JP6729402B2 - Conductive film, touch panel, and method for manufacturing conductive film - Google Patents

Description

The present invention relates to a conductive film, a touch panel, and a method for manufacturing a conductive film. More specifically, the present invention relates to a conductive film having a resin base material and a conductive film, a touch panel including the conductive film, and a method for manufacturing the conductive film.

A conductive film in which a conductive film is laminated on a base material is used in a wide range of fields as a member of electronic equipment such as a display member and an electronic member. As a method for forming a conductive film on a substrate, there is a technique of forming a dispersion of metal particles, metal oxide particles, or inorganic oxide particles by a vacuum process, a plating process, a wet process, an inkjet method, or the like. Are known.

In recent years, electronic devices have become smaller and lighter, and the performance required for members that make up electronic devices has become higher. As a base material, not only moisture and heat resistance but also improvement in bending resistance is required. Has been. Therefore, a resin base material having excellent flexibility is adopted. As the resin base material, a cyclo(cyclic) olefin resin is used as a raw material as a resin material having excellent film formability and haze and a low water permeability. There is.

However, since the cycloolefin resin has extremely low polarity, there is a problem in that the adhesiveness with the metal particles, the metal oxide particles, or the inorganic oxide particles used for forming the conductive film is low, and sufficient conductive performance cannot be obtained. It was

On the other hand, in Patent Document 1, it is considered to improve the adhesion by using a crosslinked cyclic olefin resin composition obtained by polymerizing a polymerizable composition containing a cyclic olefin monomer and an inorganic filler as a base material. Has been done.

JP, 2014-162841, A

However, since the inorganic filler is generally inferior in dispersibility to the cyclic olefin monomer, agglomeration occurs in the polymerizable composition, and stress concentrates on the agglomerated particles, resulting in bending resistance and transparency of the base material. It has been found that the electric conductivity tends to decrease, and uniform in-plane conductive performance cannot be obtained.

The present invention has been made in view of the above problems, and the problem to be solved is to provide a conductive film having sufficient bending resistance and transparency in a resin base material and capable of obtaining uniform in-plane conductive performance. Is to provide.

The inventor of the present invention, as a result of diligent studies, forms a resin substrate with a resin composition containing a cycloolefin resin having a hydrogen-bonding acceptor group, a solvent component having a hydrogen-bonding donor group, and inorganic particles, and at least an alcohol. The present invention has been completed by finding that the above problems can be solved by using the resin base material containing 10 to 1000 ppm of the solvent component containing a system solvent for a conductive film.

That is, the above problems of the present invention are solved by the following means.
1. In a conductive film having a resin base material and a conductive film,
The resin substrate is viewed contains a solvent component and inorganic particles having a cycloolefin resin and a hydrogen-bonding donor groups having hydrogen bonding accepting groups,
The solvent component includes an alcohol solvent,
The electroconductive film, wherein the solvent component is contained in the resin substrate in an amount of 10 to 1000 ppm.
2. The conductive film according to item 1, wherein the solvent component contains water.
3. A touch panel comprising the conductive film according to item 1 or 2.
4. In the method for producing a conductive film having a resin base material and a conductive film,
Wherein the resin substrate has a forming process that form a resin composition comprising a solvent component and inorganic particles having a cycloolefin resin and a hydrogen-bonding donor groups having hydrogen bonding accepting groups,
The solvent component includes an alcohol solvent,
The said solvent component is 10-1000 ppm contained in the said resin base material formed by the said formation process, The manufacturing method of the electrically conductive film characterized by the above-mentioned .

By the above-mentioned means of the present invention, it is possible to provide a conductive film which has sufficient bending resistance and transparency in a resin substrate and can obtain uniform in-plane conductive performance.

The mechanism of action or mechanism of action of the present invention has not been clarified, but is presumed as follows.

By using a cycloolefin resin having a hydrogen-bonding acceptor group, a solvent component having a hydrogen-bonding donor group, and inorganic particles, the solvent component forms a pseudo crosslinked structure between the cycloolefin resin and the inorganic particles. However, it is surmised that sufficient bending resistance, transparency, and uniform in-plane conductive performance were obtained.

The conductive film of the present invention is a conductive film having a resin base material and a conductive film, wherein the resin base material is a cycloolefin resin having a hydrogen bond accepting group and a solvent component having a hydrogen bond providing group. inorganic particles seen including, the solvent component comprises an alcohol solvent, wherein the solvent component is characterized that it contains 10~1000ppm in the resin base material. This feature is a technical feature common to the inventions according to claims 1 to 4.
In an embodiment of the present invention, the solvent component preferably contains water from the viewpoint of improving productivity.
The conductive film of the present invention is suitable for a touch panel because it has sufficient bending resistance and transparency.

As a method for producing a conductive film for producing a conductive film of the present invention, the resin base material, including the solvent component having a cycloolefin resin and a hydrogen-bonding donor groups having a hydrogen bonding acceptor group and inorganic particles has a forming process that form a resin composition, wherein the solvent component comprises an alcohol solvent, said solvent component, can contain 10~1000ppm in the resin base material formed by the formation step From the viewpoints of reducing the brittleness of the film, suppressing the decrease in productivity due to the occurrence of defects such as tearing of the film during production, and suppressing the decrease in transparency of the film.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used by the meaning including the numerical value described before and after that as a lower limit and an upper limit. In addition, in the present invention, preferable modes can be arbitrarily modified and implemented without departing from the scope of claims and the scope of equivalents thereof.
The “group” such as an alkyl group may have a substituent, unless otherwise specified. Further, in the case of a group having a limited carbon number, the carbon number means the number including the carbon number of the substituent.

<< conductive film >>
The conductive film of the present invention is characterized by having at least a resin base material and a conductive film.

Below, the structure of the electroconductive film of this invention is demonstrated in detail.

<Resin base material>
Resin base material according to the present invention, viewed it contains a solvent component and inorganic particles having a cycloolefin resin and a hydrogen-bonding donor groups having hydrogen bonding accepting groups, wherein the solvent component comprises at least an alcohol-based solvent, the resin It is characterized in that the base material contains 10 to 1000 ppm.

The resin composition according to the present invention is characterized in that, as a resin component, a cycloolefin resin is contained as a main component, that is, in the highest proportion, and 70% by mass or more of the resin component is a cycloolefin resin. Is preferable, and it is more preferable that it is 90% by mass or more because the haze and surface hardness of the resin substrate and the durability at high temperature and high humidity are excellent. Further, the resin component may be a single cycloolefin resin or a combination of a plurality of resin components.

