TW201741481A - Film formation method and manufacturing method of laminate substrate using the same capable of eliminating color difference of a long strip-shape resin film in the width direction while making etching failure difficult to occur - Google Patents

Abstract

The present invention provides a film formation method which can eliminate color difference of a long strip-shape resin film in the width direction while making etching failure difficult to occur. The film formation method of the present invention uses a dry plating method, such as a sputtering method, in a vacuum chamber 10 to form a first cover film and a second cover film respectively on two sides of the long strip-shape resin film F which is transported from a roll-out roll 11 to a take-up roll 24 in a roll-to-roll manner, and a dry etching treatment is implemented by appropriately irradiating an ion beam from an ion source 29 onto the surface of the first cover film between a first time take-up and a second-time take-up. The first time take-up is implemented by using the take-up roll 24 after the aforementioned first cover film is formed on one side of the long strip-shape resin film F, and the second time take-up is implemented by using the take-up roll 24 after the aforementioned second cover film is formed on the other side of the first cover film on the long strip-shape resin film.

Description

Film forming method and method for producing laminated substrate using same

The present invention relates to a method of forming a coating on both surfaces of a long resin film conveyed by a roll-to-roll method by a dry plating method, and a method of producing a laminated substrate using the film forming method.

The technology of providing a "touch panel" on the surface of a flat panel display (FPD) provided in an electronic device such as a mobile phone, a portable electronic book device, a vending machine, or a car navigation has begun to spread. The "touch panel" can be roughly classified into a resistive type and a capacitive type, and the main part of the "resistive type" touch panel is detected by a transparent substrate composed of a resin film and an X coordinate (or Y coordinate) provided on the substrate. The electrode sheet and the Y coordinate (or X coordinate) detection electrode sheet and the insulator spacer disposed between the electrode sheets.

The X coordinate detecting electrode sheets and the Y coordinate detecting electrode sheets are usually separated by an insulator spacer, and the two coordinate detecting electrode sheets are electrically contacted at the portion when pressed by a pen or the like. Thereby, the position (X coordinate, Y coordinate) touched by the pen can be detected, and a mechanism for recognizing each of the coordinates at any time as long as the pen is moved can finally perform character input.

On the other hand, the "static capacitance type" touch panel has the following structure: an X-coordinate (or Y-coordinate) detection electrode sheet and a Y-coordinate (or X-coordinate) detection electrode sheet with an insulating sheet interposed therebetween. The laminate is further provided with an insulator such as glass. Further, when the finger is brought close to the insulator such as glass, the capacitance of the X coordinate detecting electrode and the Y coordinate detecting electrode in the vicinity thereof is changed, so that the position detection can be performed.

As a conductive material for an electrode having a specific circuit pattern formed on the electrode sheet (also referred to as an electrode substrate film), conventionally, transparent conductive materials such as ITO (indium oxide-tin oxide) disclosed in Patent Document 1 are widely used. membrane. In addition, as the size of the touch panel has increased, a metal film having a mesh structure made of a thin metal wire disclosed in Patent Document 2 and Patent Document 3 has been used.

When the transparent conductive film is compared with a metal thin wire (metal film), since the transparent conductive film is excellent in permeability in a visible wavelength region, it has an advantage that a circuit pattern such as an electrode is hardly observed, but Since the resistance value is higher than that of the metal thin wire (metal film), it is disadvantageous in that the size of the touch panel is increased and the response speed is increased. On the other hand, since the metal thin wire (metal film) has a low resistance value, it is advantageous in increasing the size of the touch panel and increasing the response speed. However, since the reflectance in the visible wavelength region is high, even a fine mesh is processed. The ocular structure sometimes recognizes the circuit pattern under high-intensity illumination, and has the disadvantage of lowering the value of the product.

Therefore, in Patent Document 4 and Patent Document 5, in order to exhibit the characteristics of the metal thin wire (metal film) having a low electric resistance value, a method is proposed in which a transparent substrate made of a resin film and a metal film made of a metal thin wire are used. A metal absorbing layer (also referred to as a blackening film) made of a metal oxide is interposed to reduce reflection of a metal thin wire (metal film) observed from the transparent substrate side.

Fabrication of an electrode sheet having the metal absorbing layer made of a metal oxide In order to increase the efficiency of film formation efficiency of the metal oxide, a laminate substrate which is a substrate of the electrode substrate film is usually produced by the following operation: In a gas atmosphere, a metal target (metal material) is used for reactive sputtering, and a metal absorption layer is continuously formed on the surface of the continuously transported long resin film, and then a metal target such as copper is used in an inert gas atmosphere ( The metal material is sputtered while a metal layer is continuously formed on the metal absorbing layer. Then, the laminated film formed of the metal absorbing layer and the metal layer is etched by using an etching solution such as a copper chloride aqueous solution or a ferric chloride aqueous solution, and the laminated film (metal absorbing layer and metal layer) is etched. The circuit pattern of the processed electrode or the like is patterned.

