TWI772393B - Film with conductive layer and touch panel - Google Patents

Abstract

The present invention provides a film with a conductive layer, which has a conductive particle-containing resin film on a resin film containing a polyimide having an imide group concentration defined by the following formula (I) of 20.0% or more and 36.5% or less. A conductive layer with a gas barrier layer between the resin films and the conductive layer. This film with a conductive layer is suitable for use in, for example, a touch panel. The manufacturing method of this film with a conductive layer is suitable for the manufacturing method of a touch panel, for example.

(Molecular weight of imide moiety)/(Molecular weight of repeating unit of polyimide)×100[%] (I)

Description

Film with conductive layer and touch panel

The present invention relates to a film with a conductive layer, a touch panel, a method for manufacturing the film with a conductive layer, and a method for manufacturing the touch panel.

In recent years, in devices such as mobile phones and tablets, flexibility has been expected from the viewpoint of design, convenience, and durability. However, there are various problems in the flexibility of the device, and practical use has not yet been achieved.

Among them, the main subject is the improvement of bending resistance, visibility, and conductivity of the film with a conductive layer used in the device. Conventionally, as a film with a conductive layer, a thin film containing a transparent conductive metal such as indium tin oxide (ITO) has been widely used from the viewpoint of improving visibility. For example, Patent Document 1 and Patent Document 2 disclose a transparent conductive film formed by forming a thin film containing ITO on a polyimide film having excellent heat resistance. By patterning the thin film by etching, a film with a conductive layer excellent in visibility and conductivity can be obtained. However, since the ITO wiring is rigid and brittle, the bending resistance is low, and there is a problem that cracks occur when it is bent.

Therefore, various wiring techniques such as metal mesh wiring, metal nanowire wiring, and carbon nanotube wiring have been proposed as a transparent conductive layer that replaces ITO. Among them, metal mesh wiring is attracting attention as a transparent conductive layer that combines bending resistance, visibility, and high conductivity.

The metal mesh wiring can be obtained by forming the metal wiring so thin that it cannot be seen as a mesh pattern. For example, by using a metal having a small resistance value such as gold, silver, and copper, a wiring having good conductivity can be obtained. Furthermore, by containing an appropriate amount of an organic component capable of being patterned by photolithography and having excellent flexibility in the wiring, the bending resistance of the wiring can be improved. Such metal mesh wiring can also sufficiently cope with flexibility.

As a method of forming such a metal mesh wiring, for example, a method of using a conductive paste containing conductive metal particles (hereinafter referred to as conductive particles as appropriate) and an organic component, by screen printing, inkjet, optical lithography, etc. for patterning. However, it is necessary to reduce the particle diameter of the electroconductive particle to a nanometer size in order to form a fine pattern which cannot be visually recognized. Such electroconductive particles have a problem that they are fused and easily aggregated even at room temperature. Moreover, there exists a problem that the surface of an electroconductive particle reacts with an organic component, and the storage stability of an electroconductive paste falls. Furthermore, in the case of patterning using photolithography, the electroconductive particles have light reflectivity, which scatters the exposure light, so there is a problem that it is difficult to form a fine pattern.

In view of this, a method for solving the above-mentioned problems using electroconductive particles having a coating layer has been disclosed (for example, refer to Patent Document 3). By reducing the surface activity of the electroconductive particles by the coating layer, at least one of the reaction between the electroconductive particles and the reaction between the electroconductive particles and the organic component can be suppressed. In addition, in the case of using photolithography, it is also possible to suppress the scattering of exposure light and to pattern the wiring with high precision. The coating layer can be easily removed by heating the coated conductive particles at a high temperature of about 200°C. Therefore, sufficient conductivity can be exhibited in the wiring.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-186936

[Patent Document 2] Japanese Patent No. 5773090

[Patent Document 3] Japanese Patent Laid-Open No. 2013-196997

However, the technique disclosed in Patent Document 3 requires heating at about 200° C. in the presence of oxygen in order to remove the coating layer of the conductive particles. Therefore, high heat resistance and oxidation resistance are required for the substrate, and substantially only the glass substrate can be applied. Of course, it is difficult to cope with flexibility using a glass substrate. Furthermore, even when a film excellent in heat resistance is used, there is a problem in that the coloration of the film by heating in the presence of oxygen reduces the color tone, or the dimensional accuracy of the film is reduced, and positional displacement occurs, causing a problem called a so-called scale. It is a problem of poor appearance of moiré.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a film with a conductive layer, a touch panel, a method for producing a film with a conductive layer, and a touch control, which suppress yellowing when forming a conductive layer and are excellent in dimensional accuracy of the conductive layer. Method of manufacturing the panel.

As a result of diligent research conducted by the present inventors, the inventors have found that by providing a resin film (polyimide resin film) containing polyimide with a concentration of imide groups in a specific range, a gas is provided between the conductive layer and the The structure of the barrier layer can prevent the polyimide resin film from contacting with oxygen when the conductive layer is heated, thereby suppressing the polyimide resin film. Reduced color tone and dimensional accuracy.

That is, in order to solve the above-mentioned problems and achieve the object, the film with a conductive layer of the present invention is provided on a resin film containing a polyimide having an imide group concentration defined by the following formula (I) of 20.0% or more and 36.5% or less. , which has a conductive layer containing conductive particles, and the film with a conductive layer is characterized by having a gas barrier layer between the resin film and the conductive layer.

(Molecular weight of imide moiety)/(Molecular weight of repeating unit of polyimide)×100[%]…(I)

Moreover, in the film with a conductive layer of the present invention, in the above invention, the glass transition temperature of the resin film is 250° C. or higher.

Further, in the film with a conductive layer of the present invention, in the above-mentioned invention, the polyimide includes a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or A tetravalent organic group with a carbon number of 4~40 connected to each other through a cross-linking structure; R ² represents a divalent organic group with a carbon number of 4~40)

Further, in the film with a conductive layer of the present invention, in the above-mentioned invention, the polyimide includes a structural unit represented by the following general formula (2).

(In the general formula (2), R ³ represents a tetravalent organic group with 4 to 40 carbon atoms; R ⁴ represents a divalent organic group with 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, A divalent organic group having 4 to 40 carbon atoms in which organic groups having a monocyclic alicyclic structure are linked directly or via a cross-linking structure, or a divalent organic group represented by the following general formula (3))

[Chemical 3]-Ar ¹ -X ¹ -Ar ² - (3)

(In the general formula (3), X ¹ is a divalent hydrocarbon group having 1 to 3 carbon atoms which may be substituted by a halogen atom; Ar ¹ and Ar ² each independently represent a divalent aromatic group having 4 to 40 carbon atoms)

In addition, the film with a conductive layer of the present invention is characterized in that in the above-mentioned invention Among them, the polyimide has a structural unit represented by the following general formula (4) as a main component, and contains 5 mol% or more and 30 mol% or less of all structural units represented by the following general formula (5). Structural units.

(In general formula (4) and general formula (5), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic group A tetravalent organic group of carbon number 4 to 40 in which the organic group of the structure is connected directly or via a cross-linking structure; R ¹³ represents a divalent organic group represented by the following general formula (6); R ¹⁴ is the following structure The structure represented by the formula (7) or the following structural formula (8))

[hua 5]

(in the general formula (6), R ¹⁵ ~ R ²² independently represent a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 3 carbon atoms that can be substituted by a halogen atom; X ² is selected from a direct bond, oxygen structure of atoms, sulfur atoms, sulfonyl groups, divalent organic groups having 1 to 3 carbon atoms that may be substituted by halogen atoms, ester bonds, amide bonds, and thioether bonds)

Further, in the film with a conductive layer of the present invention, in the above-mentioned invention, the polyimide is characterized in that in at least one of an acid dianhydride residue and a diamine residue constituting the polyimide, It contains a repeating structure represented by the following general formula (9).

[hua 7]

(In the general formula (9), R ²³ and R ²⁴ each independently represent a monovalent organic group having 1 to 20 carbon atoms; m is an integer of 3 to 200)

In addition, in the film with a conductive layer of the present invention, in the above-mentioned invention, the polyimide includes a triamine skeleton.

In addition, in the film with a conductive layer of the present invention, in the above-mentioned invention, the gas barrier layer includes at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride.

In addition, the film with a conductive layer of the present invention is characterized in that in the above-mentioned invention, the gas barrier layer contains SiOxNy (x, y satisfy 0<x≦1, 0.55≦y≦1, and 0≦x/y≦1 value) of the components represented.

In addition, the film with a conductive layer of the present invention is characterized in that in the above-mentioned invention, the gas barrier layer is an inorganic film formed by laminating two or more layers, and a layer of the inorganic film in contact with the conductive layer is made of SiOz (z is a value that satisfies 0.5≦z≦2) represented by the composition.

Moreover, in the film with a conductive layer of the present invention, in the above-mentioned invention, the conductive particles are silver particles.

In addition, the film with a conductive layer of the present invention is characterized in that in the above-mentioned invention, the conductive layer has a film formed of an alkali-soluble resin including a cardo-based resin on the conductive layer. the insulating layer, the cardo-based resin has two or more structures represented by the following structural formula (10).

