TW202000753A - Resin film, conductive film and method for manufacturing laminated film capable of suppressing film contamination even through a vacuum process - Google Patents

Abstract

The present invention provides a resin film capable of suppressing film contamination even through a vacuum process, and also provides a conductive film obtained by using the resin film, and a method for manufacturing a laminated film. A resin film includes an antioxidant having a boiling point or a thermal decomposition point of 285 DEG C or lower at the atmospheric pressure. The boiling point or thermal decomposition point of the above-mentioned antioxidant under a vacuum of 1.3 Pa is preferably 50 DEG C or lower. Furthermore, even if the antioxidant oozes from the surface of the film during the vacuum process, the antioxidant will be evaporated or decomposed and diffused from the surface due to its lower boiling point.

Description

Method for manufacturing resin film, conductive film and laminated film

The invention relates to a method for manufacturing a resin film, a conductive film and a laminated film.

Previously, a conductive film having a conductive layer formed on the surface of a resin film has been used for flexible circuit boards, electromagnetic wave shielding films, flat panel displays, contact sensors, non-contact IC cards, solar cells, and the like. The main function of the conductive film is to conduct electricity, and the method or method for obtaining the conductivity suitable for the purpose is to select the composition or thickness of the conductive layer provided on the surface of the resin film. For the formation of the conductive layer, a vacuum process typified by sputtering is widely used (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-249688

[Problems to be solved by the invention]

However, it is clear that the film surface may be contaminated especially after film formation by vacuum process. For the contaminated film, even if the film is formed, sometimes the desired film cannot be obtained. In addition, there is a possibility that the contaminants will adhere to the film winding or conveying rollers when the film is formed by the roll-to-roll method, or the contaminants will adhere when the contaminated film is wound into a roll. In other parts, the yield of the manufacturing of the laminated film that forms the thin film through the vacuum process decreases.

An object of the present invention is to provide a resin film capable of suppressing film contamination even through a vacuum process, a conductive film obtained using the same, and a method for manufacturing a laminated film. [Technical means to solve the problem]

The inventors of the present invention conducted intensive studies in order to solve the above-mentioned problems, and as a result obtained the following insights: The fouling of the membrane may be caused by the additives contained in the membrane bleed out under vacuum. After further research, it was found that the above object can be achieved by adopting the following configuration, and the present invention has been completed.

In one embodiment of the present invention, a resin film includes an antioxidant whose boiling point or thermal decomposition point under atmospheric pressure is 285°C or lower.

By using an antioxidant with a relatively low boiling point or thermal decomposition point under atmospheric pressure (hereinafter also referred to as "boiling point etc."), the boiling point under vacuum is also reduced. In this resin film, even if the antioxidant bleeds out on the film surface during the vacuum process, the antioxidant with a lower boiling point will evaporate or decompose and diffuse from the surface, which can suppress the contamination of the resin film surface. As a result, a desired thin film can be formed on the resin film, and it is possible to prevent the contaminants from adhering to other parts of the resin film or the roller, and the yield of thin film formation can be improved. When the boiling point of the antioxidant exceeds the above range, diffusion from the surface of the resin film becomes difficult to occur, and the resin film may still be contaminated.

In general, in order to prevent membrane pollution, the following schemes can be used: use high molecular weight antioxidants, or use antioxidants with a high affinity with the resin, as far as possible to inhibit the antioxidant from seeping to the membrane surface. In contrast to this, the present invention is based on a novel concept of allowing antioxidants to bleed out to the membrane surface, and by using antioxidants with a low boiling point and the like to actively diffuse from the surface to achieve anti-pollution.

The boiling point or thermal decomposition point of the above-mentioned antioxidant under a vacuum of 1.3 Pa is preferably 50° C. or lower. This can further promote the diffusion of the antioxidant under vacuum, and can improve the cleanliness of the resin film.

In one embodiment of the present invention, a base film is provided with the resin film.

In one embodiment of the present invention, a protective film is provided with the resin film.

In one embodiment of the present invention, a conductive film includes: The substrate film, and The conductive layer disposed on one side of the base film.

Since this conductive film is used as a base film whose contamination under vacuum is suppressed, a conductive film forming a desired conductive layer can be produced with good yield.

The thickness of the base film is preferably 50 μm or more and 250 μm or less. This makes it easy to use the roll-to-roll method. If it is thinner than the above lower limit, there is a risk that the film will be deformed due to the temperature applied during sputtering, or if it is thicker than the above upper limit, there will be increased bleeding of film additives such as oligomers. Kind of risk.

The base film may be formed of polyester resin or cycloolefin resin. Even these resins, which are commonly used as substrate film forming materials, can effectively prevent pollution caused by antioxidants.

In one embodiment of the present invention, a conductive film includes: Substrate film, A conductive layer disposed on one side of the base film, and The protective film disposed on at least one of the side of the conductive layer opposite to the base film side and the other surface side of the base film.

In this way, it is possible to prevent the pollution of the protective film caused by the antioxidant, and it is possible to efficiently manufacture a conductive film with high cleanliness. In particular, as a method of forming conductive layers on both sides of the base film, the following steps are sometimes adopted: a conductive layer is formed on one side of the base film, a protective film is placed thereon, and then formed on the other side of the base film This step of the conductive layer. In this step, although the protective film is provided in the vacuum process when the conductive layer on the other side is formed, since the protective film with low pollution is used, the double-sided conductive film can be cleanly and efficiently manufactured.

The above-mentioned base film may be a base film according to an embodiment of the present invention. As a result, any of the base film and the protective film can prevent pollution caused by the antioxidant, and both the productivity and the cleanliness of the conductive film can be at a high level.

The thickness of the protective film is preferably 5 μm or more and 55 μm or less. Even if it is a thin protective film in this range, it can sufficiently prevent pollution caused by antioxidants, and the thinning of the conductive film can be achieved.

The material for forming the protective film may be an olefin resin, a polyester resin, or a cycloolefin resin. Even these resins, which are commonly used as protective film forming materials, can effectively prevent pollution caused by antioxidants.

The surface of the protective film on the side in contact with the adjacent layer has adhesiveness, and the peeling force between the protective film and the adjacent layer is preferably 1 N/50 mm or less. By setting the peeling force between the protective film and the adjacent layer to the above range, the protective film can be smoothly peeled off in the peeling step.

The conductive layer is preferably a sputtered film. In order to obtain a low-resistance conductive layer, a dense layer is preferably formed by sputtering. Even if the conductive layer is formed by sputtering which requires more severe vacuum conditions, it is possible to prevent the contamination of the substrate film or the protective film.

