Method for producing laminated film

Abstract

This method for producing a laminated film comprises: a plasma treatment step (S2) in which a first surface (10a) of a base film (10) is subjected to plasma treatment in a reduced-pressure atmosphere in a chamber; and a film formation step (S3) in which, after the plasma treatment step (S2), an inorganic material layer (20) is formed on the first surface (10a) in a reduced-pressure atmosphere. The plasma processing is performed using an inductively coupled plasma containing argon gas, which is generated by applying high-frequency power to the low-inductance antenna. In the plasma treatment step (S2), the wavelength of the maximum emission peak intensity Imax in the wavelength range of 300-900 nm in the plasma emission is set to be within 811-812 nm, and the ratio of the intensity I2 of the emission peak in the wavelength range of 603-604 nm to the intensity I1 of the emission peak in the wavelength range of 706-707 nm is set to be 0.50 or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for manufacturing a layered film. BACKGROUND

[0002] From the viewpoint of lightening and high-functioning 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 layered film provided with a base film of an organic material and an inorganic layer on the base film is known. In the manufacturing process of the layered film, for example, before the inorganic layer is formed on the base film, the surface of the base film is subjected to plasma treatment in order to remove dirt and moisture on the surface. The removal of dirt and moisture from the surface of the base film contributes to improving the adhesion of the inorganic layer formed on the surface to the base film. As to the technology relating to plasma treatment of a base film, for example, it is described in Patent Literature 1 below.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent Application Laid-Open No. 2008-31521 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] In Patent Literature 1, a plasma treatment of a base film in a capacitively coupled manner is described. The treatment is performed by a prescribed plasma treatment device. The plasma treatment device is provided with a vacuum tank, a cathode electrode, and an anode electrode. The cathode electrode and the anode electrode are disposed in the vacuum tank. The two electrodes are opposed to each other with a space therebetween. The two electrodes are formed of a metal such as stainless steel. In a state where an argon-containing gas is supplied into the vacuum tank, high-frequency electric power is applied between the cathode electrode and the anode electrode, whereby argon plasma is generated between the electrodes by ionization of argon into argon ions and electrons. In the plasma treatment of Patent Literature 1, the base film as a treatment target is passed between the two electrodes in a state where argon plasma is generated between the cathode electrode and the anode electrode.

[0008] In the plasma treatment in a capacitively coupled manner, specifically, argon ions are drawn to the cathode electrode and collide with the cathode electrode at a high speed due to a bias voltage generated between the electrodes, and are bounced off the cathode electrode to collide with the base film disposed on the anode electrode. Such a plasma treatment has been known as, for example, ion bombardment treatment. Further, in the plasma treatment in a capacitively coupled manner (ion bombardment treatment), the bias voltage generated between the electrodes is increased, whereby the kinetic energy of argon ions in the plasma can be increased. The higher the kinetic energy of argon ions colliding with the base film, the easier it is to remove dirt and moisture from the surface of the base film.

[0009] However, in a case where the kinetic energy of the argon ions in the plasma is excessively high, when the argon ions collide with the cathode electrode, metal components are ejected from the cathode electrode (sputtering effect). At least a part of the metal components adheres to the surface of the base material film. The metal components adhering to the surface of the base material film affect the optical properties of the base material film. Furthermore, the higher the kinetic energy of the argon ions colliding with the base material film, the more likely it is to cause deterioration of the surface of the base material film made of an organic material. The deterioration also affects the optical properties of the base material film.

[0010] The present application provides a method for manufacturing a laminated film that has an inorganic layer on a base material film and has good optical properties.

[0011] Solution to the problem

[0012] The present application [1] includes a method for manufacturing a laminated film, which includes: a preparation step of preparing a long base material film having a first surface and a second surface on the opposite side of the first surface; a plasma treatment step of performing plasma treatment on the first surface of the base material film under a reduced pressure atmosphere in a chamber; and a film formation step of forming an inorganic layer on the first surface under a reduced pressure atmosphere after the plasma treatment step, wherein, in the plasma treatment step, the plasma treatment is performed using inductively coupled plasma containing argon gas generated by applying high-frequency power to a low-inductance antenna, the wavelength of the intensity Imax of the maximum emission peak in the range of 300 nm to 900 nm of the wavelength of the plasma emission light is set to be within 811 nm to 812 nm, and the ratio of the intensity I2 of the emission peak within the wavelength of 603 nm to 604 nm to the intensity I1 of the emission peak within the wavelength of 706 nm to 707 nm is set to be 0.50 or less.

[0013] The present application [2] includes the method for manufacturing a laminated film described in the above [1], wherein, in the plasma treatment step, the base material film is transported while being cooled or heated by a roller having a temperature adjustment function in contact with the base material film in the chamber.

[0014] The present application [3] includes the method for manufacturing a laminated film described in the above [1] or [2], wherein the low-inductance antenna has a coil shape or an open loop shape.

[0015] The present application [4] includes the method for manufacturing a laminated film described in any one of the above [1] to [3], wherein, in the plasma treatment step, the plasma current density at an intermediate position between the low-inductance antenna and the base material film is set to be 1.0 mA / cm 3 or more. 3

[0016] ​The present application [5] includes the manufacturing method of the layered film according to any one of the above [1] to [4], wherein in the film forming step, the inorganic layer is formed by a sputtering method, an evaporation method, or a chemical vapor deposition method.

[0017] The present application [6] includes the manufacturing method of the layered film according to any one of the above [1] to [5], wherein in the film forming step, a conductive layer is formed as the inorganic layer.

[0018] The present application [7] includes the manufacturing method of the layered film according to any one of the above [1] to [5], wherein in the film forming step, an antireflection layer is formed as the inorganic layer, the antireflection layer including a plurality of transparent inorganic oxide films layered in a thickness direction.

[0019] Effects of Invention

[0020] In the manufacturing method of the layered film of the present application, as described above, in the plasma treatment step under a reduced pressure atmosphere with respect to the first face of the base film, a treatment using inductively coupled plasma containing argon gas generated by applying high-frequency power to a low-inductance antenna is performed. Such plasma treatment enables a higher plasma current density than the above-described capacitively coupled plasma treatment. The higher the plasma current density, the more dirt and moisture on the first face can be removed. This removal of dirt and moisture contributes to improving the adhesion of the inorganic layer formed on the first face in the film forming step to the first face (the base film). The removal of dirt and moisture also contributes to ensuring the original optical properties of the base film.

[0021] Further, in the plasma treatment step, as described above, the wavelength of the intensity Imax of the maximum emission peak in the range of wavelengths of 300 nm to 900 nm in the plasma emission is set to be within 811 nm to 812 nm, and the ratio (I2 / I1) of the intensity I2 of the emission peak in the wavelength of 603 nm to 604 nm to the intensity I1 of the emission peak in the wavelength of 706 nm to 707 nm is set to be 0.50 or less. By such adjustment of the plasma emission intensity in the plasma treatment step, the kinetic energy of argon particles in the plasma can be suppressed. Also, the deterioration of the surface of the base film exposed to the plasma can be suppressed. Thus, the change in the optical properties of the base film can be suppressed.

[0022] Further, in the film forming step after the plasma treatment step, as described above, the inorganic layer is formed on the first face of the base film under a reduced pressure atmosphere after the plasma treatment step. That is, the base film is not placed under an atmospheric pressure between the plasma treatment step and the film forming step. By such film forming step, the mixing of foreign matter between the base film and the inorganic layer can be suppressed. This contributes to manufacturing a layered film having good optical properties.

[0023] Therefore, according to the method for manufacturing the laminated film of the present invention, a laminated film having an inorganic layer on a substrate film and having good optical properties can be manufactured. Attached Figure Description

[0024] Figure 1 This is a process diagram illustrating one embodiment of the method for manufacturing the laminated film of the present invention.

[0025] Figure 2 Through Figure 1 A schematic cross-sectional view of an example of a laminated film manufactured by the manufacturing method shown.

[0026] Figure 3 Indicates in Figure 1 An example of a substrate film prepared in the preparation process shown.

[0027] Figure 4 This is a schematic diagram of the apparatus for a plasma treatment process and a film formation process in one embodiment of the method for manufacturing a laminated film according to the present invention.

