WO2008047549A1

WO2008047549A1 - Transparent conductive film substrate and method of forming titanium oxide based transparent conductive film for use therein

Info

Publication number: WO2008047549A1
Application number: PCT/JP2007/068790
Authority: WO
Inventors: Yoshikazu Kondo
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2006-10-12
Filing date: 2007-09-27
Publication date: 2008-04-24
Also published as: JPWO2008047549A1

Abstract

A transparent conductive film substrate having an appropriate transparent conductive film superimposed on a resin base material with the use of a material of low depletion risk without employing a material of depletion risk, such as indium. The transparent conductive film substrate is one having a titanium oxide based transparent conductive film formed on a resin base material, characterized in that the resin base material is transparent and is sequentially laminated with a silicon oxide layer and a layer of doped titanium oxide (composed mainly of the same).

Description

Specification

Transparent conductive film substrate and method for forming titanium oxide transparent conductive film used therefor

The present invention relates to a transparent conductive film substrate having a titanium oxide-based transparent conductive film and a method for forming the transparent conductive film.

Background art

[0002] Currently, transparent conductive films are used in various thin display elements, members, or devices. As a transparent conductive film, ITO (indium tin oxide) is used exclusively because of its high conductive performance. S, ITO demands a new transparent conductive film material that can be converted to indium, which has a high risk of resource depletion. It has been.

[0003] By the way, it has been found that transparent conductivity is developed in a TiO film recently.

(2006 Academic Lecture Meeting of Applied Physics Society, Proceedings 563, 30p—RA—16). As a result, transparent conductivity is developed in the TiO film, and it is expected that TiO without risk of drought will be used as a transparent conductive film material used in thin display members, solar cells and the like.

[0004] On the other hand, thin display materials such as liquid crystal and organic EL, and modules such as solar cells have been used so far in recent years, where demands for weight reduction, thickness reduction, impact resistance, etc. are increasing. Various efforts have been made to make a resin base!

[0005] However, when a TiO transparent conductive film is formed on a resin substrate using the current method, the storage performance, environmental resistance, adhesion performance, etc. of the conductive performance are deteriorated compared to the case where it is formed on a glass substrate. There were various problems.

[0006] These performance degradations are significant compared to ITO, SnO, and ZnO currently used.

Yes

[0007] Compared to ITO, SnO, ZnO, etc., which are used as TiO force and other transparent conductive film materials, when the organic polymer molecules in the resin substrate and the TiO film are in direct contact, It can be inferred that the degree of mutual diffusion is more prominent than other materials. In other words, low content such as oligomers in resin base materials and plastic materials required for base material formation Interface and with the slave component force M_〇 _2, enters the Ti_〇 _second membrane, is estimated that exacerbate conductive performance and adhesion performance.

[0008] In addition, the TiO transparent conductive film according to the current method requires a treatment at a high temperature (300 ° C or 400 ° C or higher) in order to improve conductivity when the conductive film is formed. When a plate is used, heat resistance is insufficient, and the conditions are limited. Therefore, it is difficult to obtain a conductive thin film having sufficient performance on a resin substrate.

[0009] Based on the above knowledge, it is possible to improve by coating a silicon oxide film having a Si element smaller than the titanium element between the substrate and the titanium monoxide layer. By selecting thin film formation conditions that are not required, we have found that the performance is dramatically improved.

The present invention seeks to obtain a transparent conductive film substrate having a good transparent conductive film on a resin base material using a material with a low risk of withering.

Non-Patent Document 1: 67th JSAP Scientific Lecture, Proceedings (Autumn 2006) 566-567, 30p-RA-12-12

Disclosure of the invention

Problems to be solved by the invention

Accordingly, the present invention provides a transparent conductive film substrate having a good transparent conductive film on a resin base material using a low risk material without using a material with a risk of withering such as indium. It is something to try.

Means for solving the problem

[0012] The object of the present invention is achieved by the following means.

[0013] 1. A transparent conductive film substrate having a titanium oxide-based transparent conductive film formed on a resin substrate, the silicon oxide layer being doped on the transparent resin substrate (mainly comprising doped titanium oxide) A transparent conductive film substrate, wherein the layers are sequentially laminated.

[0014] 2. The transparent conductive film substrate according to 1 above, wherein the silicon oxide layer has a thickness of 50 nm or less.

[0015] 3. The transparent resin substrate is made of polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyethersulfone (PES), polycarbonate 3. The transparent conductive film substrate as described in 1 or 2 above, wherein the transparent conductive film substrate includes any one of bonnet (PC) and polymethyl methacrylate (PMMA).

[0016] 4. The transparent conductive substrate according to any one of items 1 to 3, wherein the transparent resin substrate has a hard coat layer.

[0017] 5. The transparent conductive film substrate according to any one of;! To 4 above, wherein the method for forming the silicon oxide layer is an atmospheric pressure plasma CVD method.

[0018] 6. Niobium is contained in the titanium oxide layer-based transparent conductive film,

The transparent conductive film substrate according to any one of 1 to 5.

[0019] 7. The transparent method according to any one of the above ;! to 6, wherein the titanium oxide transparent conductive film is formed by any one of a sputtering method, a vapor deposition method, and a CVD method. Conductive film substrate.

[0020] 8. A method for forming a transparent conductive film for forming a doped titanium oxide (mainly) layer of the transparent conductive film substrate according to any one of ;;

By introducing a mixed gas containing a titanium compound, a dopant raw material, and a reactive gas into a discharge space under an atmospheric pressure or a pressure near atmospheric pressure to form a plasma state, and exposing the resin substrate to the reactive gas in the plasma state. A method for forming a transparent conductive film, comprising forming a layer mainly composed of doped titanium oxide on a resin substrate.

[0021] 9. A method for forming a titanium oxide-based transparent conductive film in the transparent conductive film substrate according to any one of the above;! To 7,

A doped titanium oxide (mainly composed of) layer formed in advance on a transparent resin substrate is brought into a plasma state by introducing a reactive gas into the discharge space at or near atmospheric pressure. A method for forming a titanium oxide-based transparent conductive film, characterized in that resistance is lowered by performing post-treatment by exposure to a reactive gas.

[0022] 10. The method for forming a titanium oxide-based transparent conductive film according to 9, wherein the post-treatment is a treatment performed in an atmosphere containing at least one of hydrogen gas and water vapor.

The invention's effect

[0023] According to the present invention, a transparent conductive film substrate having a titanium oxide-based transparent conductive film excellent in storage performance, environmental resistance, and adhesion performance of conductive performance can be obtained. Brief Description of Drawings

FIG. 1 is a cross-sectional view showing a configuration of a transparent resin substrate having a titanium oxide-based transparent conductive film of the present invention.

FIG. 2 is a schematic view showing an example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention.

FIG. 3 is a schematic diagram showing an example of a direct atmospheric pressure plasma discharge treatment apparatus used in the present invention.

FIG. 4 is a schematic view showing an example of a two-frequency atmospheric pressure plasma discharge device.

FIG. 5 is a schematic view showing an example of a direct atmospheric pressure plasma discharge treatment apparatus implemented by a two-frequency method.

FIG. 6 is a schematic view showing an example of a jet-type apparatus implemented in a two-frequency system.

Explanation of symbols

[0025] 1 Transparent resin substrate

2 Hard coat layer

3 Silicon oxide layer

4 Titanium oxide transparent conductive film

21, 130 Atmospheric pressure plasma discharge treatment equipment

135 Roll rotating electrode

131 Plasma discharge vessel

132 Discharge treatment chamber

136 prismatic fixed electrode

11 First electrode

12 Second electrode

19a, 141 1st power supply

19b, 142 Second power supply

14a, 143 1st Fino Letter

14b, 144 Second filter

150 Gas filling means 151 Gas generator

152 Air inlet

153 Exhaust port

160 Electrode temperature control means

164, 167 Guide roll

165, 166

168, 169 divider

F Substrate

G reaction gas

G, treated exhaust gas

G ° Plasma state gas

22 Gas including discharge gas

23 Gas mixture

24, 25 flow path

27 Electrode cooling material

31 Power supply

41, 41a, 41b electrode

42 Dielectric

43 Discharge space

44 Hollow structure

45 Mixing space

46 Base material

47 Moving stage, moving stage electrode

48 Waste gas exhaust passage

49 Waste gas flow path forming member

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described in detail.