In one embodiment of the present invention, a method for manufacturing a laminated film includes the following steps: The step of preparing the base film or the base film with the protective film attached; and A step of forming a thin film on at least one side of the base film by a vacuum process.

In this manufacturing method, since the base film or the protective film provided in the vacuum process is low in contamination, it can achieve the efficiency of film formation at a high level, and the anti-pollution of the base film, or the protective film, the roller can Improve the yield of laminated film in the whole manufacturing process.

In one embodiment, the vacuum process can be sputtering. Even if the film is formed by sputtering which requires more severe vacuum conditions, the contamination of the resin film can be prevented.

In one embodiment, the thin film may be a conductive layer. Even when it is convenient to form a low-resistance conductive layer based on sputtering, the cleanliness of the resin film can be improved and the production efficiency of the laminated film can be improved.

The resin film and the conductive film according to an embodiment of the present invention will be described below with reference to the drawings. In some or all of the drawings, parts that do not need to be explained are omitted, and there are parts that are shown enlarged or reduced for ease of explanation. Terms representing the upper and lower positional relationship are used only for ease of explanation, and are not intended to limit the structure of the present invention at all.

<Resin film> FIG. 1 is a schematic cross-sectional view of a resin film according to an embodiment of the present invention. The resin film 10 contains an antioxidant whose boiling point or thermal decomposition point under atmospheric pressure is 285°C or lower. By using a relatively low-boiling point antioxidant, even if the antioxidant oozes out on the surface of the resin film during the vacuum process, it can promote its diffusion and prevent surface contamination.

(Antioxidants) The antioxidant is not particularly limited as long as its boiling point or thermal decomposition point at atmospheric pressure is 285° C. or lower, and examples thereof include previously known antioxidants formulated in synthetic resins. For example, primary antioxidants such as hindered phenol antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants; and secondary antioxidants such as sulfur antioxidants or phosphorus antioxidants (Secondary antioxidant) etc.

These antioxidants can be used alone or in combination of two or more. In particular, primary antioxidants such as hindered phenol antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants can be used in combination with secondary antioxidants such as sulfur antioxidants or phosphorus antioxidants. Excellent weather resistance, or heat resistance.

The content of the antioxidant is not particularly limited, and can be appropriately set within a range where a desired antioxidant effect can be obtained.

(Resin) The resin material as the main component of the resin film 10 and the treatment of the resin film 10 can be appropriately changed according to the use of the resin film 10. Hereinafter, the case where the resin film 10 is used as the base film and the case where the resin film 10 is used as the protective film will be described separately.

(Substrate film) The resin film 10 can be suitably used as a base film. The base film is a film that has a strong base on which various films or functional layers are formed. In the case where the laminated film is incorporated in a display element, a sensor element, or the like, the base film remains in it as it is. The base film may include only the resin film 10, or may include other layers in addition to the resin film 10.

The material for forming the base film is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN ) And other polyester resins, polyimide resins such as polyimide (PI), polyolefin resins such as polyethylene (PE) and polypropylene (PP), acetate resins, and polyether resins , Polycarbonate resin, polyamide resin, cycloolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin , Polyarylate resin, polyphenylene sulfide resin, etc. Among these, from the viewpoint of heat resistance, durability, flexibility, production efficiency, cost, etc., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc. are preferred Polyimide resins such as polyester resins and polyimide (PI). In particular, from the viewpoint of cost performance, polyethylene terephthalate (PET) is preferred.

The base film can be used without stretching, or it can be uniaxially or biaxially stretched if necessary.

For the base film, before the placement or formation of the additional film or functional layer, the surface can be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. Coating treatment to ensure the adhesion with the film formed on the base film. In addition, before forming a thin film, etc., the surface of the base material film may be dedusted and purified by solvent cleaning, ultrasonic cleaning, or the like as necessary.

The thickness of the base film is preferably in the range of 50 μm or more and 250 μm or less, more preferably in the range of 80 μm or more and 200 μm or less, and further preferably in the range of 100 μm or more and 180 μm or less. In general, when the thickness of the base film is thick, it is not easily affected by heat shrinkage and the like during heating, so it is preferable. However, due to the miniaturization of electronic parts, etc., it is expected that the thickness of the base film is also reduced to some extent. On the other hand, when the thickness of the base film becomes too thin, the moisture permeability or permeability of the base film increases, allowing moisture, gas, etc. to pass through, and the thin film such as the conductive layer is easily oxidized. Therefore, in this embodiment, by making the thickness of the base material film to a certain thickness and thinning it, the laminated film (for example, conductive film, etc.) itself can also be thinned, which can suppress the use of the electromagnetic wave shielding sheet , Or the thickness of the sensor etc. Therefore, it is possible to cope with the thinning of the electromagnetic wave shielding sheet or the sensor. Furthermore, when the thickness of the base film is within the above range, the flexibility of the base film and sufficient mechanical strength can be ensured, and the operation of forming the base layer or the conductive layer continuously in a roll shape can be realized.

(Protection film) The resin film 10 can also be suitably used as a protective film. The protective film is provided to enhance the strength of the thin base film to improve workability, or to prevent oxidation or damage of the thin film formed on the base film. Therefore, it is often the case that a protective film is temporarily provided during the manufacturing process and storage process of the laminated film, and when the laminated film is incorporated into a display element, a sensor element, etc., the protective film is often peeled off and removed. Of course, according to the design, the protective film can also be directly inserted into the component, etc. The protective film may include only the resin film 10, or may include other layers in addition to the resin film 10.

The material and structure of the protective film are not particularly limited, and it is desirable to have a base material layer containing a polyolefin resin and an adhesive layer containing a thermoplastic elastomer. The protective film is arranged in such a manner that the adhesive layer and the adjacent layer (base film, base layer, conductive layer, or other thin film) face each other. As a material for forming the adhesive layer, a known adhesive such as a releasable acrylic adhesive can also be used.

The polyolefin resin forming the base material layer is not particularly limited. For example, polypropylene or block-based and random-based propylene polymers containing propylene and ethylene components; low density, high density, and low linearity Ethylene-based polymers such as density polyethylene; cycloolefin-based polymers; olefin-based polymers such as ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers and other ethylene components and other monomers Olefin polymer and so on. One type of these polyolefin resins may be used alone or two or more types may be used. Films containing these materials can be uniaxially or biaxially stretched.

The above-mentioned substrate layer contains an olefin resin as a main component, and in addition to specific antioxidants, for example, antistatic agents, fillers (calcium oxide, magnesium oxide, silicon dioxide, zinc oxide, titanium oxide, etc.), pigments , Anti-accumulation agent, lubricant, anti-blocking agent and other additives.