Moreover, the touch panel of this invention has the film with a conductive layer as described in any one of said inventions, and the said conductive layer is a wiring layer, It is characterized by the above-mentioned.

In addition, the method for producing a film with a conductive layer of the present invention is characterized by at least including: a resin film forming step of forming a resin film containing polyimide on a support substrate; and a gas barrier layer forming step of forming a gas barrier layer on the resin film a gas barrier layer; a conductive layer forming step of forming a conductive layer on the gas barrier layer; and a peeling step of peeling the resin film from the support substrate.

Further, in the method for producing a film with a conductive layer of the present invention, in the above-mentioned invention, the conductive layer forming step is characterized in that the conductive layer is formed using a conductive composition containing conductive particles having a coating layer on at least a part of the surface. the conductive layer.

In addition, in the method for producing a film with a conductive layer of the present invention, in the above-mentioned invention, the resin film forming step is characterized in that the oxygen concentration is 1000 ppm or less in a ring environment. The polyimide resin composition on the support substrate is heated at a temperature of 300°C or more and 500°C or less under ambient conditions to form the resin film, and the conductive layer forming step is performed at an oxygen concentration of 15% or more. The conductive composition on the gas barrier layer is heated at a temperature of 100° C. or higher and 300° C. or lower in an environment to form the conductive layer.

In addition, the method for producing a touch panel of the present invention uses the method for producing a film with a conductive layer according to any one of the above inventions, and the method for producing a touch panel is characterized in that the step of forming the conductive layer is: The step of forming a wiring layer as the conductive layer.

According to the present invention, it is possible to provide a film with a conductive layer, a touch panel, a method for producing a film with a conductive layer, and a method for producing a touch panel, which suppress yellowing during formation of the conductive layer and are excellent in dimensional accuracy of the conductive layer. Effect.

1: Resin film

2: Gas barrier layer

3: The first wiring layer

3A: Conductive layer

4: The first insulating layer

5: Second wiring layer

6: Second insulating layer

7: Support substrate

8: Cut the end face

10: Touch panel

11: Film with conductive layer

I-I': dotted line

S1~S7: Status

FIG. 1 is a schematic cross-sectional view showing a configuration example of a film with a conductive layer according to an embodiment of the present invention.

2 is a plan view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention.

3 is a schematic cross-sectional view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention.

FIG. 4 is a diagram showing a touch panel including a film with a conductive layer according to an embodiment of the present invention. A step diagram of an example of a manufacturing method.

Hereinafter, preferred embodiments will be described in detail about the film with a conductive layer, the touch panel, the method for producing the film with a conductive layer, and the method for producing a touch panel of the present invention. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose or application.

<Film with conductive layer>

The film with a conductive layer according to the embodiment of the present invention is a film with a conductive layer having a conductive layer containing conductive particles on a resin film containing polyimide, and has a gas barrier layer between the resin film and the conductive layer. In the present embodiment, the resin film contains a polyimide having an imide group concentration defined by the following formula (I) of 20.0% or more and 36.5% or less.

(Molecular weight of imide moiety)/(Molecular weight of repeating unit of polyimide)×100[%]…(I)

FIG. 1 is a schematic cross-sectional view showing a configuration example of a film with a conductive layer according to an embodiment of the present invention. As shown in FIG. 1 , the film 11 with a conductive layer includes a resin film 1 , a gas barrier layer 2 , and a conductive layer 3A. The resin film 1 is a polyimide resin film containing a polyimide having an imide group concentration defined by the formula (I) of 20.0% or more and 36.5% or less as described above. The gas barrier layer 2 is formed on the resin film 1 . The conductive layer 3A is a conductive layer containing conductive particles, and is formed on the gas barrier layer 2 .

In the film 11 with a conductive layer having such a configuration, as shown in FIG. 1 , the gas barrier layer 2 is interposed between the resin film 1 and the conductive layer 3A. Thereby, the gas resistance The spacer 2 can prevent oxygen from being heated to form the conductive layer 3A from coming into contact with the resin film 1 . As a result, the decrease in the color tone of the resin film 1 (for example, the decrease in color tone due to yellowing) caused by heating in the presence of oxygen is suppressed. Although not particularly shown in FIG. 1 , the film 11 with a conductive layer may further include an insulating layer on the conductive layer 3A.

2 is a plan view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention. 3 is a schematic cross-sectional view showing a configuration example of a touch panel including a film with a conductive layer according to an embodiment of the present invention. FIG. 3 shows a cross-sectional view of the touch panel 10 at the dotted line II' in FIG. 2 . The touch panel 10 is a touch panel including the film with a conductive layer 11 of the present embodiment. As shown in FIGS. 2 and 3 , the touch panel 10 includes a resin film 1 , a gas barrier layer 2 , a first wiring layer 3 , a first insulating layer 4 , a second wiring layer 5 and a second insulating layer 6 .

The resin film 1 and the gas barrier layer 2 are the same as the film 11 with a conductive layer shown in FIG. 1 . The first wiring layer 3 is an application example of the conductive layer 3A with the conductive layer film 11 . That is, the touch panel 10 includes the resin film 1 , the gas barrier layer 2 and the first wiring layer 3 as the film 11 with the conductive layer.

As shown in FIGS. 2 and 3 , the first wiring layer 3 is formed so as to form a desired wiring pattern on the gas barrier layer 2 on the resin film 1 . The first insulating layer 4 is formed on the first wiring layer 3 and the gas barrier layer 2 so as to cover other than the electrode portion in the first wiring layer 3 . The second wiring layer 5 is a wiring layer different from the first wiring layer 3 , and is formed so as to form a desired wiring pattern on the first insulating layer 4 and the gas barrier layer 2 . In the touch panel 10 , the first wiring layer 3 and the second wiring layer 5 are insulated by the first insulating layer 4 . The second insulating layer 6 covers the second wiring layer 5 are formed on the second wiring layer 5 and the first insulating layer 4 in ways other than the electrode portion.

(Resin film (polyimide resin film))

The resin film (for example, the resin film 1 shown in FIG. 1 ) used in the film with a conductive layer according to the embodiment of the present invention contains the imide group concentration defined by the above formula (I) of 20.0% or more and 36.5% or less. Polyimide.

Polyimide can be obtained by reacting diamine and tetracarboxylic dianhydride. Therefore, when the molecular weight of each monomer (diamine and tetracarboxylic dianhydride) increases, the polyimide obtained will have a higher molecular weight. The imine group concentration becomes smaller. When the imide group concentration is less than 20.0%, the interaction between the polyimide molecules formed by the imide groups becomes weak, and the glass transition temperature (Tg) of the polyimide decreases. In the film with a conductive layer, if the glass transition temperature of the resin film (polyimide resin film) serving as the substrate is low, the resin film cannot withstand the heat applied during formation of the gas barrier layer and the conductive layer. As a result, sufficient dimensional accuracy of the film with a conductive layer (eg, dimensional accuracy of the conductive layer) cannot be obtained. In addition, when the imide group concentration becomes greater than 36.5%, the interaction between the polyimide molecules formed by the imide groups becomes too strong, so that the polyimide molecules are crystallized in the resin film. As a result, the visibility of the film with a conductive layer deteriorates.

In the present invention, by setting the imide group concentration to a concentration within a range of 20.0% or more and 36.5% or less, a polyimide resin (constituting a film with a conductive layer) having a balance between heat resistance and transparency can be obtained resin film of polyimide). The imide group concentration is a value calculated by the following method.

The molecular weight of the imide moiety is the molecular weight of the (-CO-N-CO-) moiety contained in the repeating unit of the polyimide. The molecular weight of each imide group is 70.03. In addition, the molecular weight of the repeating unit of polyimide is the molecular weight of the part derived from the tetracarboxylic dianhydride and diamine which comprise one repeating unit. In this case, the imide group concentration can be calculated based on the formula (I). When a plurality of repeating units are present in the polyimide, the following value is defined as the imide group concentration of the polyimide: The value obtained by adding the contents of the cells to each other by multiplying them.

For example, in the case of polyimide represented by the following structural formula (A), the molecular weight of the imide group is the molecular weight of the portion surrounded by the dotted line. In this case, the molecular weight of the imide moiety was 140.06 (=70.03×2). In addition, the molecular weight of the repeating unit was 372.11. Therefore, based on the formula (I), the imide group concentration was 37.8% (=(140.06/372.11)×100).

In addition, in the case of a polyimide represented by the following structural formula (B) having a plurality of repeating units, based on the formula (I), the repeating unit G1 has an imide group concentration of 37.8% (= (140.06)/(372.11)×100). Based on the formula (I), the concentration of the imide group of the repeating unit G2 was 23.4% (=(140.06)/(598.66)×100). In addition, the number m contained in the repeating unit G1 and the number n contained in the repeating unit G2 have a relationship of m:n=90:10. Therefore, the imide group concentration of polyimide is 36.4% (=37.8%×0.90+23.4%×0.10).

