JP2024005997A - Production method of transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a transparent conductive film excellent in productivity.

SOLUTION: In a production method of a transparent conductive film 3, a transparent conductive layer 2 is formed on one side in the thickness direction of a long-sized substrate 1. The production method of the transparent conductive film 3 includes a first step for preparing the substrate 1, a second step for forming a part of the transparent conductive layer 2 on one side in the thickness direction of the substrate 1 under vacuum atmosphere, and a third step for forming the residue of the transparent conductive layer 2 on one side in the thickness direction of a part of the transparent conductive layer 2, while heating the part of the transparent conductive layer 2 under vacuum atmosphere.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a method for manufacturing a transparent conductive film.

BACKGROUND ART Conventionally, there has been known a method of manufacturing a conductive film by laminating a transparent conductive layer on a base film using a roll-to-roll method.

As such a method, for example, an amorphous transparent conductive film is formed by sputtering while conveying a long PET film base material by a roll-to-roll method, and then an amorphous transparent conductive film is formed by sputtering. A method has been proposed for manufacturing a transparent conductive film by heating a PET film base material on which a film is formed to crystallize the transparent conductive film (for example, see Patent Document 1).

Japanese Patent Application Publication No. 2015-146244

On the other hand, methods for producing transparent conductive films require even higher productivity.

An object of the present invention is to provide a method for manufacturing a transparent conductive film with excellent productivity.

The present invention [1] is a method for producing a transparent conductive film in which a transparent conductive layer is formed on one side in the thickness direction of a long base material, which comprises a first step of preparing the base material, and a step of preparing the base material in a vacuum atmosphere. a second step of forming a part of the transparent conductive layer on one side in the thickness direction of the base material; and a second step of forming a part of the transparent conductive layer while heating the part of the transparent conductive layer in a vacuum atmosphere. and a third step of forming the remainder of the transparent conductive layer on one side in the thickness direction of the transparent conductive film.

The present invention [2] includes the method for producing a transparent conductive film according to the above [1], which comprises a fourth step of heating the transparent conductive layer after the third step.

The present invention [3] includes the method for producing a transparent conductive film according to the above [2], in which the fourth step is carried out in a vacuum atmosphere.

The present invention [4] includes the method for producing a transparent conductive film according to the above [2], in which the fourth step is carried out in an atmospheric atmosphere.

In the present invention [5], in the third step, the transparent conductive layer is formed on the base material in contact with the surface of the film-forming roll, and the transparent conductive layer is heated by heating the film-forming roll. The method includes the method for producing a transparent conductive film according to any one of [1] to [4] above, in which a part of the film is heated.

The present invention [6] provides that in the second step, a part of the transparent conductive layer is formed by a target placed in an independent film forming chamber, and in the third step, a target placed in an independent film forming chamber is used. The present invention includes the method for producing a transparent conductive film according to any one of [1] to [5] above, in which the remainder of the transparent conductive layer is formed by the target.

The present invention [7] includes the method for producing a transparent conductive film according to any one of [1] to [6] above, wherein the transparent conductive layer after the third step is crystalline. I'm here.

The present invention [8] provides the transparent material according to any one of [1] to [7] above, wherein the second step and/or the third step is carried out in the presence of a rare gas containing krypton gas. It includes a method for manufacturing a conductive film.

In the method for producing a transparent conductive film of the present invention, in the second step, a part of the transparent conductive layer is formed, and in the third step, while heating a part of the transparent conductive layer, the remaining part of the transparent conductive layer is heated. form. In the third step, since a portion of the transparent conductive layer is heated, the remaining portion of the transparent conductive layer is crystallized together with a portion of the transparent conductive layer. That is, in the third step, the formation of the transparent conductive layer and the crystallization of the transparent conductive layer can be performed simultaneously. Therefore, productivity can be improved.

FIG. 1 shows a schematic diagram of an embodiment of a film manufacturing apparatus used in an embodiment of the method for manufacturing a transparent conductive film of the present invention. FIG. 2 shows a schematic diagram of an embodiment of a film manufacturing apparatus used in a modified example of the method for manufacturing a transparent conductive film of the present invention.

In one embodiment of the method for producing a transparent conductive film of the present invention, a transparent conductive layer 2 is formed on one side of the long base material 1 in the thickness direction while conveying the long base material 1 in the longitudinal direction. do.

Hereinafter, one embodiment of a film manufacturing apparatus used in this method will be described with reference to FIG. 1.

<Film manufacturing equipment>
In FIG. 1, the left-right direction on the paper surface is the conveyance direction. The right side of the paper is the downstream side in the conveyance direction. The left side of the paper is the upstream side in the conveyance direction. Note that the conveyance direction is a conveyance direction between adjacent units, and is not a conveyance direction within each unit. The paper thickness direction is the width direction. The front side of the paper is one side in the width direction. The back side of the paper is the other side in the width direction. The up-down direction on the paper is the up-down direction. The upper side of the paper is the upper side. The lower side of the paper is the lower side.

The film manufacturing apparatus 10 is an apparatus for manufacturing a long transparent conductive film 3. The film manufacturing apparatus 10 includes a delivery unit 5, a sputtering unit 6, a first annealing unit 7, and a winding unit 8, as shown in FIG.

[Sending unit]
The delivery unit 5 includes a delivery roll 11, a first guide roll 12, and a delivery chamber 13.

The delivery roll 11 is a cylindrical member having a rotating shaft for delivering the elongated base material 1 . The delivery roll 11 is disposed at the most upstream position in the transport direction of the film manufacturing apparatus 10 . A motor (not shown) for rotating the delivery roll 11 is connected to the delivery roll 11 .

The first guide roll 12 is a rotating member that guides the elongated base material 1 sent out from the delivery roll 11 to the sputtering unit 6 . The first guide roll 12 is arranged downstream of the delivery roll 11 in the transport direction and upstream of the second guide roll 14 (described later) in the transport direction.

The delivery chamber 13 is a casing that accommodates the delivery roll 11 and the first guide roll 12. The delivery chamber 13 is provided with a vacuum unit (not shown) that can evacuate the inside.

[Sputter unit]
The sputtering unit 6 laminates (forms) a portion of the transparent conductive layer 2 on the elongated base material 1 conveyed from the delivery unit 5 by sputtering. The sputter unit 6 is arranged downstream of the delivery unit 5 in the transport direction and upstream of the first annealing unit 7 in the transport direction, so as to be adjacent thereto. The sputter unit 6 includes a second guide roll 14, a third guide roll 15, a first film forming roll 16, a plurality of first film forming chambers 17 (four first film forming chambers 17 in FIG. 1), It includes a fourth guide roll 18 and a first chamber 19.