The thickness of the substrate layer is not particularly limited, but is preferably 18 μm or more, and more preferably 20 μm or more. On the other hand, the thickness of the base material layer is preferably 30 μm or less, and more preferably 25 μm or less. In addition, the base material layer may be a single layer or a multilayer including two or more layers.

In addition, surface treatment such as corona discharge treatment, flame treatment, plasma treatment, sputtering etching treatment, primer coating and other primer treatment may be applied to the surface of the base material layer opposite to the attachment surface of the adhesive layer.

As the thermoplastic elastomer for forming the adhesive layer, styrene elastomer, urethane elastomer, ester elastomer, olefin elastomer, etc. can be used without limitation as the elasticity of the base polymer used as the adhesive body. More specifically, examples include: styrene·butadiene·styrene (SBS), styrene·isoprene·styrene (SIS), styrene·ethylene-butene copolymer·styrene (SEBS) , Styrene·ethylene-propylene copolymer·styrene (SEPS) and other ABA block polymers; styrene·butadiene (SB), styrene·isoprene (SI), styrene·ethylene-butadiene AB block polymers such as styrene copolymer (SEB) and styrene-ethylene-propylene copolymer (SEP); styrene random copolymers such as styrene and butadiene rubber (SBR); styrene-ethylene ABC styrene and olefin crystal block polymers such as butene copolymers and olefin crystals (SEBC); CBC olefin crystalline block polymers such as olefin crystals and ethylene-butene copolymers and olefin crystals (CEBC); Olefin-based elastomers such as ethylene-α-olefins, ethylene-propylene-α-olefins, propylene-α-olefins, and their hydrides. One type of these thermoplastic elastomers may be used alone or two or more types may be used.

During the formation of the adhesive layer, for the purpose of controlling the adhesive properties, etc., the above thermoplastic elastomer can be appropriately compounded, for example, softener, olefin resin, silicone polymer, liquid acrylic copolymer, phosphate ester Compound, tackifier, anti-aging agent, hindered amine light stabilizer, ultraviolet absorber, other fillers such as calcium oxide, magnesium oxide, silicon dioxide, zinc oxide, titanium oxide, or additives such as pigments.

The thickness of the adhesive layer is not particularly limited, and may be appropriately determined according to the required adhesion, etc., and is usually about 0.1 μm, preferably 0.2 μm or more, and more preferably 0.3 μm or more. The thickness of the adhesive layer is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less.

In addition, the surface of the adhesive layer may be subjected to, for example, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, plasma treatment, or sputtering etching treatment for the purpose of controlling adhesiveness or attaching operability as needed Surface treatment. Furthermore, if necessary, a separator or the like may be temporarily adhered to the adhesive layer for protection during the period before it is put into practical use.

In addition, a mold release layer for imparting mold releasability may be formed on the surface of the base material layer opposite to the attachment surface of the adhesive layer as needed. The release layer can be formed by co-extrusion with the base material layer and the adhesive layer, or can be formed by coating.

When the release layer is formed by coextrusion, it is preferably formed using a mixture containing two or more types of polyolefin-based resins. The reason for this is that, by using a mixture containing two or more types of polyolefin-based resins, by controlling the compatibility of the two types of polyolefin-based resins, an appropriate surface roughness can be formed, and an appropriate mold releasability can be imparted. When the release layer is formed by coextrusion, the thickness is usually about 1 to 30 μm, preferably 2 to 20 μm, and more preferably 3 to 10 μm.

As a mold release agent when forming a mold release layer by coating, those that can impart mold release properties can be used without particular limitation. For example, examples of the mold release agent include those containing a silicone-based polymer or a long-chain alkyl-based polymer. The release agent can be any type of solvent-free type, solvent type dissolved in an organic solvent, and emulsified type emulsified in water. The solvent-based and emulsified type release agent can stably attach the release layer to the base Timber. Moreover, as a mold release agent, an ultraviolet curing type mold release agent etc. are mentioned. As specific examples of the release agent, Peeloil (manufactured by Ichisha Oil & Fat Co., Ltd.), Shin-Etsu Silicone (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like are available.

The thickness of the release layer is not particularly limited. As mentioned above, in view of the large effect of reducing the pollution when the film is formed, it is usually preferably about 1 to 1000 nm, and more preferably 5 to 500 nm, in particular It is preferably 10 to 100 nm.

The thickness of the protective film (when the adhesive layer or the release layer is provided, the thickness is included) is preferably 5 μm or more and 55 μm or less. The lower limit of the thickness of the protective film is more preferably 8 μm, further preferably 10 μm, and particularly preferably 15 μm. The upper limit of the thickness of the protective film is more preferably 50 μm, further preferably 45 μm, and particularly preferably 40 μm. By setting the thickness of the protective film to the above-mentioned range, it is possible to exert a sufficient protective function and achieve thinning.

As described above, the surface of the protective film on the side in contact with the adjacent layer is preferably adhesive. Specifically, the peeling force between the protective film and the adjacent layer is preferably 1 N/50 mm or less, more preferably 0.8 N/50 mm or less, and further preferably 0.6 N/50 mm or less. On the other hand, the above-mentioned peeling force is preferably 0.01 N/50 mm or more, more preferably 0.02 N/50 mm or more, and further preferably 0.04 N/50 mm or more. By setting the peeling force between the protective film and the adjacent layer to the above range, it is possible to prevent undesired peeling of the protective film and achieve smooth peeling of the protective film in the peeling step.

(Manufacturing method of resin film) The production method of the resin film 10 is not particularly limited, and a previously known film production method can be used. As the film forming method, for example, a calender film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method, etc. . Using the resin composition to which the above-mentioned resin and antioxidant are added, and to which a solvent or other additives are added as necessary, the resin film can be formed by the above-mentioned film-forming method.

<Conductive film> Hereinafter, a conductive film including the resin film 10 as a base film or a protective film will be described. 2A to 2C and FIGS. 3A to 3C are schematic cross-sectional views of a conductive film according to an embodiment of the present invention. First, the layer structure of each conductive film will be described, and then the structure other than the base film and the protective film will be described. However, the present invention is not limited to the layer structure described below, and various modifications can be made within the scope of the present invention.

(Layer structure of conductive film with resin film as base film) The conductive film 101 shown in FIG. 2A includes a base film 1 and a conductive layer 2 a disposed on one side of the base film 1. As shown in FIG. 2A, a base layer 4a may be provided between the base film 1 and the conductive layer 2a.