The resin component that can be used as a mixture with the cycloolefin resin is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose acetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate. Cellulose esters such as propionate, cellulose triacetate and cellulose nitrate or their derivatives, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene resin, polycarbonate, norbornene resin (for example, ARTON (JSR Corporation Manufactured by ZEONEX, ZEONOR (manufactured by Zeon Corporation)), polymethylpentene, polyetherketone, polyethersulfone, polysulfone-based resin, polyetherketone imide, polyamide, acrylic or polyacrylate-based resin. The present invention includes cellulose ester such as cellulose triacetate (TAC), polycarbonate, polyester, norbornene-based resin, polyacryl and the like.

The structure of the resin substrate according to the present invention is a single layer composed of a cycloolefin resin having a hydrogen-bonding acceptor group, a solvent composition having a hydrogen-bonding donor group, and a resin composition containing inorganic particles. It may have a laminated structure in which a plurality of layers are laminated, or may have a laminated structure in which one or more kinds of resin layers whose main component is other than cycloolefin resin or other functional layers are combined. Good.

The resin substrate used in the present invention preferably has excellent surface smoothness. The smoothness of the surface is preferably such that the arithmetic average roughness Ra is 5 nm or less and the maximum height Rz is 50 nm or less, more preferably Ra is 2 nm or less and Rz is 30 nm or less, and further preferably Ra is 1 nm or less. And Rz is 20 nm or less. The surface of the substrate may be smoothed by applying an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin and a radiation curable resin, or it may be smoothed by mechanical processing such as polishing. Can also Here, the smoothness of the surface can be obtained from measurement by an atomic force microscope (AFM) or the like according to the surface roughness standard (JIS B 0601-2001).

The resin substrate used in the present invention may be surface-treated or provided with an easy-adhesion layer in order to secure wettability and adhesiveness of the coating liquid. Conventionally known techniques can be used for the surface treatment and the easy-adhesion layer. Examples of the surface treatment include surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment and laser treatment. Examples of the easy-adhesion layer include polyester, polyamide, polyurethane, vinyl-based copolymers, butadiene-based copolymers, acrylic-based copolymers, vinylidene-based copolymers, and epoxy-based copolymers. it can. The easy-adhesion layer may be a single layer, but may have a structure of two or more layers in order to improve the adhesiveness.

(Cycloolefin resin)
The cycloolefin resin according to the present invention is characterized by being formed from a resin composition containing at least one hydrogen-bonding accepting group. The "hydrogen bond-accepting group" means a functional group that accepts a hydrogen atom when forming a hydrogen bond, and the "hydrogen bond-donating group" means a hydrogen atom that donates a hydrogen atom when forming a hydrogen bond. Refers to a functional group that does.

Examples of the hydrogen-bonding accepting group include an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an allyloxycarbonyl group, a cyano group, and an amide. Examples thereof include a group, an imide ring-containing group, a triorganosiloxy group, a triorganosilyl group, an acyl group, an alkoxysilyl group having 1 to 10 carbon atoms, a sulfonyl-containing group, and a carboxy group. More specifically, these polar groups will be described. Examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the acyloxy group include an acetoxy group, an alkylcarbonyloxy group such as a propionyloxy group, and benzoyl. Examples thereof include arylcarbonyloxy groups such as oxy groups; examples of alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, etc.; examples of aryloxycarbonyl groups include phenoxycarbonyl group, naphthyloxycarbonyl group, fluorescein group. Examples thereof include a nyloxycarbonyl group and a biphenylyloxycarbonyl group; examples of the triorganosiloxy group include a trimethylsiloxy group and triethylsiloxy group; and examples of the triorganosilyl group include a trimethylsilyl group and a triethylsilyl group. Examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.

The amount of the cycloolefin resin containing a hydrogen-bonding accepting group contained in the resin component is not particularly limited, but the content ratio is preferably 10 to 100% by mass. When it is 10% by mass or more, the resulting ring-opening copolymer is likely to exhibit solubility in a solvent such as toluene or dichloromethane, which is preferable. From the viewpoint of solubility, film strength, and transparency, 30 to 100 is preferable. More preferably, it is in the range of mass%.

Examples of the cycloolefin resin according to the present invention include (co)polymers represented by the following general formula (1).

〔式中、ｐは０又は１であり、ｍは０又は１以上の整数である。Ｒ_１〜Ｒ_４は、それぞれ独立に、水素原子、炭化水素基、ハロゲン原子、又は水素結合性受容基を表す。また、Ｒ_１〜Ｒ_４は、二つ以上が互いに結合して、不飽和結合、単環又は多環を形成していてもよく、この単環又は多環は、二重結合を有していても、芳香環を形成してもよい。〕

[In the formula, p is 0 or 1, and m is an integer of 0 or 1 or more. R _{1 to} R ₄ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, or a hydrogen-bonding accepting group. Two or more of R _{1 to} R ₄ may be bonded to each other to form an unsaturated bond, a monocycle or a polycycle, and the monocycle or the polycycle has a double bond. Alternatively, it may form an aromatic ring. ]

In the present invention, the preferred holding ratio of the hydrogen-bonding accepting group of the cycloolefin resin is that in General Formula (1), _{1 to} 2 of R _{1 to} R ₄ have a hydrogen-bonding accepting group.
The proportion of hydrogen-bonding acceptor groups on the cycloolefin resin can be identified using, for example, carbon-13 nuclear magnetic resonance ( ¹³ CNMR) spectroscopy.

Further, in the general formula (1), R ₁ and R ₃ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms, and at least R ₂ and R ₄ One is a hydrogen-bonding accepting group having a polarity other than a hydrogen atom and a hydrocarbon group, and p and m are m=1 and p=0 in terms of high glass transition temperature and excellent mechanical strength. Some are preferred.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group. Group; aromatic groups such as phenyl group, biphenyl group, naphthyl group, anthracenyl group, and the like. These hydrocarbon groups may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a phenylsulfonyl group.

The glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110°C or higher, preferably 110 to 350°C, more preferably 120 to 250°C, and particularly preferably 120 to 220°C. When the Tg is 110° C. or higher, deformation due to use under high temperature conditions or secondary processing such as coating and printing is suppressed, which is preferable. Further, when Tg is 350° C. or less, resin deterioration due to molding and heat during molding is suppressed, which is preferable.

