Conductive film, optoelectronic device, and method for manufacturing conductive film

Abstract

Provided is a novel conductive film having two regions with different light transmittances, an optoelectronic device having such a conductive film, and a method for manufacturing a conductive film capable of easily manufacturing such a conductive film. A conductive film having a first region and a second region, wherein the second region exhibits a higher light transmittance than the first region, the conductive film having a first film made of a conductive material and a resin film made of a fluoropolymer, the first film being disposed to overlap at least the first region among the first region and the second region, the resin film being disposed to overlap the second region, and the fluoropolymer satisfying the following (1) and (2). (1) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10-3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is 400 °C or lower. (2) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10-3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C.

Description

Technical Field

[0001] The present invention relates to a conductive film, an optoelectronic device, and a method for manufacturing a conductive film. Background Art

[0002] In various optoelectronic devices, light transmissivity that controls the input and output of optical information is a very important factor. As the first factor that hinders such light transmission, there can be cited the low light transmissivity of a conductive film used as an electrode.

[0003] Generally, in order for an optoelectronic device to operate stably, it is necessary to suppress the wiring resistance of the electrode to a certain value or less. For example, in the case of a display panel, when the panel size becomes large, an IR drop easily occurs, and there occur problems such as a voltage distribution being generated in the panel surface. Therefore, measures such as thickening the electrode to suppress the sheet resistance of the electrode to a low level are required.

[0004] On the other hand, however, the thicker the electrode, the lower the light transmissivity, which becomes a factor that hinders the light transmissivity of the optoelectronic device, and there is a contrary problem.

[0005] In response to such a problem, a conductive film having two regions with different light transmittances is known. In the following description, regarding the two regions with different light transmittances, the region with a relatively low light transmittance may sometimes be referred to as the "first region", and the region with a relatively high light transmittance may be referred to as the "second region". Such a conductive film is used in, for example, an organic electroluminescent element (hereinafter referred to as an organic EL element), a photoelectric conversion element, or the like.

[0006] As a method for manufacturing such a conductive film, the following method is known: after forming a pattern film in advance with a material that inhibits the formation of a metal film, a metal is formed on the pattern film by vapor deposition, sputtering, or the like (for example, refer to Patent Document 1 and Non-Patent Document 1).

[0007] Specifically, in the method described in Patent Document 1, as the above-mentioned "material that inhibits the formation of a metal film", an organic semiconductor material such as a polycyclic aromatic compound and polytetrafluoroethylene (PTFE) are proposed.

[0008] In addition, in the method described in Non-Patent Document 1, a solution containing a fluorine compound is used as the above-mentioned "material that inhibits the formation of a metal film", and a pattern is formed by a printing process.

[0009] According to this method, metal film formation is avoided on the pre-formed pattern film. As a result, a second region with a high light transmittance is formed in the region where the pattern film is formed with the material that inhibits the formation of a metal film. In addition, a plurality of metals are formed in the region where the pattern film is not formed, and a first region with a relatively low light transmittance is formed, obtaining a conductive film having each region.

[0010] Prior Art Documents

[0011] Patent document

[0012] Patent document 1: Specification of U.S. Patent No. 10,270,033

[0013] Non-patent document

[0014] Non-patent document 1: Materials Horizons, 2020, 7, 143 - 148 Summary of the invention

[0015] Problems to be solved by the invention

[0016] However, the above method has the following problems.

[0017] First, the effect of suppressing the formation of the metal film by the organic semiconductor material used in the method described in Patent Document 1 is insufficient, and there is room for improvement. In addition, well-known PTFE as described in Patent Document 1 is likely to depolymerize and thermally decompose during evaporation coating, making it difficult to form a stable pattern. Furthermore, when outgassing and partially decomposed products generated by such depolymerization and thermal decomposition remain in the conductive film, it is possible to reduce the element performance and element life of the electronic device having the conductive film.

[0018] In addition, in the method described in Non-patent Document 1, a solution containing a fluorine compound is coated, but the solvent may deteriorate the composition of the printed part and reduce the element performance.

[0019] The present invention has been made in view of this situation, and an object thereof is to provide a novel conductive film having two regions with different light transmittances. Another object thereof is to provide an optoelectronic element having such a conductive film. Furthermore, an object thereof is to provide a method for manufacturing a conductive film capable of easily manufacturing such a conductive film.

[0020] Solutions for solving the problems

[0021] To solve the above problems, one aspect of the present invention includes the following aspects.

[0022] [1] A conductive film having a first region and a second region, the second region showing a higher light transmittance than the first region, the conductive film having a first film made of a conductive material and a resin film made of a fluoropolymer, the first film being disposed overlapping at least the first region among the first region and the second region, the resin film being disposed overlapping the second region, and the fluoropolymer satisfying the following (1) and (2). (1) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1 × 10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is 400 °C or lower. (2) Under 1 × 10-3 When the temperature is raised at a rate of 2 °C per minute under a pressure of Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C.

[0023] [2] The conductive film according to [1] includes a second film made of a conductive material and spanning the first region and the second region. The light transmittance of the second film is higher than that of the first film at the position overlapping the first region, and the second film is in contact with the first film in the first region.

[0024] [3] The conductive film according to [1] or [2], wherein the surface energy of the resin film is 30 mN / m or less.

[0025] [4] The conductive film according to any one of [1] to [3], wherein the melting point of the fluoropolymer is 300 °C or less.

[0026] [5] The conductive film according to any one of [1] to [3], wherein the fluoropolymer is amorphous.

[0027] [6] The conductive film according to any one of [1] to [5], wherein the fluoropolymer has a trifluoromethyl moiety, and the content of the trifluoromethyl moiety in the fluoropolymer is 0.1 mmol / g or more.

[0028] [7] The conductive film according to any one of [1] to [6], wherein the fluoropolymer has a unit derived from a fluoroolefin.

[0029] [8] The conductive film according to [7], wherein the fluoropolymer has at least a unit derived from tetrafluoroethylene and a unit derived from a perfluoroalkyl vinyl ether.

[0030] [9] The conductive film according to any one of [1] to [8], wherein the fluoropolymer has an aliphatic ring structure in the main chain.

[0031]

[10] An optoelectronic device having the conductive film according to any one of [1] to [9].

[0032]

[11] The optoelectronic device according to

[10] , comprising: a substrate; an anode provided on the substrate; a cathode opposite to the anode; and an active layer disposed between the anode and the cathode, wherein the cathode is the conductive film.

[0033]

[12] A method for manufacturing a conductive film, comprising the following steps: a step of forming a resin film made of the following fluorine-containing polymer on a substrate by mask vapor deposition, the fluorine-containing polymer satisfying the following (1) and (2); and a step of dry-coating a conductive material on the resin film. (1) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is 400 °C or lower. (2) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10 -3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C.

[0034]

[13] The method for manufacturing a conductive film according to

[12] , wherein, after the step of dry coating, there is a step of removing the resin film.

[0035]

[14] The method for manufacturing a conductive film according to

[12] or

[13] , wherein, before the step of forming the resin film, there is a step of forming a conductive material film on the surface of the substrate.

[0036] Effects of the Invention

[0037] According to the present invention, a novel conductive film having two regions with different light transmittance can be provided. In addition, an optoelectronic device having such a conductive film can be provided. Furthermore, a method for manufacturing a conductive film capable of easily manufacturing such a conductive film can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a top view of the conductive film 1.

[0039] Figure 2 It is a Figure 1 sectional view taken along line II-II of.

[0040] Figure 3 It is a schematic diagram showing a method for manufacturing the conductive film 1.

[0041] Figure 4 It is a schematic diagram showing a method for manufacturing the conductive film 1.

[0042] Figure 5 It is a schematic diagram showing a method for manufacturing the conductive film 1.

[0043] Figure 6 It is a schematic diagram for explaining the conditions (1) and (2).

[0044] Figure 7 It is a schematic diagram showing the conductive film 2 obtained by removing the resin film 15.

[0045] Figure 8 This is a schematic diagram showing the conductive film 3.

[0046] Figure 9 This is a schematic cross-sectional view showing the optoelectronic device (organic EL device) 100 according to the second embodiment.

[0047] Figure 10 This is a diagram showing the results of the examples.

[0048] Figure 11 This is a diagram showing the results of the examples.

[0049] Figure 12 This is a diagram showing the results of the examples. Detailed implementation manners

[0050] The "unit" constituting the polymer in this specification refers to the part (i.e., monomer unit) derived from 1 molecule of monomer that exists in the polymer and constitutes the polymer. Hereinafter, the unit derived from each monomer is sometimes referred to by the name with "unit" appended after its monomer name.

[0051] In this specification, the "main chain" of a polymer refers to the carbon atom chain formed by the addition polymerization of monomers having a carbon-carbon unsaturated double bond and consisting of the two carbon atoms that form the carbon-carbon unsaturated double bond in the monomer.

[0052] The "reactive functional group" refers to a group having reactivity capable of reacting (excluding free radical reactions) to form a bond between the molecules of the fluoropolymer or with other components compounded together with the fluoropolymer when heated or the like.

[0053] Regarding the "aliphatic ring" in this specification, on the basis of the aliphatic ring with a carbon ring structure in which the ring skeleton is composed only of carbon atoms, it also means an aliphatic ring with a heterocyclic structure in which the ring skeleton contains atoms (heteroatoms) other than carbon atoms. Examples of heteroatoms include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0054] [First Embodiment]

[0055] Hereinafter, while referring to Figures 1 to 8 , the conductive film and the manufacturing method of the conductive film according to the first embodiment of the present invention will be described. It should be noted that in all the following drawings, the dimensions, ratios, etc. of each component are appropriately changed for easy viewing of the drawings.

[0056] Figure 1 , 2 This is an explanatory diagram showing the conductive film 1 of this embodiment. Figure 1 This is a top view of the conductive film 1, Figure 2 This is Figure 1End view taken along line II-II

[0057] As Figure 1 , 2 shown, the conductive film 1 of the present embodiment has a first film 10, a resin film 15, and a second film 20.

[0058] The conductive film 1 of the present embodiment is provided on a substrate 50. The substrate 50 is an object on which the conductive film 1 is formed. The substrate 50 has light transmissivity.

[0059] The second film 20 is provided on the substrate 50, and the first film 10 is provided on the second film 20. The resin film 15 is provided between the first film 10 and the second film 20.

[0060] (First film)

[0061] The first film 10 is a film formed of a conductive material. As the material of the first film 10, that is, the conductive material, there is no particular limitation as long as it is a material having conductivity, and preferably includes silver (Ag), gold (Au), copper (Cu), aluminum (Al), magnesium (Mg), zinc (Zn), indium (In), tin (Sn), ytterbium (Yb), etc. Specifically, metals such as silver (Ag), gold (Au), copper (Cu), aluminum (Al), magnesium (Mg), magnesium silver (MgAg), and ytterbium silver (YbAg) can be cited; conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), and zinc oxide (ZnO).

[0062] The first film 10 has a first region 10A and a second region 10B, and the light transmittance of the second region 10B is higher than that of the first region 10A. In the conductive film 1 of the present embodiment, the thick film portion 11 of the first film (hereinafter simply referred to as the thick film portion 11) is located in the first region 10A, and the thin film portion 12 of the first film (hereinafter simply referred to as the thin film portion 12) is located in the second region 10B. The thick film portion 11 and the thin film portion 12 integrally constitute the first film 10.

[0063] As Figure 1 shown, in the conductive film 1, a plurality of second regions 10B, that is, a plurality of thin film portions 12, are arranged in a matrix, and the remaining portion has a lattice-shaped first region 10A, that is, a lattice-shaped thick film portion 11. In Figure 1 , the second region 10B has a rectangular shape in a top view, but is not limited thereto, and various top view shapes conforming to the design can be adopted.

[0064] The lower surface 11a of the thick film portion 11 is in contact with the second film 20. In addition, the side surface 11b of the thick film portion 11 is in contact with the resin film 15.

[0065] The lower surface 12a of the thin film portion 12 is in contact with the resin film 15.

[0066] The thin film portion 12 is thinner than the thick film portion 11. For example, the film thickness of the thick film portion 11 is 10 nm to 10,000 nm, and the film thickness of the thin film portion 12 is 0 nm to 50 nm. The thick film portion 11 formed thinly to 50 nm or less has light transmissivity.

[0067] The thick film portion 11 is formed thicker than the thin film portion 12 in order to ensure the conductivity of the entire conductive film 1. As long as the thick film portion 11 can ensure the required conductivity, it may or may not have light transmissivity.

[0068] (Second film)

[0069] The conductive film of the present embodiment may or may not have a second film 20. (Regarding the form without the second film, it will be described later as the conductive film 3.)

[0070] When the conductive film of the present embodiment has the second film 20, the second film 20 is provided on the surface 50a of the base material 50. The second film 20 is a film formed of a conductive material. As the material of the second film 20, that is, the conductive material, the same materials as those that can be used as the material of the first film 10 described above can be cited.

[0071] The conductive material as the material of the first film 10 and the conductive material as the material of the second film 20 may be the same or different.

[0072] The second film 20 has light transmissivity. The light transmittance of the second film 20 is higher than that of the thick film portion 11. The film thickness of the second film 20 is preferably 0 nm to 200 nm, more preferably 0 nm to 100 nm, and still more preferably 0 nm to 60 nm.

[0073] In addition, the second film 20 overlaps with the thin film portion 12 in a plane. Therefore, the film thickness of the second film 20 and the total film thickness of the thin film portion 12 may be appropriately adjusted so that the second region 10B has light transmissivity.

[0074] As a transparent electrode used in various optoelectronic elements such as a light-emitting element and a light-receiving element, only the second film 20 may be used. On the other hand, the wiring resistance of the second film 20 formed thinly to the extent of having light transmissivity is high.

[0075] In contrast, in the conductive film 1 of the present embodiment, the second film 20 and the first film 10 are laminated. Therefore, at the position overlapping with the first region 10A, the thick film portion 11 and the second film 20 are laminated to thicken the film. Thereby, it is possible to ensure light transmissivity at the position overlapping with the second region 10B and to reduce the resistance of the entire conductive film 1.

[0076] (Resin film)

[0077] The resin film 15 is made of a fluoropolymer. The resin film 15 is disposed overlapping the second region 10B. As will be described in the manufacturing method of the conductive film hereinafter, the resin film 15 is used to pattern the first region 10A and the second region 10B of the first film 10.