[0027] The present invention mainly comprises a silicon oxide layer and a doped titanium oxide on a transparent resin substrate. The transparent conductive film substrate has a structure in which the layers are sequentially stacked.

[0028] When the Ti_〇 ₂ based transparent conductive film was formed on a resin base material, compared with the time of forming the glass substrate shape, save conductive performance, environmental resistance, adhesion properties, etc., ITO, SnO, Since it was inferior to materials such as ZnO, there were various problems in practical use.

[0029] This is because the titanium oxide TiO layer (thin film) is in contact with organic polymer molecules of the resin base material compared to other materials such as ITO, SnO, and ZnO used as transparent conductive film materials. Therefore, it can be assumed that the degree of diffusion of the components at the interface is more remarkable than other materials (ITO, SnO, ZnO, etc.), that is, oligomers and groups in the resin base material. Low molecular components such as plastic materials required for forming the material are knocked out by plasma energy and molecular collision during film formation, and enter the interface with TiO and the film of TiO to deteriorate the conductivity and adhesion performance. ! /, Presumed to be something.

[0030] Based on these inferences, the present inventor has the idea that a silicon oxide film having a Si element smaller than the titanium element can be improved by coating between the resin base material and the titanium oxide layer. Under the circumstances, the present inventors have found the structure of the present invention, and found that the performance of the TiO-based transparent conductive film is dramatically improved.

[0031] Therefore, in the present invention, a silicon oxide layer and a layer mainly composed of doped titanium oxide are sequentially laminated on the transparent resin substrate, so that a low resistance value can be maintained and the conductive performance can be maintained. A transparent conductive film substrate made of a transparent resin substrate having a titanium oxide-based transparent conductive film having good properties, environmental resistance performance, adhesion performance, and the like can be produced.

FIG. 1 is a cross-sectional view showing the configuration of a transparent resin substrate having a titanium oxide-based transparent conductive film of the present invention. A hard coat layer (CHC) 2 is provided on a transparent resin substrate 1, and this is used as a base material. Further, a silicon oxide layer 3 and a titanium oxide-based transparent conductive film 4 are formed.

[0033] The resin substrate used in the present invention is a transparent resin substrate, which is a transparent resin film. Preferred transparent resin films include acrylic resin (PMMA), acrylonitrile butadiene styrene resin (ABS), ethylene acetate butyl resin (EVAC), ethylene butyl alcohol resin (EVOH), polyamide (PA), polycarbonate (PC), and polybutylene. Terephthalate (PBT), polyethylene (PE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polymethylpente From resins such as polyethylene (PMP), polypropylene (PP), polystyrene (PS), poly (vinyl chloride) (PVC), poly (vinylidene chloride) (PVDC), styrene-acrylonitrile resin (SAN), triacetyl cell port (TAC), etc. It is a film.

[0034] In particular, during post-treatment such as plasma treatment, which will be described later, the transparent resin substrate is polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyethersulfone (PES), By using polycarbonate (PC) and acrylic resin (PMM A), it is possible to produce a transparent, conductive resin substrate that is light and non-destructive.

[0035] It is preferable to have a hard coat layer (CHC) on these transparent resin substrates.

[0036] When the transparent resin substrate has a hard coat layer, the surface becomes harder, scratch resistance and impact resistance can be improved, and adhesion can be further improved.

[0037] As the hard coat layer, an actinic radiation curable resin layer is preferably used. The actinic radiation curable resin layer is a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and a hard coat layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

[0038] Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, Alternatively, an ultraviolet curable epoxy resin or the like is preferably used.

[0039] The ultraviolet curable acrylic urethane resin is generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (Hereinafter, acrylate includes only acrylate as including methacrylate), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. Force S is possible. For example, those described in JP-A-59-151110 can be used. . For example, a mixture of 100 parts of Unidic 17-806 (Dainippon Ink Co., Ltd.) and part of Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

[0040] Examples of the UV curable polyester acrylate resin generally include those which are easily formed when 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer is reacted with polyester polyol. Those described in JP-A-59-151112 can be used.

[0041] As a specific example of an ultraviolet curable epoxy acrylate resin, an epoxy acrylate is an oligomer, and a reactive diluent and a photoinitiator are added to this to react with it. S can be used, and those described in JP-A-1-105738 can be used.

Yes

[0042] Specific examples of the ultraviolet curable polyol atallylate resin include trimethylolprononetriatalylate, ditrimethylolpropanetetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexatalylate, Examples include alkyl-modified dipentaerythritol pentaatarylate.

[0043] Specific examples of photoinitiators of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's keton, α-amiguchi oxime ester, thixanthone, and the like. Derivatives can be mentioned. You may use with a photosensitizer. The above photoinitiator can also be used as a photosensitizer. Moreover, when using an epoxy acrylate-based photoreaction initiator, a sensitizer such as η-butylamine, triethylamine, or tri-η-butylphosphine can be used. The photoreaction initiator or photosensitizer used in the ultraviolet ray curable resin composition is 0.;! To 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the composition. is there.

[0044] Examples of the resin monomer include monomers having one unsaturated double bond such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, butyl acetate, and styrene. Common monomers can be mentioned. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycolo-resin tallylate, divinino benzene, 1,4-cyclohexane di Examples include talirate, 1,4-cyclohexinoresimethinole asiatalylate, the above-mentioned trimethylonorepro pantoriatalylate, and pentaerythritol tetraacrylic ester.

[0045] Examples of commercially available UV curable resins that can be used in the present invention include: Adeka Obtomer KR.BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY — 320B (manufactured by Asahi Denka Co., Ltd.); Koei Hard A—101—KK, A—101—WS, C—302, C—401—N, C—501, M—dish, M—102, T—102 , D—102, NS—Dish, FT—102Q8, MAG—1—P20, AG—106, M—Dish—C (manufactured by Guangei Chemical Co., Ltd.); Se force beam PHC2210 (S), PHC X—9 ( K—3), PHC2213, DP—10, DP—20, DP—30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR90 0 (manufactured by Dainichi Chemical Industries), Aronix M—6100 M-8030, M-8060 (manufactured by Toagosei Co., Ltd.) and the like can be selected as appropriate.

[0046] Specific examples of the compound include trimethylolpropane tritalylate, ditrimethylol nonrepropane tetratalate, pentaerythritol retriate, pentaerythritol tetratalate, dipentaerythritol hexaatalylate, Examples thereof include alkyl-modified dipentaerythritol pentaacrylate.

[0047] These actinic ray curable resin layers can be coated on the transparent substrate by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method.

[0048] As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet light can be used without any limitation. For example, a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is preferably 5 to 150 mj / cm ² , particularly preferably 20 to 100 mj / cm ² . Further, when irradiating actinic radiation, it is preferable to apply tension in the film transport direction, and more preferably to apply tension in the width direction. The tension to be applied is preferably 30 to 300 N / m.

[0049] Examples of the organic solvent for the UV curable resin layer composition coating solution include hydrocarbons (toluene). , Xylene,), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, lactic acid) Methyl), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group), etc., 5% by mass or more, more preferably It is preferable to use the above organic solvent containing 5 to 80% by mass or more.

[0050] As the method for applying the ultraviolet curable resin composition coating solution, the above-described methods can be used. The coating amount is suitably 0.5;! To 30 m as a wet film thickness, and preferably 0.5 to 15 μm. The dry film thickness is 0.1-20 ^ 111, preferably; Particularly preferably, it is 8 to 20 μm.

[0051] The pencil hardness is preferably a hard coat layer of 2H to 8H. Particularly preferred is 3 H to 6H. Pencil hardness is JIS-K using the test pencil specified in JIS-S-6006 after conditioning the prepared hard coat film sample for 2 hours at 25 ° C and 60% relative humidity. According to the pencil hardness evaluation method stipulated by 5400, this is a representation of the hardness of a pencil that has been scratched 10 times with a pencil of each hardness at a weight of 1 kg and no scratches are observed.

