suppressed during the plasma treatment. Examples of the method for adjusting the plasma current density include adjusting the introduction amount of oxygen gas 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.

[0088] In the film formation step (FIG. 4C), first, in the film formation chamber C4, in a reduced-pressure atmosphere following the plasma treatment step, a adhesion layer 21 and an antireflection layer 22 are sequentially formed on the first surface 10a of the substrate film 10 with the cured resin layer by a sputtering method. The reduced-pressure atmosphere is preferably under vacuum.

[0089] In the sputtering method, while introducing a sputtering gas (inert gas) into each sputtering chamber 60 through a single second line, a negative voltage is applied to a target (film-forming material) disposed on a cathode 61 in the sputtering chamber 60. Thereby, a glow discharge is generated to ionize gas atoms, the gas ions are collided with the target surface at high speed, the target material is ejected from the target surface, and the ejected target material is deposited on the work film W. Examples of the sputtering gas 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, in addition to the sputtering gas, oxygen (reactive gas) is introduced into the sputtering chamber 60. Oxygen is introduced into the sputtering chamber 60 via another second line. In the reactive sputtering method, the target is made of, for example, the metal in the metal oxide forming each layer.

[0091] 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 work film W adjusted by the film-forming roller 54) is, for example, -10°C to 150°C.

[0092] In the film-forming step, 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. Then, reactive sputtering is performed while introducing argon and oxygen into the sputtering chamber 60a (similarly, reactive sputtering is also performed in the following sputtering methods in the sputtering chambers 60b to 60e). In this step, the material of the adhesion layer 21 as the first layer of the inorganic layer 20 is formed on the first surface 10a including a large number of dangling bond sites formed in the above plasma treatment step. Therefore, the adhesion layer 21 is formed with good adhesion to the first surface 10a.

[0093] 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, a Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60b.

[0094] Next, a low refractive index layer 22b is formed on the high refractive index layer 22a by a sputtering method in the sputtering chamber 60c. When forming an 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.

[0095] Next, a high refractive index layer 22c is formed on the low refractive index layer 22b by a sputtering method in the sputtering chamber 60d. When forming a Nb2O5 layer as the high refractive index layer 22c, a Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60d.

[0096] Next, a low refractive index layer 22d is formed on the high refractive index layer 22c by a sputtering method 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.

[0097] In the film forming process (FIG. 4C), an antifouling layer 30 is further formed in the film forming chamber C6. In this step, in the film forming chamber C6, the antifouling layer 30 is formed on the low refractive index layer 22d in the work film W by a vacuum evaporation method as a dry coating method. Specifically, with the operation of a vacuum pump, the inside of the film forming chamber C6 is depressurized to a vacuum state, and a film forming material supply material (not shown) disposed in the material holding portion 62 is heated to a predetermined temperature, and a vacuum evaporation method is performed.

[0098] In the apparatus Y, after the plasma treatment process and the film forming process, the laminated film X as the work film W reaches the winding chamber R2 and is wound by the winding roller 52.

[0099] In the above manner, a long laminated film X can be manufactured. When the laminated film X does not include the antifouling layer 30, such a laminated film X can be manufactured by not performing the step in the film forming chamber C6 in the above manufacturing process.

[0100] In the laminated film X, as described above, in the Raman spectrum of Raman spectroscopic analysis with respect to the side of the inorganic layer 20, in the range of 1455 to 1465 cm -1 derived from the C-H bond, the ratio (I2 / I1) of the intensity I2 of the peak in the range of 1625 to 1635 cm -1 derived from the C=C bond to the intensity I1 of the peak in the range is 1.66 or less. This indicates that the chemical interaction between the cured resin layer 12 and the inorganic layer 20 on the base film 11 is strong. Specifically, it indicates that there are relatively many chemical bonds formed between the cured resin layer 12 and the inorganic layer 20 through the part where a bond is generated from the C=C bond part of the resin in the cured resin layer 12 (the part where one bond of the carbon-carbon double bond is broken and a bond is generated). The more such chemical bonds there are, the higher the adhesion of the inorganic layer 20 to the cured resin layer 12. Therefore, the content of particles such as nanosilica particles in the cured resin layer 12 can be reduced. Thereby, the manufacturing cost of the laminated film X can be reduced.