In this invention, it is preferable that the glass transition temperature (Tg) of the resin film containing polyimide is 250 degreeC or more. This is because the deformation of the resin film is suppressed in the heating step when the gas barrier layer or the conductive layer is formed on the resin film, and as a result, the dimensional accuracy during processing of the conductive layer is further improved. The glass transition temperature of the resin film containing polyimide is more preferably 300°C or higher, and particularly preferably 350°C or higher.

As a measurement method of the glass transition temperature of a resin film, the measurement method (Thermomachanical Analysis (TMA) method) using a thermomechanical analyzer is mentioned. In the present invention, a small piece of resin film with a film thickness of 10 μm to 20 μm, a width of 15 mm, and a length of 30 mm is rolled up in the longitudinal direction to form a cylindrical sample with a diameter of 3 mm and a height of 15 mm. The inflection point of the TMA curve when the sample was heated in the compression mode at a temperature increase rate of 5°C/min was set as the glass transition temperature of the resin film.

In the present invention, the polyimide used for the resin film with a conductive layer film preferably contains a structural unit represented by the following general formula (1).

In the general formula (1), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly or via A tetravalent organic group with a carbon number of 4 to 40 formed by a cross-linked structure. R ² represents a divalent organic group having 4 to 40 carbon atoms.

When the polyimide contains the structural unit represented by the general formula (1), the coefficient of thermal expansion (CTE) of the polyimide becomes low. Therefore, when a polyimide film is formed on a support substrate for processes such as formation of a conductive layer, the warpage of the polyimide is reduced, and the dimensional accuracy can be improved in the processing of the conductive layer.

R ¹ in the general formula (1) represents the structure of the acid component. In the alicyclic structure in R ¹ , a part of hydrogen atoms may be substituted with halogen. The acid dianhydride having an alicyclic structure is not particularly limited, and examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4 ,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid di anhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[ 4.4.0] Decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0 <2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2 .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-5-carboxymethyl base-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6 ,7-Tetracarboxylic dianhydride, Tetrahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexanetetracarboxylic dianhydride, 3, 3',4,4'-Oxybicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene- 1,2-Dicarboxylic acid anhydride, "RIKACID" (registered trademark) BT-100 (the above are trade names, manufactured by Nippon Chemical Co., Ltd.), derivatives thereof, and the like.

R ¹ in the general formula (1) is preferably at least one selected from the group consisting of six structures represented by the following structural formulae (11) to (16).

[Chemical 12]

Among the above-mentioned six structures, R ¹ is more preferably represented by the following structural formulas (17) to (19) from the viewpoint of being commercially available and easy to obtain and from the viewpoint of reactivity with the diamine compound structure. Examples of acid dianhydrides that can provide these structures to R ¹ include 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride (for example, manufactured by Wako Pure Chemical Industries, Ltd., product name "PMDA-HH") , 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride (for example, manufactured by Wako Pure Chemical Industries, product name "PMDA-HS"), 1,2,3,4-cyclobutanetetracarboxylic acid two Anhydride etc. In addition, these acid dianhydrides can be used individually or in combination of 2 or more types.

In the general formula (1), R ² represents the structure of the diamine component. The diamine compound used for R ² is not particularly limited, and examples thereof include an aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound.

The aromatic diamine compound is not particularly limited, and examples thereof include 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6 -Naphthalenediamine, bis{4-(4-aminophenoxyphenyl)}sine, bis{4-(3-aminophenoxyphenyl)}sine, bis(4-aminophenoxyphenyl) ) biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 9,9-bis(4-aminophenyl)pyridine, 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3-aminophenyl-4-aminobenzenesulfonate, 4 -Aminophenyl-4-aminobenzenesulfonate, or a diamine compound in which a part of the aromatic ring of these compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

The alicyclic diamine compound is not particularly limited, and examples thereof include cyclobutanediamine, isophoronediamine, bicyclo[2.2.1]heptanebismethylamine, and tricyclo[3.3.1.13,7]decane Alkane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3 ,3'-Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5, 5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5 -Diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl- 4,4'-Diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4 ,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3', 5'-Dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-amino) Cyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2, 2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3',5'-dimethyl-4,4'-di aminodicyclohexyl) Propane, 2,2'-bis(4-aminocyclohexyl)hexafluoropropane, 2,2'-dimethyl-4,4'-diaminobicyclohexane, 2,2'-bis(trifluoropropane) methyl)-4,4'-diaminobicyclohexane, or a diamine compound in which a part of the aliphatic ring of these compounds is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

The aliphatic diamine compound is not particularly limited, and examples thereof include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminopentane. Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and other alkylene diamines Amines; ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether; and 1,3-bis(3- Aminopropyl) tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethyl Siloxane diamines such as base siloxane.

These aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds may be used alone or in combination of two or more.

Moreover, in this invention, it is preferable that the polyimide used for the resin film with a conductive layer film contains the structural unit represented by following General formula (2).

In the general formula (2), R ³ represents a tetravalent organic group having 4 to 40 carbon atoms. R ⁴ represents a divalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, and organic groups having a monocyclic alicyclic structure are connected to each other directly or via a crosslinking structure A divalent organic group having 4 to 40 carbon atoms, or a divalent organic group represented by the following general formula (3).

[Chemical 15]-Ar ¹ -X ¹ -Ar ² - (3)

In the general formula (3), X ¹ is a divalent hydrocarbon group having 1 to 3 carbon atoms which may be substituted by a halogen atom. Ar ¹ and Ar ² each independently represent a divalent aromatic group having 4 to 40 carbon atoms.

When the polyimide contains the structural unit represented by the general formula (2), the thermal expansion coefficient of the polyimide becomes low. Therefore, when a polyimide film is formed on a support substrate for processes such as formation of a conductive layer, the warpage of the polyimide is reduced, and the dimensional accuracy can be improved in the processing of the conductive layer.

R ³ in the general formula (2) represents the structure of an acid component. The acid dianhydride used for R ³ is not particularly limited, and other than the acid dianhydride having the above-mentioned alicyclic structure, aromatic acid dianhydrides and aliphatic acid dianhydrides may also be mentioned.

The aromatic acid dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-terphenyltetracarboxylic dianhydride, 3,3',4,4 '-Oxyphthalene Dicarboxylic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic acid dianhydride, diphenyl-3, 3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2 ,3-Dicarboxyphenyl)ethanedianhydride,bis(3,4-dicarboxyphenyl)methane dianhydride,bis(2,3-dicarboxyphenyl)methane dianhydride,bis(3,4-dicarbonate) Carboxyphenyl) ether dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-benzene, 2,2-bis(4-(4) -Aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6- Pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4 -(3,4-Dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropanedi Anhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-di-trifluoromethylpyromellitic dianhydride, 2,2'- Bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy) Phenyl]perylene dianhydride, 4,4'-((9H-phenylene)bis(4,1-phenyleneoxycarbonyl))diphthalic dianhydride, "RIKACID" (registered Aromatic tetracarboxylic dianhydrides such as trademark) TMEG-100 (trade name, manufactured by Nippon Chemical Co., Ltd.), derivatives thereof, and the like.

The aliphatic acid dianhydride is not particularly limited, and examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof things etc.

In the general formula (2), R ⁴ represents the structure of the diamine component. The diamine compound used for R ⁴ , that is, the diamine compound having an alicyclic structure is not particularly limited, and examples thereof include cyclobutanediamine, isophoronediamine, and bicyclo[2.2.1]heptanebismethyl. base amine, tricyclo[3.3.1.13,7]decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4 ,4'-Diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diamine Dicyclohexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4 '-Diaminodicyclohexylmethane, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexane Cyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3, 3',5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2, 2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl) yl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3', 5'-dimethyl-4,4'-diaminodicyclohexyl)propane, 2,2'-bis(4-aminocyclohexyl)hexafluoropropane, 2,2'-dimethyl-4, 4'-diaminobicyclohexane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobicyclohexane, or by an alkyl group, an alkoxy group, a halogen atom, etc. A diamine compound in which a part of the aliphatic ring of the compound is substituted.

The diamine that provides the structure represented by the general formula (3) is not particularly limited, and examples thereof include 2,2-bis(3-aminophenyl)propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2- Bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, etc.

In the present invention, the polyimide used in the resin film with a conductive layer film preferably has a structural unit represented by the following general formula (4) as a main component, and contains the polyimide The structural unit represented by the following general formula (5) accounts for 5 mol % or more and 30 mol % or less in all structural units of the imide.

In general formula (4) and general formula (5), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic structure A tetravalent organic group with a carbon number of 4 to 40 in which the organic groups are connected directly or via a cross-linking structure. R ¹³ represents a divalent organic group represented by the following general formula (6). R ¹⁴ is a structure represented by the following structural formula (7) or the following structural formula (8).

[Chemical 17]

In the general formula (6), R ¹⁵ to R ²² each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom. X ² is a structure selected from a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom, an ester bond, an amide bond, and a thioether bond.

In addition, the oxazole ring in structural formula (8) is produced by dehydration ring closure of the structure represented by structural formula (7).