[0052] In the present invention, the silicon oxide layer formed on the transparent resin substrate and the hard coat layer in the present invention is a titanium oxide TiO layer (thin film), which is a transparent conductive film material, and a resin substrate directly. It is a layer that avoids contact and prevents components from diffusing each other at the interface, and has a role of suppressing permeation of organic polymers, oligomers, low molecular components and the like in the resin substrate.

[0053] The silicon oxide layer according to the present invention can maintain its transparency by being 50 nm or less.

[0054] The silicon oxide layer according to the present invention can be formed by an atmospheric pressure plasma CVD method. The ability to deposit denser silicon oxide with high insulation and blocking properties by depositing a silicon oxide layer between the resin substrate and the titanium oxide thin film using the atmospheric pressure plasma CVD method S I'll do it. [0055] (Atmospheric pressure plasma CVD method)

Hereinafter, the atmospheric pressure plasma CVD method (hereinafter also referred to as “atmospheric pressure plasma method”) applied to the formation of the silicon oxide layer according to the present invention will be described.

[0056] The atmospheric pressure plasma method for performing plasma CVD processing near atmospheric pressure does not need to be reduced in pressure compared to the plasma CVD method under vacuum, and therefore has a high plasma density as well as high productivity. In addition, the film formation speed is high, and even under high pressure conditions under atmospheric pressure, the mean free path of the gas is very short compared to the conditions of normal CVD, so an extremely flat film can be obtained. Such a flat film has good optical properties.

[0057] The silicon oxide layer according to the present invention is excited by supplying a gas containing a silicon oxide film-forming gas to a discharge space where a high-frequency electric field is generated under atmospheric pressure or a pressure near the atmospheric pressure. Is exposed to the excited gas to form a silicon oxide layer on the transparent resin substrate.

[0058] The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to UOkPa, and 93 kPa to 104 kPa is preferable in order to obtain the good effects described in the present invention.

[0059] The excited gas as used in the present invention means that at least a part of the molecules in the gas move from the existing state to a higher state by obtaining energy. This includes gas molecules containing ionized gas molecules and gas molecules containing ionized gas molecules.

[0060] That is, the pressure between the opposing electrodes (discharge space) is set to atmospheric pressure or a pressure in the vicinity thereof, and a rare gas such as helium, argon, or an inert gas such as nitrogen is used as a discharge gas, and oxidation of tetraethoxysilane or the like is performed. A silicon oxide thin film in which a metal oxide forming gas containing a silicon film forming gas (raw material gas) is introduced between the opposing electrodes, a high frequency voltage is applied between the opposing electrodes to change the raw material gas into a plasma state, and then into a plasma state. The substrate is exposed to the forming gas to form a silicon oxide layer on the transparent substrate.

[0061] Examples of the organic silicon compound used as the raw material gas for forming the silicon oxide thin film (layer) include tetraethylsilane, tetramethylsilane, tetraisopropyl silane, tetrabutylensilane, tetraethoxysilane, tetraisopropoxysilane, tetra Butoxysilane, Dimethylenoresimethoxysilane, Jetinoregetoxysilane, Jetinoresilanedi (2,4-pentane dinate), Methylenotrimethoxysilane, Methylenotriethoxysilane, Ethinotritriethoxysilane Lan, 2- (3,4-epoxycyclohexenole) ethinoretrimethoxysilane, 3-glycidoxy-sidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxy

3-Atalyloxypropyl trimethoxysilane, N-2-aminoethyl-3-aminopropyl

, N-2-aminoethyl-3-amino-propyl methoxysilane, 3-aminopropyltrimethyoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl mono-N- (1,3-dimethyl monobutylidene) Propylamine, N-phenyl-1-3-aminopropyltrimethoxysilane and the like can be mentioned, and any of them can be preferably used in the present invention. Two or more of these can be mixed and used at the same time.

[0062] The reaction promoting gas is introduced to control the reaction and film quality. Examples of the reaction promoting gas include hydrogen, oxygen, nitrogen oxides, ammonia, hydrocarbons, alcohols, organic acids or moisture, and these are mixed in an amount of 0.001% to 30% by volume with respect to the gas. May be used. Of these, oxygen, hydrogen, water, carbon dioxide and the like are preferably used.

[0063] The atmospheric pressure plasma CVD method and an apparatus for performing this will be described in detail later.

Next, the titanium oxide based transparent conductive film according to the present invention will be described in detail.

[0065] In the present invention, the conductive titanium oxide thin film provided on the silicon oxide layer is a layer mainly composed of doped titanium oxide, and is any one of a sputtering method, a vapor deposition method, and a CVD method. It is preferable that the titanium oxide thin film be formed at a low temperature.

[0066] The sputtering method can form a film relatively easily even with a high melting point material or compound, and it is not necessary to dissolve the material that is formed in a thin film that is not necessary in the thermal process unlike the vapor deposition method. It is possible to form a film easily even with a high melting point material such as titanium oxide and the like.

[0067] In order to form an oxide film by sputtering, a reactive gas such as nitrogen gas or oxygen gas is introduced into a metal (for example, titanium) target by sputtering (in an atmosphere of several Pa), Example For example, a substrate is placed facing DC discharge sputtering, RF sputtering, or the target, and the target particles are repelled by the collision of ions or neutral particles on the target surface to adhere to the substrate surface and form a film. A magnetron method may be used in which a magnet is placed near the target to be sputtered to apply a magnetic field, and collisions of ions and neutral particles on the target surface are increased to increase the deposition rate.

[0068] Further, the deposition method, placing the substrate and the film forming material to be cane deposited into the container, and the entire vacuum ^(10-3 to 10-about ⁴ Pa), dissolved feedstock with hot ( Evaporate). As a result, the raw material becomes gas molecules, which collide with and adhere to the substrate to form a film. Depending on the heating and melting method, there are a resistance heating type, an electron beam type, a high frequency induction type, a laser type and the like.

[0069] CVD method, under vacuum (10 ³ about Pa), and take advantage of the reaction at the surface of the gas phase of the gaseous raw material, thin film on a substrate that a component of the elements contained in the raw material molecule It is a method to deposit on.

[0070] A method in which a substrate on which a thin film is to be deposited is heated and a source molecule is decomposed by thermal energy is called thermal CVD, but in the present invention, a method called plasma CVD is preferable. In plasma CVD, a plasma of a gas containing discharge gas and source molecules is generated, and source molecules (for example, source gas containing titanium tetraethoxide) are decomposed by electrons accelerated in the plasma. In these CVD methods, heating is not necessary for the progress of film deposition itself. Further, in the case of a raw material gas that does not easily cause a discharge, a discharge gas such as a rare gas can be added.

[0071] Any of these film forming methods is preferable because a titanium oxide thin film can be formed at a low temperature.

[0072] However, it is more preferable! / As a film forming method, there is an atmospheric pressure plasma CVD method.

[0073] (Atmospheric pressure plasma CVD method)

Atmospheric pressure plasma CVD method (hereinafter also referred to as atmospheric pressure plasma method! /) Is a plasma CVD process near atmospheric pressure (20kPa ~; about UOkPa), so the average free process of gas is very fast because the film formation speed is high. Therefore, it can be advantageously used for forming a titanium oxide-based transparent conductive film according to the present invention.

In the present invention, the layer mainly composed of titanium oxide constituting the titanium oxide-based transparent conductive film is A transparent resin substrate formed by supplying a gas containing a titanium oxide thin film forming gas to a discharge space in which a high-frequency electric field has been generated under atmospheric pressure or a pressure in the vicinity of the discharge space, and preferably forming the hard coat layer Can be formed on the transparent resin substrate through the hard coat layer and the silicon oxide layer.

Here, the layer mainly composed of titanium oxide constituting the titanium oxide-based transparent conductive film is a component such as a dopant that is intentionally added, a trace component (element) taken from a source gas, or a reducing condition. In this film formation, the titanium oxide layer contains a metal component and contains a trace component (dopant) described later. Therefore, it means a film having at least 90% or more of TiO as a composition.