Therefore, the laminated substrate which is the base material of the electrode substrate film is required to have such a property that the laminated film made of the metal absorbing layer and the metal layer is easily etched by an etching solution such as a copper chloride aqueous solution or a ferric chloride aqueous solution, and The circuit pattern of the electrode or the like which is patterned by the etching is not easily visually recognized under high-intensity illumination.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-151358

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-018194

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-069261

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2014-142462

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2013-225276

However, in the case where the laminated film is formed on both surfaces of the elongated resin film, the problem described in the following paragraph occurs; wherein the laminated film is laminated by the following method, the method In the above, a metal composed of a metal oxide is continuously formed on the surface of the elongated resin film by performing reactive sputtering using a Ni-based metal target (metal material) in a reactive gas atmosphere containing oxygen. The absorption layer is then continuously formed on the metal absorption layer by sputtering using a metal target (metal material) such as copper.

In other words, in order to improve the adhesion to the metal to be laminated, an easy-adhesion layer may be provided on both sides of the elongated resin film. In this case, first, metal absorption is continuously formed on one side of the elongated resin film. After the layer and the metal layer are taken up as a first film and then wound up in a roll shape, and then rolled up to form a second film on the other surface of the elongated resin film, the width direction of the elongated resin film is obtained. A boundary between the center portion and the end portion is defined, and a slight chromatic aberration that can be visually confirmed is found on the metal level. The chromatic aberration on the metal layer may cause poor appearance of the laminated body substrate, and if it is directly processed into an electrode circuit by etching etching in this state, an etching speed difference may occur at the boundary portion of the color to cause etching. bad.

The present invention has been made in view of such a conventional problem, and it is an object of the present invention to provide a film forming method capable of eliminating the width direction of a long resin film when a laminated body substrate is formed on both surfaces of a long resin film. The chromatic aberration is not prone to poor etching.

In order to achieve the above object, the film forming method according to the present invention is characterized in that a first coating film and a second coating film are respectively formed on both surfaces of a long resin film which is conveyed by a roll-to-roll method by a dry plating method. : performing a dry etching process on the surface of the first film between the first winding and the second winding, wherein the first winding is to form the first film in the length After one side of the strip-shaped resin film, the second winding is performed after the second coating film is formed on the other surface of the elongated resin film on which the first coating film has been formed.

According to the present invention, when a laminate substrate is formed on both surfaces of a long resin film, chromatic aberration in the width direction of the elongated resin film can be eliminated. Therefore, the width can be eliminated when etching is performed using a chemical liquid such as an oxidizing agent. The difference in etching processability of the direction.

F‧‧‧Long strip resin film

10‧‧‧vacuum room

10a‧‧‧ Spacer

11‧‧‧Rolling roll

12a, 12b, 23‧‧‧ free rolls

13‧‧‧Cooling roller

14, 22‧‧‧ Tension sensing roller

15‧‧‧Advance roll

16‧‧‧canned rolls

17, 18, 19, 20‧ ‧ magnetically controlled sputtering cathode

21‧‧‧Back feed roller

24‧‧‧Winding roller

25a. 25b, 26a. 26b, 27a. 27b, 28a. 28b‧‧‧ gas release tube

29‧‧‧dry etching

50‧‧‧ resin film (transparent substrate)

51‧‧‧Metal absorption layer

52‧‧‧Metal layer (copper layer) formed by dry film formation

53‧‧‧Metal layer (copper layer) formed by wet film formation

54‧‧‧2nd metal absorbing layer

51a‧‧‧ patterned metal absorbing layer

52a‧‧‧ Metal layer (copper layer) formed by dry film formation by patterning

53a‧‧‧Metal layer (copper layer) formed by wet film formation

54a‧‧‧ patterned second metal absorbing layer

Fig. 1 is a schematic front view of a film forming apparatus (sputtering web coater) capable of suitably performing the film forming method of the present invention.

FIG. 2 is a perspective view schematically showing an appearance defect caused by a laminate substrate produced by a conventional film formation method.

3 is a schematic cross-sectional view showing a laminated body substrate having a first metal absorbing layer and a second metal layer on both surfaces of a transparent substrate, wherein the metal absorbing layer and the metal layer are formed by the film forming method of the present invention. .

4 is a schematic cross-sectional view of a laminate substrate having a thick filmed metal layer formed by a wet film formation method on the metal layer of FIG. And get.

5 is a schematic cross-sectional view of a second laminated body substrate in which a second metal layer of a third layer is formed by a dry plating method on the thick-filmed metal layer of FIG. Obtained by the absorption layer.

Fig. 6 is a schematic cross-sectional view showing an electrode substrate film obtained by forming metal laminated thin wires on both surfaces of a transparent substrate.