Here, "the structural unit represented by the general formula (4) as a main component" means that the structure represented by the general formula (4) has 50 mol% or more in the total amount of all the structural units of the polyimide. unit. When the structural unit represented by the general formula (4) is used as the main component in the polyimide, the thermal expansion coefficient of the polyimide becomes low. therefore, When a polyimide film is formed on a support substrate for processes such as formation of a conductive layer, the warpage of the polyimide is reduced, and the dimensional accuracy can be improved in the processing of the conductive layer.

In addition, the total amount of all the structural units of the polyimide is specifically the total amount (mol basis) of the structural units represented by the general formula (4) and the general formula (5). When the polyimide contains a structure other than the structural unit represented by the general formula (4) and the general formula (5), the total amount is represented by the general formula (4) and the general formula (5). The total amount (on a mol basis) of the structural unit and the structure other than the structural unit represented by the general formula (4) and the general formula (5).

In the present invention, the content of the structural unit represented by the general formula (4) is more preferably 70 mol % or more in all the structural units of the polyimide.

In addition, when the polyimide contains the structural unit represented by the general formula (5) accounting for 5 mol % or more and 30 mol % or less in all structural units, the transparency of the resin film can be improved, and the polyimide can be improved. The thermal expansion coefficient is kept low. Thereby, the color tone of the film with a conductive layer (and thus a touch panel including the same) can be improved while maintaining the pattern processability of the conductive layer. The content of the structural unit (repeating structural unit) represented by the general formula (5) in the polyimide is more preferably 10 mol % or more and 25 mol % or less in all the structural units of the polyimide.

R ¹ in general formula (4) and general formula (5) is the same as R ¹ in general formula (1), and represents the structure of an acid component having an alicyclic structure. Preferred specific examples of R ¹ are as described above. R ¹³ in the general formula (4) and R ¹⁴ in the general formula (5) represent the structure of the diamine component.

The diamine that provides the structure represented by the general formula (6) for R ¹³ is not particularly limited, and examples thereof include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-aminophenyl) -4-Hydroxyphenyl) hexafluoropropane, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, benzidine, 2,2'-bis(triphenylene) Fluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3 ,3'-tetramethylbenzidine, 4,4-diaminobenzylaniline, 4-aminobenzoic acid-4-aminophenyl ester, 3,4-diaminobenzylaniline, 4 ,4-diaminobenzophenone, 3,3-diaminobenzophenone, or diaminobenzophenone substituted with an alkyl group, an alkoxy group, a halogen atom, etc. Amine compounds.

From the viewpoints of easiness of acquisition, transparency, and reduction of the thermal expansion coefficient of polyimide, R ¹³ is preferably selected from, for example, four structures represented by the following structural formulas (20) to (23) more than one of them.

In the present invention, the polyimide used for the resin film with a conductive layer film may contain other structural units within a range that does not inhibit the effects of the present invention. as other knots As a structural unit, polyimide which is a dehydration ring-closed body of polyamide acid, polybenzoxazole which is a dehydration ring-closed body of polyhydroxyamide, etc. are mentioned. As an acid dianhydride used for another structural unit, the said aromatic acid dianhydride or aliphatic acid dianhydride is mentioned.

Moreover, in this invention, it is preferable that the polyimide used in the resin film with a conductive layer film contains at least one of the acid dianhydride residue and the diamine residue constituting the polyimide. A repeating structure represented by the following general formula (9).

In the general formula (9), R ²³ and R ²⁴ each independently represent a monovalent organic group having 1 to 20 carbon atoms. m is an integer from 3 to 200.

Since the polyimide contains the structure represented by the general formula (9) in at least one of the acid dianhydride residue and the diamine residue, the polyimide is placed on the support substrate for processes such as conductive layer formation. The residual stress of the polyimide resin film is reduced when the film is formed from imide. Therefore, the warpage of the polyimide is reduced, and the dimensional accuracy can be improved in the processing of the conductive layer.

However, the film with a conductive layer has a problem that static electricity is generated on the film and disconnection due to electrostatic discharge (ESD) occurs. On the other hand, since the dielectric constant of the polyimide containing the structure represented by the general formula (9) is low, A film with a conductive layer including a resin film containing such a polyimide is difficult to accumulate electric charges in devices such as a touch panel using the same, and ESD resistance becomes high. Therefore, it is preferable that the polyimide used for the resin film with a conductive layer film contains the repeating structure represented by General formula (9) as mentioned above.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ²³ and R ²⁴ in the general formula (9) include a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent amine having 1 to 20 carbon atoms. Alkyl, alkoxy, epoxy, etc.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary Butyl, pentyl, hexyl, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, and the like. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the monovalent alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group. Base et al.

Among these, R ²³ and R ²⁴ are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms. The reason for this is that the obtained polyimide resin film has higher heat resistance and lower residual stress. Here, the monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms is particularly preferably a methyl group. The aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

m in the general formula (9) is preferably an integer of 10 to 200, more preferably 20 to 20 The integer of 150 is more preferably an integer of 30 to 100, and the integer of 35 to 80 is particularly preferred. When m is 3 or more, it becomes easy to reduce the residual stress of a polyimide resin film. When m is 200 or less, cloudiness of the varnish containing a polyimide precursor and a solvent which is a composition for obtaining polyimide can be suppressed.

Specific examples of the acid dianhydride containing the repeating structure represented by the general formula (9) are not particularly limited, and examples thereof include X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A (manufactured by Shin-Etsu Chemical Co., Ltd., Number average molecular weight 2,000), X22-168B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,200), DMS-Z21 (Gelest (Gelest) ) company, the number average molecular weight 600~800) and so on.

Specific examples of the diamine containing the repeating structure represented by the general formula (9) are not particularly limited, and examples include: both-terminal amino group-modified methylphenyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.; X22-1660B-3 (quantity). Average molecular weight 4,400), X22-9409 (number average molecular weight 1,300)), two-terminal amino group-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.; X22-161A (number average molecular weight 1,600), X22-161B (number average molecular weight) 3,000), KF8012 (number average molecular weight 4,400), manufactured by TORAY Dow Corning; BY16-835U (number average molecular weight 900), manufactured by Chisso Corporation; Silaplane FM3311 (number average molecular weight) Molecular weight 1000)) and so on.

Moreover, in this invention, it is preferable that the polyimide used for the resin film with a conductive layer film contains a triamine skeleton. By including the triamine backbone in the polyimide, the The toughness of the polyimide is improved, thereby enabling the yield of subsequent steps to be improved.

Among the specific examples of the triamine compound, those having no aliphatic group include 2,4,4'-triamino diphenyl ether (2,4,4'-triamino diphenyl ether, TAPE), 1,4'-triamino diphenyl ether (TAPE), 3,5-Tris(4-aminophenoxy)benzene (1,3,5-tris(4-aminophenoxy)benzene, TAPOB), Tris(4-aminophenyl)amine, 1,3,5- Tris(4-aminophenyl)benzene, 3,4,4'-triaminodiphenyl ether, etc. In addition, among specific examples of the triamine compound, those having an aliphatic group include tris(2-aminoethyl)amine (TAEA), tris(3-aminopropyl) ) amine, etc. Among these, it is preferable to use 2,4,4'-triaminodiphenyl ether and 1,3,5-tris(4-aminophenoxy)benzene from the viewpoint of heat resistance improvement. .

From the viewpoint of improving the toughness of the film with a conductive layer (and thus the toughness of the touch panel), the thickness of the resin film used for the film with a conductive layer of the present invention is preferably 1 μm or more, more preferably 2 μm or more , and more preferably 5 μm or more. On the other hand, from the viewpoint of further improving the transparency of the film with a conductive layer, the thickness of the resin film is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less.

From the viewpoint of improving the image quality of the touch panel, the transmittance at a wavelength of 450 nm of the resin film used for the film with a conductive layer of the present invention is preferably 85% or more. Moreover, it is preferable that the transmittance|permeability in wavelength 450nm of the resin film after heat-processing at 150 degreeC - 350 degreeC is 80 % or more.

The resin film used in the film with a conductive layer of the present invention can be used in the polyimide or its precursor, and an organic solvent, a surfactant, a leveling agent can be prepared as necessary. It is formed by a resin composition consisting of an agent, an adhesion improver, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye, and the like.

One of the methods of obtaining the resin film used for the film with a conductive layer of the present invention is to subject polyimide to ring-closure with polyimide, which is a precursor corresponding to the polyimide to be obtained. The method of imidization is not particularly limited, and thermal imidization or chemical imidization can be mentioned. Among them, thermal imidization is preferable from the viewpoint of the heat resistance of the polyimide resin film and the transparency in the visible light region.

Polyimide precursors such as polyamide, polyamide ester, polyamide silyl ester, etc. can be synthesized by the polymerization reaction of diamine compound and acid dianhydride or its derivatives. As a derivative of an acid dianhydride, the tetracarboxylic acid of an acid dianhydride, the monoester, diester, triester, or tetraester of this tetracarboxylic acid, oxychloride, etc. are mentioned. Specifically, examples of derivatives of acid dianhydrides include those obtained by esterification with methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and the like. . The reaction method of the polymerization reaction is not particularly limited as long as the target polyimide precursor can be produced, and a known reaction method can be used.