[0076] The layer mainly composed of titanium oxide is preferably an atmospheric pressure plasma C according to the present invention.

This is a doped titanium oxide layer formed by using a titanium oxide thin film forming gas (raw material gas) described later using the VD method.

That is, the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure near it, and a source gas containing a discharge gas and a titanium compound (for example, titanium tetraethoxide) is introduced into the discharge space to form a plasma state. Then, a titanium oxide thin film is formed on the substrate by exposing the substrate to the reactive gas in the plasma state.

Next, a gas for forming the titanium oxide thin film according to the present invention will be described. The gas to be used is basically a gas containing a discharge gas and a raw material gas containing a titanium compound as constituent components.

[0079] The discharge gas is a gas that is in an excited state or a plasma state in the discharge space and plays a role of applying energy to the transparent conductive layer forming gas to be excited or turned into a plasma state. It is a rare gas or an inert gas. It is characterized by using gas. Examples of rare gases include Group 18 elements of the periodic table, specifically, helium, neon, anoregon, krypton, xenon, radon, and the like. The discharge gas is preferably contained at 90.0-99.9% by volume with respect to 100% by volume of the total gas.

[0080] Nitrogen can also be used as the discharge gas, and nitrogen, argon and helium are preferred as the discharge gas.

[0081] In the formation of the titanium oxide thin film according to the present invention, a raw material gas comprising a titanium compound Is a gas that receives energy from the discharge gas in the discharge space and enters an excited state or a plasma state to form a titanium oxide thin film. The titanium compound raw material gas is preferably contained in an amount of 0.01 to 10% by volume, more preferably in the range of 0.01;! To 3% by volume.

[0082] Examples of the titanium compound used in the source gas for forming the titanium oxide-based transparent conductive film include an organic titanium compound, a titanium hydrogen compound, and a titanium halide. Examples of the organic titanium compound include triethoxy titanium, Methoxytitanium, triisopropoxytitanium, tributoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, methinoresimethoxytitanium, ethinoretriethoxytitanium, methinoretriisopropoxytitanium, trietinoretitan, triisopropyltitanium, tributyltitanium, tetraethyltitanium , Tetraisopropyl Titanium, Tetraptinore Titanium, Tetradimethinoreamino Titanium, Dimethinore Titanium Di (2, 4-pentanedionate), Ethyl Titanium Tri (2, 4-pentanedionate), Titanium Tris (2, 4-pentanedionate), titanium tris (acetomethylacetate), triacetoxy titanium, dipropoxypropionyloxy titanium, etc., dibutyryloxy titanium, titanium hydrogen compound as monotitanium hydrogen compound, dititanium Examples of titanium halides such as hydrogen compounds can include trichrome mouth titanium and tetrachrome mouth titanium, and any of them can be used preferably in the present invention. Two or more of these thin film forming gases can be mixed and used at the same time. It can also be dissolved in a solvent and used as a solution.

[0083] (Doping material)

One feature of the present invention is to use doped TiO. Doping

2

As the material for the metal, the valence of the periodic table is different from the Ti element of TiO.

2

In particular, V, Nb, Ta, B, Al, Ga, In, Tl and the like can be mentioned. Among them, a viewpoint of forming a low-resistance transparent conductive film which is an object effect of the present invention. Therefore, Nb, Ta, and V are preferably used.

In the formation of the titanium oxide thin film of the present invention, niobium is contained in the titanium oxide thin film to function as a dopant in the titanium oxide thin film (transparent conductive film), and the carrier (electron) And the conductivity (resistance performance) of the thin film can be improved.

[0085] For this purpose, the following niobium compound is contained in the source gas. Examples of the niobium compound used as a starting material useful for the present invention include organic niobium compounds and niobium water. Examples of organic niobium compounds include pentaethoxyniobium, pentater n-butoxyniobium, pentater n-butoxyniobium, niobium phenoxide, tetrakis (2, 2, 6, 6-tetramethyl-3). , 5-Heptanedioto) niobium, niobium hydroxide compound, niobium hydroxide, niobium halide, niobium trichloride, niobium chloride and the like can be used.

[0086] The amount contained in the source gas is such that the dopant amount in the titanium oxide thin film is within the range of 10% by mass in the present invention! /, Preferably! /,. Adjust medium ratio

In the present invention, in the formation of the titanium oxide thin film, the titanium oxide thin film forming gas contains a reducing gas selected from hydrogen, hydrocarbons such as ethylene and acetylene, and water as a reaction gas. The formed titanium oxide thin film can be made more uniform and dense, and the conductivity, adhesion, and crack resistance can be improved. The reducing gas is 0.0001 to 10% by volume with respect to 100% by volume of the total gas, more preferably 0.00; 5% by volume.

[0088] In the formation of the titanium oxide thin film according to the present invention, an oxidizing gas such as oxygen, ozone, hydrogen peroxide, carbon dioxide or the like may be mixed in an amount of 10% by volume or less.

[0089] By forming the layer mainly composed of titanium oxide by the atmospheric pressure plasma CVD method, a high-quality film with high crystallinity in which the amount of oxygen deficiency and the amount of dopant introduced is controlled on the substrate. The film can be formed at a low temperature, and the area can be increased. In addition, since it is not a vacuum film formation, the adhesion force that does not cause residual solvent and low molecular components to be deposited on the surface from the resin base material and hard coat layer (CHC), for example, in a vacuum does not deteriorate.

[0090] In addition, a thin film mainly composed of titanium oxide doped with niobium as a dopant according to the present invention, after film formation, is further at least hydrogen gas, water vapor under atmospheric pressure or pressure near atmospheric pressure. It is preferable to perform a treatment in which a mixed gas containing the above-mentioned deviation force is introduced into the discharge space as a reactive gas into a plasma state, and the substrate is exposed to the reactive gas in the plasma state.

[0091] Accordingly, in order to improve the conductivity of the conventional doped titanium oxide thin film Heat treatment at the required high temperature (300 ° C or 400 ° C or higher) is no longer necessary, and this makes it possible to have a TiO-based transparent conductive film even when using the resin base material according to the present invention having a low heat resistance temperature. It has been found that the resistance can be lowered by the advantage. In the present invention, as a film forming condition of the metal oxide thin film of 200 ° C. or less, preferably 150 ° C. or less, compared with the above-described post-treatment (heat treatment) at a high temperature, the post-treatment at a relatively low temperature is used. A highly conductive and durable transparent conductive film can be formed on the resin substrate.

Hereinafter, the atmospheric pressure plasma method according to the present invention will be described with reference to the drawings.

There are no particular limitations on the atmospheric pressure plasma discharge treatment apparatus applicable to the present invention, but the following two methods can be given as major examples.

[0094] One method is a method called a plasma jet type atmospheric pressure plasma discharge treatment apparatus, in which a high-frequency voltage is applied between opposing electrodes, a mixed gas containing a discharge gas is supplied between the opposing electrodes, and the mixing is performed. In this method, the gas is turned into plasma, and then the plasma mixed gas and the transparent conductive layer forming gas are combined and mixed, and then sprayed onto the transparent substrate to form the transparent conductive layer.

[0095] The other method is a direct type atmospheric pressure plasma discharge treatment apparatus, which mixes a mixed gas containing a discharge gas and a transparent conductive layer forming gas, and then, between the opposing electrodes, a transparent substrate. In this state, the gas is introduced into the discharge space and a high frequency voltage is applied between the opposing electrodes to form a transparent conductive layer on the transparent substrate.

FIG. 2 is a schematic view showing an example of a plasma jet type atmospheric pressure plasma discharge treatment apparatus according to the present invention. The present invention is not limited to this. In addition, the following explanation may include assertive expressions for terms, etc., but it is a preferred example of the present invention and limits the meaning and technical scope of the terms of the present invention. It is not a thing.

In FIG. 2, the atmospheric pressure plasma discharge treatment device 21 includes a pair of electrodes connected to a power source 31.

41a, 41b force 2 pairs parallel. At least one of the electrodes 41a and 41b is covered with a dielectric 42, and a high frequency voltage is applied by a power source 31 to a discharge space 43 formed between the electrodes.