[0028] Figure 5 It means Figure 4 A three-dimensional view showing the positional relationship between the low-inductance antenna and the substrate film in the plasma processing chamber.

[0029] Figure 6 It means Figure 4 A cross-sectional view showing the positional relationship between the low-inductance antenna and the substrate film in the plasma processing chamber.

[0030] Figure 7 yes Figure 4 A schematic diagram of a modified example of the device is shown. In this modified example, the plasma processing chamber does not have a roller with temperature control function. Detailed Implementation

[0031] like Figure 1 As shown, a method for manufacturing a laminated film according to one embodiment of the present invention includes a preparation step S1, a plasma treatment step S2, and a film formation step S3. This manufacturing method produces... Figure 2 The laminated film X shown is a substrate film 10 and an inorganic layer 20. The inorganic layer 20 is disposed on one side of the substrate film 10 in the thickness direction H. In this embodiment, the substrate film 10 and the inorganic layer 20 are in contact. The laminated film X extends in a direction orthogonal to the thickness direction H (plane direction D). The laminated film X is, for example, an anti-reflective film or a transparent conductive film. The laminated film X can also be other types of films. The laminated film X is an example of a laminated film manufactured by the laminated film manufacturing method of the present invention.

[0032] In this manufacturing method, firstly, in the preparation step S1, as follows: Figure 3As shown, a long base material film 10 is prepared. The base material film 10 has a first surface 10a and a second surface 10b on the side opposite to the first surface 10a. The length of the base material film 10 is, for example, 1 m or more, and, in addition, for example, 10,000 m or less. The width of the base material film 10 is, for example, 1 cm or more, and, in addition, for example, 500 cm or less.

[0033] In the present embodiment, the base material film 10 has, in the thickness direction H, in order, the resin film 11 and the cured resin layer 12. In the present embodiment, the resin film 11 is in contact with the cured resin layer 12. In the base material film 10, the cured resin layer 12 forms the first surface 10a, and the resin film 11 forms the second surface 10b.

[0034] The resin film 11 is an element that ensures the strength of the laminated film X. The resin film 11 is, for example, a transparent resin film having flexibility. As the material of the resin film 11, for example, a polyester resin, a polyolefin resin, a cellulose resin, an acrylic resin, a polycarbonate resin, a polyethersulfone resin, a polyarylate resin, a melamine resin, a polyamide resin, a polyimide resin, and a polystyrene resin can be listed. As the polyester resin, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate can be listed. As the polyolefin resin, for example, polyethylene, polypropylene, and a cyclic olefin polymer (COP) can be listed. As the cellulose resin, for example, triacetyl cellulose (TAC) can be listed. These materials can be used alone or in combination of two or more. From the viewpoints of transparency and strength, the material of the resin film 11 is preferably at least one selected from the group consisting of a polyester resin, a polyolefin resin, and a cellulose resin, and more preferably at least one selected from the group consisting of PET, COP, and TAC.

[0035] The thickness of the resin film 11 is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more, and, in addition, is preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less. In the case where the thickness of the resin film 11 is the above lower limit value or more, the strength of the laminated film X can be ensured. In the case where the thickness of the resin film 11 is the above upper limit value or less, the handleability of the base material film 10 in the process described later in the roll-to-roll system can be ensured. In addition, in order to ensure the conveyability and handleability of the base material film 10 in the process in the roll-to-roll system, a carrier film can be attached to the second surface 10b of the resin film 11.

[0036] The total light transmittance (JIS K 7375-2008) of the resin film 11 is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more, and, in addition, for example, 100% or less. In the case where the total light transmittance of the resin film 11 is the above lower limit value or more, good transparency can be ensured in the laminated film X.

[0037] The cured resin layer 12 is a functional layer containing a resin. The cured resin layer 12 is specifically a cured product of a curable resin composition containing a curable resin. The cured resin layer 12 can further contain particles. That is, the cured resin layer 12 can be a cured product of a curable resin composition containing a curable resin and particles. As the functional layer, for example, a hard coat layer, an easy-adhesion layer, and an anti-blocking (AB) layer can be listed. The hard coat layer is a layer in which a scratch is less likely to be formed on the exposed surface (the upper surface in FIG. 1) of the inorganic layer 20. The easy-adhesion layer is a layer that improves the adhesion of a layer (the inorganic layer 20 in the present embodiment) formed on the base material film 10 to the base material film 10. The AB layer is a layer having an anti-blocking property that suppresses the entanglement between the films adjacent in the radial direction in a roll of the laminated film X. The cured resin layer 12 as the AB layer contains particles in order to exhibit the anti-blocking property. The cured resin layer 12 as the hard coat layer and the cured resin layer 12 as the easy-adhesion layer can have the anti-blocking property due to the particles contained therein. Figure 2

[0038] As the curable resin, for example, a polyester resin, an acryl urethane resin, an acrylic resin (except for the acryl urethane resin), a urethane resin (except for the acryl urethane resin), an amide resin, a silicone resin, an epoxy resin, and a melamine resin can be listed. 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 an acryl urethane resin and an acrylic resin.

[0039] As the curable resin, for example, an ultraviolet-curable resin and a thermosetting resin can be listed. The curable resin is preferably an ultraviolet-curable resin. In the case where the curable resin is an ultraviolet-curable resin, the curable resin can be cured without heating at a high temperature, and thus the manufacturing efficiency of the laminated film X can be improved.

[0040] As the particles, for example, inorganic oxide particles and organic particles can be listed. As the material of the inorganic oxide particles, for example, silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide can be listed. As the material of the organic particles, for example, polymethyl methacrylate, polystyrene, polyurethane, an acryl / styrene copolymer, benzoguanamine, melamine, and polycarbonate can be listed. The particles are preferably inorganic oxide particles, and more preferably at least one selected from silica particles and zirconia particles.

[0041] ​The thickness of the cured resin layer 12 is preferably 0.5 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, and in addition, is preferably 30 μm or less, more preferably 25 μm or less, further preferably 20 μm or less. In the case where the thickness of the cured resin layer 12 is the above lower limit value or more, the function of the cured resin layer 12 can be ensured. Specifically, in the case where the cured resin layer 12 is a hard coat layer, the scratch resistance of the inorganic layer 20 can be ensured, in the case where the cured resin layer 12 is an AB layer, the above anti-blocking property can be ensured, and in the case where the cured resin layer 12 is an easy-adhesion layer, the adhesion of the inorganic layer 20 to the base material film 10 can be ensured. In the case where the thickness of the cured resin layer 12 is the above upper limit value or less, the transparency of the cured resin layer 12 can be ensured.

[0042] The total light transmittance (JIS K 7375-2008) of the base material film 10 is preferably 80% or more, more preferably 90% or more, further preferably 95% or more, and in addition, for example, 100% or less. In the case where the total light transmittance of the base material film 10 is the above lower limit value or more, good transparency can be ensured in the laminated film X.

[0043] The base material film 10 can be produced by forming the cured resin layer 12 on the resin film 11. The cured resin layer 12 can be formed by applying the above curable resin composition on the resin film 11 to form a coating film, and then curing the coating film. The curable resin composition can contain other components, in addition to the above curable resin and particles, as necessary. As the other components, for example, solvents and leveling agents can be exemplified. As the solvents, for example, butyl acetate, ethyl acetate, toluene, and cyclopentanone can be exemplified. In the case where the curable resin composition contains an ultraviolet-curable resin as the curable resin, the curable resin composition preferably contains a photopolymerization initiator. In the case where the curable resin composition contains a thermosetting resin as the curable resin, the curable resin composition preferably contains a thermal polymerization initiator.

[0044] In the case where the curable resin composition contains a solvent, the coating film on the resin film 11 is dried after the curable resin composition is applied. The drying temperature is, for example, 50°C or higher, and in addition, for example, 120°C or lower. The drying time is, for example, 10 seconds or more, and in addition, for example, 10 minutes or less.

[0045] In the case where the curable resin composition contains an ultraviolet-curable resin, the coating film on the resin film 11 is cured by ultraviolet irradiation. As the light source for the ultraviolet irradiation, for example, a high-pressure mercury lamp and an LED lamp can be exemplified. The cumulative light amount of the ultraviolet irradiation is, for example, 100 mJ / cm 2 In addition, for example, 500 mJ / cm 2 or more.