As the cycloolefin resin described above, a commercially available product can be preferably used, and as an example of the commercially available product, JSR Corporation sells the products under the trade names of Arton G, Arton F, Arton R, and Arton RX. Further, these are commercially available from Nippon Zeon Co., Ltd. under the trade name of Zeonor ZF14, ZF16, Zeonex 250 or Zeonex 280, and these can be used.

(Solvent component)
The solvent component according to the present invention is characterized by containing at least one solvent having a hydrogen-bonding donor group.

As the hydrogen bond-donating group, for example, an amino group, an acylamino group, an alkoxycarbonylamino group, an allyloxycarbonylamino group, a sulfonylamino group, a hydroxy group, a mercapto group, a carboxy group is preferable, a sulfonylamino group, an acylamino group, A C-H group in which a carbon atom is substituted with an amino group, a hydroxy group, or an electron-withdrawing group is more preferable, and the solvent component according to the present invention may have one or more kinds of these hydrogen-bonding donor groups. ..

Specifically, from the viewpoint of improving productivity, it is preferable to use an alcohol solvent having a hydroxy group and water in combination.

Since water has a plurality of hydrogen-bonding donor groups in one molecule, it can be preferably used for increasing the strength of the film. Water is preferably contained in an amount of 0.1 to 1% by mass based on the total amount of solvent. If it is 0.1% by mass or more, it is easy to interact with other alcoholic solvents, cycloolefin resins containing hydrogen-bonding accepting groups and inorganic particles, which is preferable, but if it exceeds 1% by mass, hydrophobicity is strong. The cycloolefin resin is gelated and foreign matter is likely to be generated.

As examples of the alcohol solvent, methanol, ethanol, isopropanol, n-butanol, 2-butanol and the like are preferably used.

The solvent having a hydrogen-bonding donor group is preferably contained in the solvent component in an amount of 0.5 to 15% by mass. From the viewpoint of the releasability of the film from the metal support, it is preferably 0.5% by mass or more, and from the viewpoint of the transparency of the film, it is preferably 15% by mass or less.

The more preferable range differs depending on the solvent type, and in the case of methanol, the content is preferably 0.7 to 6.5 mass% with respect to the total amount of the solvent. In the case of ethanol, the content is preferably 1.0 to 9 mass% with respect to the total amount of solvent. In the case of n-butanol, the content is preferably 1.5 to 15 mass% with respect to the total amount of solvent.

The content ratio of the solvent component contained in the resin composition is preferably 1 to 50% by mass. When the content of the solvent component is 1% by mass or more, reduction in brittleness of the film and reduction in productivity due to occurrence of defects such as tearing of the film during production are suppressed. Further, when the content is 50% by mass or less, a decrease in transparency of the film is suppressed. The content ratio of the solvent component can be appropriately adjusted depending on the production conditions of the film, the thickness of the film to be prepared, and the like.

The resin base material formed from the resin composition according to the present invention has a residual solvent amount of 10 to 1000 ppm through a solvent removal step such as a drying step. When the residual solvent amount of the resin base material is 10 ppm or less, the brittleness of the film deteriorates, which causes ductile fracture of the film. On the other hand, when the residual solvent amount is 1000 ppm or more, the solvent evaporates over time, which causes the resin base material to expand or contract, causing deformation such as wrinkles or warpage, or variation in electrode performance.

The residual solvent amount can be appropriately adjusted depending on the content ratio of the solvent component contained in the resin composition, the drying conditions at the time of film production, or the film thickness of the film to be prepared.

As the residual solvent component contained in the resin composition, water is preferably contained in addition to the alcohol solvent, and the content thereof is preferably 10 to 200 ppm. When it is 10 ppm or more, the mechanical strength and brittleness of the obtained film are improved, but it is preferably 200 ppm or less from the viewpoint of transparency of the film.

(Inorganic particles)
The resin base material according to the present invention is characterized by containing inorganic particles. Silica fine particles are preferable as the inorganic particles. At the interface between the conductive film and the resin substrate, the polarities such as hydroxy groups (OH groups) on the surface of the silica particles, sulfonyl groups, and oxygen atoms (Si-O-Si, O=Si=O) contained in siloxane bonds are It is expected that the high part interacts with the polar part of the compound used for the conductive film to obtain excellent adhesion between the resin base material and the conductive film. In order to effectively obtain the above-mentioned interaction, it is preferable that the silica fine particles are localized near the surface of the resin base material that is in contact with the conductive film.

As one embodiment for localizing silica fine particles in the vicinity of the surface, a mixed solvent contained in a resin composition (hereinafter, also referred to as a dope) according to the present invention when a resin substrate is manufactured by a solution casting method. There is a mode in which the difference in the boiling points of and the solubility of the mixed solvent and silica fine particles are utilized.

Specifically, when the dope is cast on a support and dried on the support, volatilization from the surface opposite to the support causes the silica fine particles to be distributed in the thickness direction on the support. Occurs. Since a mixed solvent volatilizes from a low boiling point, a distribution of the low boiling point solvent and the high boiling point solvent occurs in the thickness direction. At this time, due to the solubility of the silica fine particles, localization occurs in the film thickness after drying. If the silica fine particles have higher solubility in the low boiling point solvent than in the high boiling point solvent, the compound will be biased in the direction of volatilization of the low boiling point solvent (the surface opposite to the support), and the compound will be localized near the surface. Incarnate.

Further, in the present invention, from the viewpoint of improving the adhesion, it is preferable to modify the silica fine particles with a polar group, particularly preferably with a sulfo group, but the modification method is not particularly limited.

Examples of silica fine particles that can be preferably applied to the present invention include Sylysia manufactured by Fuji Silysia Chemical Ltd., Nipsil E manufactured by Nippon Silica Co., Ltd., Aerosil series manufactured by Nippon Aerosil Co., Ltd., and Nissan Chemical Industries ( Colloidal silica, organosilica sol and the like manufactured by K.K. can be applied.

In addition to silica fine particles, zirconia or titania fine particles can be used, and these can be used alone or in combination.