[0098] The inside of the electrodes 41a and 41b has a hollow structure 44 so that heat generated by the discharge can be taken by water, oil, etc. during discharge and heat exchange can be performed so as to maintain a stable temperature. Na It is.

[0099] Further, by each gas supply means not described, the gas 22 containing the discharge gas necessary for the discharge is supplied to the discharge space 43 through the flow path 24, and a high frequency voltage is applied to the discharge space 43. When the plasma discharge is generated, the gas 22 including the discharge gas is turned into plasma. The gas 22 that has been made into a plasma jets into the mixing space 45.

[0100] On the other hand, the mixed gas 23 containing the source gas necessary for forming the thin film supplied by each gas supply means (not shown) passes through the flow path 25 and is also transported to the mixed space 45, where it is converted into the plasma. A transparent resin substrate that is merged with and mixed with the discharged discharge gas 22 and placed on a moving stage 47 or a transparent resin substrate having a hard coat layer on the outermost surface (hereinafter collectively referred to as a base material! /) Sprayed up.

The thin film forming mixed gas in contact with the plasma mixed gas is activated by the energy of the plasma to cause a chemical reaction, and a desired thin film is formed on the substrate 46.

This plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a mixed gas containing a raw material gas necessary for forming a thin film is sandwiched or surrounded by an activated discharge gas.

[0103] The moving stage 47 on which the substrate is mounted has a structure capable of reciprocating scanning or continuous scanning, and if necessary, heat exchange similar to the above electrode is performed so that the temperature of the substrate can be maintained. It has a structure that can

[0104] Further, a waste gas exhaust passage 48 for exhausting the gas blown onto the substrate 46 can be provided as necessary. Thereby, unnecessary by-products formed in the space can be quickly removed from the discharge space 45 or the substrate 46.

[0105] This plasma jet type atmospheric pressure plasma discharge treatment apparatus has a structure in which a discharge gas is turned into plasma and activated, and then merged with a mixed gas containing a raw material gas necessary for forming a thin film such as a silicon oxide layer or a titanium oxide layer. It has become. As a result, it is possible to prevent deposits from being deposited on the electrode surface. As described in Japanese Patent Application No. 2003-095367, an antifouling film or the like is attached to the electrode surface to prevent discharge before discharge. A structure in which a gas and a gas necessary for forming the transparent conductive layer are mixed can also be used.

[0106] In the apparatus shown in Fig. 2, the high-frequency power supply is performed in one frequency band. As described in Japanese Patent Laid-Open No. 2003-96569, a desired two-frequency system in which a power source having a different frequency is provided for each electrode can be used.

[0107] Further, the ability of film formation can be improved by arranging a plurality of plasma jet type atmospheric pressure plasma discharge treatment apparatuses in the scanning direction of a plurality of stages.

[0108] In addition, this plasma jet type atmospheric pressure plasma discharge treatment apparatus shows! /, NA! /

By making a structure that surrounds the entire stage and does not allow outside air to enter, the inside of the apparatus can be placed in a constant gas atmosphere, and a desired high-quality thin film can be formed.

FIG. 3 is a schematic view showing an example of a direct atmospheric pressure plasma discharge treatment apparatus used in the present invention.

In the direct type atmospheric pressure plasma discharge processing apparatus shown in FIG. 3, two electrodes 41 connected to a power source 31 are provided side by side so as to be parallel to the moving stage electrode 47, respectively. At least one of the electrodes 41 and 47 is covered with a dielectric 42, and a high frequency voltage is applied by the electrode 31 to a space 43 formed between the electrodes 41 and 47. .

[0111] It should be noted that the inside of the electrodes 41, 47 has a hollow structure 44, so that heat generated by the discharge can be taken out by water, oil, etc. during discharge, and heat exchange can be performed so as to maintain a stable temperature. It has become.

[0112] Further, by each gas supply means (not shown), the gas 22 containing the discharge gas necessary for the discharge passes through the flow path 24, and the mixed gas 23 containing the source gas necessary for forming the thin film flows. It passes through channel 25 and merges and mixes in mixing space 45. The mixed gas G passes between the electrodes 41 and is supplied to the space 43 between the electrodes 41 and 47. When a high frequency voltage is applied to the space 43, plasma discharge is generated, and the gas G is turned into plasma. The The raw gas for forming the thin film is activated by the gas G that has been turned into a plasma, causing a chemical reaction, and a desired thin film is formed on the substrate 46.

[0113] The stage 47 on which the substrate is mounted has a structure capable of reciprocating scanning or continuous scanning, and heat exchange similar to the above electrode is performed so that the temperature of the substrate can be maintained as necessary. It has a structure that can

[0114] Further, a waste gas exhaust passage 48 for exhausting the gas blown onto the substrate 46 can be provided as necessary. This quickly releases unwanted by-products formed in the space. It can be removed from the electric space 45 or the base material 46.

[0115] Similarly, as described in Japanese Patent Application No. 2003-095367, a gas necessary for forming a discharge gas and a transparent conductive layer before discharge can be obtained by attaching a dirt prevention film to the electrode surface. It can also be set as the structure to mix.

[0116] Also in the apparatus shown in Fig. 3, for example, as described in Japanese Patent Application Laid-Open No. 2003-96569, a two-frequency method similar to the method described later in which a power source having a different frequency is installed on each electrode. Can also be implemented.

[0117] Further, it is possible to improve the film forming capability by arranging a plurality of direct type atmospheric pressure plasma discharge treatment apparatuses in the scanning direction of a plurality of stages.

[0118] Further, although not shown in this direct type atmospheric pressure plasma discharge treatment apparatus, the inside of the apparatus has a certain gas atmosphere by surrounding the electrodes and the stage so that outside air does not enter. A desired high-quality thin film can be formed.

[0119] As an atmospheric pressure plasma discharge apparatus, for example, when the discharge gas is mainly helium or argon, the same apparatus as each atmospheric pressure plasma discharge apparatus described in the above figure can be used. When nitrogen gas is the main component of the discharge gas, it is preferable to use an atmospheric pressure plasma discharge device that uses two high frequencies as shown in Fig. 4 below.

FIG. 4 is a schematic view showing an example of a two-frequency atmospheric pressure plasma discharge apparatus.

[0121] The outline of the device is almost the same as the configuration shown in FIG. 1. Force roll rotating electrode (first electrode)

In the discharge space (between the counter electrodes) 132 between the 135 and the square tube-shaped fixed electrode group (second electrode) 136, the tool rotating electrode (first electrode) 135 has a frequency ω from the first power source 141. High frequency voltage

1

V and the square tube type fixed electrode group (second electrode) 136 are connected to the second power source 142 at the frequency ω.

1 2 High frequency voltage V is applied.

[0122] Between the roll rotating electrode (first electrode) 135 and the first power source 141, the first filter is arranged so that the current from the first power source 141 flows toward the roll rotating electrode (first electrode) 135. 143 is installed. The first filter 1 is designed to make it difficult for current from the first power source 141 to pass to the ground side and to easily pass current from the second power source 142 to the ground side. In addition, a second filter 144 is installed between the square tube-type fixed electrode group (second electrode) 136 and the second power source 142 so that the current from the second power source flows toward the second electrode. ing. 2nd The filter 144 is designed to pass the current from the second power source 142 to the ground side and to easily pass the current from the first power source 141 to the ground side.

[0123] The roll rotating electrode 135 may be the second electrode, and the rectangular tube-shaped fixed electrode group 136 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply is capable of applying a higher high-frequency voltage (V> V) than the second power supply.

1 2

In addition, the frequency has the ability to be ω and ω.

1 2

[0124] The discharge condition in the present invention is that two or more electric fields having different frequencies are applied to the discharge space, and an electric field obtained by superimposing the first high-frequency electric field and the second high-frequency electric field is applied.

[0125] The frequency ω 2 of the second high-frequency electric field is higher than the frequency ω ΐ of the first high-frequency electric field, the strength VI of the first high-frequency electric field VI, and the strength of the second high-frequency electric field. The relationship between V2 and the strength IV of the discharge starting electric field is

V1≥IV> V2

Or V1> IV≥V2

The output density of the second high frequency electric field is lW / cm ² or more.