The second guide roll 14 is a rotating member that guides the long base material 1 conveyed from the delivery unit 5 (first guide roll 12) to the third guide roll 15. The second guide roll 14 is arranged downstream of the first guide roll 12 in the transport direction and upstream of the third guide roll 15 in the transport direction.

The third guide roll 15 is a rotating member that guides the long base material 1 conveyed from the second guide roll 14 to the first film forming roll 16. The third guide roll 15 is arranged downstream of the second guide roll 14 in the transport direction and upstream of the first film forming roll 16 in the transport direction.

The first film forming roll 16 is a cylindrical member having a rotating shaft for laminating (forming) a portion of the transparent conductive layer 2 on the elongated base material 1 . The first film forming roll 16 conveys the elongated base material 1 along the circumferential surface of the first film forming roll 16 . The first film forming roll 16 is arranged downstream of the third guide roll 15 in the transport direction and upstream of the fourth guide roll 18 in the transport direction.

The plurality of first film-forming chambers 17 are arranged on the sides and below the first film-forming roll 16 in the circumferential direction of the first film-forming roll 16 and facing the first film-forming roll 16 . Specifically, the plurality of first film forming chambers 17 (first film forming chambers 17A to 17D) are arranged adjacent to each other in order from the upstream side in the transport direction to the downstream side in the transport direction.

Further, each first film forming chamber 17 is partitioned by a wall 40. In other words, each first film forming chamber 17 is an independent film forming chamber.

Further, a first target 31 is arranged in each first film forming chamber 17 . Power can be applied to the first target 31 using any power source (for example, a DC power source or an AC power source). Further, in order to apply electric power, a magnet is arranged on the side of the first target 31 opposite to the first film forming roll 16 (not shown). That is, in the second step, a part of the transparent conductive layer 2 is formed by the first target 31 placed in the independent first film forming chamber 17. Therefore, independent film forming conditions (for example, discharge output and sputtering gas) can be set for each first film forming chamber 17 (each first target 31).

The first target 31 is made of a material containing atoms constituting the transparent conductive layer 2 , and preferably made of the material of the transparent conductive layer 2 . The first target 31 is placed near the first film forming roll 16 . Specifically, the first target 31 is disposed below the first film forming roll 16 and facing the first film forming roll 16 with an interval therebetween.

The plurality of first targets 31 (first targets 31A to 31D) are lined up in the circumferential direction of the first film forming roll 16, and spaced apart from each other in order from the upstream side in the conveyance direction to the downstream side in the conveyance direction. It is located.

The fourth guide roll 18 performs a first annealing process on the long base material 1 (the long base material 1 on which a part of the transparent conductive layer 2 is laminated (formed)) conveyed from the first film forming roll 16. This is a rotating member that guides the unit 7. The fourth guide roll 18 is arranged downstream of the first film forming roll 16 in the transport direction and upstream of the fifth guide roll 20 (described later) in the transport direction.

The first chamber 19 is a casing that accommodates the second guide roll 14 , the third guide roll 15 , the first film-forming roll 16 , the plurality of first film-forming chambers 17 , and the fourth guide roll 18 . The first chamber 19 is provided with a vacuum unit (not shown) that allows the inside to be evacuated.

[First annealing unit]
The first annealing unit 7 performs a sputtering method while heating the elongated base material 1 (the elongated base material 1 on which a part of the transparent conductive layer 2 is laminated (formed)) conveyed from the sputtering unit 6. The remaining portion of the transparent conductive layer 2 is laminated (formed) by the following steps. The first annealing unit 7 is arranged downstream of the sputtering unit 6 in the transport direction and upstream of the winding unit 8 in the transport direction so as to be adjacent thereto. The first annealing unit 7 includes a fifth guide roll 20, a sixth guide roll 21, a second film forming roll 22, and a plurality of second film forming chambers 23 (three second film forming chambers 23 in FIG. 1). , a seventh guide roll 24 , and a second chamber 25 .

The fifth guide roll 20 carries the long base material 1 (the long base material 1 on which a part of the transparent conductive layer 2 is laminated (formed)) conveyed from the sputter unit 6 (fourth guide roll 18). It is a rotating member that guides the sixth guide roll 21. The fifth guide roll 20 is arranged downstream of the fourth guide roll 18 in the transport direction and upstream of the sixth guide roll 21 in the transport direction.

The sixth guide roll 21 is a rotating member that guides the elongated base material 1 conveyed from the fifth guide roll 20 to the second film forming roll 22. The sixth guide roll 21 is arranged downstream of the fifth guide roll 20 in the transport direction and upstream of the second film forming roll 22 in the transport direction.

The second film forming roll 22 is a cylindrical member having a rotating shaft for laminating (forming) the remainder of the transparent conductive layer 2 on the elongated base material 1 . The second film forming roll 22 transports the elongated base material 1 along the circumferential surface of the second film forming roll 22 . The second film forming roll 22 is arranged downstream of the sixth guide roll 21 in the transport direction and upstream of the seventh guide roll 24 in the transport direction.

The plurality of second film-forming chambers 23 are arranged on the sides and below the second film-forming roll 22 in the circumferential direction of the second film-forming roll 22 and facing the second film-forming roll 22 . Specifically, the plurality of second film forming chambers 23 (second film forming chambers 23A to 23C) are arranged adjacent to each other in order from the upstream side in the transport direction to the downstream side in the transport direction.

Further, each second film forming chamber 23 is partitioned by a wall 40. In other words, each second film forming chamber 23 is an independent film forming chamber.

Further, a second target 32 is arranged in each second film forming chamber 23 . That is, in the third step, the remaining portion of the transparent conductive layer 2 is formed by the second target 32 placed in the independent second film forming chamber 23. Therefore, independent film forming conditions (for example, discharge output and sputtering gas) can be set for each second film forming chamber 23 (each second target 32).

The second target 32 is formed from a material containing atoms that constitute the transparent conductive layer 2 , and is preferably formed from the material of the transparent conductive layer 2 . The second target 32 is arranged near the second film forming roll 22. Specifically, the second target 32 is disposed below the second film-forming roll 22 and facing the second film-forming roll 22 with an interval therebetween.

A plurality of second targets 32 (second targets 32A to 32C) are lined up in the circumferential direction of the second film forming roll 22 and spaced apart from each other in order from the upstream side in the conveyance direction to the downstream side in the conveyance direction. It is located.