As a specific reaction method of the polymerization reaction, there may be mentioned a method in which a predetermined amount of all the diamine components and the solvent are put into a reactor, after dissolving the diamine, a predetermined amount of the acid dianhydride component is charged, and the Stir at room temperature to 80°C for 0.5 hours to 30 hours.

In the present invention, both ends of the polyimide and the polyimide precursor used in the resin film with a conductive layer film may be blocked by a blocking agent in order to adjust the molecular weight to a suitable range. As the end-capping agent to be reacted with acid dianhydride, monoamine or monovalent alcohol etc. Moreover, as a blocking agent which reacts with a diamine compound, an acid anhydride, a monocarboxylic acid, a monochloride compound, a monoactive ester compound, a dicarbonate, vinyl ether, etc. are mentioned. In addition, by reacting an end-capping agent at both ends of the polyimide or polyimide precursor, various organic groups as end groups can be introduced at both ends of these. A known compound can be used as a blocking agent.

The introduction ratio of the end-capping agent on the acid anhydride group side is preferably in the range of 0.1 mol % to 60 mol %, more preferably in the range of 0.5 mol % to 50 mol %, relative to the acid dianhydride component. In addition, the introduction ratio of the blocking agent on the amine group side is preferably in the range of 0.1 mol % to 100 mol % relative to the diamine component, and more preferably in the range of 0.5 mol % to 70 mol %. It is also possible to introduce a plurality of different end groups at both ends of the polyimide or polyimide precursor by reacting a plurality of end capping agents at both ends of the polyimide or polyimide precursor.

The capping agent introduced into the polyimide precursor or polyimide can be easily detected by the following method. For example, the polymer into which the terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component which are structural units of the polymer. These are determined using gas chromatography (GS) or nuclear magnetic resonance (NMR), whereby the capping agent can be easily detected. In addition, the polymer into which the end-capping agent has been introduced is directly subjected to measurement by pyrolysis gas chromatography (PGC), infrared spectroscopy, ¹ H NMR spectroscopy, and ¹³ C NMR spectroscopy, etc., and can also be easily detected. to the capping agent.

In addition to the polyimide or polyimide precursor in the composition for obtaining the resin film containing polyimide (hereinafter referred to as "polyimide resin composition"), Appropriate ingredients may also be included. Components that can be included in the polyimide resin composition are not particularly limited, and examples thereof include ultraviolet absorbers, thermal crosslinking agents, inorganic fillers, surfactants, internal release agents, colorants, and the like. For each of these, known compounds can be used.

In the present invention, for example, the term "tetravalent organic group having 4 to 40 carbon atoms" means a tetravalent organic group having 4 to 40 carbon atoms. The same applies to other groups whose carbon numbers are specified.

(gas barrier layer)

As exemplified by the gas barrier layer 2 shown in FIG. 1 , the film with a conductive layer according to the embodiment of the present invention has a gas barrier layer. The gas barrier layer in the present invention refers to a layer formed on a resin film serving as a substrate and having a function of preventing direct contact between the resin film and the gas in the environment. When a conductive layer containing conductive particles is formed on a resin film, a high temperature of 200° C. or higher is applied to the resin film in the presence of oxygen. Therefore, if there is no gas barrier layer, yellowing due to thermal oxidation occurs on the resin film, and the color tone of the film with a conductive layer is thus deteriorated. By forming a gas barrier layer between the resin film and the conductive layer, the resin film can be prevented from coming into contact with oxygen during heating in an oxygen environment. In this way, a film with a conductive layer excellent in color tone without yellowing can be obtained.

The material constituting the gas barrier layer may be an organic material or an inorganic material as long as it prevents the permeation of oxygen when the conductive layer is formed, but from the viewpoint of oxygen barrier properties, an inorganic material is preferred. Examples of the inorganic material include metal oxides, metal nitrides, metal oxynitrides, and metal carbonitrides. Examples of metal elements contained in these include aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), and niobium. (Nb), Molybdenum (Mo), Tantalum (Ta), calcium (Ga), etc.

In particular, the gas barrier layer preferably includes at least one of silicon oxide, silicon nitride, silicon oxynitride and silicon carbonitride. The reason for this is that by using these materials for formation of the gas barrier layer, it becomes easy to obtain a uniform and dense film with gas barrier properties, and the oxygen barrier properties of the gas barrier layer are further improved.

In addition, from the viewpoint of further improving the oxygen barrier properties, the gas barrier layer preferably contains a component represented by SiOxNy. x and y are values satisfying 0<x≦1, 0.55≦y≦1, and 0≦x/y≦1.

The gas barrier layer can be formed by, for example, sputtering, vacuum evaporation, ion plating, plasma chemical vapor deposition (chemical vapor deposition, CVD), etc., by depositing materials from a vapor phase to form a vapor deposition film. method to make. Among them, it is preferable to use a sputtering method or a plasma CVD method in order to obtain a more uniform film with high oxygen barrier properties.

The number of layers of the gas barrier layer is not limited, and it may be only one layer or a multi-layer of two or more layers. Examples of the case where the gas barrier layer is a multilayer film include a gas barrier layer in which the first layer contains SiN and the second layer contains SiO, or a gas barrier layer in which the first layer contains SiON and the second layer contains SiO.

In the present invention, it is preferable that the gas barrier layer is an inorganic film formed by laminating two or more layers, and the layer in contact with the conductive layer in the inorganic film is represented by SiOz (z is a value satisfying 0.5≦z≦2). ingredient formation. The reason for this is that the chemical resistance of the gas barrier layer at the time of processing the conductive layer (in particular, at the time of development in the case of photolithography) is improved, and the pattern processability and dimensional accuracy of the conductive layer can be improved, and residue suppression, etc. can be improved. Effect.

From the viewpoint of improving the oxygen barrier properties, the total thickness of the gas barrier layers is preferably 10 nm or more, and more preferably 50 nm or more. On the other hand, from the viewpoint of improving the bending resistance of the film with a conductive layer, the total thickness of the gas barrier layers is preferably 1 μm or less, and more preferably 200 nm or less.

(conductive layer)

As illustrated in the conductive layer 3A shown in FIG. 1 , the film with a conductive layer according to the embodiment of the present invention has a conductive layer containing conductive particles. The conductive layer preferably has a mesh structure with a line width of 0.1 μm to 9 μm. Since the conductive layer has a mesh structure with a line width of 0.1 μm to 9 μm, the conductivity and visibility of the conductive layer can be improved. The line width of the mesh structure of the conductive layer is more preferably 0.5 μm or more, and still more preferably 1 μm or more. On the other hand, the line width of the mesh structure of the conductive layer is more preferably 7 μm or less, and still more preferably 6 μm or less.

In addition, the film thickness of the conductive layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. On the other hand, the film thickness of the conductive layer is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less.

Examples of the conductive particles contained in the conductive layer include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), Metal particles such as zinc (Zn), palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), and molybdenum (Mo), and metal particles having carbon. The metal particles having carbon are, for example, a composite of carbon black and metal. As this electroconductive particle, these 2 or more types can also be used. Among them, metal particles of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum or aluminum, and metal particles having carbon are preferred, and silver particles are more preferred.

In order to form a fine conductive pattern with desired conductivity, the The primary particle size of the sexual particles is preferably 10 nm to 200 nm, more preferably 10 nm to 60 nm. Here, the primary particle diameter of the conductive particles is calculated by observing the cross section of the conductive layer with a scanning electron microscope, randomly selecting 100 particles, measuring the primary particle diameter of each particle, and taking these The arithmetic mean of the primary particle size. In addition, the particle diameter of the primary particle of each particle is the arithmetic mean value of the longest part and the shortest part of the diameter of the primary particles.

From the viewpoint of improving conductivity, the content of the conductive particles in the conductive layer is preferably 20% by mass or more, more preferably 50% by mass or more, and still more preferably 65% by mass or more. On the other hand, from the viewpoint of improving pattern workability, the content of the electroconductive particles is preferably 95% by mass or less, more preferably 90% by mass or less.

In addition, the conductive layer preferably contains an organic compound in an amount of 0.1% by mass to 80% by mass. When the conductive layer contains 0.1 mass % or more of the organic compound, flexibility can be imparted to the conductive layer, and the bending resistance of the conductive layer can be further improved. The content of the organic compound in the conductive layer is more preferably 1 mass % or more, still more preferably 5 mass % or more. On the other hand, when the conductive layer contains an organic compound in an amount of 80 mass % or less, the conductivity can be improved. The content of the organic compound in the conductive layer is more preferably 50 mass % or less, further preferably 35 mass % or less.

The organic compound contained in the conductive layer is preferably an alkali-soluble resin. As an alkali-soluble resin, the (meth)acrylic-type copolymer which has a carboxyl group is preferable. Here, a (meth)acrylic-type copolymer means the copolymer of a (meth)acrylic-type monomer and another monomer.