In the following, a film forming method by sputtering is used as a specific example of the film forming method of the present invention, and a film forming apparatus capable of appropriately performing the film forming method will be described with reference to FIG. 1 . The film forming apparatus shown in FIG. 1 is also called a sputter winding coater, and is mainly composed of a transfer means for passing the elongated resin film F from the take-up roll 11 via a can by a roll-to-roll method. The roll 16 is conveyed to the take-up roll 24, and the film forming means continuously and efficiently performs sputtering film formation on the surface of the long resin film F when it is wound around the outer peripheral surface of the can roll 16; and the vacuum chamber 10 , to accommodate these means.

Specifically, various devices (not shown) such as a dry pump, a turbo molecular pump, and a cryo coil are incorporated in the vacuum chamber 10, and the pressure in the vacuum chamber 10 is lowered to the final state at the time of sputtering film formation. After the pressure is about 10 ^-4 Pa, the pressure in the vacuum chamber 10 can be adjusted to about 0.1 to 10 Pa by introducing a sputtering gas. As the sputtering gas, a well-known gas such as argon gas is used, and a gas such as oxygen is further added depending on the purpose. The shape and material of the vacuum chamber 10 are not particularly limited as long as they can withstand such a reduced pressure state, and various shapes and materials can be used. A partition plate 10a is provided in the vacuum chamber to isolate a space for performing sputtering deposition from a space in which the transfer roller group is disposed.

On the transport path from the unwinding roller 11 to the can roller 16, the free rollers 12a and 12b are arranged in this order to guide the elongated resin film F, and the cooling roller 13 winds the elongated resin film F and cools it. The tension sensing roller 14 measures the tension of the elongated resin film F on the upstream side of the can roller 16; and the motor-driven advance roller 15 which is fed to the length of the can roller 16 The strip-shaped resin film F is adhered to the outer peripheral surface of the can roller 16 to the peripheral speed of the can roller 16 Line adjustment.

The can roller 16 is internally circulated with a refrigerant that has been tempered outside the vacuum chamber 10, and can be subjected to a heat load application process when the long resin film F wound around the outer peripheral surface is subjected to a heat load application process by a film forming means. The elongated resin film F is cooled. In the chill roll 13, the refrigerant is circulated inside, and the long resin film F can be cooled by performing a heat load application process on the long resin film F by the dry etching means 29 disposed to face the outer periphery thereof. . Further, when the dry etching means 29 is not activated, the circulation of the refrigerant in the cooling roll 13 can be stopped.

In the transport path from the can roller 16 to the take-up roller 24, except that there is no roller corresponding to the cooling roller 13 and the second free roller 12b, as described above, the motor drive is sequentially disposed. The rear feed roller 21 adjusts the peripheral speed of the can roller 16; the tension sensing roller 22 measures the tension of the elongated resin film F on the downstream side of the can roller 16; and the free roller 23 guides Long strip resin film F.

In the take-up roll 11 and the take-up roll 24, the tension balance of the elongated resin film F is maintained by the torque control by the powder clutch or the like. Further, the long resin film F wound from the take-up roll 11 is along the rotation of the can-shaped roller 16 driven by the motor and the motor-driven forward feed roller 15 and the rear feed roller 21 which are rotated in conjunction with the rotation. After being conveyed by the conveyance path defined by the roll group such as the can roller 16, the take-up roll 24 is taken up.

At the position facing the region where the elongated resin film F is wound in the outer circumferential surface of the can roller 16, the four magnetron sputtering cathodes 17, 18, 19 are sequentially disposed along the conveying path of the can roller 16. 20 as a film forming means, and in the vicinity are provided with four pairs of gas release tubes 25a capable of releasing reactive gases. 25b, 26a. 26b, 27a. 27b and 28a. 28b. In addition, if a plate-shaped target is used and the metal absorbing layer and the metal layer are sputter-deposited, a knot may be formed on the target. Nuclear (the growth of foreign bodies). If this causes a problem, it is preferable to use a cylindrical rotating target which does not generate nodules and which is also highly efficient in use of the target.

Among the four magnetron sputtering cathodes 17 to 20, for example, a target for forming a metal absorption layer is provided on a target of the first two cathodes 17 to 18, and a metal is provided on a target of the remaining two cathodes 19 to 20. By using the target material for the layer, the metal absorption layer and the metal layer made of a metal oxide can be continuously formed on one surface of the elongated resin film F. When the metal absorbing layer is formed, if a metal oxide target is used as a target for forming a metal absorbing layer, the film forming speed is slow and it is not suitable for mass production. Therefore, a Ni-based metal target (metal material) capable of forming a film at a high speed is used, and a reaction film formation method such as reactive sputtering in which the reactive gas containing oxygen is controlled while introducing the reactive gas is used.