The seventh guide roll 24 is a rotating member that guides the long transparent conductive film 3 conveyed from the second film forming roll 22 to the winding unit 8 . The seventh guide roll 24 is arranged downstream of the second film forming roll 22 in the transport direction and upstream of the eighth guide roll 26 (described later) in the transport direction.

The second chamber 25 is a casing that accommodates the fifth guide roll 20 , the sixth guide roll 21 , the second film-forming roll 2 , the plurality of second film-forming chambers 23 , and the seventh guide roll 24 . The second chamber 25 is provided with a vacuum unit (not shown) that allows the inside to be evacuated.

[Take-up unit]
The winding unit 8 includes an eighth guide roll 26, a winding roll 27, and a winding chamber 28. The winding unit 8 is arranged downstream of the sputtering unit 6 in the transport direction and adjacent to the sputtering unit 6 .

The eighth guide roll 26 is a rotating member that guides the long transparent conductive film 3 conveyed from the first annealing unit 7 to the take-up roll 27. The eighth guide roll 26 is arranged downstream of the seventh guide roll 24 in the transport direction and upstream of the take-up roll 27 in the transport direction.

The take-up roll 27 is a cylindrical member having a rotating shaft for winding up the transparent conductive film 3. The take-up roll 27 is disposed at the downstream end of the film manufacturing apparatus 10 in the transport direction. A motor (not shown) for rotating the take-up roll 27 is connected to the take-up roll 27 .

The take-up chamber 28 is a casing that accommodates the eighth guide roll 26 and the take-up roll 27. The winding chamber 28 is provided with a vacuum unit (not shown) that can evacuate the inside.

<Method for producing transparent conductive film>
Next, one embodiment of a method for manufacturing the transparent conductive film 3 using the film manufacturing apparatus 10 will be described.

In the method for manufacturing the transparent conductive film 3, the transparent conductive layer 2 is formed on one surface of the long base material 1 in the thickness direction while the long base material 1 is conveyed in the longitudinal direction.

Specifically, the method for manufacturing the transparent conductive film 3 includes a first step of preparing a long base material 1, and a step of forming a transparent conductive layer 2 on one side of the long base material 1 in the thickness direction in a vacuum atmosphere. A second step of forming a part of the transparent conductive layer 2 and forming the remainder of the transparent conductive layer 2 on one side in the thickness direction of the part of the transparent conductive layer 2 while heating the part of the transparent conductive layer 2 in a vacuum atmosphere. and a third step.

[First step]
In the first step, a long base material 1 is prepared.

An example of the long base material 1 is a long polymer film. Examples of materials for the polymer film include olefin resin, polyester resin, (meth)acrylic resin (acrylic resin and/or methacrylic resin), polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, and polyimide. resins, cellulose resins, and polystyrene resins. Examples of olefin resins include polyethylene, polypropylene, and cycloolefin polymers. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of the (meth)acrylic resin include polymethacrylate. The material for the elongated base material 1 is preferably polyester resin, more preferably polyethylene terephthalate (PET).

The thickness of the long base material 1 is, for example, 10 μm or more, preferably 30 μm or more, and, for example, 500 μm or less.

If the thickness of the elongated base material 1 is equal to or greater than the above lower limit, it will be excellent in transportability and handling.

If the thickness of the elongated base material 1 is equal to or less than the above upper limit, productivity is excellent.

Further, the length in the lateral direction (length in the width direction) of the elongated base material 1 is, for example, 100 mm or more, preferably 200 mm or more, and, for example, 5000 mm or less, preferably 2000 mm or less.

Moreover, a functional layer can be arranged in advance on one thickness direction surface and/or the other thickness direction surface of the elongated base material 1. When a functional layer is arranged on one side in the thickness direction of the elongated base material 1, for example, the transparent conductive film 3 is arranged so that the elongated base material 1, the functional layer, and the transparent conductive layer 2 are arranged on one side in the thickness direction. Prepare in order toward one side. In addition, when a functional layer is arranged on the other surface in the thickness direction of the elongated base material 1, the transparent conductive film 3 may include, for example, the functional layer, the elongated base material 1, and the transparent conductive layer 2. , in order toward one side in the thickness direction.

Examples of the functional layer disposed on one side in the thickness direction of the elongated base material 1 include a hard coat layer, an optical adjustment layer, and the like. Examples of the functional layer disposed on the other surface in the thickness direction of the elongated base material 1 include an anti-blocking layer.

The hard coat layer is formed from a hard coat composition.

The hard coat composition contains a resin and, if necessary, particles.

Examples of the resin include curable resins and thermoplastic resins (eg, polyolefin resins), and preferably curable resins. Examples of the curable resin include active energy ray-curable resins that are cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, etc.) and thermosetting resins that are cured by heating. Examples include active energy ray-curable resins. Examples of active energy ray-curable resins include polymers having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such functional groups include vinyl groups and (meth)acryloyl groups (methacryloyl groups and/or acryloyl groups). Examples of active energy ray-curable resins include (meth)acrylic ultraviolet-curable resins. Examples of the (meth)acrylic ultraviolet curable resin include urethane acrylate and epoxy acrylate. The resins can be used alone or in combination of two or more.

Examples of the particles include inorganic particles and organic particles. Examples of inorganic particles include metal oxide particles and carbonate particles. Examples of metal oxide particles include zirconium oxide, titanium oxide, zinc oxide, and tin oxide. Examples of carbonate particles include calcium carbonate. Examples of organic particles include crosslinked acrylic resin particles. The particles can be used alone or in combination of two or more.

Then, the hard coat composition is obtained by mixing the resin and optionally blended particles.

Further, the hard coat composition may contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent, if necessary.

To form the hard coat layer, a diluted solution of the hard coat composition is applied to one side in the thickness direction of the elongated base material 1, and after drying, the hard coat composition is cured by ultraviolet irradiation.

This forms a hard coat layer.

From the viewpoint of scratch resistance, the thickness of the hard coat layer is, for example, 0.1 μm or more, preferably 0.5 μm or more, and is, for example, 10 μm or less, preferably 3 μm or less.

Note that the thickness of the hard coat layer can be measured by cross-sectional observation using, for example, a transmission electron microscope.

In such a case, the obtained transparent conductive film 3 includes an elongated base material 1, a hard coat layer, and a transparent conductive layer 2 in this order.

The optical adjustment layer is made of a transparent material in order to suppress the visibility of the pattern of the transparent conductive layer 2, suppress reflection at the interface within the transparent conductive film 3, and ensure excellent transparency of the transparent conductive film 3. This layer adjusts the optical properties (for example, refractive index) of the conductive film 3.