[0046] In the case where the curable resin composition contains a thermosetting resin, the coating film on the resin film 11 is cured by heating. The heating temperature is, for example, 100°C or higher, and, in addition, for example, 150°C or lower. The heating time is, for example, 10 seconds or more, and, in addition, for example, 10 minutes or less.

[0047] As described above, the long substrate film 10 can be produced. In the present embodiment, a roll of the long substrate film 10 is prepared. Specifically, the substrate film 10 is wound so that the first face 10a of the substrate film 10 faces the radially inner side of the roll.

[0048] In the present production method, next, while the substrate film 10 is transported as the working film W in a roll-to-roll manner under a reduced pressure atmosphere, the plasma treatment step S2 and the film formation step S3 are sequentially performed. Figure 4 The illustrated device Y is one example of a device for performing the plasma treatment step S2 and the film formation step S3. The device Y is provided with: an extraction chamber R1, a take-up chamber R2, a connection chamber C1, a plasma treatment chamber C2, a connection chamber C3, a film formation chamber C4, a connection chamber C5, a connection chamber C6, and a PEM device (omitted from the illustration).

[0049] The extraction chamber R1 is provided with an extraction roller 51 for extracting the working film W. A roll of the long substrate film 10 is installed as the working film W on the extraction roller 51. In addition, a prescribed number of guide rollers G for guiding the working film W are provided inside the extraction chamber R1.

[0050] The take-up chamber R2 is provided with a take-up roller 52 for taking up the working film W. A prescribed number of guide rollers G for guiding the working film W are provided inside the take-up chamber R2.

[0051] The connection chamber C1 is disposed after the extraction chamber R1 and before the plasma treatment chamber C2 in the advancing direction of the working film W. A prescribed number of guide rollers G for guiding the working film W are provided inside the connection chamber C1. The connection chamber C1 is connected to a vacuum pump not illustrated and is configured to be able to adjust the pressure inside the chamber. When the device Y is operating, the pressure inside the connection chamber C1 is maintained at a prescribed pressure between the pressure inside the extraction chamber R1 and the pressure inside the plasma treatment chamber C2. Thereby, the pressure difference between the extraction chamber R1 and the plasma treatment chamber C2 is ensured.

[0052] The plasma treatment chamber C2 is disposed between the connection chamber C1 and the connection chamber C3 in the advancing direction of the working film W. In the plasma treatment chamber C2, the plasma treatment step S2 is performed as described later.

[0053] In the present embodiment, the plasma treatment chamber C2 is provided with a plurality of low-inductance antennas (LAs) 71. The low-inductance antenna refers to an antenna having a low inductance of 7.5 μH or less and being able to generate inductively coupled plasma by applying high-frequency electric power. In the present embodiment, as illustrated in FIG. 2, the low-inductance antennas 71 are arranged in a row in the advancing direction of the working film W.Figure 5 and Figure 6 As shown, LA71 is supported by an installation tool (fixture) 72 and covered by a cover block 73. Figure 5 (The state covered by the LA71 is omitted) is configured inside the plasma processing chamber C2 (an exemplary map shows the case where the number of LA71 is 4).

[0054] Multiple LA71s are arranged in a configuration that includes the travel direction of the substrate film 10 and a direction orthogonal to the travel direction (the width direction of the substrate film 10). The mounting tool 72 is a vacuum flange. (Example...) Figure 6 As shown, LA71 is secured to the installation tool 72 via a field through 74. Figure 4 As shown, the mounting tool 72 is assembled into the opening 75 located in the wall of the plasma processing chamber C2. Specifically, the mounting tool 72 is assembled into the opening 75 with a sealing member (not shown) sandwiched between the wall of the plasma processing chamber C2 and the mounting tool 72. Outside the plasma processing chamber C2, the LA71 is electrically connected to a high-frequency power supply (RF power supply) via an impedance matching device. Such an LA71 is formed of a conductor. Examples of conductors include copper and silver, with copper being preferred. The LA71 may also be covered by an insulator. Examples of insulators include glass and quartz.

[0055] The cover block 73 comprises a block body 73A and a plurality of partition plates 73B. The block body 73A has a plurality of receiving spaces 73a. Each receiving space 73a receives one LA71. The partition plates 73B are configured to close the receiving spaces 73a. The receiving spaces 73a are sealed spaces. In the cover block 73, the block body 73A is made of aluminum, for example. Aluminum A5052 can be listed as an example of aluminum. The partition plates 73B are made of insulating material. Quartz and glass can be listed as insulating materials, for example. Furthermore, the distance d' between the substrate film 10 traveling in the plasma processing chamber C2 and the cover block 73 (shown in...) Figure 6 For example, the diameter is 50-200 mm. Such a cover 73 will not excessively reduce the plasma conversion efficiency caused by the power applied to LA71, helps to avoid damage and contamination to LA71 caused by plasma treatment, and also helps to suppress damage to the plasma-treated substrate film 10.

[0056] like Figure 5As shown, in the present embodiment, the LA 71 has an open loop shape. The LA 71 having the open loop shape is advantageous in reducing the inductance of the LA 71. Thus, according to the LA 71 of the open loop shape, the increase in voltage due to the increase in electric power applied to the LA 71 can be suppressed. Thereby, the abnormal discharge at the time of plasma processing to be described later can be suppressed. By suppressing the abnormal discharge, the damage to the substrate film 10 subjected to plasma processing can be suppressed. Specifically, the LA 71 has a U shape with two free ends. Each of the LA 71 is fixed to the mounting tool 72 in such a manner that the two free ends are arranged in the width direction of the substrate film 10. Further, in the present embodiment, the LA 71 has an extension 71a on the side opposite to the two free ends. The extension 71a extends in parallel with respect to the substrate film 10 passing through the plasma processing chamber C2. The extension 71a extends in the width direction of the substrate film 10. Each of the extensions 71a can also extend in the traveling direction of the substrate film 10 (four LAs 71 can also be arranged in this manner). The length of the extension 71a is, for example, 50 to 150 mm (the case where the length of the extension 71a is the same as the maximum length d2 of the LA 71 to be described later is exemplarily illustrated). The LA 71 can have a coil shape instead of the open loop shape. Figure 5

[0057] The LA 71 extends from the mounting tool 72 toward the substrate film 10. The LA 71 preferably extends in a direction perpendicular to the mounting tool 72. The extension length d1 of the LA 71 from the mounting tool 72 is, for example, 30 to 150 mm. The maximum length d2 of the LA 71 in the surface direction of the substrate film 10 is, for example, 50 to 150 mm. The interval distance d3 between the LA 71 and the substrate film 10 (shown in Figure 6 ​The extension length d1 is preferably the same as the interval distance d3. The ratio (d3 / d1) of the interval distance d3 to the extension length d1 is, for example, 0.5 to 3.5. The number of LA71s (the number of columns) arranged in the traveling direction of the substrate film 10 can be 1, 2, or 3, or 4 or more if necessary, depending on the traveling speed of the substrate film 10 (i.e., the plasma treatment time). The center-to-center distance d4 between adjacent LA71s in the traveling direction of the substrate film 10 is, for example, 100 to 500 mm. The center-to-center distance d5 between adjacent LA71s in the width direction of the substrate film 10 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 substrate film 10 described later can be controlled. The center-to-center distance d4 is preferably the same as the center-to-center distance d5. 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 extensions 71a of the four LA71s preferably form a square as the apexes. With such a set of LA71s, a plasma of high in-plane uniformity and high density can be generated. As the LA71, for example, the high-frequency antenna for plasma generation described in Japanese Patent Application Publication No. 2013-258153 can be used.