As a (meth)acrylic-type monomer, (meth)acrylic acid is mentioned, for example Methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, (meth)acrylate base) isobutyl acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, butyl (meth)acrylate oxyethyl ester, butoxytriethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, ( 2-ethylhexyl meth)acrylate, glycerol (meth)acrylate, glycidyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, 2-hydroxy (meth)acrylate Ethyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate , 2-Methoxyethyl (meth)acrylate, Methoxyethylene glycol (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, Octafluoropentyl (methyl) Acrylates, phenoxyethyl (meth)acrylate, stearyl (meth)acrylate, trifluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acrylate Ethyl ethyl ester, phenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, thiophenol (meth)acrylate, benzyl mercaptan ( meth)acrylate.

Examples of other monomers include compounds having a carbon-carbon double bond, and examples thereof include aromatics such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene. Vinyl compounds; amide-based unsaturated compounds such as (meth)acrylamide, N-methylol (meth)acrylamide, and N-vinylpyrrolidone; (meth)acrylonitrile, allyl Alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether.

In order to introduce a carboxyl group that imparts alkali solubility into the alkali-soluble resin, for example, (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, acid anhydrides of these, etc. The method for copolymerizing the (meth)acrylic monomers.

From the viewpoint of increasing the speed of the hardening reaction, the (meth)acrylic copolymer preferably has a carbon-carbon double bond in a side chain or a molecular terminal. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, a (meth)acrylic group etc. are mentioned, for example.

The carboxylic acid equivalent of the alkali-soluble resin is preferably 400 g/mol to 1,000 g/mol. The carboxylic acid equivalent of the alkali-soluble resin can be calculated by measuring the acid value. In addition, it is preferable that the double bond equivalent of the alkali-soluble resin is 150 g/mol to 10,000 g/mol because both hardness and crack resistance can be achieved at a high level. The double bond equivalent of the alkali-soluble resin can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 100,000. By setting the weight average molecular weight to be within the above range, favorable coating properties of the alkali-soluble resin can be obtained, and the solubility of the alkali-soluble resin in a developing solution when patterning on the conductive layer is also improved. Here, the weight average molecular weight of the alkali-soluble resin means a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

In addition, the conductive layer may contain at least one of an organic tin compound and a metal chelate compound. By containing at least one of an organic tin compound and a metal chelate compound in the conductive layer, the adhesion between the conductive layer and the gas barrier layer can be further improved. In particular, metal chelate compounds can be used without causing environmental burdens compared to organotin compounds. Since the adhesiveness improvement effect is obtained, it is more preferable. As the organotin compound and the metal chelate compound, known compounds can be used.

From the viewpoint of further improving the substrate adhesion, the total content of the organotin compound and the metal chelate compound in the conductive layer is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more . On the other hand, from the viewpoint of improving the conductivity of the conductive layer and forming a finer pattern, the total content of these organotin compounds and metal chelate compounds is preferably 10% by mass or less, more preferably 5% by mass Below, more preferably, it is 3 mass % or less.

The conductive layer preferably also contains at least a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a solvent, a sensitizer, a pigment that absorbs visible light, and a dye in addition to this. One, an adhesion improver, a surfactant, a polymerization inhibitor, and the like.

In addition, the conductive layer in the present invention can be formed using a conductive composition. Examples of components contained in the conductive composition include conductive particles, alkali-soluble resins, organotin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, heat An acid generator, a solvent, a sensitizer, at least one of a pigment and a dye having absorption under visible light, an adhesion improver, a surfactant, a polymerization inhibitor, and the like.

It is preferable that the electroconductive particle contained in an electroconductive composition has a coating layer in at least a part of the particle|grain surface. Thereby, the surface activity of electroconductive particle can be reduced, and at least one of the reaction of electroconductive particle and the reaction of electroconductive particle and an organic component can be suppressed, and the dispersibility of electroconductive particle can be improved. Furthermore, in When photolithography is used for the processing of the conductive layer, scattering of exposure light can be suppressed, and the conductive layer can be patterned with high precision. On the other hand, the coating layer on the surface of the electroconductive particle can be easily removed by heating at a high temperature of about 150°C to 350°C in the presence of oxygen. As a result, the conductive particles in the conductive composition can express sufficient conductivity of the conductive layer.

It is preferable that the coating layer on the surface of the electroconductive particle contains at least one of carbon and a carbon compound. When the coating layer contains at least one of carbon and a carbon compound, the dispersibility of the conductive particles in the conductive composition can be further improved.

As a method of forming a coating layer containing at least one of carbon and a carbon compound on the surface of the conductive particles, for example, by a thermal plasma method, a reactive gas having carbon such as methane gas can be brought into contact with the conductive particles. method (the method described in Japanese Patent Laid-Open No. 2007-138287) and the like.

(Insulation)

The film with a conductive layer according to the embodiment of the present invention preferably has an insulating layer formed of an alkali-soluble resin on the conductive layer. The so-called alkali solubility in the present invention means that 0.1 g or more is dissolved at 25° C. with respect to a 0.045 mass % potassium hydroxide aqueous solution (100 g). It is preferable that the insulating layer formed of the alkali-soluble resin can be patterned by photolithography, whereby openings for conduction of the conductive layer can be formed.

Further, the film with a conductive layer according to the embodiment of the present invention preferably has an insulating layer formed of an alkali-soluble resin containing the (meth)acrylic copolymer on the conductive layer. The reason for this is that the flexibility of the insulating layer is improved by the (meth)acrylic copolymer in the alkali-soluble resin.

Furthermore, the film with a conductive layer according to the embodiment of the present invention preferably has, on the conductive layer, an insulating layer formed of an alkali-soluble resin containing a cardo-based resin having two or more of the following structural formulas ( 10) The structure represented. The reason for this is that the cardo-based resin can improve the hydrophobicity of the insulating layer, thereby improving the insulating properties of the insulating layer.

Cardo-type resin can be obtained, for example, by reacting the reactant of an epoxy compound and a radically polymerizable group-containing organic acid with an acid dianhydride. Examples of catalysts used for the reaction between an epoxy compound and a radically polymerizable group-containing organic acid and for the reaction between an epoxy compound and an acid dianhydride include ammonium-based catalysts, amine-based catalysts, and phosphorus-based catalysts. media, chromium catalysts, etc. As an ammonium catalyst, tetrabutylammonium acetate etc. are mentioned, for example. As an amine catalyst, 2,4,6- tris (dimethylaminomethyl) phenol, dimethylbenzylamine, etc. are mentioned, for example. As a phosphorus-type catalyst, triphenylphosphine etc. are mentioned, for example. Examples of the chromium-based catalyst include chromium acetylacetonate, chromium chloride, and the like. Moreover, as an epoxy compound, the following compounds are mentioned, for example.

Examples of the radically polymerizable group-containing organic acid include (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, mono(2-(2-() phthalate) Meth)acryloyloxyethyl) ester, mono(2-(meth)acryloyloxyethyl) tetrahydrophthalate, p-hydroxystyrene and the like.

As the acid dianhydride, from the viewpoint of improving the chemical resistance of the cured film, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3 ,3',4-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, etc. In addition, for the purpose of adjusting the molecular weight of the acid dianhydride, a part of the acid dianhydride may be substituted with the acid anhydride.

Moreover, as a cardo-type resin which has a structure represented by two or more structural formula (10), a commercial item can be used suitably. Examples of commercially available products of this cardo-based resin include "WR-301 (trade name)" (manufactured by ADEKA), "V-259ME (trade name)" (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) Company), "OGSOL (OGSOL) CR-TR1 (trade name)", "OGSOL (OGSOL) CR-TR2 (trade name)", "OGSOL (OGSOL) CR-TR3 (trade name)", "OGSOL (OGSOL) CR-TR4 (trade name)", "OGSOL (OGSOL) CR-TR5 (trade name)" Name)", "OGSOL (OGSOL) CR-TR6 (trade name)" (the above are manufactured by Osaka Gas Chemical Co., Ltd.), etc.

From the viewpoint of improving coating properties, the weight average molecular weights of the (meth)acrylic-based copolymer and the cardo-based resin are preferably 2,000 or more, respectively. In addition, from the viewpoint of improving the solubility of the insulating layer in the developing solution at the time of patterning the insulating layer, the weight average molecular weights of these are preferably 200,000 or less, respectively. Here, the weight average molecular weight means a polystyrene conversion value measured by GPC.

Moreover, when an insulating layer contains both a (meth)acrylic-type copolymer and a cardo-type resin, from the viewpoint of suppressing layer separation and forming a uniform cured film, the weight of the (meth)acrylic-type copolymer The ratio (Mw(A2)/Mw(A1)) of the average molecular weight (Mw(A1)) to the weight average molecular weight (Mw(A2)) of the cardo-based resin is preferably 0.14 or more. On the other hand, from the viewpoint of suppressing layer separation and forming a uniform cured film, the ratio (Mw(A2)/Mw(A1)) is preferably 1.5 or less, more preferably 1.0 or less.

The insulating layer in the present invention can be formed using an insulating composition containing an alkali-soluble resin. The content of the alkali-soluble resin contained in the insulating composition can be arbitrarily selected according to the desired film thickness and application, but is generally 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of solid content. .