The optical adjustment layer is formed from, for example, an optical adjustment composition.

The optical adjustment composition contains the resin described above and the particles described above.

Examples of the resin include the resins listed for the hard coat composition.

Examples of the particles include the particles listed for the hard coat composition.

The optical adjustment composition is then obtained by mixing the resin and particles.

The optical adjustment composition may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent.

To form the optical adjustment layer, a diluted solution of the optical adjustment composition is applied to one side in the thickness direction of the elongated base material 1, and after drying, the optical adjustment composition is cured by ultraviolet irradiation.

This forms an optical adjustment layer.

The thickness of the optical adjustment layer is, from the viewpoint of scratch resistance, for example, 5 nm or more, preferably 10 nm or more, more preferably 50 nm or more, and also, for example, 500 nm or less, preferably 200 nm or less, more preferably , 100 nm or less. The thickness of the optical adjustment layer can be measured, for example, by observing a cross section using a transmission electron microscope.

In such a case, the obtained transparent conductive film 3 includes the elongated base material 1, the optical adjustment layer, and the transparent conductive layer 2 in this order.

The anti-blocking layer imparts anti-blocking properties to the respective surfaces of the plurality of transparent conductive films 3 that are in contact with each other when the transparent conductive films 3 are laminated in the thickness direction.

The material of the anti-blocking layer is, for example, an anti-blocking composition.

Examples of the anti-blocking composition include the mixture described in JP-A-2016-179686.

To form the anti-blocking layer, a diluted solution of the anti-blocking composition is applied to the other surface of the elongated base material 1 in the thickness direction, and after drying, the anti-blocking composition is cured by UV irradiation.

This forms an anti-blocking layer.

The thickness of the anti-blocking layer is, for example, 0.1 μm or more and, for example, 10 μm or less.

In such a case, the obtained transparent conductive film 3 includes an anti-blocking layer, an elongated base material 1, and a transparent conductive layer 2 in this order.

One or more functional layers can be disposed on the elongated base material 1, and preferably, a hard coat layer is disposed on the elongated base material 1 in advance.

Then, the elongated base material 1 is placed on the delivery roll 11. That is, a roll body in which the elongated base material 1 is wound into a roll shape is mounted on the delivery roll 11 .

In this way, a long base material 1 is prepared.

[Second step]
In the second step, a part of the transparent conductive layer 2 is formed on one side of the elongated base material 1 in the thickness direction in a vacuum atmosphere.

In the second step, first, the long base material 1 is conveyed in the longitudinal direction.

To convey the long base material 1 in the longitudinal direction, the feed roll 11 and the take-up roll 27 are rotationally driven by a motor to feed the long base material 1 from the feed roll 11, and the first guide roll 12, 2nd guide roll 14, 3rd guide roll 15, 1st film-forming roll 16, 4th guide roll 18, 5th guide roll 20, 6th guide roll 21, 2nd film-forming roll 22, 7th guide roll 24, Then, it is sequentially conveyed by the eighth guide roll 26 and wound up by the winding roll 27.

As a result, the elongated base material 1 is transported in the transport direction from the delivery roll 11 to the take-up roll 27 in a roll-to-roll manner.

The conveyance speed is, for example, 0.5 m/min or more, preferably 1 m/min or more, more preferably 2.0 m/min or more, and, for example, 50 m/min or less, preferably 20 m/min or less. , more preferably 15 m/min or less.

Next, while conveying the long base material 1 in the longitudinal direction, a part of the transparent conductive layer 2 is formed on one surface of the long base material 1 in the thickness direction in a vacuum atmosphere.

Specifically, the elongated base material 1 is conveyed while contacting the surface of the first film forming roll 16 along the circumferential direction. Then, sputtering is performed on the elongated base material 1 being transported in a vacuum atmosphere. That is, the sputtering unit 6 is operated to form a part of the transparent conductive layer 2 on the elongated base material 1 .

Specifically, a rare gas as a sputtering gas is supplied into the first chamber 19 under vacuum (inside the plurality of first film forming chambers 17), and a voltage is applied to direct the gas to the first target. 31 (first target 31A to first target 31D). As a result, on the side and below the first film forming roll 16, the first target 31 (first target 31A to The target material repelled from the first target 31D) is attached to form a part of the transparent conductive layer 2.

That is, in this method, a part of the transparent conductive layer 2 is formed by sputtering while conveying the elongated base material 1 along the circumferential surface of the first film forming roll 16.

Furthermore, as described above, the second step is performed in the presence of sputtering gas (rare gas).

Examples of the rare gas include argon gas, krypton gas, and xenon gas, preferably krypton gas and xenon gas, and more preferably krypton gas. That is, from the viewpoint of manufacturing cost and productivity, the second step is more preferably performed in the presence of a rare gas containing krypton gas. Specifically, krypton is a heavier atom than argon, and since the voltage is higher than that of argon, the speed of sputtering becomes faster, resulting in improved productivity.

Further, the type of sputtering gas can be selected individually for each first film forming chamber 17, and preferably krypton gas is selected in the first film forming chambers 17A to 17D.

Furthermore, when the transparent conductive layer 2 is disposed by a sputtering method, sputtering gas (rare gas) is taken into the transparent conductive layer 2. That is, the transparent conductive layer 2 contains rare gas atoms (preferably krypton atoms).

In the transparent conductive layer 2, the content of rare gas atoms (preferably krypton atoms) is, for example, 0.5 atomic % or less, preferably 0.2 atomic % or less, more preferably 0.1 atomic %. % or less, more preferably less than 0.1 atomic %.

The lower limit of the above content is a proportion corresponding to when the presence of rare gas atoms can be confirmed by a fluorescent X-ray analyzer, and is at least 0.0001 atomic % or more.

Further, as the sputtering gas, a reactive gas (for example, oxygen gas) can also be used in combination with the above-mentioned rare gas.

The flow rate of the reactive gas can be adjusted individually for each first film forming chamber 17. The flow rate of the reactive gas relative to the total amount of the rare gas and the reactive gas is, for example, 0.1% or more, preferably 0.5% or more, and, for example, 5.0% or less, preferably 4%. .0 flow% or less. Further, preferably, the flow rate of the reactive gas in the first film forming chamber 17A is adjusted to be lower than the flow rate of the reactive gas in the first film forming chamber 17B to each of the first film forming chambers 17D.