[0058] In the present embodiment, the plasma treatment chamber C2 further includes a transport roller 53. The transport roller 53 is a main guide roller for transporting the work film W within the plasma treatment chamber C2. The transport roller 53 has a temperature adjustment function capable of heating or cooling the work film W. That is, the transport roller 53 is a temperature-adjusted transport roller. While the device Y is operating, the transport roller 53 transports the substrate film 10 while being in contact with the second surface 10b of the substrate film 10. The LA71 described above is arranged opposite the transport roller 53. With the device Y including such a plasma treatment chamber C2, in the plasma treatment process S2, the substrate film 10 is subjected to plasma treatment while being cooled or heated by the temperature-adjusted transport roller 53 in contact with the substrate film 10. By controlling the temperature of the substrate film 10, the thermal deformation of the substrate film 10 can be suppressed, and in addition, the influence of the thermal deformation on the transport of the substrate film 10 can be suppressed.

[0059] The PEM device is a device for implementing plasma emission monitoring (PEM) in plasma treatment, and includes a device main body and an optical fiber for light collection. The front end (one end) of the optical fiber is arranged between the work film W and the LA71 in the separation direction of the work film W and the LA71 within the plasma treatment chamber C2. The other end of the optical fiber is connected to the device main body. In addition, a first line L1 including a flow rate adjustment valve for introducing a gas into the chamber is connected to the plasma treatment chamber C2.

[0060] The connecting chamber C3 is disposed after the plasma treatment chamber C2 and before the film formation chamber C4 in the traveling direction of the work film W. A prescribed number of guide rollers G for guiding the work film W are provided in the connecting chamber C3. The connecting chamber C3 is connected to a vacuum pump not shown and is configured to be able to adjust the pressure in the chamber. The pressure in the connecting chamber C3 is maintained at a prescribed pressure between the pressure in the plasma treatment chamber C2 and the pressure in the film formation chamber C4 when the device Y is in operation. Thus, the pressure difference between the plasma treatment chamber C2 and the film formation chamber C4 is ensured.

[0061] The film formation chamber C4 is disposed after the connecting chamber C3 in the traveling direction of the work film W. Further, the film formation chamber C4 is connected to a vacuum pump not shown and is configured to be able to adjust the chamber to a prescribed degree of vacuum. The film formation process S3 is performed in the film formation chamber C4 as described later.

[0062] In the present embodiment, the film formation chamber C4 is a sputtering film formation chamber. The film formation chamber C4 is provided with a film formation roller 54 and a plurality of sputtering chambers 60 (sputtering chambers 60a to 60e) (the number of sputtering chambers 60 is exemplarily shown to be five). The film formation roller 54 is a main guide roller for transporting the work film W in 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 chambers 60 are spaces partitioned in the film formation chamber C4. The plurality of sputtering chambers 60 are disposed in the circumferential direction of the film formation roller 54. Each of the sputtering chambers 60 is open toward the film formation roller 54. A cathode 61 is provided in each of the sputtering chambers 60. A target (not shown) as a film formation material supply member is disposed on the cathode 61. The target is disposed on the target in opposition to the film formation roller 54. A power source (not shown) for applying a voltage to the target to cause glow discharge is provided in each of the sputtering chambers 60. 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. A second line (not shown) with a required number of flow rate adjustment valves for introducing a gas into the chamber is connected to each of the sputtering chambers 60. Further, a prescribed number of guide rollers G for guiding the work film W are provided in the film formation chamber C4.

[0063] The connecting chamber C5 and the connecting chamber C6 are disposed in this order between the film formation chamber C4 and the take-up chamber R2 in the traveling direction of the work film W. A prescribed number of guide rollers G for guiding the work film W are provided in the connecting chamber C5. A prescribed number of guide rollers G for guiding the work film W are provided in the connecting chamber C6. The connecting chamber C5 is connected to a vacuum pump not shown and is configured to be able to adjust the pressure in the chamber. The connecting chamber C6 is connected to a vacuum pump not shown and is configured to be able to adjust the pressure in the chamber. The pressures in the connecting chambers C5 and C6 are maintained at a prescribed pressure between the pressure in the film formation chamber C4 and the pressure in the take-up chamber R2 when the device Y is in operation. Thus, the pressure difference between the film formation chamber C4 and the take-up chamber R2 is ensured.

[0064] With the apparatus Y described above, the plasma treatment step S2 and the film formation step S3 are sequentially performed. Specifically, as described below.

[0065] The working film W is extracted from the extraction chamber R1. The working film W, after being extracted from the extraction chamber R1, sequentially passes through the connection chamber C1, the plasma treatment chamber C2, the connection chamber C3, the film formation chamber C4, the connection chamber C5, and the connection chamber C6, and is wound up in the winding chamber R2. The traveling speed of the working film W is preferably 0.5 m / minute or more, more preferably 0.7 m / minute or more, further preferably 0.9 m / minute or more, and in addition, preferably 10 m / minute or less, more preferably 8 m / minute or less, further preferably 5 m / minute or less. In the case where the traveling speed of the working film W is the above lower limit value or more, the manufacturing efficiency of the laminate X can be ensured. In the case where the traveling speed of the working film W is the above upper limit value or less, the unevenness in the quality of the laminate X can be suppressed. In addition, the series of pipelines from the extraction chamber R1 to the winding chamber R2 are not opened to the atmosphere midway, and the processes under a reduced pressure atmosphere are performed in the pipelines. The reduced pressure atmosphere is preferably under vacuum. Under vacuum means under a reduced pressure atmosphere of preferably 7 Pa or less.

[0066] The plasma treatment step S2 is performed in the plasma treatment chamber C2. In the plasma treatment step S2, the first surface 10a of the base film 10 is subjected to plasma treatment under a reduced pressure atmosphere in the plasma treatment chamber C2 (chamber). The plasma treatment can be performed while sensing the intensity of plasma emission light. The plasma treatment is a treatment performed using inductively coupled plasma containing argon gas generated by applying high-frequency power to the LA 71. Specifically, as described below.

[0067] Argon is supplied into the plasma treatment chamber C2 in the plasma treatment via the first pipeline L1. Other inert gases than argon can also be supplied into the plasma treatment chamber C2. As the other inert gases, for example, krypton and xenon can be listed. In addition, other gases than inert gases can also be contained in the gas in the plasma treatment chamber C2. As the other gases, for example, oxygen, nitrogen, hydrogen, and water vapor can be listed. The concentration of argon (Ar concentration) in the gas (argon-containing gas) in the plasma treatment chamber C2 is preferably 50 vol% or more, more preferably 65 vol% or more, further preferably 80 vol% or more, more further preferably 90 vol% or more, still further preferably 95 vol% or more, and particularly preferably 100 vol%. In the case where the Ar concentration is the above lower limit value or more, high-density argon plasma can be generated.

[0068] The pressure (first pressure) in the plasma processing chamber C2 in the plasma processing is preferably 0.1 Pa or more, more preferably 0.2 Pa or more, further preferably 0.3 Pa or more, and in addition, preferably 7 Pa or less, more preferably 5 Pa or less, further preferably 3 Pa or less. In the case where the first pressure is the above lower limit value or more, in the plasma processing, a plasma environment with a density sufficient to perform the surface modification treatment on the first surface 10a of the substrate film 10 can be formed in the plasma processing chamber C2. In the case where the first pressure is the above upper limit value or less, in the plasma processing, thermal damage to the first surface 10a due to excessively high-density plasma can be suppressed, and in addition, thermal deformation of the substrate film 10 can be suppressed. The first pressure can be adjusted by the amount of argon gas supplied into the plasma processing chamber C2.

[0069] The frequency of the high-frequency electric power applied to the LA71 in the plasma processing is preferably 1 MHz or more, more preferably 5 MHz or more, further preferably 10 MHz or more, and in addition, preferably 100 MHz or less, more preferably 80 MHz or less, further preferably 60 MHz or less. In the case where the frequency is the above lower limit value or more, the plasma current density can be increased, and the plasma discharge can be stabilized. In the case where the frequency is the above upper limit value or less, the antenna potential can be suppressed, and therefore, damage to the substrate film 10 by the plasma can be suppressed. In addition, the high-frequency electric power is preferably 0.1 kW or more, more preferably 0.3 kW or more, further preferably 1.0 kW or more, and in addition, preferably 10 kW or less, more preferably 8 kW or less, further preferably 6 kW or less. In the case where the high-frequency electric power is the above lower limit value or more, in the plasma processing using inductively coupled plasma, a high-density plasma environment can be formed in the plasma processing chamber C2. In the case where the high-frequency electric power is the above upper limit value or less, excessive damage to the substrate by the plasma can be suppressed.