The conductive film 102 shown in FIG. 2B includes a base film 1, a conductive layer 2 a arranged on one side of the base film 1, and a conductive layer 2 b arranged on the other side of the base film 1. As shown in FIG. 2B, the base layers 4a and 4b may be provided between the base film 1 and the conductive layer 2a and between the base film 1 and the conductive layer 2b.

The conductive film 103 shown in FIG. 2C includes a base film 1, a conductive layer 2a, and a protective film 3a in this order. A conductive layer 2b is further provided on the opposite side of the base film 1. As shown in FIG. 2C, the base layers 4a and 4b may be provided between the base film 1 and the conductive layer 2a and between the base film 1 and the conductive layer 2b, respectively. Furthermore, although not shown, another protective film may be arranged on the outermost surface side of the conductive layer 2b.

The conductive films 101 to 103 include a resin film 10 as the base film 1. As the protective film in the conductive film 103, the resin film 10 may be provided, or another film may be provided. In FIGS. 2A to 2C, the conductive layer and the base layer are each illustrated as a structure including one layer, or may be a multilayer structure including two or more layers.

(Layer structure of conductive film with resin film as protective film) The conductive film 201 shown in FIG. 3A includes a base film 1, a conductive layer 2a disposed on one side of the base film 1, and a protective film 3a disposed on the outermost surface side of the conductive layer 2a. As shown in FIG. 3A, a base layer 4a may be provided between the base film 1 and the conductive layer 2a.

Alternatively, as with the conductive film 202 shown in FIG. 3B, the protective film 3b may be disposed on the side of the base film 1 opposite to the side of the conductive layer 2a. Furthermore, a base layer or a conductive layer (both not shown) may be provided between the base film 1 and the protective film 3b.

Furthermore, as with the conductive film 203 shown in FIG. 3C, the protective films 3 a and 3 b may be disposed on the outermost surface side of the base film 1 on both sides. For the conductive film 203, a base layer or a conductive layer (both not shown) may be provided between the base film 1 and the protective film 3b.

The conductive films 201 to 203 include resin films 10 as protective films 3a and 3b. As the base film of the conductive films 201 to 203, the resin film 10 may be provided, or another film may be provided. In FIGS. 3A to 3C, the conductive layer and the base layer are each illustrated as a structure including one layer, or may be a multilayer structure including two or more layers.

The thickness of the conductive film may be in any of the above-mentioned forms, preferably 50 μm or more and 250 μm or less, preferably 80 μm or more and 200 μm or less, preferably 100 μm or more and 180 μm or less. By setting the thickness of the conductive film to the above range, the operation using the roll-to-roll method can be facilitated.

(Conductive layer) In order to sufficiently obtain an electromagnetic wave shielding effect, a sensor function, or the like, the resistivity of the conductive layers 2a, 2b is preferably 100 μΩcm or less. The materials for forming the conductive layers 2a and 2b are not particularly limited as long as they satisfy such resistivity and have electrical conductivity. For example, Cu, Al, Fe, Cr, Ti, Si, Nb, In, Zn, Sn, Au, Ag, Co, Cr, Ni, Pb, Pd, Pt, W, Zr, Ta, Hf, Mo, Mn, Mg, V and other metals. In addition, substances containing two or more of these metals, alloys containing these metals as main components, or oxides may also be used. When transparency is required, it is also preferable to use indium-tin composite oxide (ITO). Among these conductive compounds, it is preferable to include Cu and Al from the viewpoint of higher conductivity and lower price that contribute to electromagnetic wave shielding characteristics or sensor functions. In particular, from the viewpoint of cost performance and production efficiency, it is preferable to contain Cu, and elements other than Cu may be contained to the extent of impurities. Thereby, the electrical resistivity is sufficiently small and the electrical conductivity is high, so it is possible to improve the electromagnetic wave shielding characteristics or the sensor function.

The method for forming the conductive layers 2a and 2b is not particularly limited, and a conventionally known method can be used. Specifically, for example, from the viewpoint of uniformity of film thickness or film-forming efficiency, it is preferable to use vacuum such as sputtering, chemical vapor deposition (CVD), or physical vapor deposition (PVD). The film formation method, or ion plating method, plating method (electrolytic plating, electroless plating), hot stamping method, coating method, etc. are used to form a film. In addition, a plurality of these film-forming methods may be combined, and an appropriate method may be adopted according to the required film thickness. Among them, the sputtering method and the vacuum film forming method are preferable, and the sputtering film obtained by the sputtering method is particularly preferable. By this, continuous production can be performed by the roll-to-roll method, production efficiency can be improved, and the film thickness or surface roughness during film formation can be controlled, so that the increase in the surface resistance value of the conductive film can be suppressed. In addition, a dense conductive layer can be formed thinly and uniformly.

The thickness of the conductive layers 2a and 2b is not particularly limited, but independently preferably 10 nm or more and 250 nm or less. The lower limit of the thickness of the conductive layers 2a and 2b is preferably 20 nm, and more preferably 50 nm. On the other hand, the upper limit of the thickness of the conductive layers 2a and 2b is preferably 200 nm. When the thickness of the conductive layers 2a and 2b exceeds the above upper limit, the conductive film after heating is likely to be wound up, or the thinning of the device becomes difficult. In addition, peeling of the pattern wiring caused by the decrease in the strength of the conductive layers 2a and 2b may occur. When the thickness is less than the above lower limit value, the surface resistance value of the conductive film may easily increase resistance under humidification heat conditions, and the target humidification heat reliability may not be obtained.

(The protective layer) For example, in order to prevent the conductive layers 2a and 2b from being naturally oxidized by the influence of oxygen in the atmosphere, a protective layer (not shown) may be formed on the outermost surface side of the conductive layers 2a and 2b. The protective layer is not particularly limited as long as it exhibits the effect of preventing the rust of the conductive layer, and it is preferably a metal that can be sputtered, and can be selected from the group consisting of Ni, Cu, Ti, Si, Zn, Sn, Cr, Fe, indium, and gallium , Antimony, zirconium, magnesium, aluminum, gold, silver, palladium, tungsten, any one or more metals or oxides of these. Ni, Cu, and Ti form a passivation layer, so they are not easily corroded. Si has improved corrosion resistance and is not easily corroded. Since Zn and Cr form a dense oxide film on the surface, they are not easily corroded. Therefore, it is better.