[0078] The material of the resin film 15, that is, the fluoropolymer, has low absorbance and low refractive index. Therefore, it has the advantages of less light absorption in a wide wavelength range including the near-infrared region and excellent optical properties. Therefore, even when the resin film 15 overlaps with the light-transmissive second region 10B, it does not hinder the light transmittance of the second region 10B.

[0079] The material of the resin film 15, that is, the fluoropolymer, satisfies the following conditions (1) and (2).

[0080] (1) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is 400 °C or lower.

[0081] (2) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1×10 -3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C.

[0082] The fluoropolymer that satisfies conditions (1) and (2) has physical properties suitable for the manufacturing method described hereinafter. Therefore, if a fluoropolymer that satisfies conditions (1) and (2) is used, the conductive film 1 can be suitably manufactured.

[0083] Hereinafter, after describing the manufacturing method of the conductive film of the present embodiment, the resin film 15 and the material of the resin film 15, that is, the fluoropolymer, will be described in turn.

[0084] (Manufacturing method of conductive film)

[0085] Figures 3 to 5 is a schematic diagram showing the manufacturing method of the above-mentioned conductive film 1.

[0086] First, as Figure 3 shown, a second film 20 is formed by forming the above-mentioned conductive material on the surface of the substrate 50. The second film 20 can be formed by a dry coating method such as evaporation, sputtering, CVD (chemical vapor deposition), or ALD (Atomic Layer Deposition). The second film 20 corresponds to the "base layer" in the present invention.

[0087] Next, as Figure 4As shown, a fluorine-containing polymer P satisfying the above conditions (1) and (2) is deposited under reduced pressure on the surface 20a of the second film 20 via a mask M. The mask M has openings M2 arranged in a matrix and shielding portions M1 provided in a lattice.

[0088] The fluorinated polymer P is deposited by, for example, -3 The fluorine-containing polymer is heated at a pressure of Pa.

[0089] The fluorinated polymer P reaches the surface 20a of the second film 20 through the openings M2 of the mask M, and is blocked by the blocking portions M1 of the mask M. Thus, the resin film 15 made of the fluorinated polymer P is formed.

[0090] The resin film 15 is arranged in a matrix on the surface 20a. In addition, the second film 20 is exposed in a lattice shape in the portion where the resin film 15 is not formed.

[0091] Then, if Figure 5 As shown, the conductive material 10X is dry-coated from above the resin film 15. As the dry coating, vapor deposition, sputtering, ALD (Atomic Layer Deposition) or the like can be used.

[0092] The conductive material 10X is not easy to adhere to the surface of the resin film 15 made of a fluorine-containing polymer, but is easy to adhere to the surface of the second film 20 made of a conductive material. Therefore, by dry-coating the conductive material 10X on the entire surface of the substrate 50 without using a mask, the conductive material 10X is formed relatively thick on the surface of the second film 20, and the conductive material 10X is formed relatively thin on the surface of the resin film 15.

[0093] Thus, the thick film portion 11 is formed in a grid pattern on the surface of the second film 20. In addition, the thin film portion 12 is formed in a matrix pattern corresponding to the position of the resin film 15. The thick film portion 11 and the thin film portion 12 constitute the first film 10.

[0094] Thus, the conductive film 1 is obtained. The location where the thick film portion 11 is formed is the first region 10A. On the other hand, the location where the thin film portion 12 is formed is the second region 10B.

[0095] If it is assumed that the thick film portion 11 is to be directly manufactured by mask evaporation, a mask having a shielding portion in a matrix shape needs to be used. Such a mask requires a holding portion for holding the shielding portion, so the thick film portion 11 is not formed in the portion shielded by the holding portion, and the film thickness of the obtained thick film portion 11 is prone to change. Alternatively, it is also considered to form a grid-shaped thick film portion 11 by using a striped mask and performing evaporation multiple times, but it is difficult to align the mask, and the operation becomes complicated.

[0096] Furthermore, when the material of the mask is metal, if it is desired to form the thick film portion 11 by vapor deposition, the conductive material 10X to be vapor-deposited may slowly adhere to the metal mask, and the size of the opening portion of the mask may change. In this case, it is necessary to clean and remove the conductive material 10X adhering to the metal mask, or replace it with a new mask, which requires complicated operations and high costs.

[0097] On the other hand, in the above manufacturing method, as Figure 5 shown, by forming a resin film 15 made of a fluorine-containing polymer P on the film formation surface and then vapor-depositing the conductive material 10X over the entire surface, the first film 10 in which the thick film portion 11 and the thin film portion 12 are naturally patterned is obtained. The resin film 15 can be precisely formed by mask vapor deposition. Therefore, according to the above manufacturing method of the conductive film, a conductive film with precise patterning can be easily manufactured.

[0098] (fluorine-containing polymer)

[0099] Next, the fluorine-containing polymer will be described in detail.

[0100] (Condition (1))

[0101] The fluorine-containing polymer used in the above manufacturing method satisfies condition (1).

[0102] (1) When the temperature is raised at a rate of 2 °C / minute under a pressure of 1 × 10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is 400 °C or lower.

[0103] In the present embodiment, the thermal weight loss rate is a value measured using a vacuum differential thermal balance (manufactured by ADVANCE RIKO Co., Ltd.: VPE-9000). Specifically, 50 mg of the fluorine-containing polymer is placed in a dish with an inner diameter of 7 mm, and the weight loss rate (%) relative to the initial weight (50 mg) of the fluorine-containing polymer is measured when the temperature is raised from room temperature to 500 °C at a rate of 2 °C per minute under a vacuum of 1 × 10 -3 Pa.

[0104] "Substantially" in condition (1) means that when the thermal weight loss rate is measured under the above conditions, in the temperature range below 400 °C, the thermal weight loss is below the detection limit and the thermal weight loss cannot be confirmed.

[0105] For the fluorine-containing polymer of the present embodiment, it can be said that the lower the temperature satisfying the above condition (1), the lower the molecular weight (degree of polymerization).

[0106] When it is desired to vapor-deposit a fluorine-containing polymer that does not satisfy the above condition (1), it is necessary to heat it to a temperature exceeding 400°C. On the other hand, if heating is carried out in a temperature range exceeding 400°C, the fluorine-containing polymer may undergo depolymerization and thermal decomposition due to the high temperature. In this case, the products generated by depolymerization and thermal decomposition may cause the internal pressure of the vacuum chamber used for vapor deposition to rise. In this way, if the internal pressure of the vacuum chamber rises, the vapor deposition conditions may become unstable, and the quality of the obtained vapor-deposited film (resin film) may be unstable.

[0107] In addition, if a fluorine-containing polymer that does not satisfy the above condition (1) is heated in a temperature range exceeding 400°C, small-molecular-weight fluorine-containing polymers that have partially undergone depolymerization or thermal decomposition may be mixed into the resin film, resulting in a decrease in the heat resistance of the resin film.

[0108] Furthermore, if a fluorine-containing polymer that does not satisfy the above condition (1) is heated in a temperature range exceeding 400°C, fluorine-containing polymers with unstable ends generated by depolymerization and thermal decomposition may be mixed into the resin film, and the quality of the resin film and the components including the resin film may be damaged.

[0109] On the other hand, when a fluorine-containing polymer that satisfies the above condition (1) is used as a vapor deposition material carried out under vacuum, by heating at a temperature of 400°C or lower, appropriate vapor deposition can be achieved. Thereby, there is no risk of the above-mentioned depolymerization and thermal decomposition, and vapor deposition can be carried out under stable vapor deposition conditions.

[0110] The fluorine-containing polymer of the present embodiment preferably has a thermal weight loss rate that substantially reaches 100% at 350°C or lower, that is, the temperature at which the thermal weight loss rate substantially reaches 100% is 350°C or lower, when the temperature is raised at a rate of 2°C / minute under a pressure of 1×10 -3 Pa.

[0111] (Condition (2))

[0112] The fluorine-containing polymer used in the above manufacturing method satisfies condition (2).

[0113] (2) When the temperature is raised at a rate of 2°C / minute under a pressure of 1×10 -3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200°C.

[0114] For the fluoropolymer of the present embodiment, it can be said that the narrower the temperature range satisfying the above condition (2), the narrower the molecular weight distribution. If a fluoropolymer that does not satisfy the above condition (2) is used to manufacture a resin film, there may be a large difference between the molecular weight of the fluoropolymer vapor-deposited at the initial stage of vapor deposition and the molecular weight of the fluoropolymer vapor-deposited at the final stage of vapor deposition. In the same resin film, the molecular weight of the fluoropolymer in the thickness direction of the resin film changes, and the physical properties of the resin film are unstable.

[0115] In addition, when continuously manufacturing resin films under the same conditions, if a fluoropolymer that does not satisfy the above condition (2) is used, there may be a deviation in the quality of the manufactured resin films between batches.

[0116] Furthermore, the low molecular weight components contained in the fluoropolymer may degas during vapor deposition and adhere to the inside of the vacuum chamber, contaminating the vacuum chamber. For example, in the process of manufacturing optoelectronic components, such a pollution source may cause obvious damage to the quality of the components, such as a reduction in the component life and a short circuit.

[0117] On the other hand, for the fluoropolymer satisfying the above condition (2), the difference between the molecular weight of the fluoropolymer vapor-deposited at the initial stage of vapor deposition and the molecular weight of the fluoropolymer vapor-deposited at the final stage of vapor deposition is small, and the change in the molecular weight of the fluoropolymer in the thickness direction of the resin film is small. Therefore, the physical properties of the obtained resin film are easily stabilized.

[0118] In addition, when continuously manufacturing resin films under the same conditions, it is possible to suppress the quality deviation between batches of the manufactured resin films.

[0119] Furthermore, since it does not contain low molecular weight components that cause degassing, there is no need to worry about contaminating the vapor deposition chamber.

[0120] The temperature range of the fluoropolymer of the present embodiment satisfying the above condition (2) is preferably within 100 °C, more preferably within 60 °C.

[0121] As a method for obtaining a fluoropolymer that satisfies the above condition (2) and has a narrow molecular weight distribution, methods such as molecular weight adjustment based on controlled polymerization such as living radical polymerization; molecular weight fractionation by sublimation purification, supercritical extraction, and size exclusion chromatography can be cited.

[0122] Figure 6 It is a schematic diagram explaining conditions (1) and (2), and is a graph showing the correspondence between the thermogravimetric rate and the measurement temperature. Figure 6 The horizontal axis is the measurement temperature (unit: °C), and the vertical axis is the thermogravimetric rate (unit: %). In Figure 6Among them, the behavior of the fluoropolymer satisfying conditions (1) and (2) is represented by the symbol P, and the behavior of the fluoropolymer not satisfying conditions (1) and (2) is represented by the symbol Px.

[0123] In Figure 6 among them, for the behavior of the fluoropolymer of the present embodiment, the thermal weight loss rate of the graph P shown at a temperature (Td100) below 400 °C reaches 100%. In contrast, for the behavior of the fluoropolymer not satisfying conditions (1) and (2), the thermal weight loss rate of the graph Px shown at 400 °C does not reach 100%.

[0124] In addition, in Figure 6 among them, in the graph P showing the behavior of the fluoropolymer of the present embodiment, the value W of Td90 - Td10 is 200 °C or less.

[0125] According to Figure 6 it can be known that: the fluoropolymer of the present embodiment undergoes rapid thermal weight loss between the temperature Td10 and the temperature Td90.

[0126] If we focus on the change in the internal pressure of the vacuum chamber, the presence or absence of depolymerization, thermal decomposition, and degassing during the evaporation of the fluoropolymer can be evaluated as follows.

[0127] (Evaluation method for the change in chamber pressure during evaporation)

[0128] Put 0.1 g of the fluoropolymer into a vacuum evaporator, reduce the pressure in the chamber to 10 -4 Pa or less, and on this basis, form a 200 - nm film of the fluoropolymer at an evaporation rate of 0.1 nm / second. At this time, monitor the pressure in the chamber and measure the maximum value of the pressure during evaporation.

[0129] For a fluoropolymer with a chamber pressure increase ratio calculated by the following formula of 10 times or less, the depolymerization, thermal decomposition, and degassing are less, and evaporation can be appropriately carried out.

[0130] Chamber pressure increase ratio during evaporation = Maximum pressure during evaporation / Initial pressure before evaporation

[0131] For a fluoropolymer with an increase ratio exceeding 10 times, the depolymerization, thermal decomposition, and degassing are more, and it can be judged that it is not suitable for evaporation.

[0132] (Molecular weight fractionation)

[0133] When the fluoropolymer to be used does not satisfy the above conditions (1) and (2), by performing molecular weight fractionation of the fluoropolymer, the fluoropolymer of the present embodiment satisfying the above conditions (1) and (2) can be obtained.

[0134] The fluoropolymer satisfying the above conditions (1) and (2) can be obtained by fractionating the polymer by molecular weight. In the following description, the polymer to be fractionated by molecular weight is sometimes referred to as the "raw material polymer".

[0135] As a method for fractionating by molecular weight, for example, methods of fractionating by molecular weight through sublimation refining, supercritical extraction, and size exclusion chromatography, and adjusting the polymer to satisfy conditions (1) and (2) can be cited.

[0136] (Sublimation refining)

[0137] Sublimation refining is a method as follows: under reduced pressure, the object to be refined (raw material polymer) is heated to sublime or evaporate part or all of the object to be refined, and then, by using the temperature difference of precipitation (or condensation) of the compounds contained in the gaseous object to be refined, the target compound is separated in the form of a solid (or liquid) and recovered. This sublimation refining can be carried out using a sublimation refining apparatus having a feeding section and a trapping section and capable of maintaining a high vacuum degree, where the feeding section is for feeding the object to be refined, and the trapping section is for separating the gaseous object to be refined according to the precipitation (or condensation) temperature and trapping it in the form of a solid (or liquid).

[0138] The structure of the sublimation refining apparatus is not particularly limited, and for example, a so-called Meier's type sublimation refining apparatus can be used, which is composed of a glass condenser tube, a flask-shaped glass container surrounding the condenser tube, and a vacuum exhaust apparatus for reducing the pressure inside the glass container. In addition, as the sublimation refining apparatus, a glass tube type sublimation refining apparatus can also be used, which has a cylindrical glass sublimation tube, a heating apparatus for accommodating the sublimation tube inside and heating the sublimation tube, and a high vacuum exhaust apparatus for reducing the pressure inside the sublimation tube.