[0101] Therefore, according to the laminated film X, while suppressing the manufacturing cost, the adhesion of the inorganic layer 20 to the base film 10 with the cured resin layer can be ensured.

Example

[0102] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples. Also, the specific numerical values such as the blending amounts (contents), physical property values, parameters, etc. described below can be replaced with the upper limits (numerical values defined as "below" or "less than") or lower limits (numerical values defined as "above" or "exceeding") of the corresponding blending amounts (contents), physical property values, parameters, etc. described in the above "Mode for Carrying Out the Invention".

[0103] 〔Example 1〕 The following steps were sequentially carried out to produce the laminated film of Example 1.

[0104] First, a hard coat layer 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 an ultraviolet curable urethane acrylate resin (product 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 (product name "Viscoat #300", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.5 parts by mass of a photopolymerization initiator (product name "Omnirad127D", manufactured by BASF), and 0.06 parts by mass of a leveling agent (product name "Polyflow LE-303", a silicone-based leveling agent, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixed solution. Next, the solid content concentration of the mixed solution was adjusted to 40% by mass by adding a mixed solvent of butyl acetate and cyclopentanone (CPN) (mass ratio of butyl acetate to CPN is 70:30). Thereby, a first resin composition was prepared. On the other hand, a long TAC film (product name "KC8UAW", thickness 80 μm, manufactured by Konica Minolta) was prepared. Next, the first resin composition was applied to one side of the TAC film to form a coating film. Next, after drying this coating film by heating, it was cured by ultraviolet irradiation. Thereby, a hard coat (HC) layer with a thickness of 12 μm was formed on the TAC film. The heating temperature was 80 °C and the heating time was 1 minute. In ultraviolet irradiation, a high-pressure mercury lamp was used as a light source, and ultraviolet light with a wavelength of 365 nm was irradiated onto the coating film, and the integrated irradiation light amount was 300 mJ / cm 2 was set. As described above, a TAC film with an HC layer was produced as a base film with a cured resin layer.

[0105] Next, in a roll-to-roll process under vacuum, while transporting a substrate film with a cured resin layer as a work film, a plasma treatment step for the film and a subsequent film forming step were carried out (roll-to-roll process). For the plasma treatment step and the film forming step, an apparatus (first apparatus) capable of carrying out a roll-to-roll process on the work film was used. The first apparatus includes a pay-out chamber, a plasma treatment chamber (first plasma treatment), a first film forming chamber, a second film forming chamber, and a take-up chamber. The pay-out chamber, the plasma treatment chamber, the first film forming chamber, the second film forming chamber, and the take-up chamber are arranged in this order and communicate with each other. The pay-out chamber is provided with pay-out rollers. On the pay-out rollers, a roll of the substrate film with the cured resin layer as the work film was set. The plasma treatment chamber includes transport rollers with a temperature control function (transport roller 53 in Fig. 5) and four low inductance antennas (LA71 in Figs. 6 and 7) covered with a cover block (cover block 73 in Fig. 7) as shown in Figs. 6 and 7. Each low inductance antenna has an extension portion (extension portion 71a in Fig. 6) parallel to the work film. In the four low inductance antennas, the extension length d1 is 88 mm, the maximum length d2 (length of the extension portion) is 100 mm, the separation distance d3 is 112 mm, the center-to-center distance d4 is 290 mm, and the center-to-center distance d5 is 280 mm (Figs. 6 and 7). Each low inductance antenna is electrically connected to a high frequency power supply (RF power supply, frequency 13.56 MHz) via an impedance matcher outside the plasma treatment chamber. The separation distance d' between the work film traveling in the plasma treatment chamber and the cover block is 100 mm. The first film forming chamber is a sputtering film forming chamber and includes a film forming roller (film forming roller 54 in Fig. 5) and first to fifth sputtering chambers (sputtering chambers 60a to 60e in Fig. 5). Each sputtering chamber is a space partitioned within the first film forming chamber. The first to fifth sputtering chambers are arranged in this order in the traveling direction of the substrate film along the circumferential direction of the film forming roller. Each sputtering chamber is provided with a cathode arranged opposite to the film forming roller. To each sputtering chamber, a necessary number of second lines (not shown) with flow control valves for introducing gas into the chamber are connected.The second film-forming chamber is a vacuum evaporation chamber and includes a material holding part (material holding part 62 in FIG. 5). The winding chamber includes a winding roller.