As the material of the protective layer, from the viewpoint of ensuring the adhesion to the conductive layers 2a, 2b and preventing the conductive layers 2a, 2b from rusting, an alloy containing two kinds of metals can be used, preferably an alloy containing more than three kinds of metals . Examples of alloys containing three or more metals include Ni-Cu-Ti, Ni-Cu-Fe, Ni-Cu-Cr, etc. From the viewpoint of rust prevention function and production efficiency, Ni-Cu- is preferred Ti. Furthermore, from the viewpoint of ensuring the adhesion with the conductive layers 2a and 2b, an alloy containing the forming materials of the conductive layers 2a and 2b is preferable. Thus, the oxidation of the conductive layers 2a and 2b can be prevented.

In addition, as the material of the protective layer, for example, it may include doped indium tin oxide (ITO), antimony-containing tin oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), doped Indium zinc oxide (IZO). Not only can the increase in the surface resistance value of the conductive film at the initial stage be suppressed, but also the increase in the surface resistance value under humidified heat conditions can be suppressed, and the stability of the surface resistance value can be optimized, which is preferable.

The oxide of the above-mentioned metal is preferably an oxide such as SiO _x (x=1.0 to 2.0), copper oxide, silver oxide, or titanium oxide. Furthermore, instead of the above-mentioned metals, alloys, oxides, etc., a resin layer like an acrylic resin or an epoxy resin may be formed on the conductive layer, thereby obtaining an anti-rust effect.

The thickness of the protective layer is preferably 1 to 50 nm, more preferably 2 to 30 nm, and preferably 3 to 20 nm. As a result, the durability is improved and the oxidation from the surface layer can be prevented, so that the increase in the surface resistance value under the humidification heat condition can be suppressed.

(Base layer) For the base layer, by providing a base layer that satisfies the purposes of adhesion of the conductive layers 2a and 2b to the base film 1, strength imparting to the conductive film, and control of electrical characteristics, the high function of the conductive film can be realized Change. The base layers 4a and 4b are not particularly limited, and examples thereof include an easy-adhesion layer, a hard coat layer (including a layer that functions as an anti-adhesion layer, etc.), and a dielectric layer.

(Easily Connected Layer) The easily adhesive layer is a cured film of an adhesive resin composition. The easy-adhesion layer has good adhesion to the conductive layer.

As the adhesive resin composition, a material having sufficient adhesiveness and strength as a cured film after the formation of an easily adhesive layer can be used without particular limitation. Examples of the resin used include thermosetting resins, thermoplastic resins, ultraviolet curing resins, electron beam curing resins, two-liquid mixed resins, and mixtures of these. For the curing treatment by ultraviolet irradiation, it is more appropriate to form a UV-curable resin with an easy-to-adhesion layer efficiently by a simple processing operation. By including an ultraviolet curable resin, an adhesive resin composition having ultraviolet curability is easily obtained.

The adhesive resin composition is preferably a material that forms a cross-linked structure when cured. The reason for this is presumed that if the cross-linked structure in the easy-adhesion layer is promoted, the internal structure of the film that was looser before then becomes stronger, and the film strength is improved. This increase in film strength contributes to the improvement of adhesion.

The adhesive resin composition preferably contains at least one of (meth)acrylate monomers and (meth)acrylate oligomers. Thus, the formation of the cross-linked structure due to the C=C double bond contained in the acrylic group becomes easy, and the film strength can be effectively improved. In this specification, (meth)acrylate refers to acrylate or methacrylate.

The (meth)acrylate monomer and/or acrylate oligomer having a (meth)acryloyl group used as a main component used in this embodiment has a function of forming a coating film. Specifically, it can be exemplified by: Hydroxymethylpropane tri (meth) acrylate, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, tri Hydroxymethylpropane tetra (meth) acrylate, tri (acryloyloxyethyl) isocyanurate, caprolactone modified tri (acryloyloxyethyl) isocyanurate, pentaerythritol tri ( Methacrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, alkyl Modified dipentaerythritol tetra(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and two or more of these mixture.

Among the above (meth)acrylates, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol pentaerythritol are particularly preferred in terms of abrasion resistance and hardenability. Meth)acrylate, or a mixture of these.

In addition, urethane acrylate oligomers can also be used. Examples of urethane (meth)acrylate oligomers include: a method of reacting a polyol with a polyisocyanate and then reacting with a (meth)acrylate having a hydroxyl group; and a method of causing a polyisocyanate to react with a hydroxyl group ( The method of reacting with a polyhydric alcohol after the reaction of meth)acrylate; the method of reacting polyisocyanate, polyhydric alcohol, (meth)acrylate having a hydroxyl group, etc. are not particularly limited.

Examples of the polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and copolymers thereof, ethylene glycol, propylene glycol, 1,4-butanediol, and 2,2′- Thioethanol, etc.

Examples of the polyisocyanate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophthalic diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, and trimethyl Hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-benzenedimethylene diisocyanate, 1,4-benzenedimethylene diisocyanate Isocyanate, etc.

If the crosslinking density is too high, the performance as a primer decreases and the adhesion of the conductive layer is easily reduced. Therefore, a low-functional (meth)acrylate having a hydroxyl group (hereinafter, referred to as a hydroxyl-containing (meth)acrylate) can be used . Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and 2-hydroxy(meth)acrylate. Propyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-propene Acetyloxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc. The (meth)acrylate monomer component and/or (meth)acrylate oligomer component may be used alone, or two or more types may be used.

The adhesive resin composition having ultraviolet curability of this embodiment is formulated with a (meth)acryloyl group-containing silane coupling agent to improve blocking resistance. Examples of the (meth)acryloyl group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Sales products include KR-513 and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name).

The blending amount of the silane coupling agent is 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylate monomer and/or (meth)acrylate oligomer. Parts by weight. Within this range, the adhesion to the conductive layer is improved, and the physical properties of the coating film can be maintained.

The easily-adhesive layer of this embodiment may contain nano-silica particles. As the nano-silica particles, organic silica sol synthesized from alkyl silane or nano-silica synthesized by plasma arc can be used. As a commercially available product, the former may include PL-7-PGME (manufactured by Fuso Chemical Co., Ltd., trade name), and the latter may include SIRMIBK15WT%-M36 (manufactured by CIK NanoTek, trade name). The formulation ratio of the nano-silica particles is preferably 100 parts by weight relative to the total weight of the (meth)acrylate monomer and/or acrylate oligomer having a (meth)acryloyl group and a silane coupling agent It is 5 to 30 parts by weight, more preferably 5 to 10 parts by weight. By setting it to the lower limit or more, surface irregularities are formed, blocking resistance can be imparted, and roll-to-roll (roll to roll) production can be realized. By setting it to below the upper limit, it is possible to prevent a decrease in the adhesion with the conductive layer.