[0139] Hereinafter, taking the glass tube type sublimation refining apparatus as an example, the sublimation refining of the fluoropolymer and the method for fractionating by molecular weight based on sublimation refining will be described. It should be noted that here, the case of trapping in the form of a solid is taken as an example for description, and the case of trapping in the form of a liquid can be described in the same way.

[0140] In the sublimation refining of the fluoropolymer, the raw material polymer is fed into the feeding section of the sublimation tube, and using a high vacuum exhaust apparatus, for example, the vacuum degree inside the sublimation tube is increased until the pressure is 1×10 -3 Pa or less, and then the feeding section is heated using the heating apparatus. Thereby, the fluoropolymer contained in the raw material polymer sublimes or evaporates.

[0141] In the sublimation tube, the region closer to the exhaust side based on the high-vacuum exhaust device than the feeding section is equivalent to the "trapping section". The trapping section is set to a temperature lower than the heating temperature of the feeding section. The fluoropolymer obtained by sublimation or evaporation of the raw material polymer in the feeding section precipitates and solidifies on the wall surface of the trapping section, and thus is trapped.

[0142] The trapping temperature of the trapping section corresponds to the temperature at which the fluoropolymer sublimates from gas to solid (precipitation temperature) and corresponds to the molecular weight of the fluoropolymer. By providing a plurality of trapping sections with different trapping temperatures in the sublimation tube, it is possible to fractionate the raw material polymer into fluoropolymers with different molecular weights.

[0143] For example, specifically, when the feeding section is heated to A °C and the trapping sections are heated to B °C and C °C from the side closer to the feeding section (A > B > C), in the trapping section set to B °C, the fluoropolymer in the molecular weight range that becomes gas at A °C and solid at B °C is trapped.

[0144] Similarly, in the trapping section set to C °C, the fluoropolymer in the molecular weight range that becomes gas at B °C and solid at C °C is trapped. That is, in the trapping section set to C °C, the fluoropolymer in the trapping temperature range of B °C - C °C that is gas at B °C and becomes solid at C °C among the fluoropolymers contained in the raw material polymer is trapped.

[0145] As described above, the above condition (2) can be satisfied by controlling the trapping temperature range and performing trapping using, for example, a trapping section with a trapping temperature range of 200 °C. It should be noted that for the trapped fluoropolymer, it is confirmed whether condition (2) is satisfied. In the case where condition (2) is not satisfied, the temperature conditions of the trapping section can be controlled to narrow the trapping temperature range.

[0146] In the trapping section, the lower the set temperature of the region where the fluoropolymer is trapped, the lower the temperature at which the thermal weight loss rate reaches 100% under a pressure of 1×10 - 3 Pa, that is, the smaller the molecular weight of the fluoropolymer.

[0147] The trapping temperature range is preferably 200 °C or less, more preferably 100 °C or less, and further preferably 60 °C or less. The smaller the trapping temperature range, the less the variation in the evaporation conditions, and in addition, the quality of the resin film is likely to be stable.

[0148] If the molecular weight-fractionated fluoropolymer satisfies conditions (1) and (2), a plurality of fluoropolymers with different trapping temperature ranges can be mixed.

[0149] (Supercritical extraction)

[0150] Supercritical extraction is a technique that utilizes the high solubility and diffusivity of supercritical fluids to obtain extracts. In supercritical extraction, for example, supercritical CO2 can be used as the supercritical fluid to dissolve fluoropolymers with relatively low molecular weights in the supercritical CO2, and thus obtain them in the form of extracts.

[0151] In addition, as an additive (entrainer) for the supercritical fluid, by using a fluorinated solvent, the solubility of the fluoropolymer in the supercritical fluid can be improved.

[0152] The fluorinated solvent used as the entrainer is not particularly limited. For example, a fluorophilic parameter P F of 1 or more is preferably used as the fluorinated solvent.

[0153] (Fluorophilic parameter P F )

[0154] 30 μL of the aforementioned fluorinated solvent is added dropwise to a two-phase system of 3 g of toluene and 3 g of perfluoromethylcyclohexane, mixed well and left standing overnight, and then the aforementioned fluorinated solvent contained in the aforementioned toluene and the aforementioned fluorinated solvent contained in the aforementioned perfluoromethylcyclohexane are measured by gas chromatography. The concentration (unit: mL / L) of the aforementioned fluorinated solvent in the aforementioned toluene is denoted as M P , and the concentration (unit: mL / L) of the aforementioned fluorinated solvent in the aforementioned perfluoromethylcyclohexane is denoted as M F , and the value obtained by the following formula (A) is used as the fluorophilic parameter P F .

[0155] P F = M F / M P …(A)

[0156] Examples of the fluorinated solvent used as the entrainer include the following compounds.

[0157] 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane (AC-2000, manufactured by AGC Inc.) (P F = 12)

[0158] 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (AC-6000, manufactured by AGC Inc.) (P F = 5.6)

[0159] CYTOP CT-SOLV100E (manufactured by AGC Inc.) (P F = 8.2)

[0160] CYTOP CT-SOLV180 (manufactured by AGC Inc.) (PF = ∞)

[0161] HFE7300 (manufactured by 3M Company) (P F = 8.2)

[0162] 1,1,1,2,2,3,4,5,5,5 - Decafluoropentane (Vertre XF, manufactured by Chemours Company) (P F = 3.7)

[0163] 1H,1H,2H,2H - Perfluorooctanol (P F = 1.1)

[0164] 1,1,2,2 - Tetrafluoroethyl - 2,2,2 - trifluoroethyl ether (AE - 3000, manufactured by AGC Company) (P F = 0.6)

[0165] HCFC - 225ca / HCFC - 225cb (45 / 55) (P F = 0.3)

[0166] Perfluorobenzene (P F = 0.3)

[0167] Hexafluoro - 2 - propanol (P F = 0.24)

[0168] 1H,1H,7H - Perfluoroheptanol (P F = 0.23)

[0169] 1H,1H,5H - Perfluoropentanol (P F = 0.1)

[0170] The extraction process can be carried out using, for example, supercritical CO2 under the conditions that the extraction pressure is 7.4 MPa or more and the extraction temperature is 31 °C or more.

[0171] The extraction pressure is preferably 30 MPa or more, more preferably 50 MPa or more, and further preferably 70 MPa or more. The upper limit value of the extraction pressure is not particularly limited and is preferably 100 MPa or less. The upper and lower limit values of the extraction pressure can be arbitrarily combined.

[0172] The extraction temperature is preferably 40 °C or more, more preferably 80 °C or more. In addition, the extraction temperature is preferably 300 °C or less, more preferably 200 °C or less, and further preferably 100 °C or less. The upper and lower limit values of the extraction temperature can be arbitrarily combined.

[0173] If it is within the above range, the molecular weight fractionation of the target fluoropolymer can be carried out efficiently.

[0174] Molecular weight fractionation is also useful for the purpose of removing residual foreign substances such as initiators, chain transfer agents, solvents, and by-products used in the polymerization process of the fluoropolymer. Such residual foreign substances may be generated in the form of degassing during evaporation coating and adhere to the inside of the vacuum chamber, contaminating the vacuum chamber. Therefore, even when conditions (1) and (2) are satisfied, it is more preferable to perform sublimation purification or supercritical extraction.

[0175] If the fluoropolymer that has undergone molecular weight fractionation satisfies conditions (1) and (2), it is also possible to mix multiple fluoropolymers with different extraction conditions.

[0176] (Structure of fluoropolymer)

[0177] As the fluoropolymer used in the conductive film and the method for manufacturing the conductive film of the present embodiment, as long as it is a fluoropolymer that satisfies the above conditions (1) and (2), the units constituting the polymer are not particularly limited.

[0178] The fluorine atom content rate of the fluoropolymer is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more. The higher the fluorine atom content rate, the lower the surface energy of the obtained resin film 15 becomes, and the more difficult it is for the conductive material 10X to adhere to the surface of the resin film 15. Therefore, if a fluoropolymer having the above fluorine atom content rate is used, it is easy to pattern the thick film portion 11 and the thin film portion 12.

[0179] It should be noted that the fluorine atom content rate (% by mass) is calculated using the following formula.

[0180] (Fluorine atom content rate)=[19×NF / MA]×100

[0181] NF: For each type of unit constituting the fluoropolymer, it is the sum of the values obtained by multiplying the total atomic weight of the fluorine atoms in the constituent unit by the molar ratio of the unit to all the units.

[0182] MA: For each type of unit constituting the fluoropolymer, it is the sum of the values obtained by multiplying the total atomic weight of all the atoms in the constituent unit by the molar ratio of the unit to all the units.

[0183] The above NF and MA can be calculated based on 1 1H-NMR, 19 19F-NMR, elemental analysis, and IR to obtain the molar ratio and terminal amount of the structural units of the fluoropolymer. In addition, NF and MA can also be calculated based on the feeding amounts of the monomers and initiators used to manufacture the fluoropolymer.

[0184] The fluorine-containing polymer preferably contains a trifluoromethyl moiety. The "trifluoromethyl moiety" refers to CF3-. The trifluoromethyl moiety includes, in addition to the trifluoromethyl group, a part of substituents such as CF3- contained in the pentafluoroethyl group.

[0185] The content of the trifluoromethyl moiety is preferably 0.1 mmol / g or more, more preferably 0.3 mmol / g or more, and further preferably 0.6 mmol / g or more. The higher the content of the trifluoromethyl moiety, the lower the surface energy of the resin film 15 becomes. Thus, in Figure 5 the dry coating process shown, the conductive material 10X is not easily attached to the surface of the resin film 15, and it is easy to pattern the thick film portion 11 and the thin film portion 12.

[0186] It should be noted that the content (mmol / g) of the trifluoromethyl moiety is calculated by the following formula.

[0187] (Content of trifluoromethyl moiety) = [NCF3 / MA] × 1000

[0188] NCF3: For each type of unit constituting the fluorine-containing polymer, it is the sum of the values obtained by multiplying the number of moles of the trifluoromethyl moiety of the constituent unit by the molar ratio of the unit to all units.

[0189] MA: For each type of unit constituting the fluorine-containing polymer, it is the sum of the values obtained by multiplying the total atomic weight of all atoms of the constituent unit by the molar ratio of the unit to all units.

[0190] The above NCF3 and MA can be calculated based on the molar ratio and terminal amount of the structural units of the fluorine-containing polymer obtained by 1 1H-NMR, 19 19F-NMR, elemental analysis, and IR. In addition, NCF3 and MA can also be calculated based on the feeding amounts of the monomers and initiators used to manufacture the fluorine-containing polymer.

[0191] As the fluorine-containing polymer, the following polymers (1) and (2) are preferred.

[0192] Polymer (1): A fluorine-containing polymer having a fluorine olefin unit in the main chain and no aliphatic ring.

[0193] Polymer (2): A fluorine-containing polymer having an aliphatic ring in the main chain.

[0194] In the present invention, as the fluorine-containing polymer, either one of the polymers (1) and (2) can be used alone, or the polymers (1) and (2) can be used in combination.

[0195] 《Polymer (1)》

[0196] The polymer (1) can be a homopolymer of a fluoroolefin, a copolymer formed from two or more fluoroolefins, or a copolymer of a fluoroolefin and other monomers capable of copolymerizing with the fluoroolefin.

[0197] Examples of the fluoroolefin include perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE).

[0198] It should be noted that (perfluoroalkyl vinyl ether) can also be expressed as perfluoro(alkoxyethylene).

[0199] In addition, examples of the fluoroolefin also include fluoroolefins having hydrogen atoms or chlorine atoms such as chlorotrifluoroethylene (CTFE), trifluoroethylene (TrFE), vinylidene fluoride (VdF), 1,2-difluoroethylene, and 1-fluoroethylene.

[0200] Examples of other monomers capable of copolymerizing with the fluoroolefin include olefins such as ethylene and propylene; aromatic vinyl compounds such as vinyl ethers, vinyl esters, and styrene; allyl compounds such as allyl ethers; acryloyl compounds and methacryloyl compounds.

[0201] In addition, fluorine-containing monomers such as vinyl ethers, vinyl esters, aromatic vinyl compounds, allyl compounds, acryloyl compounds, and methacryloyl compounds having perfluoroalkyl groups or perfluoropolyether groups can also be used.

[0202] Among them, the polymer (1) preferably has a perfluoro(alkyl vinyl ether) unit. More specifically, the fluorine-containing polymer preferably has a PPVE unit.

[0203] If the content ratio of the PPVE unit changes, the crystallinity of the polymer (1) changes. Specifically, if the content ratio of the PPVE unit relative to the fluorine-containing polymer increases, the crystallinity of the fluorine-containing polymer decreases.

[0204] The content ratio of the PPVE unit is preferably 2 mol% or more, more preferably 4 mol% or more, and further preferably 6 mol% or more relative to the total number of moles of all monomer units constituting the fluorine-containing polymer. The more within the above range, the lower the crystallinity of the obtained resin film becomes, the less likely the conductive material 10X is to adhere to the surface of the resin film 15, and it is easy to pattern the thick film portion 11 and the thin film portion 12, so it is preferred.

[0205] In addition, the content rate of the PPVE unit is preferably 15 mol% or less, more preferably 12 mol% or less, and still more preferably 10 mol% or less, relative to the total number of moles of all monomer units constituting the fluoropolymer. If it exceeds the above range, there is a possibility that the softening temperature of the obtained resin film decreases, and the shape of the film formed of the fluoropolymer cannot be maintained under the process temperature in element production and the usage conditions of the element.

[0206] When the polymer (1) is a copolymer, the proportion of the fluoroolefin unit is preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 80 mol% or more.

[0207] As the polymer (1), a synthetic product or a commercially available product can be used.

[0208] Examples of the polymer (1) include the following polymers.