The insulating composition may contain a hindered amine light stabilizer. By containing the hindered amine light stabilizer in the insulating composition, the damage of the insulating layer can be further reduced. color, and the weather resistance of the insulating layer can be improved.

The insulating composition may further contain a polyfunctional monomer, a curing agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc., if necessary. additive.

<Touch Panel>

As illustrated in the touch panel 10 shown in FIGS. 2 and 3 , the touch panel according to the embodiment of the present invention includes the film with a conductive layer of the present invention. In the present invention, the conductive layer with the conductive layer film is the wiring layer of the touch panel (for example, the first wiring layer 3 shown in FIG. 2 and FIG. 3 ). As illustrated in FIGS. 2 and 3 , the touch panel of the present invention has an insulating layer (first insulating layer) on the wiring layer (first wiring layer) on the gas barrier layer, and has a second wiring on the insulating layer Floor. The touch panel of the present invention may further have a second insulating layer on the opposite side (ie, the upper surface side) of the surface of the second wiring layer in contact with the first insulating layer. By having the second insulating layer in this way, the touch panel of the present invention can prevent moisture in the atmosphere from reaching the second wiring layer. As a result, the reliability of the touch panel can be further improved.

In the touch panel of the present invention, the first insulating layer and the second insulating layer may respectively include the same material, or may include different materials. In addition, the film thicknesses of the first insulating layer and the second insulating layer are preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of further improving the insulating properties. On the other hand, the film thickness of the first insulating layer and the second insulating layer is preferably 10 μm or less, more preferably 3 μm or less, from the viewpoint of further improving the transparency of these.

Films with conductive layers suitable for such touch panels (ie, embodiments of the present invention) The thickness of the film with a conductive layer) is preferably 1 μm to 40 μm. By setting the thickness of the film with a conductive layer to a thickness within this range, defects such as cracks and warpage in the production process of the film with a conductive layer can be suppressed, so that the yield of the film with a conductive layer (and thus the touch control) can be improved. panel yield). In addition, when the touch panel of the present invention is used as a flexible touch panel, the shape followability to bending is remarkably improved. In the present invention, the thickness of the touch panel is more preferably 3 μm or more, and more preferably 5 μm or more. On the other hand, the thickness of the touch panel is more preferably 30 μm or less, and still more preferably 25 μm or less.

Regarding the film with a conductive layer according to the embodiment of the present invention, the value of b* in the L*a*b* colorimetric system defined by the International Commission on Illumination in 1976 is preferably -5 to 5. By setting the value of b* to a value within this range, excessive chromaticity adjustment of the film with a conductive layer and the touch panel using the same becomes unnecessary, and as a result, the visibility of the touch panel can be further improved. In the present invention, the value of b* is more preferably -4 to 4, further preferably -3 to 3.

<Manufacturing method of touch panel including film with conductive layer>

The manufacturing method of the touch panel which consists of the film with a conductive layer which concerns on embodiment of this invention uses this manufacturing method of the film with a conductive layer. The method for producing a film with a conductive layer includes at least a resin film forming step, a gas barrier layer forming step, a conductive layer forming step, and a peeling step. The resin film forming step is a step of forming a resin film containing polyimide on the support substrate. The gas barrier layer forming step is a step of forming a gas barrier layer on the resin film. The conductive layer forming step is a step of forming a conductive layer on the gas barrier layer. The peeling step is a step of peeling off the resin film after forming the gas barrier layer, the conductive layer, and the like from the support substrate. In the present invention, the manufacturing method of the touch panel includes a wiring layer forming step as the conductive layer in the manufacturing method of the film with a conductive layer forming steps. The wiring layer forming step is a step of forming a wiring layer as a conductive layer on the gas barrier layer.

4 is a process diagram showing an example of a method of manufacturing a touch panel with a conductive layer film according to an embodiment of the present invention. In the manufacturing method of the touch panel of the present embodiment, the resin film forming step, the gas barrier layer forming step, the first wiring layer forming step, the first insulating layer forming step, the second wiring layer forming step, and the second insulating layer are sequentially performed. forming step, and peeling step.

Specifically, first, in the resin film forming step, as shown in state S1 of FIG. 4 , the resin film 1 containing the polyimide is formed on the support substrate 7 . Next, in the gas barrier layer forming step, as shown in state S2 in FIG. 4 , the gas barrier layer 2 is formed on the resin film 1 . Next, in the first wiring layer forming step, as shown in state S3 in FIG. 4 , the first wiring layer 3 is formed on the gas barrier layer 2 . Next, in the first insulating layer forming step, as shown in state S4 in FIG. 4 , the first insulating layer 4 is formed on the gas barrier layer 2 so as to cover the first wiring layer 3 . Next, in the second wiring layer forming step, as shown in state S5 in FIG. 4 , a second wiring layer is formed on the first insulating layer 4 (in this embodiment, on the gas barrier layer 2 and the first insulating layer 4 ). 5. Next, in the second insulating layer forming step, as shown in state S6 in FIG. 4 , the second insulating layer 6 is formed on the gas barrier layer 2 so as to cover the second wiring layer 5 . Then, in the peeling step, as shown in state S7 in FIG. 4 , the laminated structure of the resin film 1 and the gas barrier layer 2 is cut at the cut end face 8 thereof. Next, the resin film 1 of the laminated structure was mechanically peeled off from the support substrate 7 . In this way, the touch panel 10 is obtained. Hereinafter, each of these steps will be described in detail.

(resin film forming step)

As described above, the resin film forming step is a step of forming the resin film 1 containing polyimide on the support substrate 7 . The resin film forming step preferably includes: a coating step of coating the polyimide resin composition on the support substrate 7 ; a prebake step of applying the polyimide resin composition on the support substrate 7 The amine resin composition is dried; and in the curing step, the dried polyimide resin composition is cured.

As the support substrate 7 , for example, a silicon wafer, a ceramic substrate, an organic substrate, and the like can be mentioned. Examples of the ceramic substrate include glass substrates such as soda glass, alkali-free glass, borosilicate glass, and quartz glass, alumina substrates, aluminum nitride substrates, and silicon carbide substrates. As an organic-type board|substrate, an epoxy board|substrate, a polyetherimide resin board|substrate, a polyetherketone resin board|substrate, a polyamide-type resin board|substrate, a polyimide film, a polyester film etc. are mentioned preferably, for example.

As a method of applying the polyimide resin composition on the support substrate 7, for example, the use of a spin coater, a bar coater, a knife coater, a roll coater, a die coater, a calender coater ( Calender coater), coating by meniscus coater (meniscus coater), screen printing, spray coating, dip coating, etc.

As a heating method in a prebaking process and a hardening process, heating by a hotplate, a hot air dryer (oven), reduced-pressure drying, vacuum drying, or infrared irradiation, etc. are mentioned, for example.

The temperature and time of prebaking of the polyimide resin composition in the prebaking step depend on the composition of the target polyimide resin composition and the dried coating film (polyimide resin composition). The film thickness of the coating film) can be appropriately determined. For example, in the prebaking step in the present invention, the coating film is preferably heated in a temperature range of 50° C. to 150° C. for 10 seconds to 30 minutes.

The curing environment, temperature, and time of the polyimide resin composition in the curing step depend on the composition of the target polyimide resin composition, and the cured coating film (coating of the polyimide resin composition). The film thickness of the cloth film) may be appropriately determined. From the viewpoint of suppressing the yellowing of the film due to heating, in this curing step, it is preferable to heat the polymer on the support substrate 7 at a temperature of 300° C. or more and 500° C. or less in an environment with an oxygen concentration of 1000 ppm or less. The coating film of the imide resin composition is heated for 5 minutes to 180 minutes to form the resin film 1 .

(gas barrier layer forming step)

As described above, the gas barrier layer forming step is a step of forming the gas barrier layer 2 on the resin film 1 . As a method of forming the gas barrier layer 2 in the gas barrier layer forming step, for example, a method of forming a film by depositing a material from a gas phase, such as sputtering, vacuum deposition, ion plating, and plasma CVD, can be used. Vapor deposition method. Among them, it is preferable to use a sputtering method or a plasma CVD method in order to obtain a more uniform film (gas barrier layer 2 ) with high oxygen barrier properties.

In the present invention, the polyimide resin preferably used in the resin film 1 has a high glass transition temperature, so the substrate temperature (the temperature of the support substrate 7 ) at the time of forming the gas barrier layer 2 can also be increased. The higher the substrate temperature, the higher the crystallinity of the gas barrier layer 2, and therefore the higher the gas barrier performance. On the other hand, when the film-forming temperature of the gas barrier layer 2 is too high, the bending resistance of the gas barrier layer 2 decreases. From these viewpoints, the lower limit of the film forming temperature of the gas barrier layer 2 is preferably 80°C or higher, more preferably 100°C or higher. In addition, the upper limit of the film forming temperature of the gas barrier layer 2 is preferably 400°C or lower, more preferably 350°C or lower.