The average particle size of the nano-silica particles is preferably 100-500 nm. When the average particle diameter is less than 100 nm, the amount of addition required to form irregularities on the surface increases. Therefore, the adhesion to the conductive layer cannot be obtained. On the other hand, if it exceeds 500 nm, the irregularities on the surface become larger and pinholes are generated. Question.

In order to impart ultraviolet curability, the adhesive resin composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin ethers such as benzoin n-butyl ether and benzoin isobutyl ether, benzoyl ketals such as benzoyl dimethyl ketal, and benzoyl diethyl ketal. , 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone and other acetophenones, 1-hydroxycyclohexyl phenyl ketone, [2-hydroxy-2-methyl-1 -(4-ethylidene)propane-1-one], 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)benzene Alpha]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propane-1-one and other α-hydroxyalkanes Benzophenones, 2-methyl-1-[4-(methylthio)phenyl]-1-morpholinylpropane, 2-benzyl-2-dimethylamino-1-(4- Morpholinylphenyl)-1-butanone and other α-aminoalkyl benzophenones, 2,4,6-trimethylbenzyl diphenylphosphine oxide, 2,4,6-trimethyl Monoacyl phosphine oxides such as benzoyl phenyl ethoxy phosphine oxide, bis (2,6-dimethoxy benzoyl acetyl)-2,4,4-trimethylpentyl phosphine oxide, bis (2,4,6-Trimethylbenzyl) phenyl phosphine oxide and other mono-acyl phosphine oxides.

From the aspects of resin hardenability, light stability, compatibility with resin, low volatility, and low odor, alkyl ketone-based photopolymerization initiators are preferred, and 1-hydroxycyclohexyl is more preferred Phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl )-Benzyl]phenyl}-2-methyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane -1-one. Examples of commercially available products include Irgacure 127, 184, 369, 651, 500, 891, 907, 2959, Darocure 1173, TPO (manufactured by BASF JAPAN Co., Ltd., trade name), etc. Photopolymerization initiator The solid content is 3 to 10 parts by weight relative to 100 parts by weight of the (meth)acrylate monomer and/or acrylate oligomer having a (meth)acryloyl group.

In the formation of an easily adhesive layer, an adhesive resin composition mainly composed of (meth)acrylate and/or (meth)acrylate oligomers having (meth)acryloyl groups in the molecule is used in toluene , Butyl acetate, isobutanol, ethyl acetate, cyclohexane, cyclohexanone, methylcyclohexanone, hexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, It is diluted in solvents such as diethyl ether and ethylene glycol to prepare a varnish with a solid content of 30-50%.

The easy-adhesion layer is formed by applying the above-mentioned varnish on the resin film 1. The coating method of the varnish can be appropriately selected according to the conditions of the varnish and the coating step, for example, dip coating method, air knife coating method, curtain coating method, roll coating method, wire bar coating method, gravure coating The coating method, die coating method, or extrusion coating method is applied.

After the varnish is applied, the coating film is hardened, whereby an easily adhesive layer can be formed. As the curing treatment of the adhesive resin composition having ultraviolet curability, when the varnish contains a solvent, the following steps may be mentioned: after removing the solvent based on drying (for example, at 80°C for 1 minute), use an ultraviolet irradiation machine to The irradiation intensity of 500 mW/cm ² to 3000 mW/cm ² is cured by ultraviolet treatment at a dose of 50 to 400 mJ/cm ² . As the ultraviolet generating source, an ultraviolet lamp is generally used, and specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. When irradiated, it may be in the air or in nitrogen, Inert gas such as argon.

Preferably, heating is performed during ultraviolet curing. By ultraviolet irradiation, the curing reaction of the adhesive resin composition proceeds, and at the same time, a cross-linked structure is formed. At this time, by heating, the formation of the cross-linked structure can be sufficiently promoted with a low ultraviolet light amount. The heating temperature can be set according to the degree of crosslinking, and is preferably 50°C to 80°C. The heating means is not particularly limited, and a hot air dryer, a radiant heat dryer, heating of the film conveying roller, etc. can be suitably used.

The thickness of the easy-adhesion layer is not particularly limited, but it is preferably 0.2 μm to 2 μm, more preferably 0.4 μm to 1.5 μm, and still more preferably 0.6 μm to 1.2 μm. By setting the thickness of the easy-adhesion layer to the above range, the adhesion of the conductive layer and the flexibility of the film can be improved.

(Hard coating) As the base layer, a hard coat layer may be provided. Furthermore, in order to prevent adhesion between the conductive layer and the protective film and between the conductive layer and the protective film when wound into a roll, the roll-to-roll method can be used for manufacturing, and particles can be formulated in the hard coat layer.

For the formation of the hard coat layer, the same adhesive composition as the easily adhesive layer can be suitably used. In order to impart anti-blocking properties, it is preferable to blend particles in the adhesive composition. As a result, irregularities can be formed on the surface of the hard coat layer, and it is possible to appropriately impart anti-blocking properties to the conductive film.

As the above particles, particles having transparency such as various metal oxides, glass, and plastics can be used without particular limitation. For example, inorganic particles such as silica, alumina, titania, zirconia, and calcium oxide, including polymethyl methacrylate, polystyrene, polyurethane, acrylic resin, and acrylic-styrene Copolymer, benzoguanamine, melamine, polycarbonate and other polymers, cross-linked or uncross-linked organic particles, silica particles, etc. One kind or two or more kinds of the above particles can be appropriately selected and used.

The average particle diameter of the above particles or the blending amount can be appropriately set in consideration of the degree of surface irregularities. The average particle diameter is preferably 0.5 μm to 2.0 μm, and the compounding amount is preferably 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the resin solid content of the composition.

(Dielectric layer) As the base layer, one or more dielectric layers may be provided. The dielectric layer is formed of an inorganic substance, an organic substance, or a mixture of an inorganic substance and an organic substance. Examples of the material for forming the dielectric layer include NaF, Na ₃ AlF ₆ , LiF, MgF ₂ , CaF ₂ , SiO ₂ , LaF ₃ , CeF ₃ , Al ₂ O ₃ , TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , Inorganic substances such as ZnO, ZnS, SiOx (x is 1.5 or more and less than 2), or organic substances such as acrylic resin, urethane resin, melamine resin, alkyd resin, and siloxane polymer. In particular, as the organic substance, it is preferable to use a thermosetting resin containing a mixture of melamine resin, alkyd resin, and organosilane condensate. The dielectric layer can be formed by using the above-mentioned materials by a coating method such as a gravure coating method or a bar coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or the like.