[0070] In the plasma treatment step S2, the intensity of the plasma emission in the plasma treatment can be monitored by the PEM device. Then, for example, based on the monitoring result, the wavelength of the intensity Imax of the maximum emission peak in the range of 300 nm to 900 nm in the plasma emission is controlled to be within 811 nm to 812 nm. Further, the ratio (I2 / I1) of the intensity I2 of the emission peak within the wavelength of 603 nm to 604 nm to the intensity I1 of the emission peak within the wavelength of 706 nm to 707 nm is controlled to be 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less, and further preferably 0.35 or less. The maximum emission peak in the range of 300 nm to 900 nm in the plasma emission is an emission peak attributed to the transition from the ground state 11.55 eV to the excited state 13.08 eV of the argon radical. The emission peak within the wavelength of 706 nm to 707 nm is an emission peak attributed to the transition from the ground state 11.55 eV to the excited state 13.30 eV of the argon radical. The emission peak within the wavelength of 603 nm to 604 nm is an emission peak attributed to the transition from the ground state 13.08 eV to the excited state 15.13 eV of the argon radical. The wavelength of the intensity Imax of the maximum emission peak is within 811 nm to 812 nm, and the ratio (I2 / I1) is 0.50 or less, which indicates that the kinetic energy of the argon particles in the plasma is suppressed. Specifically, as shown in the examples and comparative examples described later. In the case where the ratio (I2 / I1) is the above upper limit value or less, the excessive increase in the kinetic energy of the argon particles in the plasma can be controlled, and the damage to the surface of the plasma treatment target can be suppressed. The ratio (I2 / I1) is preferably 0.01 or more, more preferably 0.10 or more, and further preferably 0.20 or more. In the case where the ratio (I2 / I1) is the above lower limit value or more, the moderate active movement of the argon particles is ensured, and the activation of the surface of the plasma treatment target can be promoted. As the control method of the intensity of the plasma emission, for example, the adjustment of the amount of the argon gas introduced into the plasma treatment chamber C2, the adjustment of the frequency of the high-frequency power of the high-frequency power source, and the adjustment of the magnitude of the applied power can be cited.

[0071] In the plasma treatment step S2, the plasma current density at the intermediate position between the LA 71 and the substrate film 10 is preferably 1.0 mA / cm 3 More preferably, it is 2.0 mA / cm 3 Further preferably, it is 3.0 mA / cm 3 Furthermore, it is preferably 10 mA / cm 3 More preferably, it is 8 mA / cm 3 Further preferably, it is 4 mA / cm 3The lower limit value of the plasma current density is preferably 0.1 A / dm2or more. In the case where the plasma current density is the above lower limit value or more, in the plasma treatment, sufficient plasma-ized argon particles can be ensured within the plasma treatment chamber C2, and the first surface 10a of the substrate film 10 can be appropriately surface-modified. In the case where the plasma current density is the above upper limit value or less, in the plasma treatment, damage to the first surface 10a caused by excessively high-density plasma-ized argon particles can be suppressed. As a method of adjusting the plasma current density, for example, adjustment of the amount of argon gas introduced into the plasma treatment chamber C2, adjustment of the frequency of the high-frequency power of the high-frequency power source, and adjustment of the magnitude of the applied power can be cited.

[0072] In the film formation process S3, after the plasma treatment process S2, the inorganic layer 20 is formed on the first surface 10a of the substrate film 10 in a reduced-pressure atmosphere. The reduced-pressure atmosphere is preferably under vacuum. As the inorganic layer 20, for example, a conductive layer and an antireflection layer can be cited. The laminated film X provided with the conductive layer as the inorganic layer 20 is a transparent conductive film. The laminated film X provided with the antireflection layer as the inorganic layer 20 is an antireflection film. The inorganic layer 20 can be another kind of layer.

[0073] As the material of the conductive layer, for example, a metal and a metal oxide can be cited. As the metal, for example, copper, silver, gold, nickel, chromium, and alloys of these metals can be cited. As the metal oxide, for example, an indium-containing conductive oxide and an antimony-containing conductive oxide can be cited. As the indium-containing conductive oxide, for example, indium tin complex oxide (ITO), indium zinc complex oxide (IZO), indium gallium complex oxide (IGO), and indium gallium zinc complex oxide (IGZO) can be cited. As the antimony-containing conductive oxide, for example, antimony tin complex oxide (ATO) can be cited.

[0074] In the case where the conductive layer is formed as the inorganic layer 20, the inorganic layer 20 (conductive layer) is formed, for example, by a sputtering method in at least one of the sputtering chambers 60 of the film formation chamber C4. Thus, the laminated film X is manufactured.

[0075] In the sputtering method, a target disposed on a cathode 61 in the sputtering chamber 60 is applied with a negative voltage while a sputtering gas (inert gas) is introduced into the film formation chamber C4. Thus, glow discharge is generated to ionize the gas atoms, and the gas ions collide with the target surface at high speed to eject the target material from the target surface, and the ejected target material is deposited on the substrate film 10. As the sputtering gas, for example, argon, krypton, and xenon can be cited. The sputtering gas is introduced into the film formation chamber C4 via one second line. The target is composed of, for example, the material forming the inorganic layer 20.

[0076] In the case where the material of the inorganic layer 20 is a metal oxide, the sputtering method can be a reactive sputtering method. In the reactive sputtering method, oxygen (reactive gas) is introduced into the film formation chamber C4 in addition to a sputtering gas. The oxygen is introduced into the film formation chamber C4 via the other second line. In the reactive sputtering method, the target is composed of, for example, a metal that forms the metal oxide of the inorganic layer 20.

[0077] In the sputtering method, the pressure (second pressure) in the film formation chamber C4 is, for example, 0.1 to 5.0 Pa depending on the kind of the inorganic layer 20 to be formed. The film formation temperature (temperature of the substrate film 10 subjected to temperature adjustment by the film formation roll 54) is, for example, -10°C to 150°C depending on the kind of the inorganic layer 20. As to these, the same applies to the sputtering method described later in the case where the inorganic layer 20 is formed as an antireflection layer.

[0078] The thickness of the inorganic layer 20 as the conductive layer is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more from the viewpoint of lowering the resistance of the inorganic layer 20. The thickness of the inorganic layer 20 as the conductive layer is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less from the viewpoint of thinning the stacked film X.

[0079] The antireflection layer contains, for example, a plurality of transparent inorganic oxide films stacked in the thickness direction H. The inorganic layer 20 as the antireflection layer contains, for example, 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 as the transparent inorganic oxide films in this order from the substrate film 10 side. Each high refractive index layer is composed of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm. As the high refractive index material, for example, niobium oxide (Nb2O5), titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO) can be listed, and niobium oxide is preferable. The thickness of each high refractive index layer is, for example, 3 to 50 nm. Each low refractive index layer is composed of a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm. As the low refractive index material, for example, silicon dioxide (SiO2) and magnesium fluoride can be listed, and silicon dioxide is preferable. The thickness of each low refractive index layer is, for example, 8 to 50 nm. In the case where such an antireflection layer is formed as the inorganic layer 20, the inorganic layer 20 (antireflection layer) is formed, for example, by the sputtering method in the plurality of sputtering chambers 60 in the film formation chamber C4. For example, as described below.

[0080] First, a first high refractive index layer is formed on the substrate film 10 by sputtering in the sputtering chamber 60a. In the case where an Nb2O5layer is formed as the first high refractive index layer, an Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60a. Also, reactive sputtering is performed while argon and oxygen are introduced into the film formation chamber C4 (reactive sputtering is also performed in the following sputtering in the sputtering chambers 60b to 60d).

[0081] Next, a first low refractive index layer is formed on the first high refractive index layer by sputtering in the sputtering chamber 60b. In the case where a SiO2layer is formed as the first low refractive index layer, a Si target is used as the target disposed on the cathode 61 in the sputtering chamber 60b.

[0082] Next, a second high refractive index layer is formed on the first low refractive index layer by sputtering in the sputtering chamber 60c. In the case where an Nb2O5layer is formed as the second high refractive index layer, an Nb target is used as the target disposed on the cathode 61 in the sputtering chamber 60c.