Furthermore, the applied output (discharge output) can be adjusted individually for each first film forming chamber 17. The discharge output is, for example, 0.1 W/mm or more, preferably 0.5 W/mm or more, more preferably 1.0 W/mm or more, and, for example, 20 W/mm or less, preferably 10 W/mm or less. , more preferably 7.0 W/mm or less. Further, preferably, the discharge output of the first film forming chamber 17A is adjusted to be lower than the discharge output of the first film forming chamber 17B to each of the first film forming chambers 17D. Further, the applied voltage (film-forming voltage) can be adjusted individually for each first film-forming chamber 17. The absolute value of the film forming voltage is, for example, 10V or more, preferably 100V or more, and, for example, 600V or less, preferably 500V or less, and preferably 400V or less. Further, preferably, the film forming voltage of the first film forming chamber 17A is adjusted to be lower than the film forming voltage of the first film forming chamber 17B to each of the first film forming chambers 17D.

The material of the first target 31, that is, the material of the transparent conductive layer 2 (a part of the transparent conductive layer 2) is, for example, indium-based oxide (for example, indium tin composite oxide, indium zinc composite oxide, and indium Gallium composite oxide) Metal oxides such as antimony tin composite oxide, metal nitrides such as aluminum nitride, titanium nitride, tantalum nitride, chromium nitride, gallium nitride, and composite nitrides thereof, such as gold, silver, Examples include metals such as copper, nickel, and alloys thereof, preferably indium-based oxides, and more preferably indium-tin composite oxides.

That is, preferably, the transparent conductive layer 2 (a part of the transparent conductive layer 2) contains an indium-based oxide as a main component, and more preferably contains an indium-tin composite oxide as a main component.

When the transparent conductive layer 2 (a part of the transparent conductive layer 2) contains indium-based oxide as a main component, the specific resistance of the transparent conductive layer 2 can be lowered.

When using indium tin composite oxide as a material for the transparent conductive layer 2 (part of the transparent conductive layer 2), the content ratio of tin oxide is, for example, 0.5 mass with respect to the total amount of tin oxide and indium oxide. % or more, preferably 2% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

If the content of tin oxide is at least the above-mentioned lower limit, lowering of resistance will be promoted. If the content of tin oxide is below the above-mentioned upper limit, the transparent conductive layer 2 (a part of the transparent conductive layer 2) will have excellent strength and crystallinity.

Further, since the target material ejected from the first target 31 collides with the elongated base material 1 and generates thermal energy, in this method, a part of the transparent conductive layer 2 is is cooled to suppress crystallization of a portion of the transparent conductive layer 2.

Specifically, the temperature of the first film forming roll 16 is, for example, -20°C or higher, preferably -10°C or higher, and also, for example, 50°C or lower, preferably 20°C or lower, and more preferably 0°C or lower. It is.

If the temperature of the first film forming roll 16 is at least the above lower limit or below the above upper limit, the transparent conductive layer 2 (part of the transparent conductive layer 2) can be sufficiently cooled, and the transparent conductive layer 2 (transparent conductive layer 2) can be sufficiently cooled. 2) can be suppressed (a part of the amorphous transparent conductive layer 2 can be obtained).

[Third step]
In the third step, the remaining part of the transparent conductive layer 2 is formed on one side in the thickness direction of the part of the transparent conductive layer 2 while heating the part of the transparent conductive layer 2 in a vacuum atmosphere.

Specifically, the elongated base material 1 is conveyed while contacting the surface of the second film forming roll 22 along the circumferential direction. Then, sputtering is performed on the elongated base material 1 being transported in a vacuum atmosphere while heating a part of the transparent conductive layer 2. That is, the first annealing unit 7 is operated to simultaneously form the remaining portion of the transparent conductive layer 2 and crystallize the transparent conductive layer 2.

Specifically, a rare gas as a sputtering gas is supplied into the second chamber 25 under vacuum (inside the plurality of second film forming chambers 23), and a voltage is applied to transfer the gas to the second target. 32 (second target 32A to second target 32C). As a result, on the side and below the second film forming roll 22, a second target is placed on the lower surface (one surface) of a part of the transparent conductive layer 2 in the elongated base material 1 conveyed from the upstream side in the conveyance direction. The target material ejected from 32 (second targets 32A to 32C) is attached to form the remainder of the transparent conductive layer 2.

That is, in this method, the remaining portion of the transparent conductive layer 2 is formed by sputtering while conveying the elongated base material 1 along the circumferential surface of the first film forming roll 16.

Further, as described above, the third step is performed in the presence of sputtering gas (rare gas).

Examples of the rare gas include the rare gases exemplified in the second step, preferably krypton gas. That is, from the viewpoint of manufacturing cost and productivity, the third step is more preferably performed in the presence of a rare gas containing krypton gas. Specifically, krypton is a heavier atom than argon, and the voltage applied to krypton is higher than that of argon, resulting in faster sputtering and, as a result, improved productivity.

Further, the type of sputtering gas can be selected individually for each second film forming chamber 23, and preferably krypton gas is selected in the second film forming chambers 23A to 23C.

The flow rate of the reactive gas can be adjusted individually for each second film forming chamber 23. The flow rate of the reactive gas with respect to the total amount of the rare gas and the reactive gas is the same as the flow rate of the reactive gas in the second step.

Further, the applied output (discharge output) can be adjusted individually for each second film forming chamber 23. The discharge output is the same as the discharge output in the second step. The total discharge of each second film forming chamber 23 that forms the thickness of the remaining part of the transparent conductive layer 2 relative to the sum of the total discharge output of each first film forming chamber 17 that forms the thickness of a part of the transparent conductive layer 2 The output ratio (total discharge output of each second film forming chamber 23/total discharge output of each first film forming chamber 17) is, for example, 0.010 or more, preferably 0.030 or more, more preferably 0. .050 or more, more preferably 0.060 or more, particularly preferably 0.080 or more, particularly preferably 0.100 or more, and, for example, 0.800 or less, preferably 0.500 or less, More preferably, it is 0.400, still more preferably 0.300 or less, particularly preferably 0.200 or less. The applied voltage (film-forming voltage) can be adjusted individually for each second film-forming chamber 23. The film forming voltage is the same as the film forming voltage in the second step.

The material of the second target 32 is the same as that of the first target 31. Preferably, the material of the second target 32 is an indium-based composite oxide, and more preferably an indium-tin composite oxide.

Moreover, in this method, a part of the transparent conductive layer 2 is heated by the second film forming roll 22 to crystallize the rest of the transparent conductive layer 2 together with the part of the transparent conductive layer 2 .