[0126] The high frequency means a frequency having a frequency of at least 0.5 kHz.

[0127] When both of the superimposed high-frequency electric fields are sine waves, the frequency ω 1 of the first high-frequency electric field is superimposed on the frequency ω 2 of the second high-frequency electric field higher than the frequency ω 1. The waveform is a sawtooth waveform in which a sine wave with a higher frequency ω 2 is superimposed on a sine wave with a frequency ω 1.

[0128] In the present invention, the strength of the discharge starting electric field refers to the discharge space (electrode configuration etc.) used in the actual thin film formation method and the reaction conditions (gas conditions etc.). The lowest electric field strength that can be used. The discharge starting electric field strength is governed by the discharge starting electric field strength of the discharge gas in the same discharge space, which varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes.

[0129] Force described above for superposition of continuous wave such as sine wave Not limited to this, both pulse wave, one wave may be continuous wave and the other may be pulse wave . Further, it may have a third electric field having a different frequency.

[0130] As a specific method of applying a high-frequency electric field to the same discharge space, as described above, A first power source that applies a first high-frequency electric field having a frequency ω って and an electric field strength VI is connected to the first electrode constituting the counter electrode, and a frequency ω 2 and an electric field strength V2 is connected to the second electrode. An atmospheric pressure plasma discharge treatment apparatus connected to a second power source for applying a second high-frequency electric field is used.

[0131] Also, the first filter is connected to the first electrode, the first power supply, or any of them, and the second filter is connected to the second electrode, the second power supply, or any of them. The first filter facilitates the passage of the current of the first high-frequency electric field from the first power source to the first electrode, grounds the current of the second high-frequency electric field, and the first power source from the second power source It is difficult to pass the current of the second high-frequency electric field to. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, Use a power supply with a function that makes it difficult to pass the current of the first high-frequency electric field to the power supply. Here, the phrase “difficult to pass” preferably means that only 20% or less, more preferably 10% or less of the current can pass. On the contrary, being easy to pass means preferably passing 80% or more, more preferably 90% or more of the current.

[0132] For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several H can be used depending on the frequency of the second power supply. The second filter can be used as a filter by using a coil of 10 H or higher according to the frequency of the first power supply and grounding it through these coils or capacitors.

[0133] Further, the first power source of the atmospheric pressure plasma discharge treatment apparatus of the present invention has the ability to apply a higher electric field strength than the second power source!

Here, the applied electric field strength and the discharge start electric field strength as used in the present invention are those measured by the following methods.

[0135] Measurement method of applied electric field strength VI and V2 (unit: kV / mm):

A high-frequency voltage probe (P6015A) is installed at each electrode, and the output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.

[0136] Measurement method of electric field intensity IV (unit: kV / mm):

A discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the discharge starts. The full electric field strength is defined as the discharge starting electric field strength IV. The measuring instrument is the same as the applied electric field strength measurement.

[0137] When the discharge gas is nitrogen gas according to the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first application By applying the electric field strength as Vl≥3.7kV / mm, the nitrogen gas can be excited and put into a plasma state.

Here, the frequency of the first power supply is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1kHz.

[0139] On the other hand, the frequency of the second power supply is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is about 200MHz! /.

[0140] The application of a high-frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge starting electric field strength by the first high-frequency electric field, and the second high-frequency electric field. It is important to form a thin film by increasing the plasma density due to the high frequency and high power density.

[0141] The atmospheric pressure plasma discharge treatment apparatus used in the present invention, as described above, discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and leaves the gas between the counter electrodes or A thin film is formed on the substrate by exposing the substrate transferred between the electrodes to the plasma state gas.

[0142] In the apparatus shown in Fig. 3, a power supply having a different frequency is installed in each electrode, and the two-frequency system can be similarly implemented as an apparatus as shown in Fig. 5, for example. Where 31a is the first power supply, 31b is the second power supply, 101a is the first filter, and 101b is the second filter.

[0143] Further, a discharge is caused between the counter electrodes, the gas introduced between the counter electrodes is excited or put into a plasma state, and a gas in an excited or plasma state is blown out of the counter electrode in a jet form. This is performed in a two-frequency system in which a thin film is formed on the substrate by exposing the substrate in the vicinity of the counter electrode (standing still, transported! /, Or even! /,). Jet type equipment An example of the device is shown schematically in FIG.

[0144] The jet type atmospheric pressure plasma discharge treatment apparatus has a counter electrode composed of a first electrode 11 and a second electrode 12, and the first electrode 11 is connected to the first electrode 11 between the counter electrodes. A first high-frequency electric field of frequency ω 1 from power source 19a, electric field strength VI, current II is applied, and second electrode 12 has a second frequency ω 2, electric field strength V2, current 12 from second power source 19b. The high-frequency electric field is applied. The first power supply 19a has a higher high-frequency electric field strength (VI> V2) than the second power supply 19b, and the first frequency ωΐ of the first power supply 19a is lower than the second frequency ω2 of the second power supply 19b. Apply frequency.

[0145] A first filter 14a is installed between the first electrode 11 and the first power supply 19a, and it is easy to pass the current from the first power supply 19a to the first electrode 11, and the second power supply It is designed so that the current from 19b is grounded and the current from the second power source 19b to the first power source 19a passes.

[0146] In addition, a second filter 14b is installed between the second electrode 12 and the second power source 19b to facilitate passage of current from the second power source 19b to the second electrode. Designed to source the current from 19a and make it difficult to pass the current from the first power source 19a to the second power source.

[0147] The thin film forming gas G described above is introduced from the gas supply means into the gap between the first electrode 11 and the second electrode 12 (discharge space) 13, and the first power source 19a and the second power source 19b The above-described high-frequency electric field is applied between the first electrode 11 and the second electrode 12 to generate a discharge, and the thin film forming gas G described above is in a plasma state while jetting in the lower side of the counter electrode (lower side of the paper). Blow out, fill the processing space created by the lower surface of the counter electrode and the base material F with a plasma gas G °, and form a thin film on the base material F near the processing position 14. During the thin film formation, although not shown, the electrode heats or cools the electrode through the pipe from the electrode temperature adjusting means. Depending on the temperature of the substrate during the plasma discharge treatment, the physical properties, composition, etc. of the resulting thin film may change, and it is desirable to appropriately control this. An insulating material such as distilled water or oil is preferably used as the temperature control medium. During the plasma discharge treatment, it is desirable to adjust the temperature inside the electrode evenly so that the temperature unevenness force S in the width direction or longitudinal direction of the substrate does not occur as much as possible. [0148] Fig. 6 shows a measuring instrument used for measuring the applied electric field strength and the discharge starting electric field strength and the measurement position. 15 and 16 are high-frequency voltage probes, and 17 and 18 are oscilloscopes.

[0149] By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment devices in parallel with the transport direction of the substrate and simultaneously discharging the gas in the same plasma state, it becomes possible to form a plurality of thin films at the same position, A desired film thickness can be formed in a short time. In addition, multiple thin films with different layers can be formed by arranging multiple units in parallel with the transport direction of the base material F, supplying different thin film forming gases to each device, and jetting gas in different plasma states. .

[0150] Each of the electrodes described above is obtained by thermally spraying ceramics as a dielectric material on a conductive metallic base material and then sealing with an inorganic compound sealing material. The ceramic dielectric need only have a thickness of about 1 mm. As the ceramic material used for thermal spraying, ananoremina 'silicon nitride or the like is preferably used. Among these, alumina is particularly preferred because it is easy to process. In addition, the dielectric layer may be a lining-treated dielectric provided with an inorganic material by lining.

[0151] Examples of the conductive metallic base material include titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, and the like, a composite material of iron and ceramics, or a composite of aluminum and ceramics. The ability to mention the material Titanium metal or titanium alloy is particularly preferred for reasons described below!