In the present invention, the average particle size of the inorganic particles is preferably 5 nm or more and 1.0 μm or less, and more preferably 5 nm or more and 500 nm or less. This is because if the particle size is too large, light scattering increases and the transmittance decreases. The average particle diameter of the inorganic particles is obtained by observing the inorganic particles with an electron microscope, obtaining the particle diameters of 100 arbitrary primary particles, and obtaining the simple average value (number average) thereof. Here, each particle diameter is represented by a diameter assuming a circle equal to the projected area.

In the present invention, the content ratio of the inorganic particles contained in the resin substrate is not particularly limited as long as it satisfies the conditions specified in the present invention, but preferably 0.1 to 100% by mass of the cycloolefin resin. 45% by mass, more preferably 0.2 to 10% by mass from the viewpoint of improving adhesion and the viewpoint of transparency of the obtained film. More preferably, it is 0.2 to 1 mass %.

(Other additives)
In the resin composition, a specific hydrocarbon described in, for example, JP-A-9-221577, JP-A-10-287732, and JP-A-2014-159082 is used as long as the effect of the present invention is not impaired. -Based resin, or known thermoplastic resin, thermoplastic elastomer, rubbery polymer, organic fine particles, inorganic fine particles, etc. may be blended, and a specific wavelength dispersant, surfactant, dispersant, sugar ester compound, oxidation Additives such as an inhibitor, a peeling accelerator, rubber particles, a plasticizer, and an ultraviolet absorber may be included.

As an additive, it is preferable to contain an ultraviolet absorber from the viewpoint of improving light resistance. The ultraviolet absorber is intended to improve the light resistance by absorbing ultraviolet rays having a wavelength of 400 nm or less, and in particular, the transmittance at a wavelength of 370 nm is preferably in the range of 0 to 30%, more preferably 1 To 20%, more preferably 1 to 10%.

The ultraviolet absorber preferably used in the present invention is a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, or a triazine type ultraviolet absorber.

Further, as the ultraviolet absorber, a polymeric ultraviolet absorber can also be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used. Further, the ultraviolet absorber preferably does not have a halogen group.

<Method of manufacturing resin base material>
The method for molding the resin substrate according to the present invention will be described.
Examples of the method for molding the resin substrate according to the present invention include known methods such as a melt extrusion method, a solution casting method (solution casting method), a calender method, and a compression molding method.

(Solution casting method)
As the solvent used in the solution casting method, it is preferable to use one or a mixture of alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, and 2-butanol, and the alcohol solvent, Chlorine solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether, water and the like may be used in combination.

As one of the embodiments for molding the resin substrate according to the present invention by the solution casting method, a cycloolefin resin having a hydrogen-bonding accepting group, a solvent component having a hydrogen-bonding donor group, and a resin containing inorganic particles A step of preparing the composition (dope), a step of casting the dope on a belt-shaped or drum-shaped support, a step of drying the cast dope as a web (first drying step), a step of peeling from the support The present invention is characterized by including a step of further drying the peeled web (second drying step), a step of stretching, and a step of winding the finished resin base material.

(1) Dope preparation step This is a step of preparing a dope by adding and mixing a cycloolefin resin having a hydrogen-bonding accepting group, a solvent component having a hydrogen-bonding donor group, and inorganic particles, and dissolving them. The dissolution is carried out under normal pressure, below the boiling point of the main solvent, under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557, or JP-A-9-95557. Various dissolution methods can be used, such as a cooling dissolution method described in JP-A 9-95538 and a high pressure method described in JP-A No. 11-21379. It is preferable that the method is carried out by applying pressure.

(2) Casting step This is a step of casting the dope prepared in the above dope preparing step from a pressure die slit to a casting position on a metal support such as a stainless belt or a rotating metal drum. .. In the liquid casting method, the concentration of the cyclopolyolefin resin in the dope is preferably the higher the concentration because the drying load after casting on the metal support can be reduced. Load increases, and the filtration accuracy deteriorates. The concentration satisfying these requirements is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass. The metal support in the casting step is preferably one whose surface is mirror-finished, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The width of the cast can be 1 to 4 m.

(3) First Drying Step This is a step of heating a web (the dope is cast on a casting support and the formed dope film is called a web) on the casting support to evaporate the solvent. .. The surface temperature of the support in the casting step is set to -50°C or higher and below the temperature at which the web does not boil and foam. A higher temperature is preferable because the drying speed of the web can be increased, but if the temperature is too high, the web may foam or the flatness may deteriorate.

The temperature of the support is preferably 0 to 100° C., more preferably 5 to 30° C. Alternatively, it is also a preferable method that the web is gelated by cooling and peeled from the drum in a state of containing a large amount of solvent. The method of controlling the temperature of the support is not particularly limited, but there are a method of blowing hot air or cold air and a method of bringing hot water into contact with the back side of the support. It is preferable to use warm water because the heat can be efficiently transferred, and thus the time until the temperature of the support becomes constant is short.

When using hot air, in consideration of the temperature decrease of the web due to the latent heat of evaporation of the solvent, while using hot air above the boiling point of the solvent, while preventing foaming, there may be a case where the air temperature is higher than the target temperature. .. In particular, it is preferable to change the temperature of the support and the temperature of the drying air between the casting and the peeling to efficiently perform the drying.

(4) Peeling step This is a step of peeling the web having the solvent evaporated on the support at the peeling position. The peeled web is sent to the next step.

In order for the resin substrate to exhibit good flatness, the amount of solvent when peeling the web from the support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. , Particularly preferably 20 to 30% by mass or 70 to 120% by mass.

The amount of solvent is defined by the following formula.
Solvent amount (mass %) for peeling the web={(M−N)/N}×100
In addition, M is the mass of the sample taken at any time during or after the production of the web or film, and N is the mass of M after heating at 115° C. for 1 hour.

(5) Second Drying Step This is a step of further evaporating the solvent contained in the web separated from the support. In the present invention, the web that has undergone the second drying step is referred to as a resin base material.

In the second drying step, the residual solvent amount is preferably 1000 ppm or less, more preferably 10 to 1000 ppm.
When the residual solvent amount of the resin base material is within the above range, a conductive film having sufficient bending resistance and excellent adhesion between the conductive film and the resin base material can be obtained.

In the second drying step, generally, the web is dried while being conveyed by a roll drying method (a method in which the web is alternately passed through a large number of rolls arranged above and below to dry) or a tenter method described in JP 2012-13824A. The method is adopted.

When the tenter is performed, the drying temperature is preferably 30 to 180°C, more preferably 50 to 170°C.