[0106] In the roll-to-roll process, in the plasma treatment chamber, the surface of the cured resin layer (first surface) on the work film was subjected to plasma treatment (plasma treatment step). The running speed of the base film (film running speed) was 1.0 m / min. The temperature of the conveying roller with a temperature adjustment function was -8°C. The conditions for the plasma treatment are as follows.

[0107] After evacuating the inside of the apparatus until the ultimate vacuum degree of the plasma treatment chamber reached 1.0×10 -4 Pa, oxygen was introduced into the plasma treatment chamber, and the pressure in the plasma treatment chamber was set to 1.5 Pa. By applying 2 kW of high-frequency power to four low-inductance antennas with a high-frequency power supply, an inductively coupled plasma of an oxygen-containing gas was formed around the antennas (the surface of the cured resin layer of the work film was treated with this plasma). The plasma current density at the intermediate position between the low-inductance antenna and the work film was 1.3 mA / cm 3 . The plasma current density was measured with a Langmuir probe for plasma measurement.

[0108] In the first film-forming chamber, an adhesion layer, a first high refractive index layer, a first low refractive index layer, a second high refractive index layer, and a second low refractive index layer were sequentially formed on the work film (base film with a cured resin layer) after the plasma treatment. Specifically, while conveying the work film while cooling it with a film-forming roll in the first film-forming chamber, an adhesion layer was formed on the cured resin layer of the work film in the first sputtering chamber, a first high refractive index layer was formed on the adhesion layer in the second sputtering chamber, a first low refractive index layer was formed on the first high refractive index layer in the third sputtering chamber, a second high refractive index layer was formed on the first low refractive index layer in the fourth sputtering chamber, and a second low refractive index layer was formed on the second high refractive index layer in the fifth sputtering chamber (these layers form an inorganic layer). The film-forming temperature (temperature of the film-forming roll) was -8°C. More specifically, it is as follows.

[0109] In the first sputtering chamber, an ITO layer with a thickness of 4 nm was formed as an adhesion layer by reactive sputtering (adhesion layer formation step). In this step, after the inside of the first film formation chamber was evacuated to a vacuum degree of 1.0×10 -4 Pa, argon as an inert gas and oxygen as a reactive gas were introduced into the first sputtering chamber, and the pressure in the first sputtering chamber was set to 0.2 Pa. The oxygen introduction amount per 100 volume parts of argon introduced into the first sputtering chamber was set to 10 volume parts. As the target, a sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 30 mass%) was used. As the power supply for applying voltage to the target, an MF-AC power supply was used (the same applies to the second to fifth sputtering chambers described later). The discharge power was set to 4.3 kW.

[0110] 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 step, after the inside of the first film formation chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the second sputtering chamber, and the pressure in the second sputtering chamber was set to 0.5 Pa. The oxygen introduction amount per 100 volume parts of argon introduced into the second sputtering chamber was set to 5 volume parts. As the target, a Nb target was used. The discharge power was set to 13 kW.