As a method of controlling the reactive gas, there are known four methods: (1) a method of releasing a reactive gas having a fixed flow rate, and (2) releasing a reactive gas in such a manner that a pressure in a vacuum chamber is maintained at a fixed pressure. Method (3) releasing a reactive gas (impedance control) method in such a manner that the impedance of the sputtering cathode is fixed, and (4) releasing the reactive gas in a manner of fixing the strength of the sputtered plasma (plasma emission control) method.

When the metal absorbing layer is formed by reactive sputtering or the like as described above, the reactive gas forming the sputtering environment is a mixed gas formed by adding oxygen to argon gas or the like. By performing reactive sputtering using a Ni-based metal target (metal material) in a reactive gas atmosphere containing oxygen, a NiO film (not completely oxidized) or the like can be formed. The appropriate oxygen concentration in the reactive gas varies depending on the type of the film forming apparatus and the metal target (metal material), and is appropriately set in consideration of the optical characteristics such as the reflectance of the metal absorbing layer and the etching property of the etching liquid. That is, generally, it is desirable to be 15% by volume or less.

When the two sputtering cathodes 17 and 18 are used as described above to form the metal absorbing layer located in the first layer from the side of the elongated resin film F as the transparent substrate, the gas is released from the two pairs of gas tubes 25a. 25b and 26a. 26b introduces a reactive gas. Further, when a metal absorbing layer and a metal layer are formed on both surfaces of the elongated resin film F, the operation may be performed as follows: as shown in FIG. 1, the take-up roll 11 and the take-up roll 24 are hollowed out as shown in FIG. The film is formed on one side of the elongated resin film F by rotating in the counterclockwise direction indicated by the arrow, and the elongated resin film F is taken up to the take-up roll 24, and then the wound roll is taken from The take-up roll 24 is detached and attached to the take-up roll 11 to rotate the take-up roll 11 in the clockwise direction as indicated by the solid arrow of Fig. 1, and from the take-up roll 11 toward the free roll 12a as indicated by a broken line The long resin film F is taken up, whereby film formation is performed on the other surface.

In addition, in the surface of the elongated resin film used for the dry plating such as the sputtering film formation, an easy-adhesion layer may be formed to improve the adhesion to the plating layer. The method for forming the easy-adhesion layer may be a chemical formation method in which a compound such as a decane compound or an isocyanate compound is applied, or a mechanical formation formed by decomposing constituent molecules of the surface by corona discharge or the like, or roughening the surface. law. If the metal absorbing layer and the metal layer are formed as the first coating film on one side of the long resin film on which the easy-to-adhere layer is provided on both sides, and then the long resin film is wound up, the first coating film may be worried. The first coating film is subjected to chemical influence such as partial transfer of the easy-adhesion layer to the first coating film, in contact with the other unformed side surface of the elongated resin film. The process will be described in detail below.

If the film is formed on the long resin film by the dry plating method, the winding is also performed under a reduced pressure environment. Therefore, after the long resin film in which the first coating film has been formed is wound up, there is almost no gas molecule contact between the first coating film and the unformed surface of the elongated resin film. Further, the elongated resin film that has been wound up is wound up by the conveyance tension when it is wound up. In this case, the conveyance tension differs in the width direction of the elongated resin film, the tension at both end portions in the width direction is the weakest, and the center portion in the width direction is the strongest. In other words, when the elongated resin film in which only the first coating film is formed is wound up in the film forming apparatus, the contact state of the metal surface of the first coating film and the portion in contact with the easily-adhesive layer is in accordance with the elongated resin film. Since the position in the width direction is different, chromatic aberration is sometimes found in the width direction as shown in FIG. 2. Further, in the winding after the formation of the second coating, since the second coating is in contact with the first coating, the problem of chromatic aberration in the width direction does not occur.

When the chromatic aberration in the width direction is observed on the surface of the first film, there is a concern that the workability is different when the first film is subjected to chemical etching or the like by a chemical liquid such as an oxidizing agent. Therefore, in the film forming apparatus of FIG. 1, the surface of the first film can be subjected to dry etching treatment by the dry etching means 29 before the long resin film F after the second film is formed is wound up. Further, in the film forming apparatus of Fig. 1, the first coating film is subjected to dry etching treatment, and then the second coating film is formed. However, the second coating film may be formed first, and then the first coating may be performed. The film is subjected to a dry etching process.

By performing the dry etching process on the first film as described above, it is possible to remove the surface portion of the first film which causes chromatic aberration in the width direction. Thereby, the etching property in the width direction of the elongated resin film does not differ. Examples of the dry etching treatment include a reverse sputtering treatment, a plasma irradiation treatment, an ion beam irradiation treatment, and the like which are performed by causing argon ions or the like to hit the surface of the first coating film. Among these processes, since the ion beam irradiation treatment is strong in directivity, it is preferable to perform dry etching treatment efficiently. In addition, when the surface portion of the chromatic aberration in the width direction of the first film is removed, even when the film is formed by dry plating or wet plating on the surface of the first film, the elongated resin is used. The difference in etching property is less likely to occur in the width direction of the film, and the film provided on the first film may be subjected to dry etching treatment as needed.