[0083] Next, a second low refractive index layer is formed on the second high refractive index layer by sputtering in the sputtering chamber 60d. In the case where a SiO2layer is formed as the second low refractive index layer, a Si target is used as the target disposed on the cathode 61 in the sputtering chamber 60d.

[0084] In the apparatus Y, after the plasma treatment step S2 and the film formation step S3, the laminated film X as the work film W passes through the inside of the connecting chambers C5, C6 to reach the inside of the take-up chamber R2, and is taken up by the take-up roll 52.

[0085] In the method of manufacturing the laminated film X, as described above, in the plasma treatment step S2 under a reduced pressure atmosphere performed on the first face 10a of the substrate film 10, treatment using inductively coupled plasma containing argon gas generated by applying high-frequency power to the LA 71 (low-inductance antenna) is performed. Such plasma treatment enables a higher plasma current density than the above-described plasma treatment of the capacitive coupling type (for example, a plasma density of about 100 times higher can be achieved). The higher the plasma current density, the more dirt and moisture on the first face 10a can be removed. This removal of dirt and moisture contributes to improvement in adhesion of the inorganic layer 20 formed on the first face 10a in the film formation step S3 to the first face 10a (substrate film 10). Removal of dirt and moisture also contributes to securing of the original optical properties of the substrate film 10.

[0086] Further, in the plasma treatment step S2, as described above, the wavelength of the maximum intensity Imax of the light emission in the wavelength range of 300 nm to 900 nm in the plasma light emission is set to be within 811 nm to 812 nm, and the ratio (I2 / I1) of the intensity I2 of the light emission peak in the wavelength range of 603 nm to 604 nm to the intensity I1 of the light emission peak in the wavelength range of 706 nm to 707 nm is set to be 0.50 or less. By adjusting the intensity of the plasma light emission in the plasma treatment step S2 in this way, the kinetic energy of the argon particles in the plasma can be suppressed. Also, the deterioration of the surface of the substrate film 10 exposed to the plasma can be suppressed. Thus, the change in the optical characteristics of the substrate film 10 can be suppressed.

[0087] Further, in the film formation step S3 after the plasma treatment step S2, as described above, the inorganic layer 20 is formed on the first surface 10a of the substrate film 10 under a reduced pressure atmosphere after the plasma treatment step S2. That is, the substrate film 10 is not placed under an atmospheric pressure between the plasma treatment step S2 and the film formation step S3. According to such a film formation step S3, the mixing of foreign matter between the substrate film 10 and the inorganic layer 20 can be suppressed or prevented. This contributes to the production of the laminated film X having good optical characteristics.

[0088] Thus, according to the above-described laminated film production method, the laminated film X having the inorganic layer 20 on the substrate film 10 and having good optical characteristics can be produced.

[0089] The inorganic layer 20 of the laminated film X can have a conductive layer on the substrate film 10 and an antireflection layer on the conductive layer. The antireflection layer can include the above-described first high refractive index layer, the first low refractive index layer, the second high refractive index layer, and the second low refractive index layer in the order from the conductive layer side. In the case where such an inorganic layer 20 is formed, in the film formation chamber C4, the conductive layer is formed by the sputtering method in the sputtering chamber 60a, the first high refractive index layer is formed by the sputtering method in the sputtering chamber 60b, the first low refractive index layer is formed by the sputtering method in the sputtering chamber 60c, the second high refractive index layer is formed by the sputtering method in the sputtering chamber 60d, and the second low refractive index layer is formed by the sputtering method in the sputtering chamber 60e. In this way, a transparent conductive film with an antireflection layer can be produced.

[0090] The inorganic layer 20 of the laminated film X may include an adhesive layer on the substrate film 10 and the aforementioned antireflective layer on the adhesive layer. The adhesive layer is used to ensure the adhesion of the antireflective layer to the substrate film 10 (which is mainly formed of organic materials). Examples of materials for such an adhesive layer include oxides of metals such as silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium. From the viewpoint of balancing adhesion to both the substrate film 10 and the antireflective layer, and the transparency of the adhesive layer, the material of the adhesive layer is preferably indium tin oxide (ITO) or silicon oxide (SiOx). Silicon oxide is preferably SiOx with a low oxygen content compared to its stoichiometric composition, and more preferably SiOx with x being 1.2 or higher and 1.9 or lower.

[0091] The anti-reflective layer on the sealing layer can include, from the sealing layer side, the first high refractive index layer, the first low refractive index layer, the second high refractive index layer, and the second low refractive index layer in the following order. When forming such an inorganic layer 20, in the film formation chamber C4, the sealing layer is formed by sputtering in the sputtering chamber 60a, the first high refractive index layer is formed by sputtering in the sputtering chamber 60b, the first low refractive index layer is formed by sputtering in the sputtering chamber 60c, the second high refractive index layer is formed by sputtering in the sputtering chamber 60d, and the second low refractive index layer is formed by sputtering in the sputtering chamber 60e.

[0092] like Figure 7 As shown, the above-mentioned device Y can include a plasma processing chamber C2' instead of the plasma processing chamber C2 ( Figure 4 The plasma processing chamber C2' differs from the plasma processing chamber C2 in that it does not have the conveyor roller 53. That is, the device Y may not have the conveyor roller 53.

[0093] In the above embodiment, the inorganic layer 20 is formed by sputtering in the film formation step S3. Alternatively, the inorganic layer 20 can be formed by vapor deposition instead of sputtering in the film formation step S3. In this case, the apparatus Y includes a vapor deposition chamber as the film formation chamber C4, replacing the sputtering chamber. Alternatively, the inorganic layer 20 can be formed by chemical vapor deposition (CVD) instead of sputtering in the film formation step S3. In this case, the apparatus Y includes a CVD chamber as the film formation chamber C4, replacing the sputtering chamber. The method for forming the inorganic layer 20 can be selected based on factors such as the material and thickness of the inorganic layer 20.

[0094] [Example]

[0095] The following examples specifically illustrate the present application. However, the present application is not limited to the examples. Furthermore, the specific numerical values of the compounding amounts (contents), physical property values, parameters, etc. described below can be replaced with the upper limits (numerical values defined by "below" or "less than") or lower limits (numerical values defined by "above" or "more than") of the compounding amounts (contents), physical property values, parameters, etc. corresponding thereto described in the "DETAILED DESCRIPTION OF THE INVENTION" above.

[0096] Example 1

[0097] The following procedures were sequentially performed to produce the sample film of Example 1.

[0098] First, a hard coat layer was formed on one side of a triacetyl cellulose (TAC) film as a resin film to produce a base film (preparation step). Specifically, first, 100 parts by mass (solid content conversion value) of a butyl acetate solution of an ultraviolet-curable acryl urethane resin (trade name "LUXYDIR 17-806", solid content concentration 80% by mass, manufactured by DIC Corporation), 5 parts by mass of a photopolymerization initiator (trade name "Omnirad 907", manufactured by IGM Resins Corporation), 0.03 parts by mass of a leveling agent (trade name "GRANDIC PC4100", manufactured by DIC Corporation), and butyl acetate as a solvent were mixed to prepare a first resin composition having a solid content concentration of 75% by mass. Subsequently, cyclopentanone was added to the first resin composition as another solvent to prepare a second resin composition having a solid content concentration of 50% by mass. Meanwhile, a long TAC film (length 100 m, width 340 mm, thickness 40 μm) was prepared. Subsequently, the second resin composition was applied to one side of the TAC film to form a coating film. Subsequently, after the coating film was dried by heating, it was cured by ultraviolet irradiation. Thus, a hard coat (HC) layer having a thickness of 5 μm was formed on the TAC film. The temperature of the heating was set to 100°C, and the time of the heating was set to 60 seconds. In the ultraviolet irradiation, a high-pressure mercury lamp was used as a light source, and ultraviolet light having a wavelength of 365 nm was irradiated to the coating film, and the cumulative light amount was set to 300 mJ / cm 2 . In this manner, a TAC film with an HC layer was produced as a base film.