[0209] Polytetrafluoroethylene (PTFE)

[0210] Tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA)

[0211] Tetrafluoroethylene / hexafluoropropylene copolymer (FEP)

[0212] Tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA)

[0213] Ethylene / tetrafluoroethylene copolymer (ETFE)

[0214] Polyvinylidene fluoride (PVDF)

[0215] Polyvinyl fluoride (PVF)

[0216] Polychlorotrifluoroethylene (PCTFE)

[0217] Ethylene / chlorotrifluoroethylene copolymer (ECTFE)

[0218] Among these, from the aspect of facilitating patterning of the thick film portion 11 and the thin film portion 12, a polymer in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine is preferred. That is, preferred are:

[0219] Polytetrafluoroethylene (PTFE),

[0220] Tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA),

[0221] Tetrafluoroethylene / hexafluoropropylene copolymer (FEP),

[0222] Tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA).

[0223] It should be noted that the above-mentioned "tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA)" can be a polymer having at least tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units, and further having perfluoro monomer units other than them.

[0224] Polymer (1) can be manufactured by a known method.

[0225] As Polymer (1), a synthetic product or a commercially available product can be used.

[0226] 《Polymer (2)》

[0227] Polymer (2) is a fluorinated polymer having an aliphatic ring in the main chain.

[0228] "Fluorinated polymer having an aliphatic ring in the main chain" means that the fluorinated polymer contains units having an aliphatic ring structure, and one or more carbon atoms constituting the aliphatic ring are carbon atoms constituting the main chain. The aliphatic ring can be a ring having a heteroatom such as an oxygen atom.

[0229] For the "main chain" of a polymer, in the polymer of a monoene, it refers to the chain of carbon atoms derived from the two carbon atoms constituting the polymerizable double bond.

[0230] In addition, in the cyclized polymer of a diene capable of undergoing cyclopolymerization, it refers to the chain of carbon atoms derived from the four carbon atoms constituting the two polymerizable double bonds.

[0231] Furthermore, in the copolymer of a monoene and a diene capable of undergoing cyclopolymerization, it refers to the chain of carbon atoms derived from the above two carbon atoms of the monoene and the above four carbon atoms of the diene.

[0232] When the above monoene has a polymerizable double bond between one carbon atom of the ring skeleton constituting the aliphatic ring and a carbon atom outside the ring, the main chain of the polymer having an aliphatic ring in the main chain has one carbon atom constituting the ring skeleton, and the ring skeleton constitutes the polymerizable double bond of the monoene. In addition, when the above monoene has a polymerizable double bond between two adjacent carbon atoms of the ring skeleton constituting the aliphatic ring, the main chain of the polymer having an aliphatic ring in the main chain has two carbon atoms constituting the ring skeleton, and the ring skeleton constitutes the polymerizable double bond of the monoene.

[0233] In the case of the above-mentioned diene capable of undergoing cyclopolymerization, the main chain of the polymer having an aliphatic ring in the main chain has four carbon atoms constituting the two polymerizable double bonds of the diene, and 2 to 4 of the four carbon atoms constitute the ring skeleton of the aliphatic ring.

[0234] The number of atoms constituting the ring skeleton of the aliphatic ring in the polymer (2) is preferably 4 to 7, particularly preferably 5 to 6. That is, the aliphatic ring is preferably a 4- to 7-membered ring, particularly preferably a 5- to 6-membered ring. When a heteroatom is present as an atom constituting the ring of the aliphatic ring, examples of the heteroatom include an oxygen atom and a nitrogen atom, and an oxygen atom is preferred. In addition, the number of heteroatoms constituting the ring is preferably 1 to 3, more preferably 1 or 2.

[0235] The aliphatic ring may or may not have a substituent. "May have a substituent" means that a substituent may be bonded to an atom constituting the ring skeleton of the aliphatic ring.

[0236] The hydrogen atom bonded to the carbon atom of the aliphatic ring constituting the polymer (2) is optionally substituted with a fluorine atom. In addition, when the aliphatic ring has a substituent and the substituent has a hydrogen atom bonded to a carbon atom, it is also preferred that the hydrogen atom be substituted with a fluorine atom. Examples of the substituent having a fluorine atom include a perfluoroalkyl group, a perfluoroalkoxy group, =CF2, etc.

[0237] As the aliphatic ring in the polymer (2), a perfluoroaliphatic ring (an aliphatic ring in which all hydrogen atoms bonded to carbon atoms, including substituents, are substituted with fluorine atoms) is preferred.

[0238] Examples of the polymer (2) include the following polymers (21) and (22).

[0239] Polymer (21): A fluoropolymer having a unit derived from a cyclic fluoromonoene;

[0240] Polymer (22): A fluoropolymer having a unit formed by the cyclopolymerization of a fluorodiene capable of undergoing cyclopolymerization (hereinafter also simply referred to as "fluorodiene").

[0241] Polymer (21):

[0242] "Fluorinated cyclic monoene" means a fluorinated monomer having one polymerizable double bond between carbon atoms constituting an aliphatic ring and a fluorinated monomer having one polymerizable double bond between a carbon atom constituting an aliphatic ring and a carbon atom other than the aliphatic ring.

[0243] As the fluorinated cyclic monoene, the following compound (1) and compound (2) are preferred.

[0244]

[0245] [In the formula, X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2Each independently is a fluorine atom, a perfluoroalkyl group optionally containing an etheric oxygen atom (-O-), or a perfluoroalkoxy group optionally containing an etheric oxygen atom. X 3 and X 4 Optionally bond to each other to form a ring.]

[0246] X 1 、X 2 、X 3 、X 4 、Y 1 and Y 2 In the perfluoroalkyl group of, the number of carbon atoms is preferably 1 to 7, particularly preferably 1 to 4. The aforementioned perfluoroalkyl group is preferably linear or branched, particularly preferably linear. Specifically, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, etc. can be cited, and trifluoromethyl is particularly preferred.

[0247] As X 1 、X 2 、X 3 、X 4 、Y 1 and Y 2 In the perfluoroalkoxy group of, a group in which an oxygen atom (-O-) is bonded to the aforementioned perfluoroalkyl group can be cited, and trifluoromethoxy is particularly preferred.

[0248] In formula (1), X 1 is preferably a fluorine atom.

[0249] X 2 is preferably a fluorine atom, trifluoromethyl or a perfluoroalkoxy group having 1 to 4 carbon atoms, particularly preferably a fluorine atom or trifluoromethoxy.

[0250] X 3 and X 4 Each independently is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a fluorine atom or trifluoromethyl.

[0251] X 3 and X 4 Optionally bond to each other to form a ring. The number of atoms in the ring skeleton constituting the aforementioned ring is preferably 4 to 7, particularly preferably 5 to 6.

[0252] As preferred specific examples of compound (1), compounds (1-1) to (1-5) can be cited.

[0253]

[0254] In formula (2), Y 1 and Y 2 Each independently is preferably a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a perfluoroalkoxy group having 1 to 4 carbon atoms, particularly preferably a fluorine atom or trifluoromethyl.

[0255] As preferred specific examples of the compound (2), the compounds (2-1) and (2-2) can be cited.

[0256]

[0257] The polymer (21) can be a homopolymer of the aforementioned fluorinated cyclic monoene or a copolymer of the fluorinated cyclic monoene and other monomers capable of copolymerization.

[0258] Among them, the proportion of the units derived from the fluorinated cyclic monoene in the polymer (21) relative to all the units is preferably 20 mol% or more, more preferably 40 mol% or more, and further preferably 100 mol%.

[0259] As other monomers capable of copolymerizing with the fluorinated cyclic monoene, for example, fluorinated dienes, monomers having a reactive functional group in the side chain, tetrafluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, etc. can be cited.

[0260] As the fluorinated diene, the same substances as those cited in the description of the polymer (22) described later can be cited. As the monomer having a reactive functional group in the side chain, monomers having a polymerizable double bond and a reactive functional group can be cited. As the polymerizable double bond, CF2=CF-, CF2=CH-, CH2=CF-, CFH=CF-, CFH=CH-, CF2=C-, CF=CF-, etc. can be cited.

[0261] It should be noted that the polymer obtained by copolymerization of the fluorinated cyclic monoene and the fluorinated diene is used as the polymer (21).

[0262] Polymer (22):

[0263] "Fluorinated diene" means a fluorinated monomer having 2 polymerizable double bonds and fluorine atoms and capable of undergoing ring-opening polymerization. As the polymerizable double bond, vinyl, allyl, acryloyl, and methacryloyl are preferred. As the fluorinated diene, the following compound (3) is preferred.

[0264] CF2=CF-Q-CF=CF2 ··· (3)

[0265] In the formula (3), Q is an optionally branched perfluoroalkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, which optionally contains an etheric oxygen atom and in which a part of the fluorine atoms are optionally substituted by halogen atoms other than fluorine atoms. As the halogen atom other than fluorine, chlorine atom, bromine atom, etc. can be cited.

[0266] Q is preferably a perfluoroalkylene group containing an etheric oxygen atom. In this case, the etheric oxygen atom in the perfluoroalkylene group may be present at one end of the perfluoroalkylene group, may be present at both ends of the perfluoroalkylene group, or may be present between the carbon atoms of the perfluoroalkylene group. From the viewpoint of cyclopolymerizability, it is preferable that the etheric oxygen atom is present at one end of the perfluoroalkylene group.

[0267] As a specific example of the compound (3), the following compounds can be cited.

[0268] CF2=CFOCF2CF=CF2,

[0269] CF2=CFOCF(CF3)CF=CF2,

[0270] CF2=CFOCF2CF2CF=CF2,

[0271] CF2=CFOCF2CF(CF3)CF=CF2,

[0272] CF2=CFOCF(CF3)CF2CF=CF2,

[0273] CF2=CFOCFClCF2CF=CF2,

[0274] CF2=CFOCCl2CF2CF=CF2,

[0275] CF2=CFOCF2OCF=CF2,

[0276] CF2=CFOC(CF3)2OCF=CF2,

[0277] CF2=CFOCF2CF(OCF3)CF=CF2,

[0278] CF2=CFCF2CF=CF2,

[0279] CF2=CFCF2CF2CF=CF2,

[0280] CF2=CFCF2OCF2CF=CF2.

[0281] As the unit formed by the cyclopolymerization of the compound (3), the following units (3-1) to (3-4) can be cited.

[0282]

[0283] The polymer (22) can be a homopolymer of a fluorodiene or a copolymer of a fluorodiene and other monomers capable of copolymerizing.

[0284] Examples of other monomers capable of copolymerizing with fluorodienes include monomers having a reactive functional group in the side chain, tetrafluoroethylene, chlorotrifluoroethylene, perfluoro(methyl vinyl ether), and the like.

[0285] As a specific example of the polymer (22), for example, a polymer represented by the following formula (3-1-1) obtained by cyclopolymerizing CF2=CFOCF2CF2CF=CF2 (perfluoro(3-butenyl vinyl ether)) can be cited.

[0286] It should be noted that hereinafter, perfluoro(3-butenyl vinyl ether) will be referred to as "BVE".

[0287]

[0288] In the formula (3-1-1), p is an integer of 5 to 1000.

[0289] p is preferably an integer of 10 to 800, and particularly preferably an integer of 10 to 500.

[0290] As the polymer (2), a synthetic product or a commercially available product can be used.

[0291] As a specific example of the polymer (2), preferably a BVE cyclopolymer (manufactured by AGC Inc.: CYTOP (registered trademark)), a tetrafluoroethylene / perfluoro(4-methoxy-1,3-dioxolene) copolymer (manufactured by SOLVAY Co., Ltd.: HIFLON (registered trademark) AD), a tetrafluoroethylene / perfluoro(2,2-dimethyl-1,3-dioxolene) copolymer (manufactured by Dupont Co., Ltd.: Teflon (registered trademark) AF), a perfluoro(4-methyl-2-methylene-1,3-dioxolane) polymer (MMD polymer).

[0292] In the present invention, as the fluoropolymer, either one of the polymers (1) and (2) can be used alone, or the polymers (1) and (2) can be used in combination.

[0293] (Terminal Structure of Fluoropolymer)

[0294] Fluoropolymers are generally polymerized by radical polymerization of the above-mentioned monomers using a radical polymerization initiator. In this case, it can be considered that the terminal structure of the molecular chain (main chain) in the fluoropolymer at the end of polymerization is a structure obtained by the addition of fragments of the radical polymerization initiator used in the polymerization. In addition, when a chain transfer agent is used during polymerization, the terminal structure of the molecular chain (main chain) can exhibit a structure obtained by the addition of fragments of the chain transfer agent.

[0295] The above terminal structure in the fluoropolymer can be converted into other structures. For example, by heat-treating the fluoropolymer at the end of the above polymerization to above 250 °C, the terminal structure of the main chain will become -C(=O)-F, and the fluoropolymer forms an acyl fluoride.

[0296] In addition, by subjecting the above acyl fluoride to methanol treatment, the terminal structure of the main chain will become a methyl ester group. The methyl ester group can be converted from the highly reactive acyl fluoride by a simple methanol treatment. Therefore, it is easy to improve the stability of the obtained fluoropolymer, so it is preferred.

[0297] Furthermore, by subjecting the above acyl fluoride to fluorination treatment, the terminal structure of the main chain will become a trifluoromethyl group. As the fluorination treatment, for example, the treatment method described in paragraph 0040 of Japanese Patent Laid-Open No. 11-152310 can be cited. The trifluoromethyl group has high heat resistance, and it is easy to improve the heat resistance of the obtained fluoropolymer, so it is preferred. In addition, if the terminal is a trifluoromethyl group, the surface energy of the obtained resin film becomes low, the conductive material 10X is not easily attached to the surface of the resin film 15, and it is easy to pattern the thick film portion 11 and the thin film portion 12, so it is preferred.

[0298] In addition, if the terminal structure of the main chain of the fluoropolymer is a methyl ester group or a trifluoromethyl group, the intermolecular interaction at the main chain terminal is small and it is easy to perform evaporation coating, so it is preferred.

[0299] The above terminal structure of the main chain can be confirmed by infrared spectroscopic analysis.

[0300] (Crystallinity of fluoropolymer)

[0301] The fluoropolymer of the present embodiment is preferably low in crystallinity or amorphous. In the case of high crystallinity, in the evaporation coating of the conductive film, the grain boundary (interface) becomes the starting point of nucleation, and the adhesion probability of the conductive film increases. That is, the lower the crystallinity or the more amorphous it is, the easier it is to pattern the thick film portion 11 and the thin film portion 12, so it is preferred.

[0302] As an index for judging the crystallinity of the fluoropolymer, the melting point can be cited.