The thickness of the resin base material (after drying) of the present invention varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, preferably in the range of 10 to 150 μm, and when the device is made thinner, the thickness is 100 μm or less. It is particularly preferable that

(6) Stretching Step The resin base material used in the present embodiment may be an unstretched base material or a stretched base material, but a stretched base material is preferable from the viewpoint of improving strength and suppressing thermal expansion. The stretching method is not particularly limited. For example, a method in which the peripheral speed difference is applied to multiple rolls and the roll peripheral speed difference between them is used to stretch in the longitudinal direction, both ends of the web are fixed with clips or pins, and the spacing between the clips or pins is widened in the traveling direction. And a method of stretching in the longitudinal direction, a method of stretching in the lateral direction and stretching in the lateral direction in the same manner, a method of simultaneously stretching in the longitudinal and lateral directions and stretching in both the longitudinal and lateral directions, oblique stretching and the like.
A plurality of these methods may be used in combination, or the stretching operation may be performed in multiple stages. That is, it may be stretched in the transverse direction with respect to the film-forming direction, in the longitudinal direction, or in both directions. When it is further stretched in both directions, it may be simultaneous stretching or sequential stretching. May be. Further, it may be performed at the same time as the second drying step described above. By dividing into several times, it is possible to more uniformly stretch even in high-strength stretching. Before the oblique stretching, stretching may be performed in a width or a length to such an extent that shrinkage in the width direction is prevented.

The in-plane retardation value Ro of the resin substrate of the present invention at the measurement wavelength of 589 nm is preferably in the range of 0 to 150 nm. More preferably, Ro is in the range of 0 to 20 nm or 40 to 200 nm.

The retardation value Rt in the thickness direction at the measurement wavelength of 589 nm is preferably in the range of 0 to 400 nm, and particularly preferably in the range of Rt of 0 to 70 nm or in the range of Rt of 80 to 300 nm. By setting Rt in the preferable range, the visibility when wearing sunglasses using a polarizing plate is improved.

The retardation values Ro and Rt are calculated by the following equations (i) and (ii), respectively.
Formula (i) Ro=(nx-ny)*d
Formula (ii) Rt=((nx+ny)/2-nz)*d
(In the formula, Ro is the in-plane retardation value, Rt is the thickness direction retardation value, nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz represents the refractive index in the film thickness direction, and d represents the film thickness (nm).)
In the present invention, the in-plane retardation value Ro and the thickness direction retardation value Rt at the measurement wavelength of 589 nm are 23° C. and 55% RH under the environment of the phase difference measuring device “KOBRA-21ADH” (Oji measuring instrument ( Co., Ltd.).

The retardation value of the resin substrate can be controlled by selection of the resin material, stretching ratio during film formation and the like. Specifically, it can be controlled to an arbitrary value by appropriately selecting the stretching ratio in the longitudinal direction and the transverse direction.

(7) Winding step This is a step of winding the resin base material formed through the above steps into a long roll shape. As a winding method, a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like, and these may be used properly.

Before winding, the ends may be slit to have a product width and cut off, and knurling (embossing) may be applied to both ends in order to prevent sticking and scratches during winding. The knurling can be performed, for example, by heating or pressurizing a metal ring having an uneven pattern on its side surface.

The resin base material of the present invention can achieve desired optical properties by appropriately adjusting process conditions such as the structure of the cycloolefin resin used, the type and amount of additives, the draw ratio, and the amount of solvent during peeling. it can. For example, the retardation Rt in the thickness direction can be widely controlled to 180 to 300 nm by adjusting the amount of the solvent at the time of peeling within 40 to 85% by mass. Generally, the larger the amount of solvent at the time of peeling, the smaller the Rt, and the smaller the amount of solvent at the time of peeling, the larger the Rt. For example, by shortening the drying time on a metal endless support and increasing the amount of solvent at the time of peeling, it is possible to relax the plane orientation and lower Rt, and by adjusting the process conditions. It is possible to express various retardations according to various uses.

The equilibrium water content of the resin base material of the present invention at 25° C. and 60% relative humidity is preferably 3% or less from the viewpoint of phase difference variation and bending resistance, and more preferably 1% or less. By setting the equilibrium water content to 3% or less, it is easy to respond to changes in humidity, and it is more difficult for optical characteristics and dimensions to change, which is preferable.

The equilibrium water content is determined by leaving the sample film in a room conditioned at 23° C. and a relative humidity of 20% for 4 hours or more and then in a room conditioned at 23° C. 80% RH for 24 hours. Using a meter (for example, CA-20 type manufactured by Mitsubishi Chemical Co., Ltd.), water is dried and vaporized at a temperature of 150° C., and then quantified by the Karl Fischer method.

By subjecting the surface of the resin base material to surface activation treatment, it is possible to improve the formability of the conductive film or other layers that form the conductive film disposed on the surface of the resin base material. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

<Conductive film>
The conductive film according to the present invention is a metal film that is extremely thin to the extent that the light transmissivity can be maintained and that the radiated light does not cause plasmon loss. Further, the conductive film is a metal film which is continuous so as to have conductivity. Specifically, the light transmittance at a wavelength of 550 nm is preferably 60% or more, particularly preferably 80% or more, and the total light transmittance is preferably 80% or more. The film thickness is 1 to 30 nm, preferably 1 to 20 nm, and the sheet resistance is 0.0001 to 50 Ω/□, preferably 0.01 to 40 Ω/□. When the film thickness is less than or equal to the above upper limit value, the absorption component or reflection component of the layer can be suppressed low, and the light transmittance can be maintained, which is preferable. Further, when the film thickness is equal to or more than the above lower limit value, conductivity is secured.

The material used for the conductive film is not particularly limited as long as it has the above-mentioned light transmittance, total light transmittance, and sheet resistance physical properties, and silver, indium phosphide, copper or the like is preferably used.

As a material used for the conductive film of the present invention, it is particularly preferable to use silver or an alloy containing silver as a main component. As a method for forming such a conductive film, for example, a method using a wet process such as a coating method, an inkjet method, a coating method, a dipping method, a vapor deposition method (resistance heating, an EB method, etc.), a sputtering method, a CVD method, etc. And a method using the dry process of Among them, the vapor deposition method is preferably applied. The conductive film is characterized in that it has sufficient conductivity even without high temperature annealing treatment after formation. Further, when the conductive film is formed on the resin substrate according to the present invention, it is preferable that the glass transition temperature (Tg) of the cycloolefin resin which is the main component of the resin substrate is not exceeded. The formation process temperature is preferably 20° C. or more lower than the glass transition temperature (Tg) of the cycloolefin resin, and more preferably 40° C. or more lower.
By setting the glass transition point of the cycloolefin resin to be not higher than that in the process, damage to the thermal resin can be prevented. Therefore, a conductive film having excellent transparency and stability over time can be formed.