Specifically, the temperature of the second film forming roll 22 is, for example, 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher, and also, for example, 200°C or lower, preferably 180°C or lower. .

Thereby, a transparent conductive film 3 is obtained, which includes an elongated base material 1 and a transparent conductive layer 2 in this order on one side in the thickness direction.

Thereafter, the transparent conductive film 3 produced below the second film-forming roll 22 is transported by the second film-forming roll 22 and the eighth guide roll 26 toward the take-up roll 27 on the downstream side in the transport direction. Ru.

In the obtained transparent conductive film 3, the transparent conductive layer 2 is preferably crystalline. If the transparent conductive layer 2 is crystalline, the specific resistance described below can be reduced.

Note that a method for confirming the crystallinity of the transparent conductive layer 2 will be described in detail in Examples described later.

The thickness of the transparent conductive layer 2 is, for example, 10 nm or more, preferably 20 nm or more, and also, for example, 300 nm or less, preferably 200 nm or less, and more preferably 170 nm or less. Specifically, the thickness of a portion of the transparent conductive layer 2 is, for example, 5 nm or more, preferably 10 nm or more, and, for example, 290 nm or less, preferably 200 nm or less, and preferably 160 nm or less. The thickness of the remaining portion of the transparent conductive layer 2 is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and, for example, 200 nm or less, preferably 100 nm or less. Further, the ratio of the thickness of the remaining part of the transparent conductive layer 2 to the thickness of the part of the transparent conductive layer 2 (thickness of the remaining part of the transparent conductive layer 2/thickness of a part of the transparent conductive layer 2) is, for example, 0.01 or more. , preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.06 or more, particularly preferably 0.08 or more, particularly preferably 0.10 or more, and, for example , 0.80 or less, preferably 0.50 or less, more preferably 0.40, still more preferably 0.30, particularly preferably 0.20 or less.

Note that the thickness of the transparent conductive layer 2 can be measured, for example, by observing the cross section of the transparent conductive film 3 using a transmission electron microscope.

The specific resistance of the transparent conductive layer 2 is, for example, 4.0×10 ⁻⁴ Ω·cm or less, preferably 3.0×10 ⁻⁴ Ω·cm or less, more preferably 2.2×10 ⁻⁴ Ω.・cm or less, more preferably 2.0×10 ⁻⁴ Ω·cm or less.

Note that the specific resistance can be determined by multiplying the surface resistance value measured by the four-probe method and the thickness of the transparent conductive layer 2 in accordance with JIS K7194.

The surface resistance value of the transparent conductive layer 2 is, for example, 200 Ω/□ or less, preferably 100 Ω/□ or less, more preferably 50 Ω/□ or less.

The lower limit of the surface resistance value of the transparent conductive layer 2 is not particularly limited. For example, the surface resistance value of the transparent conductive layer 2 is usually more than 0Ω/□, or more than 1Ω/□.

Note that the surface resistance value can be measured by a four-terminal method in accordance with JIS K7194.

<Effect>
In the method for manufacturing the transparent conductive film 3, in the second step, a part of the transparent conductive layer 2 is formed, and in the third step, while heating the part of the transparent conductive layer 2, the transparent conductive layer 2 is heated. form the remainder. In the third step, since a part of the transparent conductive layer 2 is heated, the remaining part of the transparent conductive layer 2 is crystallized together with the part of the transparent conductive layer 2. That is, in the third step, the formation of the transparent conductive layer 2 and the crystallization of the transparent conductive layer 2 can be performed simultaneously. Therefore, productivity can be improved.

<Modified example>
In the modified example, the same reference numerals are given to the same members and steps as in the embodiment, and detailed description thereof will be omitted. Moreover, the modified example can have the same effects as the one embodiment except as otherwise specified. Furthermore, one embodiment and the modified examples can be combined as appropriate.

In one embodiment, there are four first film forming chambers 17, but the number is not particularly limited.

In one embodiment, there are three second film forming chambers 23, but the number is not particularly limited.

In one embodiment, in the third step, a part of the transparent conductive layer 2 is heated by heating the second film forming roll 22; Instead, a heater (not shown) can also be used. Preferably, by heating the second film-forming roll 22 from the viewpoint of uniformly applying heat to the transparent conductive layer 2 and promoting crystallization by physically contacting the transparent conductive film 3, A part of the transparent conductive layer 2 is heated.

Moreover, the manufacturing method of the transparent conductive film 3 can also be provided with the 4th process of heating the transparent conductive layer 2 after a 3rd process.

Hereinafter, a modification of the film manufacturing apparatus that can carry out the fourth step will be described with reference to FIG. 2.

The film manufacturing apparatus 10 includes a second annealing unit 9 between the first annealing unit 7 and the winding unit 8.

The second annealing unit 9 heats the transparent conductive film 3 conveyed from the first annealing unit 7. The second annealing unit 9 is arranged downstream of the first annealing unit 7 in the transport direction and upstream of the winding unit 8 in the transport direction so as to be adjacent thereto.

The second annealing unit 9 includes a ninth guide roll 29 , a tenth guide roll 30 , a heating roll 31 , an eleventh guide roll 32 , and a third chamber 33 .

The ninth guide roll 29 is a rotating member that guides the transparent conductive film 3 conveyed from the first annealing unit 7 (seventh guide roll 24 ) to the tenth guide roll 30 . The ninth guide roll 29 is arranged downstream of the seventh guide roll 24 in the transport direction and upstream of the tenth guide roll 30 in the transport direction.

The tenth guide roll 30 is a rotating member that guides the transparent conductive film 3 conveyed from the ninth guide roll 29 to the heating roll 31. The tenth guide roll 30 is arranged downstream of the ninth guide roll 29 in the transport direction and upstream of the heating roll 31 in the transport direction.

The heating roll 31 is a cylindrical member having a rotating shaft for heating the transparent conductive layer 2 . The heating roll 31 conveys the transparent conductive film 3 along the circumferential surface of the heating roll 31 . The heating roll 31 is arranged downstream of the tenth guide roll 30 in the transport direction and upstream of the eleventh guide roll 32 in the transport direction.

The eleventh guide roll 32 is a rotating member that guides the long transparent conductive film 3 conveyed from the heating roll 31 to the winding unit 8 . The eleventh guide roll 32 is arranged downstream of the heating roll 31 in the transport direction and upstream of the eighth guide roll 26 in the transport direction.

The third chamber 33 is a casing that accommodates the ninth guide roll 29, the tenth guide roll 30, the heating roll 31, and the eleventh guide roll 32. The third chamber 33 is provided with a vacuum unit that can vacuum the inside.