The ion beam treatment is performed by irradiating ions from the ion source to the elongated resin film as the object to be processed. As the kind of gas used for the ion beam, oxygen gas, argon gas, nitrogen gas, carbon dioxide gas, or water vapor may be used, or a mixed gas of two or more of the gases may be used. The dry etching means 29 is preferably provided so that the ion beam is irradiated in a substantially linear shape and the effective width of the irradiation is equal to the width of the elongated resin film to be treated. Further, the irradiation time of the ion beam depends on the transport speed of the elongated resin film. The electric power [W] supplied to the ion source for the ion beam treatment is affected by the structure of the film formation apparatus and the chemical type of the first coating film. Therefore, the processing property of the first coating film and the like are appropriately set. Just fine. At this time, it is preferable to set the supply electric power of the ion source based on the irradiation electric power [W/(m.m/min)] defined by the following mathematical expression 1.

[Math 1] Irradiation power = Supply power of ion source [W] / (effective width [m] × transport speed [m/min])

When the surface of the first coating formed on the elongated resin film F is subjected to ion beam treatment, it is preferable that the opposite side portion is brought into contact with the outer peripheral surface of the cooling roll 13 to be cooled. The reason for this is that the directivity of the ion beam treatment is high, and there is concern that the ion beam irradiation portion of the elongated resin film F has a high local temperature and wrinkles. In addition, when the ion beam treatment is excessive or the cooling by the cooling roll 13 is insufficient, wrinkles are likely to occur. Therefore, it is preferable to appropriately adjust the supply power of the ion beam, the temperature of the refrigerant, and the like.

By using the film forming apparatus, it is possible to suppress unevenness in quality when producing a laminated body substrate having a laminated structure for a base material of an electrode substrate film for a touch panel or the like. The laminated body substrate is made of, for example, a transparent substrate 50 made of a long resin film as shown in FIG. 3, and a metal absorbing layer 51 and a metal layer 52, which are formed by the film forming apparatus. Formed on both sides of the transparent substrate 50.

The material of the elongated resin film to be applied to the laminate substrate is not particularly limited, and is preferably selected from the group consisting of polyethylene terephthalate (PET), polyether oxime (PES), and polyarylate (PAR). a resin film of a resin material such as polycarbonate (PC), polyolefin (PO), triacetyl cellulose (TAC) or norbornene, or a resin film selected from the resin material, and covering the elemental substance A composite of a single-sided or two-sided acrylic organic film. As a typical material of the norbornene resin material, ZEONOR (trade name) of Japan's Rayon Co., Ltd., and ARTON (trade name) of JSR Corporation, etc. are mentioned. In addition, the electrode substrate film produced by using the laminate substrate of the present invention is mainly used for a touch panel. Therefore, among the resin films, a resin film excellent in transparency in a visible wavelength region is preferable.

The metal absorbing layer 51 is preferably a layer composed of a metal oxide layer using a metal material composed of a simple substance of Cu, a simple substance of Ni, or a Ni-based alloy in a reactive gas atmosphere containing oxygen. The film forming method is obtained by forming a film; wherein the Ni-based alloy is added to a group selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn. Formed from the above elements. In the case of a Ni-based alloy, a Ni-Cu alloy is preferred.

On the other hand, the metal layer 52 can be formed in a general inert gas atmosphere, and the constituent material thereof is not particularly limited as long as it is a metal having a low electric resistance value. For example, Cu may be added as a simple substance or added to Cu. a Cu-based alloy formed of one or more elements of Ti, Al, V, W, Ta, Si, Cr, or Ag, or a simple substance of Ag, or added to Ag, selected from the group consisting of Ti, Al, V, W, Ta, Si, Among these materials, an Ag-based alloy formed of one or more elements of Cr and Cu is preferably a simple substance of Cu from the viewpoint of workability of a circuit pattern and a resistance value.

The film thickness of the metal absorbing layer 51 is preferably about 15 to 30 nm. Film thickness of the metal layer Since it affects electrical characteristics, it is not determined only by optical requirements, but it is preferable to set the film thickness of the level which cannot be measured by transmitted light. In general, the film thickness of the metal layer is preferably 50 to 5000 nm, and more preferably 3 μm (3000 nm) or less from the viewpoint of processing the metal layer into a wiring pattern.

Further, a metal layer may be formed on the metal layer 52 formed by the dry plating method by a wet plating method such as a plating method to form a thick film. In other words, as shown in FIG. 4, after the metal absorbing layer 51 and the metal layer 52 are formed on both surfaces of the transparent substrate 50 made of a long resin film by a dry plating method, the wet layer may be used on the metal layer 52. A metal layer 53 is formed by plating.