[0099] Subsequently, the base film was transported in a roll-to-roll manner under vacuum while plasma treatment was performed on the base film (plasma treatment step). In this step, a device capable of performing a roll-to-roll process on a work film was used. The device was provided with an extraction chamber, a plasma treatment chamber, a film formation chamber, and a winding chamber. The extraction chamber, the plasma treatment chamber, the film formation chamber, and the winding chamber were arranged in this order and communicated. The extraction chamber was provided with an extraction roll. The roll of the above-described base film was provided as a work film on the extraction roll. The plasma treatment chamber was provided with a transport roll having a temperature adjustment function (Figure 4 Conveyor roller 53) and like Figure 5 and Figure 6 As shown, use a cover block ( Figure 6 The cover block 73 covers four low-inductance antennas ( Figure 5 and Figure 6 (LA71 in the text). Each low-inductance antenna has an extension parallel to the substrate film ( Figure 5 The extension 71a). Among the four low-inductance antennas, the extension length d1 is 88 mm, the maximum length d2 (length of the extension) is 100 mm, the spacing 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 and Figure 6 Each low-inductance antenna is electrically connected to a high-frequency power supply (RF power supply, frequency 13.56MHz) outside the plasma processing chamber via an impedance matching device. The spacing d' between the substrate film and the cover block traveling within the plasma processing chamber is 100mm. Furthermore, the film-forming chamber is a sputtering film-forming chamber, equipped with a film-forming roller and a cathode disposed opposite to the film-forming roller. The winding chamber is equipped with a winding roller.

[0100] In this process, specifically, while the substrate film is conveyed from the extraction chamber to the winding chamber via a roll-to-roll method, the plasma emission intensity of the HC surface (first side) of the substrate film is sensed and plasma treatment is performed in the plasma treatment chamber. The substrate film travel speed (film travel speed) is set to 1.0 m / min. The temperature of the conveyor roller with temperature control function is set to -8°C. The sensing of plasma emission intensity is performed via an optical fiber positioned at the front end in the plasma treatment chamber and through a beam splitter (trade name "Qwave2", manufactured by Broadcom). The plasma treatment conditions are as follows.

[0101] The device was evacuated until the ultimate vacuum level of the plasma processing chamber reached 1.0 × 10⁻⁶. －4 After Pa, argon gas, acting as an inert gas, was introduced into the plasma processing chamber, and the pressure inside the chamber was set to 0.5 Pa. A high-frequency power of 2.0 kW was applied to four low-inductance antennas using a high-frequency power supply, thereby forming an argon-containing inductively coupled plasma around the antennas (this plasma was used to treat the HC layer surface of the substrate film). Consequently, the wavelength of the maximum emission peak intensity Imax in the 300 nm–900 nm wavelength range of plasma emission was set to 811 nm, and the ratio (I2 / I1) of the emission peak intensity I2 in the 603 nm–604 nm wavelength range to the emission peak intensity I1 in the 706 nm–707 nm wavelength range was set to 0.32. Furthermore, the plasma current density at the midpoint between the low-inductance antenna and the substrate film was set to 1.3 mA / cm².3 The plasma current density was measured by a Langmuir probe for plasma measurement.

[0102] As described above, the substrate film was subjected to the plasma treatment step. The substrate film thus obtained was set as the sample film of Example 1. The above plasma treatment in Example 1 was a treatment (Ar-LAICP treatment) using inductively coupled plasma containing argon gas generated by applying high-frequency power to a low-inductance antenna (the plasma treatment in Examples 2 and 3 was also the same).

[0103] [Example 2]

[0104] The sample film of Example 2 was obtained in the same manner as the sample film of Example 1 except for the following. In the plasma treatment step, the applied high-frequency power was set to 3.5 kW, the above ratio (I2 / I1) was set to 0.31, and the plasma current density was set to 2.4 mA / cm 3 .

[0105] [Example 3]

[0106] The sample film of Example 3 was obtained in the same manner as the sample film of Example 1 except for the following. In the plasma treatment step, the applied high-frequency power was set to 5.0 kW, the above ratio (I2 / I1) was set to 0.29, and the plasma current density was set to 4.2 mA / cm 3 .

[0107] [Comparative Example 1]

[0108] First, the substrate film (TCA film / HC layer) was produced in the same manner as the preparation step in Example 1 to form the HC layer on one side of the TAC film.

[0109] Next, the substrate film was transported in a roll-to-roll manner under vacuum, and plasma treatment was performed on the substrate film (plasma treatment step). In this step, a device capable of performing a roll-to-roll process on a work film was used. The device was provided with an extraction chamber, a plasma treatment chamber, a film formation chamber, and a winding chamber. The extraction chamber, the plasma treatment chamber, the film formation chamber, and the winding chamber were arranged in this order and communicated. The extraction chamber was provided with an extraction roller. The roll of the substrate film described above was set as the work film on the extraction roller. The plasma treatment chamber was provided with a cathode electrode and an anode electrode as a pair of planar electrodes for plasma generation (both were rectangular electrodes made of SUS304). The pair of planar electrodes was arranged in parallel with the substrate film passing through the plasma treatment chamber at an interval of 50 mm. The anode electrode was arranged at a position 35 mm apart from the substrate film passing through the plasma treatment chamber and was grounded outside the plasma treatment chamber. The cathode electrode was arranged so as to face the HC layer surface of the substrate film and was electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. The length of each electrode in the film travel direction was 110 mm, and the length in the width direction was 430 mm. Further, the film formation chamber was a sputtering film formation chamber provided with a film formation roller and a cathode arranged opposite to the film formation roller. The winding chamber was provided with a winding roller.

[0110] In this step, specifically, the substrate film was transported from the extraction chamber to the winding chamber in a roll-to-roll manner, and the HC surface (first surface) of the substrate film was subjected to sensing of plasma emission intensity and plasma treatment (bombardment treatment) in the plasma treatment chamber. The travel speed of the substrate film (film travel speed) was set to 1.0 m / min. The sensing of the plasma emission intensity was performed via an optical fiber arranged at the front end in the plasma treatment chamber and by a spectrometer (trade name "Qwave2", manufactured by Broadcom). The conditions of the plasma treatment were as described below.

[0111] After the device was evacuated until the limit vacuum degree of the plasma treatment chamber reached 1.0 x 10 －4 After the device was evacuated until the limit vacuum degree of the plasma treatment chamber reached 1.0 x 10

[0112] As described above, the substrate film was subjected to the plasma treatment step. The substrate film thus obtained was set as the sample film of Comparative Example 1. The above plasma treatment in Comparative Example 1 was ion bombardment treatment, specifically, treatment using a capacitively coupled plasma using an argon-containing gas (Ar-BB) (the plasma treatment in Comparative Example 2 was also the same).

[0113] [Comparative Example 2]

[0114] The sample film of Comparative Example 2 was obtained in the same manner as the sample film of Comparative Example 1 except for the following. In the plasma treatment step, the applied electric power was set to 550 W, and the ratio of the emission peak intensity (I2 / I1) was set to 1.01.

[0115] 〈Surface Free Energy〉

[0116] The surface free energy of the plasma-treated surface of each sample film of Examples 1 to 3 and Comparative Examples 1 and 2 was obtained as described below.

[0117] First, the sample film was placed on a glass slide arranged horizontally. Specifically, the sample film was placed on the glass slide with the plasma-treated surface (HC layer surface) of the sample film facing upward. Next, 2 μL of a prescribed liquid was added to the plasma-treated surface of the sample film on the glass slide in an atmosphere of 23°C and a relative humidity of 50% to form a droplet (droplet formation). Next, the contact angle of the droplet with respect to the surface of the sample film (plasma-treated surface) was measured using a contact angle meter (trade name "DMs-401", manufactured by Kyowa Interface Science Co., Ltd.) (contact angle measurement). As the liquid, water (H2O), diiodomethane (CH2I2), and 1-bromonaphthalene were used. Each liquid was subjected to a series of operations including droplet formation and subsequent contact angle measurement five times. The measurement was performed within 24 hours after the plasma treatment of the substrate film. The average of the five measurement values of each liquid was taken as the contact angle of the liquid. In this manner, the contact angle of water θw, the contact angle of diiodomethane θi, and the contact angle of 1-bromonaphthalene θb of the sample film were obtained.