[0303] For example, in the case where the above polymer (1) has a PPVE unit, if the content rate of the PPVE unit increases, the crystallinity of the fluoropolymer decreases and the melting point also decreases.

[0304] In addition, the polymer (2) has the property of low crystallinity or amorphousness because its aliphatic ring structure easily loses crystallinity. In the amorphous case, no melting point is observed.

[0305] In this embodiment, the melting point is a value measured using a differential scanning calorimeter (for example, DSC 204 F1 Phoenix manufactured by NETZSCH). Specifically, 9 mg of the fluoropolymer is placed in a sample container, and the heat capacity is measured while heating from -70°C to 350°C at a rate of 10°C per minute, and the melting point is determined based on the obtained melting peak.

[0306] In this embodiment, the melting point of the fluoropolymer used is preferably 300°C or lower, more preferably 270°C or lower, and still more preferably 240°C or lower. The lower limit of the melting point is not particularly limited, and from the viewpoint of shape retention of the film formed from the fluoropolymer, it is preferably 100°C or higher.

[0307] In addition, the fluoropolymer is also preferably amorphous. In this case, no melting point is observed by the above method.

[0308] (Molecular weight of fluoropolymer)

[0309] A fluoropolymer with high crystallinity has low solubility in a solvent, so it is difficult to measure the molecular weight. However, an amorphous fluoropolymer has high solubility in a fluorinated solvent, so the molecular weight can be measured using gel permeation chromatography (GPC) or the like.

[0310] The weight average molecular weight (hereinafter represented by "Mw") of the fluoropolymer is preferably 1,000 to 20,000, more preferably 1,500 to 15,000, and still more preferably 2,000 to 10,000.

[0311] When the weight average molecular weight is less than 1,000, the softening temperature of the fluororesin becomes low, and it may not be possible to maintain the shape of the film formed from the fluoropolymer under the process temperature during device fabrication and the usage conditions of the device.

[0312] When the weight average molecular weight is greater than 20,000, the main chain of the fluoropolymer cracks during evaporation deposition, the fluoropolymer is degraded into low molecular weight substances, the strength of the formed layer is insufficient, and further, defects due to decomposition products are generated, making it difficult to obtain a smooth surface. In addition, it is conceivable that molecules or ions generated by the cracking of the main chain and undesirably mixed in may affect the conductivity of the conductive film. In addition, it may shorten the lifespan of the device having the conductive film of this embodiment (for example, the light-emitting lifespan of an organic EL device).

[0313] Therefore, if the Mw of the fluoropolymer is in the range of 1,000 to 20,000, the main chain of the fluoropolymer does not crack, and a layer with sufficient strength and a smooth surface can be formed.

[0314] The weight-average molecular weight of the fluoropolymer is a value measured using gel permeation chromatography (GPC). First, PMMA standard samples with known molecular weights are measured using GPC, and a calibration curve is created based on the elution time and molecular weight at the peak. Next, the fluoropolymer is measured, and Mw and Mn are determined from the calibration curve. The mobile phase solvent used is a mixed solvent of 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane / hexafluoroisopropyl alcohol (85 / 15 by volume).

[0315] "Molecular weight distribution" refers to the ratio of Mw to the number-average molecular weight (hereinafter represented by "Mn"), i.e., Mw / Mn.

[0316] From the perspective of the quality stability of the formed layer, the molecular weight distribution (Mw / Mn) of the fluoropolymer is preferably small, preferably 2 or less. The molecular weight distribution of the fluoropolymer is more preferably 1.5 or less, and further preferably 1.2 or less. It should be noted that the theoretical lower limit value of the molecular weight distribution is 1.

[0317] The smaller the molecular weight distribution of the fluoropolymer, the less the variation in the evaporation conditions, and in addition, it is easy to form a phase separation structure that is uniform in the film thickness direction.

[0318] As a method for obtaining a fluoropolymer with a small molecular weight distribution, examples include molecular weight adjustment based on controlled polymerization such as living radical polymerization; methods for fractionating the molecular weight using sublimation purification, supercritical extraction, and size exclusion chromatography.

[0319] In this specification, the weight-average molecular weight and the molecular weight distribution are values measured using gel permeation chromatography (GPC).

[0320] (Surface energy of the resin film)

[0321] Regarding the resin film 15 made of the above fluoropolymer as a material, the surface energy is preferably 30 mN / m or less, more preferably 25 mN / m or less, and further preferably 20 mN / m or less. If the resin film 15 has such a surface energy, when the conductive material 10X is dry-coated, the conductive material 10X is not easily attached to the surface of the resin film 15, and patterning is easy.

[0322] The surface energy of the resin film 15 can be adjusted by changing the fluorine atom content and the content of the trifluoromethyl group of the fluoropolymer used. If the fluorine atom content and the content of the trifluoromethyl group of the fluoropolymer are increased respectively, the surface energy of the resin film 15 becomes smaller.

[0323] According to the conductive film having the above configuration, a new conductive film having two regions with different light transmittances is formed.

[0324] In addition, according to the method for manufacturing a conductive film as described above, such a conductive film can be easily manufactured.

[0325] It should be noted that in the present embodiment, although the thin film portion 12 exists in the second region 10B of the conductive film 1, the thin film portion 12 may not exist.

[0326] In addition, in the present embodiment, although the resin film 15 exists in the second region 10B of the conductive film 1, there may be a step of removing the resin film after the step of dry coating as shown. If the resin film 15 is removed, the resin film 15 and the thin film portion 12 can be removed simultaneously. Figure 5 Shown is a schematic diagram of the conductive film 2 obtained by removing the resin film 15, which is a diagram corresponding to

[0327] Figure 7 As shown, the conductive film 2 has a first film 13 and a second film 20. In the first region 13A of the conductive film 2, the lattice-shaped thick film portion 11 overlaps with the second film 20. In addition, the second film 20 exists in the second region 13B of the conductive film 2. Figure 2 Corresponding figure. As Figure 7 Shown, the conductive film 2 has a first film 13 and a second film 20. In the first region 13A of the conductive film 2, the lattice-shaped thick film portion 11 overlaps with the second film 20. In addition, the second film 20 exists in the second region 13B of the conductive film 2.

[0328] In the conductive film 2 having such a configuration, the light transmittance of the second region 13B is higher than that of the second region 10B of the above-described conductive film 1, and the contrast between the first region 13A and the second region 13B becomes higher.

[0329] As a method for removing the resin film 15, for example, a method of dissolving or peeling off the fluorine-containing polymer using a fluorine-containing solvent and a method of removing it by dry etching can be cited.

[0330] As the fluorine-containing solvent, a solvent that dissolves the resin film 15 and substantially does not dissolve other materials constituting the substrate on which the conductive film 1 is formed is used. Therefore, the fluorine-containing polymer can be removed without damaging the quality of the organic optoelectronic element.

[0331] The fluorine-containing solvent for removing the fluorine-containing polymer is preferably, for example, a fluorine-containing solvent having a fluorophilic parameter P F Of 1 or more.

[0332] In addition, in the present embodiment, although the second film 20 exists, the second film 20 may not exist.

[0333] Figure 8 Shown is an explanatory diagram of a modification of the present embodiment, which is a diagram corresponding to Figure 2 Corresponding figure.

[0334] Figure 8 Shown, the conductive film 3 has a first film 10 and a resin film 15. The first film 10 is provided on the substrate 50. The resin film 15 is provided between the first film 10 and the substrate 50.

[0335] The lower surface 11a of the thick film portion 11 of the first film 10 is in contact with the substrate 50. In addition, the side surface 11b of the thick film portion 11 is in contact with the resin film 15.

[0336] The lower surface 12a of the thin film portion 12 of the first film 10 is in contact with the resin film 15.

[0337] This conductive film 3 does not have Figure 3 the process shown. Fluorine-containing polymer P is directly vapor-deposited on the surface 50a of the substrate 50. Other than that, it can be manufactured in the same manner as the manufacturing method of the above conductive film.

[0338] Furthermore, after manufacturing the conductive film 3 by the process of dry coating shown Figure 5 it can have a process of removing the above resin film 15.

[0339] [Second Embodiment]

[0340] A second embodiment of the present invention is an optoelectronic device having the first embodiment of the present invention, i.e., the conductive film.

[0341] As this optoelectronic device, an organic EL device is preferably used, which includes a substrate, an anode provided on the substrate, a cathode opposed to the anode, and an active layer disposed between the anode and the cathode, and the cathode is the first embodiment of the present invention, i.e., the conductive film.

[0342] Figure 9 is a cross-sectional schematic view showing an organic EL device (the optoelectronic device according to the second embodiment of the present invention) 100. The organic EL device 100 has a structure in which a substrate 110, an anode 111, a partition wall 112, a functional layer 113, and a cathode 115 are laminated. The functional layer 113 includes a light-emitting layer.

[0343] The organic EL device 100 of the present embodiment uses a top emission method in which light generated in the functional layer 113 is emitted to the outside through the cathode 115.

[0344] (Substrate)

[0345] The substrate 110 may have light transmissivity or may not have light transmissivity. As the material for forming the substrate 110, inorganic substances such as glass, quartz glass, and silicon nitride; organic polymers (resins) such as polyimide resin, acrylic resin, and polycarbonate resin can be used. In addition, if the surface insulation is ensured, a metal material can also be used as the material for forming the substrate 110.

[0346] In addition, the substrate 110 includes various wirings and driving elements (not shown) that are electrically connected to the organic EL device.

[0347] (Anode)

[0348] Anode 111 is formed on substrate 110, and supplies holes to functional layer 113. In addition, anode 111 has light reflectivity for reflecting the light emitted from the light-emitting layer included in functional layer 113.

[0349] As the material for forming anode 111, it is formed of a conductive material. As the conductive material, conductive metal oxides such as ITO and IZO can be used. In addition, in order to impart light reflectivity to anode 111, a reflective film formed of a metal can be provided on the substrate 110 side or the functional layer 113 side of anode 111. That is, anode 111 can have a laminated structure of a layer formed of a conductive metal oxide and a reflective film formed of a metal.

[0350] In addition, as the material for forming anode 111, metals such as silver can be used.

[0351] The thickness of anode 111 is not particularly limited, and is preferably 30 to 300 nm. For example, the thickness of anode 111 is 100 nm.

[0352] (Partition wall)

[0353] Partition wall 112 overlaps the peripheral portion of anode 111 and is formed, for example, in a lattice shape. Functional layer 113 is formed in the opening portion of partition wall 112, and divides organic EL element 100.

[0354] Partition wall 112 is made of a material such as resin, for example, polyimide.

[0355] (Functional layer)

[0356] Functional layer 113 is formed to overlap anode 111. Functional layer 113 has a light-emitting layer. In the light-emitting layer, holes injected from anode 111 and electrons injected from cathode 115 recombine to emit photons. The emission wavelength at this time is determined according to the material for forming the light-emitting layer. The light-emitting layer corresponds to the "active layer" in the present invention.

[0357] The light-emitting layer can be formed using materials known as materials for the light-emitting layer of an organic EL element.

[0358] The materials for forming the light-emitting layer can be used alone or in combination of two or more, and are appropriately selected according to the desired emission wavelength.

[0359] Functional layer 113 can have a hole injection layer and a hole transport layer between the light-emitting layer and anode 111.

[0360] The hole injection layer has a function of easily injecting holes from the anode into the hole transport layer.

[0361] The hole transport layer has a function of transporting well the holes injected from the anode 111 toward the light-emitting layer.

[0362] In addition, the functional layer 113 may have an electron transport layer and an electron injection layer between the light-emitting layer and the cathode 115.

[0363] The electron transport layer has a function of transporting well the electrons injected from the cathode 115 toward the light-emitting layer.

[0364] The electron injection layer has a function of easily injecting electrons from the cathode 115 into the electron transport layer.

[0365] (Cathode)

[0366] The cathode 115 is formed to cover the entire surface of the partition wall 112 and the functional layer 113. The cathode 115 has a function of injecting electrons into the functional layer.

[0367] In the optoelectronic device of the present embodiment, the cathode 115 employs the conductive film in the above-described present invention. The cathode 115 has a first film 116, a resin film 117, and a second film 118.

[0368] The second film 118 is formed to cover the partition wall 112 and the functional layer 113. Regarding the constitution and material of the second film 118, the constitution and material shown for the second film 20 in the first embodiment can be adopted.

[0369] The resin film 117 overlaps with the functional layer 113 in a plane, and is formed on the upper surface 118a of the second film 118. Regarding the constitution and material of the resin film 117, the constitution and material shown for the resin film 15 in the first embodiment can be adopted.

[0370] The first film 116 is formed to overlap with the partition wall 112 in a plane. Regarding the constitution and material of the first film 116, the constitution and material shown for the first film 10 in the first embodiment can be adopted.

[0371] That is, the first region of the cathode 115 overlaps with the partition wall 112, and the second region of the cathode 115 overlaps with the functional layer 113 including the light-emitting layer.

[0372] (Microcavity structure)

[0373] In the organic EL element 100 of the present embodiment, the anode 111 and the cathode 115 form an optical resonance structure (microcavity) that causes light to resonate between the anode 111 and the cathode 115, that is, between the upper surface of the reflective film of the anode 111 and the lower surface of the second film 118. Between the anode 111 and the cathode 115, the light generated in the light-emitting layer is repeatedly reflected, and the light having a wavelength that matches the optical path length between the anode 111 and the cathode 115 resonates and is amplified. On the other hand, the light having a wavelength that does not match the optical path length between the anode 111 and the cathode 115 is attenuated.

[0374] The "optical path length" mentioned here refers to a value calculated using the wavelength of the desired light emitted to the outside of the element and the refractive index of each layer at the wavelength of the desired light.

[0375] The optical path length between the anode 111 and the cathode 115 is set to an integer multiple of the center wavelength of the light L generated in the light-emitting layer included in the functional layer 113, for example. In this case, the light L emitted from the light-emitting layer is amplified more as it approaches the center wavelength, and is attenuated more as it moves away from the center wavelength, and is emitted to the outside of the organic EL element 100. By operating in this way, the half-value width of the emission spectrum of the light L emitted from the organic EL element 100 is narrow, and the color purity is improved.

[0376] In the organic EL element 100 having such a configuration, since the cathode 115 has the conductive film of the present invention, it is possible to maintain a high light extraction efficiency in the second region and reduce the wiring resistance of the cathode 115, and good driving can be achieved.