Then, in the fourth step, the transparent conductive layer 2 is heated after the third step.

Specifically, the elongated base material 1 (transparent conductive film 3) is conveyed while contacting the surface of the heating roll 31 along the circumferential direction. Then, the transparent conductive layer 2 is heated in a vacuum atmosphere with respect to the elongated base material 1 (transparent conductive film 3) being transported. That is, the second annealing unit 9 is operated to crystallize the transparent conductive layer 2.

More specifically, the transparent conductive layer 2 is heated by the heating roll 31.

Specifically, the temperature of the heating roll 31 is, for example, 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher, and, for example, 200°C or lower, preferably 180°C or lower.

Furthermore, in the above description, in the fourth step, the transparent conductive layer 2 is heated by heating the heating roll 31. ) can also be used. Preferably, from the viewpoint of uniformly applying heat to the transparent conductive layer 2 and promoting crystallization, a part of the transparent conductive layer 2 is heated by heating the heating roll 31.

Furthermore, in the above description, the fourth step is carried out under a vacuum atmosphere, but it is also possible to carry out the fourth step under an air atmosphere. Specifically, from the viewpoint of promoting crystallization of the transparent conductive layer 2 in the same process as sputtering and improving productivity, a vacuum atmosphere was selected, and by promoting oxidation of the transparent conductive layer 2, stable From the viewpoint of crystallizing the transparent conductive layer 2, the atmosphere is selected.

Examples and Comparative Examples are shown below to further specifically explain the present invention. Note that the present invention is not limited to the Examples and Comparative Examples. In addition, the specific numerical values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description are the corresponding blending ratios ( Substitute with the upper limit value (value defined as "less than" or "less than") or lower limit value (value defined as "more than" or "exceeding") of the relevant description, such as content percentage), physical property value, parameter, etc. be able to.

1. Production of transparent conductive film <Example 1>
A film manufacturing apparatus 10 shown in FIG. 1 was used to manufacture the transparent conductive film.
[First step]
An ultraviolet curable resin containing an acrylic resin was applied to one side in the thickness direction of a PET film (50 μm thick, manufactured by Toray Industries, Inc.) serving as a long base material 1 to form a coating film. Next, the coating film was cured by ultraviolet irradiation. As a result, a hard coat layer (thickness: 2 μm) was formed on one side of the elongated base material 1 in the thickness direction. Next, the elongated base material 1 was mounted on a delivery roll 11 as a roll body. In this way, a long base material 1 was prepared.

[Second step]
Next, the delivery roll 11 and the take-up roll 27 were rotated by a motor to convey the long base material 1 in the longitudinal direction. At this time, the conveyance speed was 2.3 m/min.

Next, sputtering (reactive sputtering method) was performed in a vacuum atmosphere while conveying the long base material 1 in the longitudinal direction. That is, the sputtering unit 6 was operated to form a part of the transparent conductive layer 2 on the elongated base material 1 .

The sputtering conditions are as follows.
[First film forming chamber 17A]
Sputtering power supply: DC power supply Discharge output: 1.05W/mm
Horizontal magnetic field strength on target: 90mT
Sputtering gas: After evacuating the film forming chamber until the water pressure reaches 0.9×10 ^-4 Pa or less, krypton gas (rare gas) and oxygen gas (reactive gas) are supplied.Total amount of krypton gas and oxygen gas Oxygen gas flow rate: approx. 2.3% flow rate
Pressure: 0.2Pa
[First film forming chamber 17B to first film forming chamber 17D]
Sputtering power source, horizontal magnetic field strength on target, sputtering gas and pressure: Same as first film forming chamber 17A Discharge output: 6.05 W/mm
Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: Approximately 3.6% flow rate
[target]
First target 31A to first target 31D: Sintered body of indium oxide and tin oxide (indium tin composite oxide with a tin oxide concentration of 10% by mass)
[First film forming roll 16]
Temperature: -5℃

[Third step]
While conveying the long base material 1 in the longitudinal direction, sputtering (reactive sputtering method) was performed while heating a part of the transparent conductive layer 2 in a vacuum atmosphere. That is, the first annealing unit 7 was operated to simultaneously form the remaining portion of the transparent conductive layer 2 and crystallize the transparent conductive layer 2.

The conditions for sputtering are as follows.
[Second film forming chamber 23A to second film forming chamber 23C]
Sputtering power supply, discharge output, horizontal magnetic field strength on target, sputtering gas and pressure: Same as first film forming chamber 17A Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: Approximately 0.7% flow rate
[target]
Second target 32A to second target 32C: same as first target 31A [second film forming roll 22]
Temperature: 160℃
Through the above steps, a transparent conductive film 3 was obtained.

<Example 2>
A transparent conductive film 3 was obtained in the same manner as in Example 1.

However, in the second step, in order to obtain the transparent conductive layer 2 with the same thickness as in Example 1, the conveyance speed was changed to 2.1 m/min.

Furthermore, in the second step, the following sputtering conditions were changed.
[First film forming chamber 17A]
Sputtering gas: After evacuating the film forming chamber until the water pressure reaches 0.9×10 ^-4 Pa or less, krypton gas (rare gas) and oxygen gas (reactive gas) are supplied.Total amount of krypton gas and oxygen gas Oxygen gas flow rate: approx. 2.2% flow rate
Pressure: 0.2Pa
[First film forming chamber 17B to first film forming chamber 17D]
Sputtering power source, horizontal magnetic field strength on target, sputtering gas and pressure: Same as first film forming chamber 17A Discharge output: 6.05 W/mm
Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: Approximately 3.4% flow rate

Furthermore, in the third step, the following sputtering conditions were changed.
[Second film forming chamber 23A]
Sputtering power supply, discharge output, horizontal magnetic field strength on target, sputtering gas and pressure: Same as first film forming chamber 17A Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: Approximately 0.7% flow rate
[Second film forming chamber 23B to second film forming chamber 23C]
No sputtering was performed.

<Example 3>
A transparent conductive film 3 was obtained in the same manner as in Example 2. However, in the second step, in order to obtain the transparent conductive layer 2 with the same thickness as in Example 2, the conveyance speed was changed to 2.0 m/min, and the first film forming chamber 17A to the first film forming chamber 17D , and the sputtering gas in the second film forming chamber 23A was changed from krypton gas to argon gas.

<Example 4>
A transparent conductive film 3 was obtained in the same manner as in Example 1.

However, in the second step, the conveyance speed was changed to 10.2 m/min.