A second metal absorbing layer may be further formed on the metal layer 53. In other words, as shown in FIG. 5, for example, a metal absorbing layer 51 having a film thickness of 15 to 30 nm and a film thickness of 50 to 1000 nm may be formed on both surfaces of a transparent substrate 50 made of a long resin film by dry plating. After the metal layer 52, the metal layer 53 is formed by wet plating, and then the second metal absorbing layer 54 having a film thickness of 15 to 30 nm is formed on the metal layer 53 by dry plating. Similarly to the metal absorbing layer 51, the second metal absorbing layer is formed by a reaction film forming method using a metal material composed of a simple substance of Cu, a simple substance of Ni, or a Ni-based alloy in a reactive gas atmosphere containing oxygen. The Ni-based alloy is formed by adding one or more elements selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn to Ni.

When the metal absorbing layer is formed on both surfaces of the metal layer which is thickened by the dry plating method and the wet plating method, the electrode substrate film produced by using the laminated body substrate can be assembled to the touch panel. It is difficult to see the circuit pattern of the mesh structure composed of the metal laminated thin wires by reflection. In addition, even if a transparent base composed only of a long resin film is used When a laminate substrate obtained by forming a metal absorbing layer and a metal layer on one side of a sheet is used to form an electrode substrate film, it is also difficult to see a circuit pattern from the transparent substrate.

Further, when the metal oxide constituting the metal absorbing layer formed by the reaction film formation method is excessively oxidized, the metal absorbing layer becomes transparent. Therefore, it is preferable to suppress the oxidized level to a degree that visually becomes a blackened film. If a metal absorbing layer is formed by a reactive film formation method, each metal element forms a non-stoichiometric compound with an oxygen atom, and this non-stoichiometric oxide is visually black.

As the reaction film formation method, in addition to the sputtering method using the magnetron sputtering cathodes 17 to 20 as shown in Fig. 1, there are dry plating such as ion beam sputtering, vacuum evaporation, ion plating, and CVD. law. The optical constant (refractive index, extinction coefficient) of the metal absorbing layer at each wavelength is largely affected by the degree of oxidation, that is, the degree of oxidation, and is not determined only by the metal material composed of the Ni-based alloy. Further, in the case of a Ni-Cu alloy, depending on the mixing ratio of Ni and Cu, a method of not using a reaction film forming method (that is, a film forming method without using a reactive gas) may be formed. The metal absorbing layer of the black film is considered.

By forming a laminated film of the laminated body substrate produced by the above method to form a metal laminated thin wire having a line width of, for example, 20 μm or less, an electrode substrate film can be obtained. Specifically, the laminated film of the laminated body film shown in FIG. 5 is patterned by the following etching treatment or the like, whereby an electrode substrate film as shown in FIG. 6 can be obtained. The electrode substrate film shown in FIG. 6 has a circuit pattern of a mesh structure, and the circuit pattern is provided on both surfaces of a transparent substrate 50 made of a resin film, and is formed of, for example, a metal laminated thin wire having a line width of 20 μm or less. The metal laminated thin wires are composed of a metal absorbing layer 51a which is a first layer from the side of the transparent substrate 50, metal layers 52a and 53a which are second layers, and a second metal absorbing layer 54a which is a third layer.

By forming the electrode (wiring) pattern of the electrode substrate film in a stripe shape or a lattice shape as described above, it can be used for a touch panel. Since the metal laminated thin wires which are wire-formed into the electrode (wiring) pattern in this manner maintain the laminated structure of the laminated substrate, the circuit pattern of the electrode or the like which is extremely difficult to visually recognize the transparent substrate even under high-intensity illumination is provided. Characteristics. In other words, when reactive sputtering is performed in a reactive gas atmosphere obtained by adding oxygen to argon gas, a black film as a metal absorbing layer is obtained, so that the reflectance of light can be suppressed when irradiated. The circuit pattern of the electrode or the like obtained by etching the metal absorption layer is not easily recognized by high-intensity illumination.

As a method of forming the electrode substrate film by patterning the laminated body substrate, a well-known subtractive method can be mentioned. The subtractive method is a method in which a photoresist film is formed on the surface of the laminated film of the laminated body substrate, and a portion where the electrode pattern is to be formed is exposed and developed in such a manner as to retain the photoresist film, and the photoresist film is removed by chemical etching. The exposed laminated film is partially removed to form an electrode pattern. As the etching liquid for the chemical etching, an aqueous solution of ferric chloride or an aqueous solution of copper chloride can be used.