[0377] It should be noted that, in the above embodiment, an organic EL element is exemplified and described as the optoelectronic element, but the optoelectronic element to which the conductive film of the present invention is applied is not limited to the organic EL element.

[0378] The optoelectronic element of the present invention can be, for example, a semiconductor laser. As the semiconductor laser, a known configuration can be adopted. By using the above conductive film for the cathode of the semiconductor laser, the cathode is made to have a low resistance, and a semiconductor laser with an increased output power is formed.

[0379] In addition, the optoelectronic element of the present invention can be, for example, a light-receiving element such as a photosensor or a solar cell. As the photosensor and the solar cell, a known configuration can be adopted in which holes and electrons generated in the active layer according to the intensity of the light received by the active layer (light-receiving layer) are conducted to the cathode and the anode through a semiconductor layer.

[0380] By using the above conductive film for the electrodes (anode, cathode) of the photosensor and the solar cell, it is possible to form a photosensor with improved detection performance and a solar cell with improved power generation efficiency.

[0381] Furthermore, the transmissivity of the entire element of the conductive film and the optoelectronic element of the present invention is increased, so it is useful in applications such as transparent displays. In addition, for under-screen cameras, under-screen sensors, etc., it is necessary to increase the transmittance of the display above the camera and sensor, and the conductive film of the present invention is very useful.

[0382] Furthermore, the conductive film of the present invention can also be used when forming patterned electrodes and wirings in addition to optoelectronic elements.

[0383] As described above, the preferred embodiments of the present invention have been described with reference to the drawings, but are not limited to the examples described in the present invention. The shapes, combinations, etc. of the respective constituent members shown in the above examples are examples, and various changes can be made according to design requirements and the like without departing from the gist of the present invention.

[0384] Examples

[0385] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

[0386] <Evaluation method>

[0387] In the present embodiment, the following methods are used for evaluation.

[0388] [Measurement of the thermal weight loss rate of the fluoropolymer under vacuum]

[0389] Measurement was carried out using a vacuum differential thermal balance (manufactured by ADVANCE RIKO: VPE-9000). 50 mg of the fluoropolymer was put into a dish with an inner diameter of 7 mm, and the weight loss rate (%) with respect to the initial weight (50 mg) of the fluoropolymer when heated from room temperature to 500 °C at 2 °C per minute under a vacuum of 1×10 -3 Pa was measured.

[0390] Through this measurement, the temperature (T d100 ) at which the weight loss rate becomes 100%, the temperature (T d10 ) at which the weight loss rate becomes 10%, and the temperature (T d90 ) at which the weight loss rate becomes 90% were obtained.

[0391] [Measurement of melting point]

[0392] Measurement was carried out using a differential scanning calorimeter (manufactured by NETZSCH: DSC 204 F1 Phoenix). 9 mg of the fluoropolymer was put into a sample container, and the heat capacity when heated from -70 °C to 350 °C at 10 °C per minute was measured, and the melting point was obtained based on the resulting melting peak.

[0393] [Measurement of the surface energy of the resin film]

[0394] (Preparation of Specimen for Measuring Contact Angle)

[0395] On a silicon substrate with a side length of 25 mm, a fluoropolymer is vapor-deposited at a vapor-deposition rate of 0.1 nm / second to form a 100-nm resin film, and a specimen for measurement is obtained.

[0396] (Evaluation of Surface Energy)

[0397] Using a contact angle meter (manufactured by KRUSS: DSA25), 2-μL droplets of water and n-hexadecane are respectively dropped onto the surface of the resin film of the specimen for measurement placed horizontally, and the contact angle is measured.

[0398] Using the obtained contact angle and the following formula (A), calculate the surface energy γ S of the dispersion term γ S d and the surface energy γ S of the polar term γ S p , and use the obtained values and the following formula (B) to calculate the surface energy γ S .

[0399] γ L (cosθ + 1) / (2(γ L d )) = (γ 1 / 2 ) S p ) 1 / 2 ×(γ L p ) 1 / 2 / (γ L d ) 1 / 2 +(γ S d ) 1 / 2 …

[0400] (A)

[0401] γ L : Surface energy of water or n-hexadecane

[0402] γ L d : Dispersion term of the surface energy of water or n-hexadecane

[0403] γ L p : Polar term of the surface energy of water or n-hexadecane

[0404] θ: Contact angle of water or n-hexadecane

[0405] γ S = γS d +γ S p …(B)

[0406] γ S : Surface energy of the resin film

[0407] γ S d : Dispersion term of the surface energy of the resin film

[0408] γ S p : Polar term of the surface energy of the resin film

[0409] It should be noted that for the dispersion term, polar term, and surface energy of water and n-hexadecane, the values in Table 1 below are used.

[0410] [Table 1]

[0411] <![CDATA[γ L d (mN / m)]]> <![CDATA[γ L p (mN / m)]]> <![CDATA[γ L (mN / m)]]> Water 29.1 43.7 72.8 n-Hexadecane 27.6 0 27.6

[0412] (Measurement of CF3 concentration)

[0413] The content of the trifluoromethyl moiety (mmol / g) is determined using the following formula.

[0414] (Content of trifluoromethyl moiety) = [NCF3 / MA] × 1000

[0415] NCF3: For each type of unit constituting the fluoropolymer, the sum of the values obtained by multiplying the number of moles of the trifluoromethyl moiety of the constituent unit by the molar ratio of that unit to all units.

[0416] MA: For each type of unit constituting the fluoropolymer, the sum of the values obtained by multiplying the total atomic weight of all atoms of the constituent unit by the molar ratio of that unit to all units.

[0417] It should be noted that the number of moles of the trifluoromethyl moiety, the total atomic weight of all atoms of the constituent unit, the molar ratio, etc. used in the above formula are calculated using the molar ratio and end group amount of the structural unit of the fluoropolymer obtained by NMR analysis and IR analysis of the fluoropolymer.

[0418] (Measurement of fluorine atom content)

[0419] The fluorine atom content (mass%) is determined using the following formula.

[0420] (Fluorine atom content) = [19×NF / MA] × 100

[0421] NF: The sum of the values obtained by multiplying the total atomic weight of the fluorine atoms in the constituent units by the molar ratio of each such unit to all the units for each type of unit constituting the fluoropolymer.

[0422] MA: The sum of the values obtained by multiplying the total atomic weight of all the atoms in the constituent units by the molar ratio of each such unit to all the units for each type of unit constituting the fluoropolymer.

[0423] It should be noted that the atomic weight of fluorine atoms, the total atomic weight of all the atoms in the constituent units, the molar ratio, etc. used in the above formula are calculated using the molar ratio and terminal amount of the structural units of the fluoropolymer obtained by NMR analysis and IR analysis of the fluoropolymer.

[0424] <Synthesis of Fluoropolymer>

[0425] The fluoropolymer used in the evaluation was synthesized as follows.

[0426] [Synthesis Example 1]

[0427] Weigh 30 g of perfluoro(3-butenyl vinyl ether) (BVE), 30 g of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane (1H-PFH), 0.5 g of methanol, and 0.44 g of diisopropyl peroxydicarbonate (IPP) respectively, and put them into a glass reactor with an internal volume of 50 ml. After purging the inside of the reactor with high-purity nitrogen, heat it to 40 °C and carry out polymerization for 24 hours.

[0428] Remove the solvent from the resulting solution under the conditions of 666 Pa (absolute pressure) and 50 °C to obtain 28 g of a polymer.

[0429] Next, heat the resulting polymer in an oven at 300 °C, and then treat it using the method described in paragraph

[0040] of Japanese Patent Laid-Open No. 11-152310. Replace the unstable terminal groups with -CF3 groups using fluorine gas to obtain fluoropolymer A.

[0430] Put the obtained fluoropolymer A into the raw material feeding section of the above glass tube type sublimation refining device, and reduce the pressure in the trapping section to 3.0×10 -3 Pa. Then, slowly heat the raw material feeding section to 330 °C to sublime fluoropolymer A. In the sublimation refining device, heat the trapping section from the side close to the feeding section at set temperatures of 310 °C, 280 °C, 250 °C, and 200 °C.

[0431] Among them, recover the substances precipitated in the trapping sections at set temperatures of 200 °C, 250 °C, 280 °C, and 310 °C to obtain 2 g of refined fluoropolymer A1.

[0432] [Synthesis Example 2]

[0433] The polymer produced by the same operation as in Synthesis Example 1 was heated in an oven at 300 °C, then immersed in methanol, and heated in an oven at 75 °C for 20 hours to convert the terminal groups into methyl ester groups, obtaining fluoropolymer B.

[0434] Fluoropolymer B was sublimated by the same operation as in Synthesis Example 1. The substances deposited in the trapping parts set at 200 °C, 250 °C, and 280 °C were recovered to obtain 2 g of purified fluoropolymer B1.

[0435] [Synthesis Example 3]

[0436] 152.9 g of perfluoro(propyl vinyl ether) (PPVE), 805 g of AC2000 (manufactured by AGC Inc.), 2.40 g of methanol, and 1.15 g of azobisisobutyronitrile (AIBN) were charged into a stainless-steel autoclave with an internal volume of 1006 mL, and freeze-degassed with liquid nitrogen.

[0437] After the autoclave was heated to 70 °C, 56.3 g of tetrafluoroethylene (TFE) was introduced into the autoclave to start polymerization. Since the pressure inside the autoclave decreased due to the progress of polymerization, TFE was continuously supplied, and polymerization was carried out while keeping the temperature and pressure of the autoclave constant. After 5 hours from the start of polymerization, the autoclave was cooled, polymerization was stopped, and the gas in the system was discharged to obtain a reaction solution.

[0438] 800 g of methanol was added to the reaction solution and mixed. After the polymer dissolved in the reaction solution precipitated, liquid separation was carried out, and the lower layer in which the polymer was dispersed was recovered. The obtained polymer dispersion was dried with hot air at 80 °C for 16 hours, and then dried in vacuo at 100 °C for 16 hours to obtain a polymer.

[0439] The composition of the obtained polymer was PPVE unit:TFE unit = 14:86 (mol%).

[0440] Next, the obtained polymer was heated in an oven at 330 °C, then immersed in methanol, and heated in an oven at 75 °C for 40 hours to convert the terminal groups into methyl ester groups, obtaining fluoropolymer C.

[0441] Fluoropolymer C was sublimated by the same operation as in Synthesis Example 1. The substances deposited in the trapping part set at 280 °C were recovered to obtain 4 g of purified fluoropolymer C1.

[0442] [Synthesis Example 4]

[0443] Using 78.9 g of PPVE, 767 g of AC2000, 4.23 g of methanol, 1.27 g of AIBN, and 48.4 g of TFE, and otherwise operating in the same manner as in Synthesis Example 3, a polymer was obtained.

[0444] The composition of the obtained polymer was PPVE units:TFE units = 9:91 (mol%).

[0445] Next, operating in the same manner as in Synthesis Example 3, the end groups of the polymer were replaced with methyl ester groups to obtain a fluoropolymer D.

[0446] Operating in the same manner as in Synthesis Example 1, the fluoropolymer D was sublimated. The substances deposited in the trap parts set at temperatures of 250 °C and 280 °C were recovered to obtain 4 g of purified fluoropolymer D1.

[0447] [Synthesis Example 5]

[0448] Using 57.9 g of PPVE, 4.13 g of methanol, and 1.24 g of AIBN, and otherwise operating in the same manner as in Synthesis Example 3, a polymer was obtained.

[0449] The composition of the obtained polymer was PPVE units:TFE units = 6:94 (mol%).

[0450] Next, operating in the same manner as in Synthesis Example 4, the end groups of the polymer were replaced with methyl ester groups to obtain a fluoropolymer E.

[0451] Operating in the same manner as in Synthesis Example 1, the fluoropolymer E was sublimated. The substances deposited in the trap parts set at temperatures of 200 °C, 250 °C, and 280 °C were recovered to obtain 5 g of purified fluoropolymer E1.

[0452] [Synthesis Example 6]

[0453] A jacketed polymerization tank (made of stainless steel) with an internal volume of 1.351 L was degassed, and 649 g of 1,1,2,2 - tetrafluoroethyl - 2,2,2 - trifluoroethyl ether (AE - 3000, manufactured by AGC Inc.), 152 g of perfluoropropyl vinyl ether (PPVE), 109 g of tetrafluoroethylene (TFE), and 15.5 g of methanol were weighed and charged into the polymerization tank.

[0454] The temperature of the polymerization tank was maintained at 60 °C, and 18.9 mL of a 0.79 mass% solution of tert - butyl perpivalate (PBPV) (solvent: AE - 3000) was charged to start the polymerization.

[0455] During the polymerization, the polymerization pressure decreased as the polymerization proceeded. Therefore, TFE was continuously introduced into the polymerization tank in such a manner that the polymerization pressure was substantially constant. The polymerization pressure was maintained at 1.04 ± 0.04 MPaG (gauge pressure).

[0456] The polymerization was terminated when the input amount of TFE reached 121 g to obtain a polymer.

[0457] The composition of the obtained polymer was PPVE unit:TFE unit = 4:96 (mol%).

[0458] Next, the obtained polymer was heated in an oven at 330 °C, and then the end groups of the polymer were replaced with -CF3 groups by the same method as in Synthesis Example 1 to obtain a fluoropolymer F.

[0459] Using 20 g of the fluoropolymer F, the fluoropolymer F was sublimated in the same manner as in Synthesis Example 1. The substances deposited in the trapping sections set at 250 °C and 280 °C were recovered to obtain 2 g of purified fluoropolymer F1.

[0460] In addition, 20 g of the obtained fluoropolymer F was put into a pressure vessel of a supercritical extraction apparatus, and supercritical extraction based on carbon dioxide was carried out.

[0461] After extracting 0.2 g under the conditions of an extraction temperature of 40 °C, an extraction pressure of 30 MPa, and a carbon dioxide flow rate of 30 ml / min (Condition 1), the extraction temperature was raised to 80 °C, the extraction pressure was raised to 60 MPa, and further, AC-2000 (manufactured by AGC Inc.) as an entrainer was used at a ratio of 10% by volume relative to carbon dioxide (Condition 2) to obtain 1.4 g of an extract.

[0462] The extract obtained by supercritical extraction was used as fluoropolymer F2.