[0152] The distance between the first electrode and the second electrode facing each other is such that when a dielectric is provided on one of the electrodes, the surface of the dielectric and the surface of the conductive metallic base material of the other electrode This is the shortest distance. When dielectrics are provided on both electrodes, this is the shortest distance between the dielectric surfaces. The distance between the electrodes is determined by taking into account the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of carrying out the process, 0.;! To 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

[0153] The plasma discharge treatment vessel 131 in Fig. 4 may be made of metal as long as it can be insulated from the force electrode for which a treatment vessel made of Pyrex (registered trademark) glass or the like is preferably used. For example, the inner surface of an aluminum or stainless steel frame Ceramic metal spraying may be performed on the metal frame, which may be pasted with a mid resin or the like, to provide insulation. In Fig. 1, it is preferable to cover both sides of the parallel electrodes (up to the surface of the base material) with an object of the above-mentioned material.

As the first power supply (high frequency power supply) installed in the atmospheric pressure plasma discharge treatment apparatus of the present invention

A1 Shinko Electric 3kHz SPG3-4500

A2 Shinko Electric 5kHz SPG5-4500

A3 Kasuga Electric 15kHz AGI-023

A4 Shinko Electric 50kHz SPG50— 4500

A5 HEIDEN Laboratory 100kHz water PHF-6k

A6 Pearl Industry 200kHz CF— 2000— 200k

A7 Pearl Industry 400kHz CF— 2000— 400k

And the like, and any of them can be used.

[0155] As the second power source (high frequency power source),

Applied power supply symbol Manufacturer Frequency Product name

B1 Nonore Industry 800kHz CF—2000 800k

B2 Pearl Industrial 2MHz CF— 2000— 2M

B3 Norore Industries 13. 56MHz CF— 5000 13M

B4 NORORE INDUSTRY 27MHz CF- 2000- 27M

B5 Norore Industries 150MHz CF- 2000- 150M

And the like, and any of them can be preferably used.

[0156] Of the above power sources, * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

[0157] In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field to the atmospheric pressure plasma discharge treatment apparatus.

[0158] In the present invention, the power applied between the opposing electrodes is to supply power (power density) of lW / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas and to generate plasma. Raised And applying energy to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area where discharge occurs between the electrodes.

[0159] Also, the first electrode (first high-frequency electric field), by supplying a lW / cm ² or more power (power density), while maintaining uniformity of the second high-frequency electric field, power density Can be improved. As a result, a further uniform high-density plasma can be generated, and a further improvement in film formation speed and improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

[0160] Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called continuous mode and an intermittent oscillation mode called pulse mode that performs ON / OFF intermittently. Either of them can be used, but at least the second electrode side (second The high-frequency electric field of the continuous sine wave is preferable because a denser and better quality film can be obtained. Example

[0161] The present invention will be specifically described below with reference to examples.

[0162] Examples

The performance of the transparent conductive film produced in the examples was evaluated according to the following method.

[0163] [Evaluation method]

(1) Transmission performance

Membrane permeability = (Transmissivity of substrate with transparent conductive film) / (Transmittance of substrate without transparent conductive film)

)

X 100

It was.

The transmittance at a wavelength of 550 nm was used as a representative value. Measurement 製 ASCO V-530

(2) Resistance performance

Measuring machine Mitsubishi Chemical Hiresta MCP-HT450 and probe MCP-HTP12 were used. According to JIS K 7194, the surface resistivity (Ω) / mouth was measured.

[0164] (3) Adhesion performance After making a grid-like scratch on the surface of the transparent conductive film using a cutter, the same part is peeled off using an adhesive cellophane tape [Nichiban Co., Ltd., industrial 24mm width cellophane tape]. The area of the non-exposed part is shown as a percentage. (Tape peel test). In other words, 100/100 when not peeled off at all, and 0/100 when the entire surface peeled off.

[0165]

Initial evaluation:

After the film formation, 12 hours was left in a normal atmosphere (25 ° C., humidity 50% RH) to evaluate the above (1) to (3).

Evaluation after storage at high temperature and high humidity:

The above (1) to (3) were evaluated by leaving it for 1000 hours in an atmosphere at a temperature of 60 ° C and a humidity of 90% RH, and then in a normal atmosphere for 12 hours.

[0166] In the evaluation, ◎, ○, △, and X are respectively

A: Clear enough performance for practical use!

〇: Satisfies the performance required for practical use!

(Triangle | delta): There is no trouble and performance in practical use.

X: Performance impeding practical use.

It is shown at the same time.

[0167] <Preparation of transparent conductive film substrate>

Examples as shown in Table 1, combining clear hard coat (CHC) layer, undercoat (silicon oxide layer), titanium oxide transparent conductive film, and post-treatment under the following conditions;! ~ 3, comparative example 1 transparent conductive film substrate was produced.

Using a biaxially stretched polyethylene terephthalate film with a size of 200mm x 200mm and a thickness of 125m as the transparent resin substrate, the clear hard coat (CHC) layer and the undercoat coating (silicon oxide layer) are sequentially laminated in the following procedure. Used as a resin base material.

[0169] <Hard coat layer application>

(Clear hard coat layer (CHC) coating composition) Dipentaerythritol Hexaatalyle 60 parts by mass Dipentaerythritol Hexaatalylate 2 20 parts by mass Dipentaerythritol Hexatalylate Trimer or higher component 20 parts by mass Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.)

50 parts by mass of isopropylenoleanolone

Ethinole acetate 50 parts by mass

50 parts by mass

The clear hard coat layer coating composition was extrusion coated onto the film, then dried in a drying section set at 80 ° C., and then irradiated with ultraviolet rays using an ultraviolet irradiation facility. The UV lamp used an output of 3kW (high pressure mercury type manufactured by Eye Graphic Co., Ltd.), and the illuminance was 0.1 lW / cm ² . In addition, the holding plate was set so that the surface temperature of the substrate was 25 ° C during irradiation.

[0170] A transparent resin film substrate having a clear hard coat layer (CHC layer) having a film thickness of 6 am was obtained. Using the transparent resin film substrate as a resin base material, the following undercoating was performed.

[0172] <Undercoating>

In Examples 2 and 3, the SiO film was coated using the direct atmospheric pressure plasma (CVD) method.

[Atmospheric pressure plasma (CVD) method]

A high frequency was applied at two frequencies using the apparatus shown in FIG.

[0174] (Power Conditions) Power 1: Low frequency side 1 OOKHz 5w / cm ²

Power supply 2: High frequency side 13.56MHz 6W / cm ²

(Gas condition) Tetraethoxysilane (TEOS) was vaporized by bubbling as a raw material for SiO. N gas: lslm, 40 ° C.

[0175] Discharge gas N: 60slm

Reaction promoting gas O: 6slm

[Moving platform electrode] The moving platform electrode is attracted to the surface of a 200mm wide and 300mm long titanium plate. Alumina was produced by thermal spraying as the electrical material. In addition, a heat sink and a heater were installed on the back side so that the temperature of the substrate surface was always constant.

[0176] Dielectric thickness: lmm

Electrode width: 200mm

Material: Titanium

Temperature of moving platform electrode: 100 ° C

A substrate was placed on the movable gantry electrode, and a thin film was formed while continuously scanning to produce a silicon oxide thin film with the desired film thickness (shown in Table 1).

[0177] Example 1 was performed by a vacuum deposition method using an electron beam (EB) heating method.

[0178] [Vapor deposition method]

Using a mixture of silicon monoxide and silicon as a deposition source and supplying oxygen gas, a deposited film of silicon oxide having a thickness of 50 nm was formed under the following deposition conditions.

[0179] (Vapor deposition conditions)

Degree of vacuum in the deposition chamber; 0.02 Pa

Electron beam power; 35kW

Cold plate insulation temperature; 150 ° C

(1) Atmospheric pressure plasma (CVD) method

In Example 3, a titanium oxide-based transparent conductive film layer was formed by an atmospheric pressure plasma (CVD) method.

Yes

[0180] A remote atmospheric pressure plasma method (two-frequency method described in JP-A-2004-068143) was used. Figure 2 shows the equipment used.

[0181] (Power requirements)

Power supply 1: (SEREN high frequency power supply) Low frequency side lOOKHz 5w / cm ²

Power supply 2: (Pearl Industries high frequency power supply) High frequency side 13. 56MHz 3W / cm ² (Electrode condition) Electrode square electrode is ceramic sprayed as a dielectric to 30mm square hollow titanium pipe! / Made.