The thickness of the dielectric layer is preferably 10 nm to 250 nm, more preferably 20 nm to 200 nm, and further preferably 20 nm to 170 nm. If the thickness of the dielectric layer is too small, it is difficult to form a continuous coating. In addition, if the thickness of the dielectric layer is too large, there is a tendency for cracks to easily occur in the dielectric layer.

The dielectric layer may have nanoparticles with an average particle size of 1 nm to 500 nm. The content of nanoparticles in the dielectric layer is preferably 0.1% by weight to 90% by weight. The average particle diameter of the nanoparticles used in the dielectric layer is preferably in the range of 1 nm to 500 nm as described above, and more preferably 5 nm to 300 nm. In addition, the content of nanoparticles in the dielectric layer is more preferably 10% by weight to 80% by weight, and further preferably 20% by weight to 70% by weight.

Examples of inorganic oxides forming nanoparticles include silicon oxide (silica), hollow nanosilica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and niobium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and niobium oxide are preferred. These can be used alone or in combination of two or more.

(Manufacturing method of conductive film) The conductive film can be manufactured by the roll-to-roll method as follows: after forming the conductive layer on one side of the base film with the base layer formed as needed, it is rolled into a roll shape, and then the film is self-rolled out on one side. A protective film is attached on the conductive layer. Alternatively, the protective film may be attached to the downstream of the production line forming the conductive layer and wound into a roll shape. In the case of forming a conductive layer on both sides, after forming a conductive layer on one side of the base film, take up a roll, and then release the film while attaching a protective film on the formed conductive layer, and roll it again in the form of a film take. Then, a conductive layer is formed on the surface opposite to the surface to which the protective film is attached while releasing the film, whereby a conductive film can be manufactured.

For example, when the conductive layers 2a and 2b containing copper are formed by sputtering, preferably, copper (preferably oxygen-free copper) is used as a target. First, the exhaust is carried out into the sputtering apparatus The vacuum degree (attained vacuum degree) is preferably 1×10 ⁻³ Pa or less, and becomes an atmosphere for removing impurities such as moisture in the sputtering apparatus or organic gas generated by the resin film 1.

An inert gas such as Ar is introduced into the sputtering apparatus that has been exhausted as described above, and it is preferable to carry out sputtering deposition under reduced pressure while conveying the resin film under the condition of giving tension. The temperature of the resin film when the conductive layer is formed is preferably 10°C to 100°C, more preferably 15°C to 80°C, and still more preferably 20°C to 60°C. The pressure during film formation is preferably 0.05 Pa to 1.0 Pa, and more preferably 0.1 Pa to 0.7 Pa. If the film-forming pressure is too high, the film-forming rate tends to decrease. Conversely, if the pressure is too low, the discharge tends to become unstable.

The pressure for bonding the protective film is not particularly limited, but it is preferably 0.05 MPa or more and 3 MPa or less, more preferably 0.1 MPa or more and 2 MPa or less, and still more preferably 0.15 MPa or more and 1 MPa or less.

(Characteristics of conductive film) The surface resistance value R1 of the conductive layers 2a and 2b is preferably 0.001 Ω/□ to 20 Ω/□, more preferably 0.01 Ω/□ to 10 Ω/□, and further preferably 0.1 Ω/□ to 5 Ω/□. This can provide a practical conductive film with a protective film excellent in production efficiency.

From the viewpoint of transportability or handling properties, the conductive film may be wound into a roll shape. By continuously forming the base layer or the conductive layer on the resin film by the roll-to-roll method, the conductive film can be efficiently manufactured.

(Use of conductive film) The conductive film with a protective film can be used for various purposes, for example, it can be applied to electromagnetic wave shielding sheets, planar sensors, and displays. The protective film is peeled off before loading these devices. The electromagnetic wave shielding sheet uses a conductive film with a peel-off protective film, and can be suitably used in the form of a touch panel or the like. The thickness of the electromagnetic shielding sheet is preferably 20 μm to 300 μm.

In addition, the shape of the electromagnetic wave shielding sheet is not particularly limited, and the shape observed from the stacking direction (the same direction as the thickness direction of the sheet) can be selected according to the shape of the object to be set, such as a square shape, a round shape, and a triangle shape Shape, polygonal shape and other suitable shapes.

Surface sensors use conductive films, including: force-sensitive sensors used to measure loads on the user interface of mobile devices, touch panels, or controllers; the sensor area of the object, such as the surface of the car, robots, Or a sensor that senses various physical quantities represented by external forces exerted on the surface of the doll. The planar sensor can be suitably used in the form of force-sensitive sensors, shields, and the like. The thickness of the planar sensor is preferably 20 μm to 300 μm.

<Manufacturing method of laminated film> The manufacturing method of the laminated film of this embodiment includes the following steps: a step of preparing (i) a base film, or (ii) a base film to which a protective film is bonded; and a vacuum process on at least one side of the base film The step of forming a thin film on the side. In the present embodiment, at least the base film of (i) and the protective film of (ii) each have a resin film 10. Furthermore, the base film of (ii) may include the resin film 10.

The laminated film can be manufactured by the roll-to-roll method as follows: a film is formed by vacuum process on one side of the base film forming the base layer as required, and then wound into a roll shape, and then the film is released from the roll on the side The protective film is attached to the conductive layer. Alternatively, the protective film may be laminated downstream of the production line where the film is formed, and then wound into a roll shape. In the case of forming a thin film on both sides, a laminated film can be manufactured by: forming a thin film on one side of a base film by a vacuum process and winding it into a roll shape, and then releasing the film on one side and attaching the protective film to the The formed film is wound up again in the form of a film. Then, a film layer was formed on the surface opposite to the surface to which the protective film was attached while releasing the film, thereby manufacturing a laminated film.

The vacuum process is not particularly limited, and examples include physical vapor deposition methods such as vacuum evaporation, sputtering, and ion plating, and chemical vapor deposition methods such as plasma CVD. Among them, from the viewpoint of uniformity of film quality, or control of film pressure, and compactness, sputtering is preferred.

The film is not particularly limited, and examples thereof include a conductive layer, an easily adhesive layer, a dielectric layer, and a gas barrier layer. By selecting the formed film according to the application, various laminated films can be produced. For example, by using a conductive layer as a thin film, a laminated film as a conductive film can be efficiently manufactured. Examples

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist is not exceeded.