Furthermore, in the second step, the following sputtering conditions were changed.
[First film forming chamber 17B and first film forming chamber 17C]

Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: Approximately 3.9% flow rate
[First film forming chamber 17D]
No sputtering was performed.
[target]
First target 31C: Sintered body of indium oxide and tin oxide (indium tin composite oxide with a tin oxide concentration of 3% by mass)

Furthermore, in the third step, the following sputtering conditions were changed.
[Second film forming chamber 23A]
Flow rate of oxygen gas relative to the total amount of krypton gas and oxygen gas: approximately 0.7% flow rate
[Second film forming chamber 23B to second film forming chamber 23C]
No sputtering was performed.
[target]
Second target 32A: sintered body of indium oxide and tin oxide (indium tin composite oxide with a tin oxide concentration of 3% by mass)

<Comparative example 1>
A transparent conductive film 3 was obtained in the same manner as in Example 1.

However, in the second step, in order to obtain the transparent conductive layer 2 with the same thickness as in Examples 1 and 2, the conveyance speed was changed to 2.0 m/min.

Furthermore, in the third step, the following sputtering conditions were changed.
[Second film forming chamber 23A to second film forming chamber 23C]
No sputtering was performed.

<Comparative example 2>
A transparent conductive film 3 was obtained in the same manner as in Example 2.

However, in the second step, in order to obtain the transparent conductive layer 2 with the same thickness as in Example 3, the conveyance speed was changed to 1.9 m/min.

Furthermore, in the third step, the following sputtering conditions were changed.
[Second film forming chamber 23A to second film forming chamber 23C]
No sputtering was performed.

<Comparative example 3>
A transparent conductive film 3 was obtained in the same manner as in Example 3.

However, in the second step, in order to obtain the transparent conductive layer 2 with the same thickness as in Example 4, the conveyance speed was changed to 9.4 m/min.

Furthermore, in the third step, the following sputtering conditions were changed.
[Second film forming chamber 23A to second film forming chamber 23C]
No sputtering was performed.

2. Evaluation <Thickness of transparent conductive layer>
The thickness of the transparent conductive layer in each Example and each Comparative Example was measured by FE-TEM observation. Specifically, first, samples for cross-sectional observation of each transparent conductive layer in each Example and each Comparative Example were prepared by the FIB microsampling method. In the FIB microsampling method, an FIB device (trade name "FB2200", manufactured by Hitachi) was used, and the acceleration voltage was set to 10 kV. Next, the thickness of the transparent conductive layer in the sample for cross-sectional observation was measured by FE-TEM observation. In the FE-TEM observation, an FE-TEM device (trade name "JEM-2800", manufactured by JEOL) was used, and the acceleration voltage was set to 200 kV. The results are shown in Table 1.

<Crystallinity of transparent conductive layer>
The transparent conductive films of each Example and each Comparative Example were cut out and fixed to a sample holder of an ultramicrotome. Next, a microtome knife was placed at an extremely acute angle with respect to the ITO film surface, and the sample was cut so that the cut surface was substantially parallel to the ITO film surface to obtain an observation sample. This observation sample was observed for crystal grains in a plan view using a transmission electron microscope (the observation magnification was adjusted to a magnification that allowed crystal grains to be clearly observed). As a result of the observation, if the area where crystal grains were present was 70% or more and 100% or less, it was determined to be crystalline. Here, near the grain boundaries, which are the ends of the crystal grains, the crystallinity may inevitably be low, and even if the crystallinity is crystalline, it is not necessary to be 100%. In addition, crystal grains were observed on almost the entire surface of the transparent conductive layers of Examples 1 to 3.

<Transport speed>
In the film forming environment and conditions (sputtering power source, discharge output, target, horizontal magnetic field strength on the target, sputtering gas, oxygen gas, and pressure) when creating each example and each comparative example, each example and For each comparative example, the transport speed in the longitudinal direction of the base material 1, which is necessary to obtain the thickness of the transparent conductive layer, was determined.

<Consideration>
Examples 1 and 2 and Comparative Example 1 have the same conditions except for the conditions of the second film forming roll (discharge output and temperature) and the conveyance speed. Comparing Example 1 and Example 2 with Comparative Example 1, in the second step, a part of the transparent conductive layer is formed, and in the third step, while heating a part of the transparent conductive layer, a transparent Examples 1 and 2 in which the remainder of the conductive layer was formed were compared to Comparative Example 1 in which the entire transparent conductive layer was formed in the second step and no transparent conductive layer was formed in the third step. It can be seen that the conveyance speed is high.

From this, productivity can be improved by forming part of the transparent conductive layer in the second step, and forming the remaining part of the transparent conductive layer while heating part of the transparent conductive layer in the third step. Recognize.

This also applies to the comparison between Example 3 and Comparative Example 2, and the comparison between Example 4 and Comparative Example 3.

1 Long base material 2 Transparent conductive layer 3 Transparent conductive film 16 First film forming roll 17 First film forming chamber 22 Second film forming roll 23 Second film forming chamber

Claims (8)

A method for producing a transparent conductive film, comprising forming a transparent conductive layer on one side in the thickness direction of a long base material,
A first step of preparing the base material;
a second step of forming a part of a transparent conductive layer on one side in the thickness direction of the base material in a vacuum atmosphere;
A third step of forming the remaining part of the transparent conductive layer on one side in the thickness direction of the part of the transparent conductive layer while heating the part of the transparent conductive layer in a vacuum atmosphere. Film manufacturing method. The method for producing a transparent conductive film according to claim 1, further comprising a fourth step of heating the transparent conductive layer after the third step. The method for producing a transparent conductive film according to claim 2, wherein the fourth step is performed in a vacuum atmosphere. The method for manufacturing a transparent conductive film according to claim 2, wherein the fourth step is performed in an atmospheric atmosphere. In the third step, the transparent conductive layer is formed on the base material in contact with the surface of the film-forming roll, and the film-forming roll is heated to partially heat the transparent conductive layer. A method for producing a transparent conductive film according to any one of claims 1 to 4. In the second step, a part of the transparent conductive layer is formed by a target placed in an independent film forming chamber,
The method for producing a transparent conductive film according to any one of claims 1 to 4, wherein in the third step, the remainder of the transparent conductive layer is formed by a target placed in an independent film forming chamber. The method for producing a transparent conductive film according to any one of claims 1 to 4, wherein the transparent conductive layer that has undergone the third step is crystalline. The method for producing a transparent conductive film according to any one of claims 1 to 4, wherein the second step and/or the third step is performed in the presence of a rare gas containing krypton gas.

Images