[0182] Dielectric thickness: lmm Electrode width: 300mm

Applied electrode temperature: 90 ° C

Raw material introduction slit gap: 1.5 mm

Electrode (discharge) gap: 0 · 5mm

Moving platform Electrode gap: 1. Omm

(Gas condition)

Tetrizopropoxytitanium (TIPT) was vaporized by publishing as a raw material for TiO (N gas: 3 slm, 60 ° C).

[0183] Further, pentaethoxyniobium as a dopant was similarly vaporized by bubbling (N 2 gas: 3 slm, 80 ° C).

[0184] This mixed gas was introduced from the raw material introduction slit. Further, the following discharge gas and reaction gas were mixed in the following proportions and introduced from the interelectrode (discharge) slit.

[0185] Discharge gas N: 50slm + 50slm

Reaction gas H: 0.5slm + 0.5slm

(Moving base electrode)

The movable gantry electrode was manufactured by spraying alumina as a dielectric on the surface of a 200 mm wide and 300 mm long titanium plate. In addition, a heat sink and a heater were installed on the back side so that the temperature of the substrate surface was always constant.

[0186] Dielectric thickness: lmm

Electrode width: 200mm

Material: Titanium

Temperature of moving gantry electrode: The temperature of the gantry was set so that the surface of the base material was at the temperature shown in Table 1.

[0187] The substrate was placed on the movable gantry electrode, and the film was formed while continuously scanning.

Nb-doped TiO film was prepared.

In Comparative Example and Examples 1 and 2, a titanium oxide transparent conductive film was formed by the following sputtering method.

[0189] (2) Sputtering method TiO powder (99.99%) and NbO powder (99.99%) were mixed at a ratio of 95: 5, then shaped and fired to produce a 20cm diameter TiO-NbO-based high-density sintered body. .

[0190] The obtained sintered body was used as a target for deposition in a batch type DC magnetron sputtering apparatus. The magnetic flux density on the target was lOOOGauss. The ultimate vacuum within the chamber one, not more than 5 X 10- ⁶ Pa, gas pressure during the sputtering was set to 2 X 10- ⁴ Pa. Argon gas and a mixed gas of argon and oxygen were used as the sputtering gas and introduced into the chamber as a separate system. Under these conditions, a TiO: Nb-based thin film having a film thickness of lOOnm was formed on the base material held on a heat insulating plate at 150 ° C. The quantity ratio of argon and oxygen was 10: 1, 100: 1, 500: 1, 1000: 1, and the conditions of 500: 1, which were the best in permeation performance and resistance performance, were used as representative values. .

[0191] 《Post-processing (AGP annealing) condition》

(1) Atmospheric pressure plasma method (Direct)

Atmospheric pressure plasma discharge treatment (single frequency) was performed on a substrate on which a thin film containing TiO as the main component was formed in advance by sputtering or atmospheric pressure plasma.

[0192] The apparatus shown in Fig. 3 was used.

[0193] (Power supply conditions)

Power supply: (High frequency power supply manufactured by Adtech Plasma Technology) 27MHz 10W / cm ²

(Electrode condition)

The electrode square electrode was fabricated by ceramic spraying as a dielectric material on a 30mm square hollow titanium pipe.

[0194] Dielectric thickness: lmm

Electrode width: 300mm

Applied electrode temperature: 90 ° C

Electrode (discharge) gap: 2.0 mm

(Gas condition)

Discharge gas: Ar / 60slm

Reaction promoting gas H / lslm

[Moving platform] Temperature of moving platform electrode: AGP (atmospheric pressure plasma method) annealing is shown in Table 1.

[0195] Under the above-described conditions, a substrate on which a thin film containing TiO as a main component was formed was placed on the movable gantry electrode, and plasma was irradiated for 30 seconds while continuously scanning.

[0196] Under the above conditions, each of CHC, silicon oxide subbing, and titanium oxide-based conductive film was laminated by changing the production method as shown in Table 1, respectively. A conductive film substrate was produced.

[0197] The transparent conductive film substrate of Example 4 was produced as follows.

[0198] As in Example 3, except that the titanium oxide transparent conductive film was formed by atmospheric pressure plasma.

A titanium oxide transparent conductive film having tantalum as a dopant was formed using the (CVD) method under the following conditions for forming a titanium oxide transparent conductive film.

[0199] [Gas conditions]

(Raw material gas)

Tetrizopropoxytitanium (TIPT) publishing as a raw material for TiO film formation

2

More vaporized (N gas: 3slm, 60.C).

2

[0200] Pentaethoxytantalum was vaporized by bubbling as a doping material (N gas

2 S: 3slm ゝ 90. C).

[0201] (Discharge gas) N: 60slm

2

(Auxiliary gas) H: 1 · Oslm

2

Other conditions were the same as in Example 3. A base material is placed on the movable gantry electrode, and film formation is performed while continuously scanning to form a Ta-doped TiO film of about 100 nm, and the transmission of Example 4 is performed.

2

A bright conductive film substrate was produced.

[0202] The transparent conductive film substrates of Examples;! To 4 were evaluated for the permeation performance, resistance performance, and adhesion performance after storage under the initial or high temperature and high humidity conditions.

[0203] Table 1 shows the results of evaluation by the above evaluation methods.

[0204] [Table 1]

The transparent conductive film substrate of Comparative Example 1 has a poor resistance performance and particularly poor adhesion to the base material, and the permeation performance after storage under high temperature and high humidity conditions. It can be seen that is also lower than the others. It can also be seen that the formation of the silicon oxide layer is more preferable than the vapor deposition method from the viewpoint of adhesion. When it gets thicker The transmission performance is slightly reduced.

Claims

The scope of the claims

[1] A transparent conductive film substrate having a titanium oxide-based transparent conductive film formed on a resin substrate,

A transparent conductive film substrate, wherein a silicon oxide layer and a doped titanium oxide (mainly) layer are sequentially laminated on a transparent resin substrate.

[2] The transparent conductive film substrate according to [1], wherein the silicon oxide layer has a thickness of 50 nm or less.

[3] The transparent resin substrate is made of polyethylene terephthalate (PET), triacetyl cellulose (T

AC), polyethylene naphthalate (PEN), polyethersulfone (PES), polycarbonate (PC), polymethyl methacrylate (PMMA) The transparent conductive film substrate according to item 1 or item 2.

[4] The transparent conductive substrate according to any one of [1] to [3], wherein the transparent resin substrate has a hard coat layer.

[5] The transparent conductive film substrate according to any one of [1] to [4], wherein the silicon oxide layer is formed by an atmospheric pressure plasma CVD method.

[6] The transparent conductive film substrate according to any one of [1] to [5], wherein the titanium oxide layer-based transparent conductive film contains niobium.

[7] The method according to any one of claims 1 to 6, wherein the method of forming the titanium oxide-based transparent conductive film is any one of a sputtering method, a vapor deposition method, and a CVD method. The transparent conductive film substrate according to item.

[8] A method for forming a transparent conductive film, comprising forming a titanium oxide (based mainly) layer doped on the transparent conductive film substrate according to any one of claims 1 to 7. A mixed gas containing a titanium compound, a dopant raw material, and a reactive gas is introduced into a discharge space under a pressure at or near atmospheric pressure to form a plasma state, and the resin base material is a reactive gas in the plasma state. A method for forming a transparent conductive film, characterized in that a layer mainly composed of doped titanium oxide is formed on a resin base material by exposing to water.

[9] A method for forming a titanium oxide-based transparent conductive film in the transparent conductive film substrate according to any one of claims 1 to 7, A doped titanium oxide (mainly composed of) layer formed in advance on a transparent resin substrate is brought into a plasma state by introducing a reactive gas into the discharge space at or near atmospheric pressure. A method for forming a titanium oxide-based transparent conductive film, characterized in that resistance is lowered by performing post-treatment by exposure to a reactive gas.

10. The method for forming a titanium oxide-based transparent conductive film according to claim 9, wherein the post-treatment is a treatment performed in an atmosphere containing at least one of hydrogen gas and water vapor.