When the conductive film is composed of silver, the purity of silver is preferably 99% or more. Further, palladium, copper, gold or the like may be added to ensure the stability of silver.

When the conductive film is made of an alloy containing silver as a main component, the silver content is preferably 50% or more. Examples of such alloys are silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn), silver gold (AgAu), silver aluminum (AgAl). , Silver zinc (AgZn), silver tin (AgSn), silver platinum (AgPt), silver titanium (AgTi), silver bismuth (AgBi), and the like.

In addition, the conductive film as described above may have a configuration in which a layer of silver or an alloy containing silver as a main component is divided into a plurality of layers and laminated as necessary. That is, for example, the silver layer and the alloy layer may be alternately laminated a plurality of times, or a plurality of different alloy layers may be laminated.

<Functional layer>
In the conductive film of the present invention, functional layers such as a hard coat layer, a barrier layer, a protective layer, a smoothing layer, an optical adjustment layer, an adhesive layer, an adhesive layer, and a base layer are appropriately arranged within the range where the effect of the present invention is exhibited. You can A plurality of each of these functional layers may be provided, or a combination of a plurality of layers may be provided. For these functional layers, a method using a wet process such as a coating method, an inkjet method, a coating method, a dipping method, or a dry process such as a vapor deposition method (resistance heating, EB method), a sputtering method, a CVD method, or the like is appropriately used. It is formed by the method used.

In the present invention, the underlayer is a layer arranged for the purpose of obtaining a uniform film thickness of the conductive film. When the main component of the conductive film is silver, the underlayer preferably includes either the adhesive layer or the nitrogen-containing layer. Further, it may be configured to include both the adhesive layer and the nitrogen-containing layer. Further, in the case where the conductive film is divided into a plurality of layers and stacked, the conductive film and the base layer may be alternately stacked a plurality of times.

As the adhesive layer, a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, a radiation curable resin or the like is preferably used. The adhesive layer preferably contains a metal oxide or a metal nitride containing atoms such as titanium, platinum, palladium, cobalt, nickel and molybdenum, and more preferably contains titanium oxide and niobium oxide. It is preferably provided adjacent to the conductive film or the nitrogen-containing layer.

The nitrogen-containing layer is a layer formed using a compound containing a nitrogen atom and is provided adjacent to the conductive film. When the nitrogen-containing layer is formed on the resin substrate, the vapor deposition method is preferably applied.

The compound containing a nitrogen atom constituting the nitrogen-containing layer is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule, but a compound having a heterocycle having a nitrogen atom as a hetero atom is preferable. The heterocycle having a nitrogen atom as a hetero atom, for example, aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, Indole, isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and the like can be mentioned.

The optical adjustment layer is a layer arranged for the purpose of exerting a working effect on incident light to the conductive film of the present invention, such as a high refractive index layer, a low refractive index layer, an antiglare layer, and a light scattering layer. .. A thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, a radiation curable resin or the like is preferably used as the optical adjustment layer. Further, the optical adjustment layer may contain particles of metal oxide such as silicon oxide, silicon nitride, silicon oxynitride, aluminum nitride, aluminum oxide, niobium oxide, and titanium oxide, and metal nitride.

<Use>
The conductive film of the present invention is preferably contained in an electronic device. Electronic devices include touch panels or membrane switches, TVs equipped with them, mobile communication devices, personal computers, game devices, in-vehicle display devices, internet communication devices, lighting/display LEDs, electronic wiring devices for solar cell control, RFIDs, etc. Wireless communication device, or equipment controlled by a semiconductor wiring board or an organic TFT wiring board.
The conductive film of the present invention can be particularly suitably used for a touch panel because it has sufficient bending resistance and transparency.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “parts” or “%” is used, but unless otherwise specified, “parts by mass” or “% by mass” is shown.

<<Example 1>>
<Production of conductive film 1>
(Preparation of fine particle dispersion)
Silica fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.)
11 mass%
Ethanol 89% by mass
After stirring and mixing the above with a dissolver for 50 minutes, dispersion was carried out using a Manton-Gorlin disperser to prepare a fine particle dispersion.

(Preparation of fine particle additive liquid 1)
Dichloromethane was placed in the dissolution tank, and the fine particle dispersion liquid prepared above was slowly added to 50% by mass while sufficiently stirring the dichloromethane. Further, the secondary particles were dispersed by an attritor so that the particle size would be a predetermined size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive liquid 1.

(Synthesis of cycloolefin resin P)
8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 . 75 mass% of 1 ^7,10 ]-3-dodecene (DNM), 24 mass% of dicyclopentadiene (DCP), 1 mass% of 2-norbornene, 9 parts of 1-hexene as a molecular weight regulator and 200 parts of toluene, nitrogen. The reaction vessel was replaced, and the reaction vessel was charged and heated to 110°C. A polymer was obtained by adding 0.005 parts of triethylaluminum and 0.005 parts of methanol-modified WCl ₆ (anhydrous methanol:PhPOCl ₂ :WCl ₆ =103:630:427 mass ratio) to the mixture for 1 hour. The obtained polymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, 0.006 parts of RuHCl(CO)[P(C ₆ H ₅ )] ₃ , which is a hydrogenation catalyst, was added, and after heating to 90° C., hydrogen gas was introduced into the reactor, and the pressure was adjusted to 10 MPa. did. Then, the reaction was carried out at 165° C. for 3 hours while maintaining the pressure at 10 MPa. After the reaction was completed, it was precipitated in a large amount of methanol solution, and the precipitate was reprecipitated and purified using toluene and methanol to obtain a copolymer P.

The copolymer P has a weight average molecular weight (Mw)=7.2×10 4, a molecular weight distribution (Mw/Mn)=3.3, an intrinsic viscosity (ηinh)=0.59, a glass transition temperature (Tg)=143° C. Met. The addition rate of the methoxycarbonyl group of the copolymer P was determined by ¹³ CNMR measurement, and it was confirmed that 75% by mass of the monomer having the methoxycarbonyl group was added. The copolymer P obtained above is used as a cycloolefin resin P having 75% by mass of a monomer having a methoxycarbonyl group as a hydrogen-bonding accepting group.