<Example 1: Preparation of conductive film on both sides with protective film on one side> (Formation of conductive layer) As the resin film, an annealed PET film (manufactured by Toray Film Processing Co., Ltd., 150) with a thickness of 150 μm and a width of 1100 mm was used. -TT00A"), a single layer is sputter-plated to form a conductive layer. The sputtering conditions are as follows. In the sputtering apparatus, a high vacuum of 3.0×10 ^-3 Torr or less (0.4 Pa or less) is performed, and in this state, the long-length resin film is sputter-deposited while being sent from the feed roller to the take-up roller. In a 3.0×10 ^-3 Torr atmosphere containing 100% by volume of Ar gas, a Cu target material was used to sputter the conductive layer to a thickness of 150 nm on one side by DC magnetron sputtering of the sintered body. The film-formed film is taken up on a take-up roll, thereby producing a wound body of a single-sided conductive film with a conductive layer formed on one side.

(Lamination of protective film) A protective film containing antioxidant (manufactured by Toray, "MS05") shown in Table 1 was attached to the conductive layer formed by sputtering. The bonding conditions are as follows. On the one hand, the produced single-sided conductive film is sent from the delivery roller to the take-up roller, and on the other hand, the protective film is attached to the conductive layer (sputtered surface) with a pressure of 0.3 MPa, and the film is taken up onto the take-up roller. In this way, a wound body in which a laminate as the outermost layer of the protective film is laminated on the conductive surface (sputtered surface) of the single-sided conductive film is produced.

(Formation of conductive layer) On the side of the wound body of the single-sided conductive film produced opposite to the surface on which the conductive layer is disposed, the conductive layer was sputter-sputtered into a film with a thickness of 140 nm under the same conditions as the formation of the above conductive layer, thereby making A conductive layer is formed on both sides of the resin film, and a wound body of a conductive film on both sides with a protective film attached to a single side with a protective film bonded to one side.

<Example 2> As the protective film, using the "MS05" manufactured by Toray Co., Ltd. containing the antioxidant shown in Table 1, except that the same method as in Example 1 was used to produce a half-cut wound body of a conductive film on both sides with a protective film on one side .

<Comparative Example 1> As the protective film, "FSA020M" manufactured by FUTAMURA Corporation containing the antioxidant shown in Table 1 was used, and a half-cut wound body of a double-sided conductive film with a protective film on one side was produced by the same method as in Example 1.

<Comparative example 2> As the protective film, "FSA020M" manufactured by FUTAMURA Corporation containing the antioxidant shown in Table 1 was used, and a half-cut wound body of a double-sided conductive film with a protective film on one side was produced by the same method as in Example 1.

<Evaluation> The following evaluation was performed on the produced conductive film with protective film. Table 1 shows the respective results.

(1) Determination of the boiling point or thermal decomposition point of antioxidants at atmospheric pressure Determine the boiling point or thermal decomposition point according to "OECD Test Guideline 103". In addition, the antioxidant is a known situation, and use the nominal value included in the chemical data base or product safety data sheet. Furthermore, the atmospheric pressure is 1013 hPa.

(2) Calculation of boiling point or thermal decomposition point of antioxidant under vacuum (1.3 Pa) In the "Boiling Point Conversion Graph" shown in Figure 4 (Source: Science of Petroleum, Vol. II. p. 1281 (1938)), take the boiling point at atmospheric pressure found in (1) above on line B and use a straight line The boiling point is connected to the degree of reduced pressure (1.3 Pa) on line C, and the intersection point of the straight line and line A is determined as the boiling point under reduced pressure (1.3 Pa).

(3) Observation of pollution occurrence By visually observing the presence or absence of attachments on the surface of the conveying roller in the sputtering step. The case where no attachment is observed is evaluated as "no pollution", and the case where the attachment is observed is evaluated as "contaminated".

[Table 1]

(result) According to Table 1, the conductive films of the examples did not cause contamination of the roller. On the other hand, pollution occurred in the comparative example. Based on the above, it is presumed that the result of the pollution evaluation of the conductive film of the embodiment is due to the promotion of the diffusion of the antioxidant from the surface of the protective film, thereby reducing or suppressing the adhesion to the roller.

1‧‧‧ Base film 2a, 2b‧‧‧conductive layer 3‧‧‧Protection film 4a, 4b ‧‧‧ basal layer 10‧‧‧Resin film 101, 102, 103, 201, 202, 203‧‧‧ conductive film

FIG. 1 is a schematic cross-sectional view of a resin film according to an embodiment of the present invention. 2A is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. 2B is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. 2C is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. 3A is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. 3B is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. 3C is a schematic cross-sectional view of a conductive film according to an embodiment of the present invention. Fig. 4 is a boiling point conversion graph for obtaining the boiling point under vacuum.

10‧‧‧Resin film

Claims (16)

A resin film containing an antioxidant whose boiling point or thermal decomposition point under atmospheric pressure is 285°C or lower. The resin film according to claim 1, wherein the boiling point or thermal decomposition point of the above-mentioned antioxidant under a vacuum of 1.3 Pa is 50°C or lower. A base film provided with the resin film according to claim 1 or 2. A protective film provided with the resin film according to claim 1 or 2. A conductive film provided with the base film as claimed in claim 3, and The conductive layer disposed on one side of the base film. The conductive film according to claim 5, wherein the thickness of the base film is 50 μm or more and 250 μm or less. The conductive film according to claim 5 or 6, wherein the base film is formed of a polyester resin or a cycloolefin resin. A conductive film with: Substrate film, A conductive layer disposed on one side of the base film, and The protective film according to claim 4 is disposed on at least one of the side of the conductive layer opposite to the base film side and the other surface side of the base film. The conductive film according to claim 8, wherein the base film is the base film according to claim 3. The conductive film according to claim 8 or 9, wherein the thickness of the protective film is 5 μm or more and 55 μm or less. The conductive film according to claim 8 or 9, wherein the forming material of the protective film is an olefin resin, a polyester resin, or a cycloolefin resin. The conductive film according to claim 8 or 9, wherein the surface of the protective film on the side in contact with the adjacent layer has adhesiveness, The peeling force between the protective film and the adjacent layer is 1 N/50 mm or less. The conductive film according to claim 5 or 8, wherein the conductive layer is a sputtering film. A method for manufacturing a laminated film includes the following steps: The step of preparing the substrate film as claimed in claim 3, or the substrate film with the protective film as claimed in claim 4, and A step of forming a thin film on at least one side of the base film by a vacuum process. The method for manufacturing a laminated film according to claim 14, wherein the vacuum process is sputtering. The method for manufacturing a laminated film according to claim 14, wherein the thin film is a conductive layer.

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