[0111] 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 step, after the inside of the first film formation chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the third sputtering chamber, and the pressure in the third sputtering chamber was set to 0.2 Pa. The oxygen introduction amount per 100 volume parts of argon introduced into the third sputtering chamber was set to 30 volume parts. As the target, a Si target was used. The discharge power was set to 25 kW.

[0112] 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 deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fourth sputtering chamber, and the pressure in the fourth sputtering chamber was set to 0.5 Pa. The oxygen introduction amount per 100 volume parts of argon introduced into the fourth sputtering chamber was set to 13 volume parts. As the target, a Nb target was used. The discharge power was set to 27.5 kW.

[0113] 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 deposition chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fifth sputtering chamber, and the pressure in the fifth sputtering chamber was set to 0.2 Pa. The oxygen introduction amount per 100 volume parts of argon introduced into the fifth sputtering chamber was set to 30 volume parts. As the target, a Si target was used. The discharge power was set to 20.5 kW.

[0114] In the second film deposition chamber, an antifouling layer was formed on the second low refractive index layer. Specifically, a vacuum evaporation method using a perfluoropolyether group-containing alkoxysilane compound as an evaporation source was used to form an 8-nm-thick antifouling layer on the second low refractive index layer. The evaporation source was the solid content obtained by drying "KY1903-1" (a perfluoropolyether group-containing alkoxysilane compound represented by the above general formula (2), solid content concentration 20 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. Further, the heating temperature of the evaporation source in the vacuum evaporation method was set to 260°C.

[0115] As described above, the laminated film of Example 1 was produced. The laminated film of Example 1 includes a base 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 base film with an HC layer in the laminated film of Example 1, the surface of the HC layer is plasma-treated. This plasma treatment is a treatment by inductively coupled plasma using an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to a low-inductance antenna. Also, the adhesion layer, antireflection layer, and antifouling layer on the base film with an HC layer form a multilayer film.

[0116] 〔Examples 2 to 5 and Comparative Examples 1 and 2〕 In the curing resin layer forming step, each laminated film of Examples 2 to 5 and Comparative Examples 1 and 2 was produced in the same manner as the laminated film of Example 1, except that the amount and type of the leveling agent used were changed as shown in Table 1. The leveling agent used in Example 3 is "Megafac S-333" (silicone-based leveling agent) manufactured by DIC Corporation. The leveling agent used in Comparative Example 2 is "Megafac F-556" (fluorine-based leveling agent) manufactured by DIC Corporation.

[0117] 〔Comparative Example 3〕 First, in the same manner as the curing resin layer forming step in Example 1, an HC layer was formed on one side of a TAC film to obtain a base film with a curing resin layer (TCA film with an HC layer).

[0118] Next, in a roll-to-roll process under vacuum, while transporting a substrate film with a cured resin layer as a work film, a plasma treatment step for the film and a subsequent film forming step were carried out (roll-to-roll process). For the plasma treatment step and the film forming step, a second apparatus capable of carrying out a roll-to-roll process on the work film was used. The second apparatus has the same configuration as the first apparatus, except that it is provided with a second plasma treatment chamber instead of the first plasma treatment. The second plasma treatment chamber is provided with a cathode electrode and an anode electrode (both are rectangular electrodes made of SUS304) as a pair of planar electrodes for plasma generation. The pair of planar electrodes are arranged in parallel with respect to the work film passing through the second plasma treatment chamber with a space of 50 mm. The anode electrode is arranged at a position 35 mm away from the work film passing through the plasma treatment chamber and is grounded outside the plasma treatment chamber. The cathode electrode is arranged so as to face the surface of the HC layer of the work film and is electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. The length of each electrode facing the work film in the film running direction is 110 mm, and the length in the width direction is 430 mm.

[0119] In the second plasma treatment chamber, plasma treatment (bombardment treatment) was carried out on the surface of the cured resin layer (the first surface) of the work film. The running speed of the substrate film (film running speed) was set to 1.0 m / min. The conditions for the plasma treatment are as follows.