[0118] Next, for each sample film, the values of the contact angle of water θw, the contact angle of diiodomethane θi, and the contact angle of 1-bromonaphthalene θb were used to solve the three simultaneous equations in the kitazaki-hata theory, whereby the surface free energy γ represented by γ = γ d + γ p + γ h γ d , γ p , γ hThe Kihashi-Hata theory is described, for example, in the Journal of the Adhesion Society of Japan, Vol. 8, No. 3, p. 131-141 (1972). In the formula, γ d is the dispersion component of the surface free energy, γ p is the polar component of the surface free energy, γ h is the hydrogen bond component of the surface free energy. Also, the value (γ) obtained by summing γ d , γ p , and γ h is taken as the surface free energy of the plasma-treated surface of the test film. As the values required for derivation, the dispersion component γ d of the surface free energy of water was set to 29.1 mN / m, the polar component γ p was set to 1.3 mN / m, and the hydrogen bond component γ h was set to 42.4 mN / m. The dispersion component γ d of the surface free energy of diiodomethane was set to 46.8 mN / m, the polar component γ p was set to 4.0 mN / m, and the hydrogen bond component γ h was set to 0.0 mN / m. The dispersion component γ d of the surface free energy of 1-bromonaphthalene was set to 44.4 mN / m, the polar component γ p was set to 0.1 mN / m, and the hydrogen bond component γ h was set to 0.0 mN / m. The surface free energy (mN / m) of the plasma-treated surface of the test film is shown in Table 1.

[0119] Elemental Composition Analysis

[0120] The proportions of chromium (Cr) and iron (Fe) present in the plasma-treated surface of each test film of Examples 1 to 3 and Comparative Examples 1 and 2 were investigated.

[0121] Specifically, first, a test film piece (1 cm x 1 cm) was cut from the central portion in the width direction of the test film. Next, the elemental composition of the plasma-treated surface of the test film piece was analyzed by X-ray photoelectron spectroscopy (XPS). An X-ray photoelectron spectrometer (trade name "Quantera SXM", manufactured by ULVAC-PHI, Inc.) was used for the analysis. In this analysis, a narrow scan with Cr and Fe as the analysis targets was performed under the following conditions, and the elemental ratio (atomic %) of Cr and Fe was determined. The results are shown in Table 1. In the test films of Examples 1 to 3, Cr and Fe were not detected (in Table 1, shown as less than the detection limit of 0.1 atomic %).

[0122] Excitation X-ray source: monochromatic Al Kα.

[0123] X-ray settings: 100 μm φ (15 kV, 25 W).

[0124] Photoelectron take-off angle: 45° with respect to the sample surface.

[0125] Neutralization condition: combination of neutralization gun and Ar ion gun (neutralization mode).

[0126] [Optical properties]

[0127] For each of the sample films of Examples 1 to 3 and Comparative Examples 1 and 2, the luminous transmittance (Y value) at wavelengths of 380 nm to 780 nm and the hue b ＊ of the transmitted light were investigated. Specifically, for the sample film, a transmittance spectrum in the range of wavelengths of 380 nm to 780 nm was measured by a spectrophotometer (trade name "U4100", manufactured by Hitachi, Ltd.), and based on the transmittance spectrum, the luminous transmittance and the hue b ＊ of the transmitted light were calculated. The measurement was performed in an integrating sphere measurement mode of the spectrophotometer. In the measurement, a D65 light source was used as a light source, and the sample film was disposed in the spectrophotometer in such a manner that light was irradiated from the HC layer side of the sample film. The luminous transmittance is the transmittance (Y value) in the CIE-XYZ color system. The hue b ＊ of the transmitted light is the hue b ＊ of the L ＊ a ＊ b ＊ color system. The Y value (%) and the b ＊ value are shown in Table 1.

[0128] [Evaluation]

[0129] The plasma treatment in the manufacturing process of each of the sample films of Comparative Examples 1 and 2 was, as described above, a treatment using a capacitively coupled plasma using an argon-containing gas (ion bombardment treatment), in which the wavelength of the maximum intensity Imax of the light emission in the range of wavelengths of 300 nm to 900 nm in the plasma light emission was 750 nm, and the ratio (I2 / I1) of the intensity I2 of the light emission peak in the range of wavelengths of 603 nm to 604 nm to the intensity I1 of the light emission peak in the range of wavelengths of 706 nm to 707 nm was significantly more than 0.50. In contrast, the plasma treatment in the manufacturing process of each of the sample films of Examples 1 to 3 was, as described above, a treatment using an inductively coupled plasma using an argon-containing gas generated by applying high-frequency power to a low-inductance antenna, in which the wavelength of the above-mentioned intensity Imax was in the range of 811 nm to 812 nm, and the above-mentioned ratio (I2 / I1) was 0.50 or less. Therefore, as shown in Table 1, each of the sample films of Examples 1 to 3 had a higher Y value and a smaller b ＊Low. That is, the sample films of Examples 1 to 3 were further purified compared to the sample films of Comparative Examples 1 and 2, and had good optical properties. Further, the surface free energy of the plasma-treated surface of each of the sample films of Examples 1 to 3 was higher compared to the sample films of Comparative Examples 1 and 2. That is, the sample films of Examples 1 to 3 were further purified compared to the sample films of Comparative Examples 1 and 2, and had a high active surface. The results of the elemental composition analysis described above showed that each of the sample films of Examples 1 to 3 was further purified compared to the sample films of Comparative Examples 1 and 2.

[0130]

[0131] It should be noted that the above-described application is provided as an example of an embodiment of the present application, but this is merely an example and should not be interpreted restrictively. Variations of the present application that will be apparent to those skilled in the art are included within the scope of the claims.

[0132] Industrial Applicability

[0133] The method of manufacturing the laminated film of the present application is suitable for manufacturing a laminated film having good optical properties for use in electronic products and the like.

[0134] Explanation of Reference Numerals

[0135] X: laminated film; H: thickness direction; D: surface direction; 10: base film; 10a: first surface; 10b: second surface; 11: resin film; 12: cured resin layer; 20: inorganic layer; 71: low-inductance antenna (LA); C2: plasma treatment chamber; C4: film formation chamber; 53: conveyance roll (roll with temperature adjustment function).

Claims

1. A method for manufacturing a laminated film, comprising: The preparation process involves preparing a strip of substrate film having a first side and a second side opposite to the first side; The plasma treatment process involves performing plasma treatment on the first surface of the substrate film under a reduced pressure atmosphere within a chamber. as well as In the film-forming process, following the plasma treatment process, an inorganic layer is formed on the first surface under reduced pressure. In the plasma processing step, the plasma processing is performed using an argon-containing inductively coupled plasma generated by applying high-frequency power to a low-inductance antenna. The wavelength of the maximum emission peak intensity Imax in the wavelength range of 300nm to 900nm in plasma emission is set to 811nm to 812nm, and the ratio of the emission peak intensity I2 in the wavelength range of 603nm to 604nm to the emission peak intensity I1 in the wavelength range of 706nm to 707nm is set to 0.50 or less.

2. The method for manufacturing a laminated film according to claim 1, wherein, In the plasma treatment process, within the chamber, the substrate film is conveyed while being cooled or heated by a temperature-regulating roller that is in contact with the substrate film.

3. The method for manufacturing a laminated film according to claim 1, wherein, The low-inductance antenna has a coil shape or an open-loop shape.

4. The method for manufacturing a laminated film according to claim 1, wherein, In the plasma processing step, the plasma current density at the midpoint between the low-inductance antenna and the substrate film is set to 1.0 mA / cm². 3 Above and 10mA / cm 3 the following.

5. The method for manufacturing a laminated film according to claim 1, wherein, In the film-forming process, the inorganic layer is formed by sputtering, vapor deposition, or chemical vapor deposition.

6. The method for manufacturing a laminated film according to any one of claims 1 to 5, wherein, In the film-forming process, a conductive layer is formed as the inorganic layer.

7. The method for manufacturing a laminated film according to any one of claims 1 to 5, wherein, In the film-forming process, an anti-reflective layer is formed as the inorganic layer, the anti-reflective layer comprising a plurality of transparent inorganic oxide films stacked in the thickness direction.

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