[0463] [Synthesis Example 7]

[0464] Under the same conditions as in Synthesis Example 3, the end groups of the polymer produced by the same operation as in Synthesis Example 6 were replaced with methyl ester groups to obtain a fluoropolymer G.

[0465] The fluoropolymer G was sublimated in the same manner as in Synthesis Example 1. The substances deposited in the trapping section set at 250 °C were recovered to obtain 4 g of purified fluoropolymer G1.

[0466] [Synthesis Example 8]

[0467] Using 701 g of AE-3000, 57 g of PPVE, 108 g of TFE, 35.7 g of methanol, and 18.9 mL of a 0.53 mass% solution of PBPV (solvent: AE-3000), and otherwise operating in the same manner as in Synthesis Example 6, a polymer was obtained.

[0468] The composition of the obtained fluoropolymer was PPVE unit:TFE unit = 2:98 (mol%).

[0469] Next, using the same method as in Synthesis Example 1, the terminal groups of the polymer were replaced with -CF3 groups to obtain a fluoropolymer H.

[0470] The fluoropolymer H was sublimated in the same manner as in Synthesis Example 1. The substances deposited in the trapping section set at a temperature of 280 °C were recovered to obtain 4 g of purified fluoropolymer H1.

[0471] [Synthesis Example 9]

[0472] Under the same conditions as in Synthesis Example 3, the terminal groups of the polymer produced by the same operation as in Synthesis Example 8 were replaced with methyl ester groups to obtain a fluoropolymer I.

[0473] The fluoropolymer I was sublimated in the same manner as in Synthesis Example 1. The substances deposited in the trapping sections set at temperatures of 250 °C and 280 °C were recovered to obtain 4 g of purified fluoropolymer I1.

[0474] [Commercially available fluoropolymers]

[0475] As commercially available fluoropolymers, the following materials were used for evaluation.

[0476] · Fluon PTFE L173JE (AGC): Tetrafluoroethylene polymer

[0477] · Fluon PFA P-63 (AGC): Tetrafluoroethylene / perfluoropropyl vinyl ether copolymer

[0478] · TEFLON AF 1600 (DuPont): Tetrafluoroethylene / perfluoro(2,2-dimethyl-1,3-dioxolene) copolymer

[0479] · kynar301F (Arkema): Vinylidene fluoride polymer

[0480] · kynar720 (Arkema): Vinylidene fluoride polymer

[0481] Furthermore, 50 g of TEFLON AF 1600 was weighed and sublimated in the same manner as in Synthesis Example 1. The substances deposited in the trapping sections set at temperatures of 250 °C and 280 °C were recovered to obtain 2 g of purified fluoropolymer J1.

[0482] [Evaluation]

[0483] Using the obtained fluoropolymers, the following evaluations 1 to 4 were carried out.

[0484] [Evaluation 1: Chamber pressure change during evaporation]

[0485] Put 0.1 g of fluoropolymer into the vacuum evaporation apparatus, and reduce the pressure in the chamber to 10 -4 Pa or less. On this basis, deposit the fluoropolymer at a deposition rate of 0.1 nm / second to form a 200-nm film. At this time, monitor the pressure in the chamber and measure the maximum value of the pressure during deposition. Using the measured value, calculate the pressure increase ratio according to the following calculation formula.

[0486] [Pressure increase ratio of the chamber pressure during deposition] = [Maximum pressure during deposition] / [Initial pressure before deposition]

[0487] Evaluate the fluoropolymer with a pressure increase ratio of 2 or less as "qualified product", and evaluate the fluoropolymer with a pressure increase ratio exceeding 2 as "defective".

[0488] It should be noted that for the fluoropolymer evaluated as defective in this evaluation, since there is a concern about contaminating the chamber, the following evaluation of the conductive film is abandoned.

[0489] [Evaluation 2: Evaluation 1 of patterning property of conductive film]

[0490] (Production of sample for transmittance measurement)

[0491] Use a quartz substrate of 25 mm × 25 mm × 0.525 mm. At the center of the top view of the quartz substrate, use a metal mask with a rectangular opening of 21 mm × 5 mm to deposit the fluoropolymer to produce a quartz substrate with a resin film.

[0492] The deposition of the fluoropolymer is carried out under the condition of a deposition rate of 0.1 nm / second. In addition, the deposition of the fluoropolymer is carried out until the measured value by the film thickness meter attached to the deposition apparatus reaches 10 nm.

[0493] Next, for the quartz substrate with a resin film, deposit Ag over the entire surface without using a mask from the resin film to produce a conductive film sample for transmittance measurement.

[0494] The deposition of Ag is carried out under the condition of a deposition rate of 0.05 nm / second. In addition, the deposition of Ag is carried out until the measured value by the film thickness meter attached to the deposition apparatus reaches 15 nm.

[0495] (Transmittance measurement)

[0496] The transmittance of the produced conductive film sample is measured using a spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3600Plus). According to the obtained results, the higher the transmittance, the better the patterning property (easier to pattern) is judged.

[0497] [Examples 1 to 11]

[0498] The resin film is formed using the above fluorine-containing polymers A1 to J1, and the above evaluations 1 and 2 are carried out.

[0499] [Example 12]

[0500] Using Fluon PTFE L173JE as the fluorine-containing polymer, a resin film is formed, and except for this, the evaluation is carried out in the same manner as in Example 1.

[0501] In Evaluation 1, the rise in the chamber during evaporation was significantly large, so no other evaluations were carried out.

[0502] [Example 13]

[0503] Using Fluon PFA P-63 as the fluorine-containing polymer, a resin film is formed, and except for this, the evaluation is carried out in the same manner as in Example 1.

[0504] In Evaluation 1, the rise in the chamber during evaporation was significantly large, so no other evaluations were carried out.

[0505] [Example 14]

[0506] Using TEFLON AF 1600 as the fluorine-containing polymer, a resin film is formed, and except for this, the evaluation is carried out in the same manner as in Example 1.

[0507] In Evaluation 1, the rise in the chamber during evaporation was significantly large, so no other evaluations were carried out.

[0508] [Example 15]

[0509] Using kynar301F as the fluorine-containing polymer, a resin film is formed, and except for this, the evaluation is carried out in the same manner as in Example 1.

[0510] In Evaluation 1, the rise in the chamber during evaporation was significantly large, so no other evaluations were carried out.

[0511] [Example 16]

[0512] Using kynar720 as the fluorine-containing polymer, a resin film is formed, and except for this, the evaluation is carried out in the same manner as in Example 1.

[0513] In Evaluation 1, the rise in the chamber during evaporation was significantly large, so no other evaluations were carried out.

[0514] [Example 17]

[0515] Instead of using a fluoropolymer, a resin film was formed using the following 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (hereinafter referred to as TAZ). Except for this, the evaluation was carried out in the same manner as in Example 1. TAZ is a polycyclic organic semiconductor used in the existing patent document 1 (U.S. Patent No. 10270033 specification).

[0516]

[0517] Instead of using a fluoropolymer, a resin film was formed using the following N-(diphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine (hereinafter referred to as HT211). Except for this, the evaluation was carried out in the same manner as in Example 1.

[0518]

[0519] Ag was formed on a quartz substrate to a film thickness of 15 nm, and Evaluation 2 was carried out.

[0520] The film thickness of the Ag film in Reference Example 1 was the same as the film thickness of the metal film formed at a position not overlapping with the resin film in Evaluation 2 of Examples 1 to 18.

[0521] [Reference Example 2]

[0522] Ag was formed on a quartz substrate to a film thickness of 2 nm, and Evaluation 2 was carried out.

[0523] In the above Examples 1 to 18, Examples 1 to 11 corresponded to Examples, and Examples 12 to 18 corresponded to Comparative Examples. The evaluation results are shown in Tables 2 and 3. Separately, Table 2 is a table summarizing the relevant physical property values of the resin film material, and Table 3 is a table summarizing the evaluation results. It should be noted that "-" in the table indicates the absence of data.

[0524] [Table 2]

[0525]

[0526] [Table 3]

[0527]

[0528] In addition, the results of Evaluation 2 are shown in Figure 10 .

[0529] From the results of the evaluation, it was found that in Examples 1 to 11, there was no increase in the chamber pressure during evaporation, and no depolymerization, thermal decomposition, or outgassing was observed.

[0530] In addition, it is known that the light transmittance of the second region in the specimens produced in Examples 1 to 11 is greater than that of Comparative Example 1. Therefore, it can be known that in Examples 1 to 11, patterning of the first region and the second region can be performed.

[0531] In addition, it was confirmed that Examples 1 to 11 have a high transmittance particularly in the long wavelength region including the near-infrared region, and are very useful for the use of an under-screen sensor equipped with an optical authentication sensor using near-infrared rays.

[0532] In particular, regarding Examples 1 to 5, the light transmittance is higher than that of Comparative Example 2 (Ag 2 nm) in the wavelength range of 450 nm or more, and regarding Examples 1, 3, and 4, the light transmittance is higher than that of Comparative Example 2 in all the measured wavelength ranges.

[0533] On the other hand, it can be known that in Examples 12 to 16, an increase in the chamber pressure during evaporation was observed, and depolymerization, thermal decomposition, and outgassing occurred during evaporation, and it can be known that it is not substantially suitable for the production of the conductive film of the present embodiment.

[0534] In addition, it can be evaluated that the light transmittance of the second region in the specimens produced in Examples 17 and 18 is greater than that of Comparative Example 1, but it can be known that the light transmittance is lower than that of Examples 1 to 11. That is, it can be known that the resin film formed in Examples 17 and 18 is more likely to form a metal film on the upper surface than the resin film formed in Examples 1 to 11, and it is difficult to perform patterning in a state where the contrast between the first region and the second region is large. It can be known that the transmittance is particularly low in the long wavelength region including the near-infrared region, and the patterning property is significantly poor compared with the conductive film of the present embodiment.

[0535] [Evaluation 3: Evaluation 2 of the patterning property of the conductive film]

[0536] (Production of specimens for transmittance measurement)

[0537] A 25 mm × 25 mm × 0.525 mm quartz substrate was used. Ag was evaporated without using a mask over the entire surface of the quartz substrate to form a second film.

[0538] The evaporation of Ag was carried out under the condition that the evaporation rate was 0.05 nm / second. In addition, the evaporation of Ag was carried out until the measured value by the film thickness meter attached to the evaporation apparatus reached 10 nm.

[0539] Next, for the quartz substrate having Ag evaporated over the entire surface, a fluorine-containing polymer was evaporated using a metal mask having a rectangular opening of 21 mm × 5 mm at the center in plan view of the substrate to produce a quartz substrate having a resin film.

[0540] The vapor deposition of the fluoropolymer is carried out under the condition that the vapor deposition rate is 0.1 nm / second. In addition, the vapor deposition of the fluoropolymer is carried out until the measured value by the film thickness gauge attached to the vapor deposition apparatus reaches 50 nm.

[0541] Next, for a quartz substrate having an entire surface vapor deposition film of Ag and a resin film, Ag or Mg is vapor deposited on the entire surface without using a mask from above the resin film to produce a conductive film specimen for transmittance measurement.

[0542] The vapor deposition of Ag or Mg is carried out under the condition that the vapor deposition rate is 0.05 nm / second. In addition, the vapor deposition of Ag or Mg is carried out until the measured value by the film thickness gauge attached to the vapor deposition apparatus reaches 15 nm.

[0543] (Transmittance measurement)

[0544] The transmittance of the produced conductive film specimen is measured using a spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3600Plus). It is judged from the obtained results that the higher the transmittance, the better the patterning property.

[0545] [Example 19]

[0546] Using the above-mentioned fluoropolymer D1, a resin film is formed, and the above evaluation 3 is carried out.

[0547] [Example 20]

[0548] Instead of the fluoropolymer, TAZ is used to form a resin film, and otherwise, the same operations as in Example 19 are carried out and evaluated.

[0549] [Reference Example 3]

[0550] On a quartz substrate, Ag is formed to a film thickness of 10 nm, and then, Ag or Mg is formed to a film thickness of 15 nm, and evaluation 3 is carried out.

[0551] The film thicknesses of the Ag film and the Mg film in Reference Example 3 are the same as the film thicknesses of the metal films formed at positions not overlapping with the resin film in Evaluation 3 of Example 19 and Example 20.

[0552] Example 19 corresponds to an example, and Example 20 corresponds to a comparative example. The evaluation results are shown in Table 4.

[0553] [Table 4]

[0554]

[0555] In addition, the results of Evaluation 3 are shown in Figure 11 .

[0556] It can be known that the light transmittance of the second region in the specimen produced in Example 19 is greater than that of Reference Example 3. Therefore, it can be known that in Example 19, patterning of the first region and the second region can be performed. In addition, it can be confirmed that the transmittance of Example 19 is high in the long wavelength region including the near-infrared region, and it is useful for the under-screen sensor application equipped with an optical authentication sensor using near-infrared rays.

[0557] In contrast, it can be known that the light transmittance of the second region in the specimen produced in Example 20 is equal to or less than that of Reference Example 1. That is, it can be known that the resin film formed in Example 20 is more likely to form a metal film on the upper surface than the resin film formed in Example 19, and it is difficult to perform patterning of the first region and the second region.

[0558] [Evaluation 4: Evaluation 3 of the patterning property of the conductive film]

[0559] (Fabrication 1 of the conductive film specimen: for total light transmittance measurement)

[0560] (Process 1)

[0561] Ag is deposited without using a mask on the entire surface of a 25 mm × 25 mm × 0.525 mm quartz substrate to form a second film.

[0562] The deposition of Ag is carried out under the condition that the deposition rate is 0.05 nm / second. In addition, the deposition of Ag is carried out until the measured value by the film thickness meter attached to the deposition apparatus reaches 30 nm.

[0563] (Process 2)

[0564] Next, for the above substrate with Ag deposited on the entire surface, a fluoropolymer is deposited using a metal mask having a rectangular opening of 21 mm × 5 mm at the center in plan view of the substrate to produce a quartz substrate with a resin film.

[0565] The deposition of the fluoropolymer is carried out under the condition that the deposition rate is 0.1 nm / second. In addition, the deposition of the fluoropolymer is carried out until the measured value by the film thickness meter attached to the deposition apparatus reaches 50 nm.