[0120] After evacuating the inside of the apparatus until the ultimate vacuum degree of the second plasma treatment chamber reaches 1.0×10 -4 Pa, argon was introduced into the second plasma treatment chamber, and the pressure in the plasma treatment chamber was set to 0.5 Pa. By applying 500 W of power to the space between the planar electrodes with a high-frequency power source, capacitively coupled plasma (CCP) was generated. In this plasma environment, bombardment treatment (Ar-BB treatment) with argon ions was carried out on the surface of the HC layer of the work film.

[0121] In the first film-forming chamber, on the work film (substrate film with a cured resin layer) after plasma treatment, in the same manner as described above for Example 1, the adhesion layer to the second low refractive index layer were sequentially formed. In the second film-forming chamber, in the same manner as described above for Example 1, an antifouling layer was formed on the second low refractive index layer.

[0122] 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 (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 Comparative Example 3, the surface of the HC layer is bombarded with argon ions (Ar-BB treatment).

[0123] 〈Raman Spectroscopic Analysis〉 For the inorganic layers in the laminated films of the examples and comparative examples, Raman spectra were obtained by Raman spectroscopic analysis. Specifically, it is as follows.

[0124] The sample for analysis was prepared by cutting out a size of 10 mm × 10 mm from the central part in the width direction of the laminated film. For the analysis, a Raman spectrometer (product name "alpha300 RSA", manufactured by WITec) was used. The analysis was carried out under the following conditions with the focus of the irradiation light adjusted to the surface of the hard coat layer of the laminated film. For the obtained spectra, a baseline was drawn so that the intensity I (intensity of Raman scattering) at a wavenumber of 2000 cm -1 became zero. Then, the ratio (I2 / I1) of the intensity I2 of the peak in the range of 1625 - 1635 cm -1 derived from the C=C bond to the intensity I1 of the peak in the range of 1455 - 1465 cm -1 derived from the C-H bond was calculated. The values of the peak intensities I1, I2 and the ratio (I2 / I1) are shown in Table 1.

[0125] Figure 8 shows the Raman spectra obtained for the laminated films of Example 1 and Comparative Example 1. In Figure 8, the horizontal axis represents the Raman shift (cm -1 ), and the vertical axis represents 1460 cm -1represents the relative intensity (normalized intensity) normalized based on the intensity at [wavenumber], and the positions at wavenumber 1460 cm -1 and the position at wavenumber 1630 cm -1 are represented by the dashed lines. Also, in FIG. 8, the solid-line spectrum is the Raman spectrum of Example 1, and the dotted-line spectrum is the Raman spectrum of Comparative Example 1.

[0126] [Conditions for Raman spectroscopic analysis] Excitation wavelength: 532 nm Measured wavenumber range: 200 cm -1 to 2800 cm -1 Objective lens: 100× Detector: Electron multiplying CCD (EMCCD)

[0127] 〈Initial adhesion〉 For each of the laminated films of the examples and comparative examples, the adhesion of the inorganic layer to the substrate film with a cured resin layer was examined as follows (First adhesion test).

[0128] First, the side of the substrate film in the laminated film was fixed to a glass plate. Next, with respect to the multilayer film (adhesion layer / antireflection layer / antifouling layer) in the laminated film on the glass plate, 11 parallel first cuts (at 2 mm intervals) linearly extending in the first direction and 11 parallel second cuts (at 2 mm intervals) linearly extending in the second direction orthogonal to the first direction were formed by a cutter knife, and 100 meshes were formed by the first and second cuts. Next, while continuously dropping isopropyl alcohol at 2 mL / min onto the 100-mesh region in the laminated film, a polyester wiper (product name "Anticon Gold", manufactured by Sampratech 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 / sec, and 1000 reciprocations. Next, among the 100 meshes, the number of meshes with peeling of 1 mm 2 or more was counted. Next, the peeling rate (%) was calculated by dividing the count number by 100.