In the above, the method for producing the laminated substrate for an electrode substrate film according to a specific example of the present invention has been described. The use of the laminated substrate is not limited to the electrode substrate film for a touch panel, and can be used for a flexible wiring substrate or the like. When the laminated substrate is used for a flexible wiring board, the laminated substrate is a laminated structure in which each of the first coating and the second coating is at least two layers. For example, the first layer is preferably a Ni-based alloy layer, and the second layer is preferably second. The layer is composed of a metal layer formed of a copper layer added with a group selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn. It is formed by one or more elements.

A third layer may be further disposed on the metal layer of the second layer, and the third layer Preferably, the layer is composed of a second Ni-based alloy layer, and the second Ni-based alloy layer is added, for example, from Ni, selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn. One or more elements of the group are formed. These first and second Ni alloy layers are preferably Ni-Cr alloys, and the film thickness thereof is preferably 3 to 50 nm. Further, the film thickness of the copper layer is preferably 50 nm or more, and more preferably 15 μm or less. In addition to the "resin film constituting the transparent substrate" used in the laminated body film for an electrode substrate film, a colored film can be used as long as it does not require transparency. For example, a resin film such as a polyimide film can be used.

[Examples]

The first film is formed on both surfaces of the elongated resin film F by performing a reaction sputtering using a film forming apparatus (sputter coating coater) as shown in FIG. 1 in a reactive gas atmosphere containing oxygen. And the second film. Specifically, the can roller 16 is a stainless steel cylindrical member having an outer diameter of 600 mm and a width of 750 mm, and the surface thereof is subjected to hard chrome plating. Both the forward feed roller 15 and the rear feed roller 21 were made of a stainless steel cylindrical member having an outer diameter of 150 mm and a width of 750 mm, and the surface thereof was subjected to hard chrome plating. A Ni-Cu target for the metal absorbing layer is mounted on the magnetron sputtering cathodes 17, 18, and a Cu target for the metal layer is mounted on the magnetron sputtering cathodes 19, 20.

A PET film having a width of 600 mm and a length of 1200 m was used as the elongated resin film F constituting the transparent substrate. The elongated resin film F is placed on the take-up roll 11 and its leading end portion is wound around the take-up roll 24 through various roll groups. The temperature of the refrigerant circulated in the can roller 16 was controlled to 0 °C. In this state, the inside of the vacuum chamber 10 was evacuated to 5 Pa by a plurality of dry pumps, and then exhausted to 1 × 10 ^-4 Pa using a plurality of turbo molecular pumps and a low temperature coil. Then, the elongated resin film F was conveyed at a conveyance speed of 2 m/min, and sputtering was performed to form a film.

Magnetron sputtering cathode for film formation of a metal absorbing layer during sputtering film formation 17, 18, from the gas release tube 25a respectively disposed in the vicinity thereof. 25b, 26a. 26b was introduced with argon gas at a flow rate of 300 sccm, oxygen gas was introduced at a flow rate of 15 sccm, and electric power control was performed so that a Ni-Cu oxide layer having a film thickness of 30 nm was obtained. On the other hand, in the magnetron sputtering cathodes 19, 20 for film formation of the metal layer (copper layer), the gas release tubes 27a are respectively disposed in the vicinity thereof. 27b, 28a. 28b was introduced with argon gas at a flow rate of 300 sccm, and electric power control was performed so that a Cu layer having a film thickness of 80 nm was obtained.

After the film formation of the first film is completed on one surface of the elongated resin film F, the atmosphere is introduced into the vacuum chamber 10, and the elongated resin film that has been taken up is detached from the take-up roll 24 and placed on the roll-out. Roller 11. Then, after the vacuum evacuation is performed by the same method as the film formation of the first film, the elongated resin film F is conveyed at a transport speed of 2 m/min, and the following is performed in addition to the ion beam treatment described below. In the same procedure as in the case of film formation of the first film, film formation of the second film is performed.

In the film formation of the second film, the cooling film 13 of the refrigerant whose temperature is controlled to 0° C. is used to form the elongated resin film F, unlike the case of the film formation of the first film. The ion source as the dry etching means 29 was started while cooling, and the ion beam treatment was performed on the film formation side of the first film with a gas supply amount of 100 sccm. In addition, in order to investigate the effect when the dry etching treatment conditions are changed, the ion beam treatment is performed by changing the supply power to the ion source and the type of the ion beam supply gas every fixed time. Further, for comparison, the film formation of the second film is performed under the condition that the ion source is stopped and the ion beam supply gas is not supplied.

After the film formation of the second film is completed, the laminated body substrate that has been wound up is taken up in the air, and the chromatic aberration at both ends in the width direction of the first film is visually confirmed. Then, both the first coating film and the second coating film are formed by plating so that the copper thickness becomes 1 μm, and the film is re-passed. In the film forming apparatus, a second metal absorbing layer having a film thickness of 30 nm was formed on the first film and the second film by the same method as described above. Further, ion beam treatment was not performed at the time of film formation of the second metal absorption layer. In this manner, a laminate substrate of Samples 1 to 7 which is formed by laminating a film of a two-layer layer of a transparent substrate, which is a metal absorbing layer which is the first layer from the number of the transparent substrates, is produced. The Ni-Cu oxide film is a Cu film as a metal layer of the second layer and a Ni-Cu oxide film as a second metal absorbing layer of the third layer.