(Preparation of dope A)
The cycloolefin polymer P synthesized above was put into a pressure dissolution tank containing ethanol while stirring. This was heated and completely dissolved with stirring. Then, after adding the fine particle additive liquid 1, Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. Dope A was prepared by filtration using 244. The composition of dope A is shown below. Ethanol corresponds to the solvent component having a hydrogen-bonding donor group according to the present invention.

(Composition of dope A)
Cycloolefin resin P 100.0% by mass
Dichloromethane 290.0% by mass
Ethanol 10.0% by mass
Fine particle dispersion liquid 14.0% by mass

(Formation of Resin Base Material 1)
The dope A prepared above was cast on a stainless casting support (support temperature 22° C.) using a band casting device. The dope A was peeled off in a state where the amount of the solvent was about 20% by mass, both ends in the width direction of the film were held by tenters, and in the state where the amount of the solvent was 10% by mass, 1. It was dried while being stretched 05 times (5%). Then, the resin base material 1 was manufactured by further transporting it between rolls of a heat treatment apparatus at 100° C. for 30 minutes to further dry it. The thickness was 60 μm and the width was 1492 mm.

(Formation of conductive film)
A conductive film (20 nm thick) was formed of ITO on one surface of the resin base material 1 by a sputtering method to prepare a conductive film 1.

<Production of conductive film 2>
Using 30% by mass of DNM, 50% by mass of DCP and 20% by mass of 2-norbornene, the same method as in the synthesis of the cycloolefin resin P was used to prepare 30 parts of the monomer having a methoxycarbonyl group as a hydrogen-bonding accepting group. A cycloolefin resin Q having a mass% content was synthesized. Then, the resin film 2 is produced in the same manner as the resin substrate 1 except that the cycloolefin resin P is replaced by the cycloolefin resin Q, and the conductive film 1 is prepared except that the resin substrate 1 is used as the resin substrate 2. Conductive film 2 was produced in the same manner as in 1. In addition, when the methoxycarbonyl group addition rate of the cycloolefin resin Q was obtained by ¹³ CNMR measurement, it was confirmed that 30% by mass of the monomer having a methoxycarbonyl group was added.

<Production of conductive film 3>
A cycloolefin resin R having 25% by mass of a monomer having a methoxycarbonyl group as a hydrogen-bonding accepting group was synthesized by the same method as in the synthesis of the cycloolefin resin P except that DNM was 25% by mass. Then, the conductive film 1 is manufactured except that the resin base material 3 is manufactured in the same manner as the resin base material 1 except that the cycloolefin resin P is the cycloolefin resin R, and the resin base material 1 is the resin base material 3. Conductive film 3 was produced in the same manner as in 1. The addition ratio of the methoxycarbonyl group of the cycloolefin resin R was determined by ¹³ CNMR measurement, and it was confirmed that 25% by mass of the monomer having a methoxycarbonyl group was added.

<Production of conductive film 4>
A resin base material 4 is produced in the same manner as the resin base material 1 except that the dope A is used as the dope B, and the conductive film 1 is produced in the same manner as the resin base material 1 except that the resin base material 4 is used. , The conductive film 4 was produced.
(Composition of dope B)
Cycloolefin resin P 100.0% by mass
Dichloromethane 300.0% by mass
Methanol 15.0 mass%
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 5>
A resin base material 5 was produced in the same manner as the resin base material 1 except that the dope A was used as the dope C, and the conductive film 1 was produced in the same manner as the resin base material 1 except that the resin base material 1 was used. A conductive film 5 was produced.
(Composition of dope C)
Cycloolefin resin P 100.0% by mass
Dichloromethane 280.0% by mass
Butanol 20.0% by mass
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 6>
A resin base material 6 was produced in the same manner as the production of the resin base material 1 except that the dope A was used as the dope D, and the same manner as the production of the conductive film 1 except that the resin base material 1 was used as the resin base material 6. , The conductive film 6 was produced.
(Composition of dope D)
Cycloolefin resin P 100.0% by mass
Dichloromethane 280.0% by mass
Ethanol 9.0 mass%
Distilled water 1.0% by mass
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 7>
A resin base material 7 was prepared in the same manner as the resin base material 1 except that the dope A was used as the dope E, and the conductive film 1 was prepared in the same manner as the resin base material 1 was used. A conductive film 7 was produced.
(Composition of dope E)
Cycloolefin resin P 100.0% by mass
Dichloromethane 277.0% by mass
Ethanol 10.5% by mass
Distilled water 2.5 mass%
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 8>
On one surface of the resin substrate 1, a base layer (film thickness 25 nm) is formed by using the following compound B by a vapor deposition method, and subsequently, a conductive film (film thickness 8 nm) made of silver (Ag) is vapor deposited by a vapor deposition method. To form a conductive film 8.

<Production of conductive film 9>
In the production of the conductive film 8, a conductive film 9 was produced in the same manner as the production of the conductive film 8 except that the conductive film was formed of ITO by a sputtering method to have a film thickness of 20 nm.

<Production of conductive film 10>
A resin base material 10 was prepared in the same manner as the resin base material 1 except that the condition of the drying step after stretching was 10 minutes between rolls of a heat treatment apparatus at 100° C. A conductive film 10 was produced in the same manner as the production of the conductive film 1 except that the number was changed to 10.

<Production of conductive film 11>
A resin base material 11 was prepared in the same manner as the resin base material 1 except that the drying step after stretching was carried out for 15 minutes between rolls of a heat treatment device at 90° C. A conductive film 11 was produced in the same manner as the production of the conductive film 1 except that No. 11 was used.