[0129] Then, regarding the adhesion of the inorganic layer to the substrate film with a cured resin layer, when the peeling rate was 10% or less, it was evaluated as "excellent", when the peeling rate was more than 10% and 30% or less, it was evaluated as "good", when the peeling rate was more than 30% and 80% or less, it was evaluated as "poor", and when the peeling rate was more than 80%, it was evaluated as "extremely poor". The evaluation results are shown in Table 1.

[0130] 〈Adhesion after weather resistance test〉 For each laminated film of the examples and comparative examples, the adhesion of the inorganic layer to the substrate film with a cured resin layer was examined as follows.

[0131] First, the side of the substrate film in the laminated film was fixed to a glass plate. Next, for the multilayer film in the laminated film on the glass plate, ultraviolet light was irradiated for 32.5 hours under the conditions of a temperature of 85°C, a relative humidity of 45%, and an irradiation intensity (integrated illuminance of 290 nm to 450 nm) of 1500 W / m 2 (Accelerated weather resistance test). This test was carried out using an "Eye Super UV Tester SUV-W161" manufactured by Iwasaki Electric Co., Ltd. After the accelerated weather resistance test, the above first adhesion test was carried out (second adhesion test). Then, regarding the adhesion of the inorganic layer to the substrate film with a cured resin layer, it was evaluated according to the same criteria as those described above for the first adhesion test. The evaluation results are shown in Table 1.

[0132] [Evaluation] In each of the laminated films of Examples 1 to 5, in the Raman spectrum of Raman spectroscopic analysis on the inorganic layer side, the intensity I1 of the peak in the range of 1455 to 1465 cm -1 derived from the C-H bond, with respect to the intensity of the peak in the range of 1625 to 1635 cm -1The ratio (I2 / I1) of the intensity I2 of the peak within the range was 1.66 or less. This indicates that there are relatively many chemical bonds formed between the cured resin layer and the inorganic layer through the portion where a bond was formed from the C=C bond portion in the resin in the cured resin layer of the laminated film (the portion where one bond of the carbon-carbon double bond was cleaved to form a bond). Therefore, in each of the laminated films of Examples 1 to 5, the adhesion of the inorganic layer to the base film with the cured resin layer could be ensured.

[0133] On the other hand, in each of the laminated films of Comparative Examples 1 to 3, the above ratio (I2 / I1) exceeded 1.66. This indicates that there are fewer chemical bonds formed between the cured resin layer and the inorganic layer through the portion where a bond was formed from the C=C bond portion in the resin in the cured resin layer of the laminated film than in each of the laminated films of the examples. Therefore, in each of the laminated films of Comparative Examples 1 to 3, the adhesion of the inorganic layer to the base film with the cured resin layer could not be ensured.

[0134]

Table 1

Explanation of Reference Signs

[0135] X Laminated Film H Thickness Direction D Plane Direction 10 Base Film with Cured Resin Layer 10a First Surface 10b Second Surface 11 Base Film 12 Cured Resin Layer 20 Inorganic Layer 21 Adhesion Layer 22 Anti-Reflection Layer 22a, 22c High Refractive Index Layers 22b, 22d Low Refractive Index Layers 30 Anti-Fouling Layer

Claims

1. A laminated film comprising a base film, a cured resin layer on the base film, and an inorganic layer on the cured resin layer, In the Raman spectrum of Raman spectroscopic analysis with respect to the inorganic layer side in the laminated film, the intensity I of the peak within the range of 1455 to 1465 cm －１ derived from the C-H bond １ with respect to, the intensity I of the peak within the range of 1625 to 1635 cm －１ derived from the C═C bond ２ is 1.66 or less, the laminated film.

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-based compound.

4. The laminated film according to any one of claims 1 to 3, further comprising an antifouling layer on the inorganic layer.

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