The laminated substrates of the obtained samples 1 to 7 were sampled at positions of 100 m, 500 m, and 900 m after the film formation was started, and etching was performed using an aqueous solution of ferric chloride as an etching solution to evaluate the etching property. . As a criterion for evaluation, if the difference in etching speed between the central portion in the width direction and the portion at 50 mm from the end portion is less than 3 seconds, it is judged as "pass", and if the speed difference is 3 seconds or more, it is judged as "fail". In addition, it was visually confirmed whether or not wrinkles were generated. These evaluation results are shown in Table 1 below together with the evaluation of the color difference obtained by the above-described visual observation and the electric power supplied from the ion source using the mathematical expression 1 and the electric power calculated by the value.

According to the above Table 1, it was found that ions were applied to the film formation surface side of the first coating film. In the bundled samples 1 to 6, none of them had chromatic aberration, and the etching property was also good. On the other hand, in the sample 7 which was not subjected to the ion beam treatment, the occurrence of wrinkles was not observed as in the samples 1 to 6, but chromatic aberration was observed at both end portions of the first film. In addition, in the evaluation of the etching property, all the samples of the sample 7 were unacceptable.

F‧‧‧Long strip resin film

10‧‧‧vacuum room

10a‧‧‧ Spacer

11‧‧‧Rolling roll

12a, 12b, 23‧‧‧ free rolls

13‧‧‧Cooling roller

14, 22‧‧‧ Tension sensing roller

15‧‧‧Advance roll

16‧‧‧canned rolls

17, 18, 19, 20‧ ‧ magnetically controlled sputtering cathode

21‧‧‧Back feed roller

24‧‧‧Winding roller

25a, 25b, 26a, 26b, 27a, 27b, 28a, 28b‧‧‧ gas release tube

29‧‧‧dry etching

Claims (10)

In a film forming method, a first coating film and a second coating film are respectively formed on both surfaces of a long resin film which is conveyed by a roll-to-roll method by a dry plating method, and are characterized in that the first winding and the second coating are performed. The surface of the first film is subjected to a dry etching process between the second winding, and the first winding is performed after the first film is formed on one surface of the elongated resin film, and the second winding is performed. The second coating film is formed on the other surface of the elongated resin film on which the first coating film has been formed. The film forming method of claim 1, wherein the dry etching treatment is ion beam irradiation. The film forming method according to claim 1 or 2, wherein, when the dry etching treatment is performed, the opposite side portion is brought into contact with the cooling roll. The film forming method according to claim 1 or 2, wherein the dry plating method is a sputtering method. The film forming method of claim 3, wherein the dry plating method is a sputtering method. In the method for producing a laminate substrate, the first coating film and the second coating film are formed on both surfaces of the elongated resin film, respectively, wherein the first coating film and the second coating film each have a laminate of at least two layers. The first coating film and the second coating film are formed by the film forming method according to any one of claims 1 to 5. The method for producing a laminated substrate according to the sixth aspect of the invention, wherein the laminated structure is such that the first layer is a Ni-based alloy layer and the second layer is a copper layer, and the Ni-based system is the number of the elongated resin film. The alloy layer is added to Ni from the group consisting of Ti, Al, V, W, Ta, Si, Cr, One or more elements of the group consisting of Ag, Mo, Cu, and Zn are formed. The method for producing a laminated substrate according to claim 7, wherein a second Ni-based alloy layer is further provided as a third layer on the second layer, and the second Ni-based alloy layer is added to Ni. One or more elements of a group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn. The method for producing a laminated substrate according to the sixth aspect of the invention, wherein the laminated structure is such that the first layer is made of a simple substance of Cu, a simple substance of Ni, or a Ni-based alloy. The material is a metal absorption layer formed by a reaction film formation method in a reactive gas atmosphere containing oxygen, and the second layer is a copper layer formed under an inert gas atmosphere, and the Ni-based alloy is added to Ni from the group consisting of Ti and Al. One or more elements of a group consisting of V, W, Ta, Si, Cr, Ag, Mo, Cu, and Zn. The method for producing a laminated substrate according to claim 9, wherein a metal material composed of a simple substance of Cu, a simple substance of Ni, or a Ni-based alloy is further provided on the second layer in a reactive gas atmosphere containing oxygen. The second metal absorbing layer formed by the reaction film forming method is a third layer, and the Ni-based alloy is added with Ni selected from the group consisting of Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, and One or more elements of the group consisting of Zn are formed.