<Production of conductive film 12>
A resin base material 12 is manufactured in the same manner as the resin base material 1 except that the dope A is replaced by the dope E, and the conductive film 1 is manufactured in the same manner as the resin base material 12 except that the resin base material 1 is used. , The conductive film 12 was produced.
(Composition of dope E)
Cycloolefin resin P 100.0% by mass
Dichloromethane 300.0% by mass
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 13>
A resin base material 13 was produced in the same manner as the production of the resin base material 1 except that the dope A was used as the dope F, and the same manner as the production of the conductive film 1 except that the resin base material 1 was used as the resin base material 13. , The conductive film 13 was produced.
(Composition of dope F)
Cycloolefin resin P 100.0% by mass
Dichloromethane 290.0% by mass
Acetonitrile 10.0% by mass
Fine particle dispersion liquid 14.0% by mass

<Production of conductive film 14>
In the synthesis of the cycloolefin resin P, a resin S1 was synthesized as a cycloolefin resin having no hydrogen-bonding acceptor group in the same manner as in the synthesis of the cycloolefin resin P except that 70% by mass of DCP and 30% by mass of 2-norbornene were used. Then, the conductive film 14 was manufactured in the same manner as the conductive film 1 except that the cycloolefin resin P was the cycloolefin resin S1.

<Production of conductive film 15>
(Preparation of cycloolefin resin S2 synthesis solution)
Silica fine particles, 10-undecenoic acid, a phenolic stabilizer, a phosphorus stabilizer, and a hindered amine light stabilizer are added to the norbornene-based monomer mixture solution to be solubilized or dispersed, and further triphenylphosphine and the compound C shown below. Ruthenium catalyst was added and mixed with a line mixer to prepare a cycloolefin resin S2 synthetic solution. The composition of the cycloolefin resin S2 synthesis solution is shown below.
(Composition of cycloolefin resin S2 synthesis liquid)
Norbornene-based monomer mixed solution (dicyclopentadiene 90 parts, tricyclopentadiene 10 parts) 100.0% by mass
Silica fine particles (Aerosil R812 manufactured by Nippon Aerosil Co., Ltd.) 10.0% by mass
10-undecenoic acid 0.3 mass%
Phenolic stabilizer 1.0 mass%
Phosphorus stabilizer 1.0 mass%
Hindered amine light stabilizer 1.0 mass%
Triphenylphosphine 1.0% by mass
Ruthenium catalyst 1.7% by mass

The cycloolefin resin S2 synthetic solution prepared above was applied at 25° C. onto a carrier film made of polyethylene terephthalate having a thickness of 0.075 mm to form a cast film, and immediately thereafter, the same as above prepared separately from the coating layer. Carrier film was laminated. After that, heating is performed at 200° C. for 3 minutes, then, after cooling to 20° C., the upper and lower carrier films are peeled off, and a resin base material 15 containing a hydrogen-bonding acceptor-free cycloolefin resin S2 as a main component is obtained. It was made. A conductive film 15 was produced in the same manner as the production of the conductive film 1, except that the resin substrate 1 was used as the resin substrate 15.

<<Evaluation of sample>>
The residual amount of alcohol or distilled water in each resin substrate constituting the conductive films 1 to 15 produced above was evaluated by the following method and is shown in Table 1.

<Amount of residual solvent>
The residual amount of alcohol or distilled water used as a solvent component was cut into a fixed shape, placed in a 20 ml closed glass container, treated at 120° C. for 20 minutes, and then subjected to gas chromatography (instrument: HP company 5890 SERIES). II, column: J&W company DB-WAX (inner diameter 0.32 mm, length 30 m), detection: FID), after holding the GC temperature rising conditions at 40° C. for 5 minutes, then heating to 80° C./minute up to 100° C. I asked.

The performance of each of the conductive films 1 to 15 prepared above was evaluated by the following method. Table 1 shows the constitution and evaluation of each conductive film.
<Bending resistance>
The transparency of the above-prepared conductive films 1 to 15 was evaluated for the bending resistance according to the method specified in JIS K5400. For the evaluation of bending resistance, a stainless rod having a diameter of 10 mm was used for winding the optical film sample. The rank of the electrode layer was evaluated as follows.
◎: No change ○: Slightly deformed, but practically no problem △: Wrinkle or warp deformation, practically problem ×: Electrode layer has fine cracks, practically problematic is there

<Haze>
The haze is also called a haze value and represents the degree of haze or the degree of diffusion. The haze (%) was measured according to JISK-7136 using a commercially available haze meter (manufactured by Nippon Denshoku Co., Ltd., product name "NDH 2000"), and evaluated according to the following criteria. The smaller the haze (%), the more haze and the higher the transparency. The measured haze was evaluated according to the following criteria. When the haze of the conductive film is 2% or more, white blurring occurs and the visibility of the touch panel deteriorates.
◎: Less than 0.5% ○: 0.5% or more and less than 2% ×: 2% or more

<Conductivity>
The electroconductive performance of the electroconductive films 1 to 15 produced above was evaluated using the surface resistivity. The surface resistivity of the conductive region of the conductive layer was measured using Loresta (registered trademark)-GP MCP-T600 manufactured by Mitsubishi Chemical Corporation. The surface resistivity was measured at 20 randomly selected locations in the central part of the conductive region of the 10 cm×10 cm sample, and the variation in the surface resistivity was evaluated. The surface resistivity in the range of 0 to 200 Ω/□ is a practically preferable range.
◯: Practical problem with surface resistivity variation of 10Ω or less when measured at 20 points. Δ: Practical problem with surface resistivity variation of 10Ω or more when measured at 20 points. ×: When measured at 20 points. The surface resistivity variation of 15Ω or more is a practical problem.

As is clear from Table 1, it was found that the conductive film of the present invention has sufficient bending resistance and transparency, and can obtain uniform in-plane conductive performance.

INDUSTRIAL APPLICATION This invention can be utilized especially suitably for the conductive film which has a resin base material and a conductive film, the touch panel provided with the said conductive film, and the manufacturing method of the said conductive film.

Claims (4)

In a conductive film having a resin base material and a conductive film,
The resin substrate is viewed contains a solvent component and inorganic particles having a cycloolefin resin and a hydrogen-bonding donor groups having hydrogen bonding accepting groups,
The solvent component includes an alcohol solvent,
The electroconductive film, wherein the solvent component is contained in the resin substrate in an amount of 10 to 1000 ppm. The conductive film according to claim 1, wherein the solvent component includes water. A touch panel comprising the conductive film according to claim 1. In the method for producing a conductive film having a resin base material and a conductive film,
Wherein the resin substrate has a forming process that form a resin composition comprising a solvent component and inorganic particles having a cycloolefin resin and a hydrogen-bonding donor groups having hydrogen bonding accepting groups,
The solvent component includes an alcohol solvent,
The said solvent component is 10-1000 ppm contained in the said resin base material formed by the said formation process, The manufacturing method of the electrically conductive film characterized by the above-mentioned .