[0566] (Process 3)

[0567] Next, for the quartz substrate with a resin film produced in Process 2, Ag is deposited without using a mask on the entire surface from above the resin film to produce a conductive film specimen for total light transmittance measurement. In the produced conductive film specimen, the region where the resin film is not formed corresponds to the "first region" in the present invention, and the region where the resin film is formed corresponds to the "second region" in the present invention.

[0568] The evaporation of Ag was carried out under the condition that the evaporation rate was 0.05 nm / second. In addition, the evaporation of Ag was carried out until the measured value by the film thickness gauge attached to the evaporation apparatus reached 70 nm.

[0569] (Fabrication of conductive film specimen 2: for film thickness measurement)

[0570] A conductive film specimen for film thickness measurement was fabricated in the same manner as in the fabrication of the conductive film specimen 1, except that a 25 mm × 25 mm silicon substrate was used instead of the quartz substrate.

[0571] In addition, Process 1 was performed on the silicon substrate to fabricate a reference specimen 1 having only the second film formed thereon, and Process 1 and Process 2 were performed on the silicon substrate to fabricate a reference specimen 2 having the second film and the resin film formed thereon.

[0572] (Measurement of total light transmittance)

[0573] For the conductive film specimen for total light transmittance measurement, a haze meter (manufactured by Suga Test Instruments Co., Ltd., model: HZ-V3, measurement light: D65 light) was used to measure the total light transmittance of the second region.

[0574] (Film thickness measurement)

[0575] In the first region of the conductive film specimen for film thickness measurement, damage was made from the surface of the first film to reach the silicon substrate, and the film thickness from the surface of the first film to the surface of the silicon substrate (total film thickness in the first region) was measured.

[0576] Similarly, in the second region of the conductive film specimen for film thickness measurement, damage was made from the surface of the first film to reach the silicon substrate, and the film thickness from the surface of the first film to the surface of the silicon substrate (total film thickness in the second region) was measured.

[0577] Similarly, in the reference specimen 1, damage was made from the surface of the second film to reach the silicon substrate, and the film thickness from the surface of the second film to the surface of the silicon substrate (film thickness of the second film of the reference specimen 1) was measured.

[0578] Similarly, in the second region of the reference specimen 2, damage was made from the surface of the resin film to reach the silicon substrate, and the film thickness from the surface of the resin film to the surface of the silicon substrate (total film thickness of the second film and the resin film of the reference specimen 2) was measured.

[0579] It should be noted that the film thickness was measured using a stylus surface measurement device (manufactured by BRUKER AXS Inc., DektakXT).

[0580] The film thickness a of the first film in the first region and the film thickness b of the first film in the second region were calculated according to the following formula.

[0581] The film thickness a (nm) of the first film in the first region = the total film thickness (nm) in the first region - the film thickness (nm) of the second film of the reference specimen 1

[0582] The film thickness b (nm) of the first film in the second region = the total film thickness (nm) in the second region - the total film thickness (nm) of the second film and the resin film of the reference specimen 2

[0583] (Patterning property evaluation)

[0584] Regarding whether the resin film can be used for patterning, the evaluation is carried out according to the following criteria. A and B are evaluated as good, and C and D are evaluated as bad.

[0585] A: The film thickness b is 0% or more and 10% or less with respect to the film thickness a

[0586] B: The film thickness b exceeds 10% and is 50% or less with respect to the film thickness a

[0587] C: The film thickness b exceeds 50% and is 90% or less with respect to the film thickness a

[0588] D: The film thickness b exceeds 90% and is 100% or less with respect to the film thickness a

[0589] [Example 21]

[0590] A resin film is formed using the above-mentioned fluoropolymer A1, and the above-mentioned evaluation 4 is carried out.

[0591] [Reference Example 4]

[0592] Ag is formed on a quartz substrate to a film thickness of 30 nm, and then Ag is formed to a film thickness of 70 nm. For the obtained specimen, the total transmittance is measured. The film thickness of the Ag film in Reference Example 4 is the same as the film thickness of the metal film formed in the first region of the conductive film specimen produced in Example 21.

[0593] Example 21 corresponds to an example.

[0594] As a result of the evaluation, the total transmittance of the second region of Example 21 is 27%.

[0595] In addition, the film thickness a of the first film in the first region of Example 21 is 68 nm, the film thickness b of the first film in the second region is 0 nm, and the result of the patterning property evaluation is an A evaluation.

[0596] In addition, the total transmittance of Reference Example 4 is 0.6%.

[0597] From the measurement results of the total transmittance of the second region of the conductive film specimen of Example 21 and the specimen of Reference Example 4, it can be seen that in the conductive film specimen of Example 21, the second region has higher light transmittance than the first region.

[0598] In addition, based on the results of the film thickness measurement in Example 21, it was confirmed that in the conductive film sample of Example 21, the formation of the first film in the second region could be suppressed.

[0599] From these results, it was found that the conductive film sample of Example 21 could be patterned well in the first region and the second region.

[0600] [Evaluation 5: Confirmation of the patterned shape of the conductive film]

[0601] (Fabrication of the conductive film: for microscopic observation)

[0602] A 25 mm × 25 mm × 0.525 mm quartz substrate was used. A metal mask with circular openings having a diameter of 30 μm arranged at intervals of 60 μm in the X-axis direction and the Y-axis direction on the plane was used, and a fluoropolymer was vapor-deposited on the quartz substrate to fabricate a quartz substrate with a resin film.

[0603] The vapor deposition of the fluoropolymer was carried out under the condition that the vapor deposition rate was 0.1 nm / second. In addition, the vapor deposition of the fluoropolymer was carried out until the measured value by the film thickness meter attached to the vapor deposition apparatus reached 30 nm.

[0604] Next, for the quartz substrate with a resin film, Ag for forming the first film was vapor-deposited over the entire surface without using a mask from above the resin film to fabricate a conductive film sample for confirmation of the patterned shape.

[0605] The vapor deposition of Ag was carried out under the condition that the vapor deposition rate was 0.5 nm / second. In addition, the vapor deposition of Ag was carried out until the measured value by the film thickness meter attached to the vapor deposition apparatus reached 70 nm.

[0606] (Microscopic observation and pattern size measurement)

[0607] A digital microscope (manufactured by KEYENCE CORPORATION, model: VHX-2000) was used to observe the fabricated conductive film sample for confirmation of the patterned shape. In addition, the diameter of region B was measured.

[0608] [Example 22]

[0609] The resin film was formed using the above-mentioned fluoropolymer A1, and the above Evaluation 5 was carried out.

[0610] [Example 23]

[0611] The resin film was formed using the above-mentioned fluoropolymer C1, and the above Evaluation 5 was carried out.

[0612] [Example 24]

[0613] The resin film was formed using the above-mentioned fluoropolymer D1, and the above Evaluation 5 was carried out.

[0614] [Reference Example 5]

[0615] Regarding the metal mask used when vapor-depositing a fluoropolymer in Evaluation 5, the same operation as in the pattern size measurement in Evaluation 5 was performed to measure the diameter of the opening. The measured value was 27 μm.

[0616] The microscope image and the measurement results of the diameter of Region B (in μm) are shown in Table 5.

[0617] As shown in Table 5, the conductive film obtained using the fluoropolymer has Region B that reflects the design of the metal mask, forming a conductive film with a fine patterning process of several tens of μm.

[0618] [Table 5]

[0619]

[0620] [Evaluation 6: Evaluation of Sheet Resistance of Conductive Film]

[0621] (Fabrication of Conductive Film: for Sheet Resistance Measurement)

[0622] (Process 1)

[0623] On the entire surface of a 75 mm × 75 mm quartz substrate, Mg:Ag was vapor-deposited without using a mask to form a second film with a thickness of 15 nm. The vapor deposition was adjusted so that the volume ratio of Mg to Ag was 1:10. In addition, the total vapor deposition rate of Mg and Ag was set to 0.1 nm / second.

[0624] (Process 2)

[0625] Next, for the quartz substrate vapor-deposited with Mg:Ag on the entire surface, a metal mask having circular openings with a diameter of 150 μm arranged at intervals of 250 μm in the X-axis and Y-axis directions on a plane was used to vapor-deposit a fluoropolymer to fabricate a quartz substrate with a resin film. The vapor deposition of the fluoropolymer was carried out under the condition that the vapor deposition rate was 0.1 nm / second until the measured value by the film thickness gauge attached to the vapor deposition apparatus reached 50 nm.

[0626] (Process 3)

[0627] Next, for the quartz substrate with a resin film fabricated in Process 2, Mg:Ag for forming the first film was vapor-deposited on the entire surface without using a mask from above the resin film to fabricate a conductive film specimen for sheet resistance measurement. The vapor deposition was adjusted so that the volume ratio of Mg to Ag was 1:10 and was carried out until the measured value by the film thickness gauge attached to the vapor deposition apparatus reached 15 nm. In addition, the total vapor deposition rate of Mg and Ag was set to 0.1 nm / second.

[0628] (Fabrication of Conductive Films with Different Thicknesses of the First Film)

[0629] The same operations as in the above-described steps 1 to 3 were performed to produce conductive film specimens for measuring sheet resistance with film thicknesses of 45 nm and 75 nm for the first film in step 3.

[0630] (Measurement of sheet resistance)

[0631] The sheet resistance of the produced conductive film specimen for measuring sheet resistance was measured using a low-resistance resistivity meter (manufactured by Nitto Seiko Analytech Co., Ltd., Loresta). The four-probe detector of Loresta was pressed against the upper surface of the conductive film specimen to measure the sheet resistance.

[0632] [Example 25]

[0633] A resin film was formed using the above-described fluoropolymer D1, and Evaluation 6 was performed.

[0634] [Reference Example 6]

[0635] Mg:Ag was vapor-deposited over the entire surface of a 75 mm × 75 mm quartz substrate without using a mask to form a second film with a film thickness of 15 nm. The vapor deposition was adjusted so that the volume ratio of Mg to Ag was 1:10. In addition, the total vapor deposition rate of Mg and Ag was set to 0.1 nm / second.

[0636] Without forming a resin film and a first film, the sheet resistance measurement of Evaluation 6 was performed.

[0637] Example 25 corresponds to an example.

[0638] The measurement results of the sheet resistance are shown in Figure 12 .

[0639] As a result of the evaluation, the sheet resistance of Example 25 became a low value compared to Reference Example 6 without a first film. In addition, it was confirmed that the sheet resistance decreased as the film thickness of the first film increased among 15 nm, 45 nm, and 75 nm.

[0640] Based on the above results, it was confirmed that the present invention is useful.

[0641] It should be noted that the entire contents of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2020-112962 filed on June 30, 2020 are incorporated herein by reference as the disclosure of the specification of the present invention.

[0642] Explanation of reference numerals

[0643] 1, 2, 3, 11, 12... conductive films; 10, 13, 116... first films; 10A, 13A... first regions; 10B, 13B... second regions; 10X... conductive material; 15, 117... resin films; 20, 118... second films; 20a, 50a... surfaces; 50... substrate; 110... substrate; 111... anode; 115... cathode; P... fluoropolymer; M... mask.

Claims

1. A conductive film having a first region and a second region, wherein the second region exhibits a higher light transmittance than the first region. The conductive film has a first film made of a conductive material and a resin film made of a fluoropolymer. The first film is disposed overlapping at least the first region among the first region and the second region. The resin film is disposed overlapping the second region. The fluoropolymer satisfies the following (1) and (2): (1) When the temperature is increased at a rate of 2 °C per minute under a pressure of 1×10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is below 400 °C; (2) When the temperature is raised at a rate of 2 °C per minute under a pressure of 1×10 -3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C; The fluoropolymer is at least one selected from polymer (1) and polymer (2). Polymer (1) is a fluoropolymer having a main chain with fluoroolefin units and perfluoro(alkyl vinyl ether) units and no aliphatic ring. Polymer (2) is a fluoropolymer having an aliphatic ring in the main chain.

2. The conductive film according to claim 1, further comprising a second film made of a conductive material and spanning the first region and the second region. The light transmittance of the second film is higher than that of the first film at the position overlapping the first region. The second film contacts the first film in the first region.

3. The conductive film according to claim 1 or 2, wherein The surface energy of the resin film is 30 mN / m or less.

4. The conductive film according to claim 1 or 2, wherein The melting point of the fluoropolymer is 300 °C or less.

5. The conductive film according to claim 1 or 2, wherein, The fluoropolymer is amorphous.

6. The conductive film according to claim 1 or 2, wherein The fluoropolymer has a trifluoromethyl moiety. The content of the trifluoromethyl moiety in the fluoropolymer is 0.1 mmol / g or more.

7. The conductive film according to claim 1 or 2, wherein The main chain terminal structure of the fluoropolymer is a methyl ester group and / or a trifluoromethyl group.

8. The conductive film according to claim 1, wherein The fluoropolymer has at least units derived from tetrafluoroethylene and units derived from perfluoroalkyl vinyl ether.

9. An optoelectronic device having the conductive film according to any one of claims 1 to 8.

10. The optoelectronic device according to claim 9, comprising: A substrate; An anode provided on the substrate; A cathode opposite to the anode; and An active layer disposed between the anode and the cathode, wherein the cathode is the conductive film.

11. A method for manufacturing a conductive film, comprising the following steps: A step of forming a resin film made of the fluoropolymer by mask evaporation of a fluoropolymer satisfying the following (1) and (2) on a substrate; and A step of dry coating a conductive material on the resin film, (1) When the temperature is increased at a rate of 2 °C per minute under a pressure of 1×10 -3 Pa, the temperature at which the thermal weight loss rate substantially reaches 100% is below 400 °C; (2) When heating at a rate of 2 °C per minute under a pressure of 1×10 -3 Pa, the temperature range from the temperature at which the thermal weight loss rate reaches 10% to the temperature at which the thermal weight loss rate reaches 90% is within 200 °C; wherein the fluoropolymer is at least one selected from polymer (1) and polymer (2). Polymer (1) is a fluoropolymer having a main chain with fluoroolefin units and perfluoro(alkyl vinyl ether) units and no aliphatic ring. Polymer (2) is a fluoropolymer having an aliphatic ring in the main chain.

12. The manufacturing method of the conductive film according to claim 11, wherein, After the step of dry coating, there is a step of removing the resin film.

13. The method for manufacturing a conductive film according to claim 11 or 12, wherein, Before the step of forming the resin film, there is a step of forming a conductive material film on the surface of the substrate.

Images