(First wiring layer forming step)

As described above, the first wiring layer forming step is a step of forming the first wiring layer 3 on the gas barrier layer 2 . The first wiring layer forming step preferably includes: a coating step, coating the conductive composition on the gas barrier layer 2; a pre-baking step, drying the coating film of the conductive composition; A step (exposure step and development step) of exposing and developing the dried coating film (pre-bake film) to form a mesh pattern; and a curing step of curing the patterned pre-bake film.

Especially in the 1st wiring layer formation process, it is preferable to form the 1st wiring layer 3 using the electroconductive composition containing the electroconductive particle which has a coating layer in at least a part of the surface. The reason for this is that the conductive particles having a coating layer on at least a part of the surface suppress scattering of exposure light in the exposure step, whereby the wiring of the first wiring layer 3 can be patterned with high precision.

In the first wiring layer forming step, as a method of applying the conductive composition on the gas barrier layer 2, and drying in the prebaking step and the curing step for the coating film of the conductive composition As a method, the method illustrated in the polyimide resin composition of the said resin film formation process is mentioned.

As the light source used in the exposure step of the coating film of the conductive composition, for example, j-rays, i-rays, h-rays, and g-rays of a mercury lamp are preferable. As the developer used in the development step of the coating film of the conductive composition, a known developer can be used. As the developer, for example, sodium hydroxide, potassium hydroxide, tetrakis An alkaline aqueous solution obtained by dissolving an alkaline substance in water, such as tetramethylammonium hydroxide (TMAH). The developing solution may be a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone added appropriately among the above. In addition, in order to obtain a better conductive pattern of the coating film of the conductive composition by this developing step, it is also preferable that the content in the developing solution be 0.01 mass %~ Surfactants such as nonionic surfactants are added in an amount of 1 mass %.

The environment, temperature, and time for curing the coating film of the conductive composition in the curing step (pre-baked film forming a pattern) depend on the composition of the conductive composition, the cured coating film (the The film thickness of the coating film) may be appropriately determined. In this curing step, for example, it is preferable to heat the coating film of the conductive composition in the air at a temperature ranging from 100° C. to 300° C. for 5 minutes to 120 minutes. In particular, when the first wiring layer 3 contains conductive particles having a coating layer on the surface, in order to reliably remove the coating layer on the surface of the conductive particles and to express sufficient conductivity, it is preferable in the curing step. The first wiring layer 3 is formed by heating the coating film of the conductive composition on the gas barrier layer 2 at a temperature of 100° C. or higher and 300° C. or lower in an environment with an oxygen concentration of 15% or higher.

In particular, in order to obtain the touch panel 10 with less yellowing and excellent electrical conductivity, the manufacturing method of the touch panel 10 preferably includes a step of forming a resin film at a temperature of 300° C. or higher in an environment where the oxygen concentration is 1000 ppm or less. The polyimide resin composition is heated at a temperature below 500°C to form a resin film 1 containing polyimide; and the wiring layer forming step is performed at a temperature of 100°C or more in an environment where the oxygen concentration is 15% or more. The conductive composition is heated at a temperature of 300° C. or lower to form a wiring layer (eg, the first wiring layer 3 ).

(First insulating layer forming step)

As described above, the first insulating layer forming step is a step of forming the first insulating layer 4 on the gas barrier layer 2 so as to cover the first wiring layer 3 . The first insulating layer forming step preferably includes: a coating step of coating the insulating composition on the first wiring layer 3; a pre-baking step of drying the coating film of the insulating composition ; a step of exposing and developing the dried coating film (pre-baked film) to form a pattern (exposure step, developing step); and a curing step of forming the patterned pre-baked film (insulating film) cured. The steps included in the first insulating layer forming step can be performed in the same manner as in the case of the first wiring layer forming step.

(Second wiring layer forming step, second insulating layer forming step)

As described above, the second wiring layer forming step is a step of forming the second wiring layer 5 on the first insulating layer 4 . In this second wiring layer forming step, the second wiring layer 5 can be formed by the same method as the first wiring layer 3 described above. As described above, the second insulating layer forming step is a step of forming the second insulating layer 6 so as to cover the second wiring layer 5 . In the second insulating layer forming step, the second insulating layer 6 can be formed by the same method as the first insulating layer 4 .

In the manufacturing method of the touch panel 10, the second insulating layer 6 may not be formed on the second wiring layer 5, but the second insulating layer 6 is preferably formed as described above. The reason for this is that by forming the second insulating layer 6 , moisture in the atmosphere can be prevented from reaching the second wiring layer 5 , thereby improving the heat and humidity resistance of the touch panel 10 .

(peeling step)

As described above, the peeling step is a step of peeling off the resin film 1 from the supporting substrate 7 . In this peeling step, as a method of peeling off the resin film 1 containing polyimide from the supporting substrate 7, for example, a method of irradiating the resin film 1 with a laser from the back surface of the supporting substrate 7 to peel off the resin film 1; The support substrate 7 before the control panel 10 (hereinafter appropriately referred to as a support substrate with a touch panel) is immersed in at least one of a solvent and purified water maintained at 0° C. to 80° C. for 10 seconds to 10 hours to be peeled off. method; a method of cutting the resin film 1 from the upper surface, and mechanically peeling it from the cut end face 8, and the like. Among them, a method of mechanically peeling from the cut end face 8 is preferable in consideration of the influence on the reliability of the touch panel 10 .

In addition, the peeling step can be performed directly on the support substrate with a touch panel, or a protective film or a transparent adhesive layer (OCA: Optical Clear Adhesive) can also be attached to the support substrate with a touch panel. ) after that. Furthermore, from the viewpoint of lamination accuracy, after laminating the support substrate with a touch panel to a member such as a display substrate via OCA, it is also preferable to carry out the lamination of the resin film 1 from the support substrate with a touch panel. Peeling (ie, removal of the touch panel 10 ).

In the touch panel of the embodiment of the present invention, yellowing of the resin film containing polyimide is suppressed when the wiring layer is formed by the gas barrier layer, and therefore visibility is good. Moreover, since the dimensional change of the resin film at the time of forming a wiring layer is suppressed by a gas barrier layer, the touch panel excellent in dimensional accuracy can be provided. The touch panel of the embodiment of the present invention can be suitably used as a display member for a smartphone, a tablet terminal, or the like.

<Manufacturing method of film with conductive layer>

The manufacturing method of the film with a conductive layer according to the embodiment of the present invention includes at least a resin film forming step, a gas barrier layer forming step, a conductive layer forming step, and a peeling step. Among these steps, as illustrated in state S1 , state S3 , and state S7 in FIG. 4 , the resin film forming step, the gas barrier layer forming step, and the peeling step are the same as the manufacturing method of the touch panel. The conductive layer forming step is a step of forming a conductive layer on the gas barrier layer. This conductive layer forming step is the same as the step after replacing the first wiring layer in the first wiring layer forming step with a conductive layer in the manufacturing method of the touch panel. In the present invention, the conductive layer forming step is preferably a step of forming a conductive layer using a conductive composition containing conductive particles having a coating layer on at least a part of the surface. In addition, the conductive layer forming step is preferably a step of heating the conductive composition on the gas barrier layer at a temperature of 100° C. or more and 300° C. or less in an environment with an oxygen concentration of 15% or more to form a conductive layer. .

In addition, the manufacturing method of the film with a conductive layer may include an insulating layer forming step of forming an insulating layer on the gas barrier layer so as to cover the conductive layer. This insulating layer forming step can be performed by, for example, the same method as the first insulating layer forming step in the manufacturing method of the touch panel. By forming the insulating layer on the conductive layer by the insulating layer forming step, moisture in the atmosphere can be suppressed from reaching the conductive layer, thereby improving the heat-and-moisture resistance of the film with the conductive layer.

[Example]

The present invention will be described below by way of examples, but the present invention is not limited to the following examples. First, the materials used in the following examples and comparative examples, all The measurement and evaluation performed will be described.

(acid dianhydride)

In the following Examples and Comparative Examples, as the acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 3,3',4,4'-biphenyl were used as needed Tetracarboxylic dianhydride (BPDA), 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), 3,3',4,4'-diphenyl Dimethyl ether tetracarboxylic dianhydride (ODPA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), two-terminal acid anhydride modified methylphenyl silicone oil (X22-168-P5) manufactured by Shin-Etsu Chemical Co., Ltd. -B).

(diamine compound)

In the following Examples and Comparative Examples, as the diamine compound, trans-1,4-diaminocyclohexane (CHDA), 2,2'-bis(trifluoromethyl)benzidine ( TFMB), 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane (HFHA), bis(3-aminophenyl) bis(3,3' -DDS), bis[4-(3-aminophenoxy)phenyl]sine (m-BAPS), both-terminal amine-modified methylphenyl silicone oil (X22-1660B-3) manufactured by Shin-Etsu Chemical Co., Ltd.

(solvent)

In the following Examples and Comparative Examples, as the solvent, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), propylene glycol monomethyl ether (PGMEA), and dipropylene glycol monomethyl ether were used as necessary. methyl ether (DPM).

(alkali-soluble resin)

In the following Examples and Comparative Examples, the alkali-soluble resin AR was used as needed. Alkali-soluble resin AR is relative to containing methacrylic acid/methyl methacrylate/styrene The carboxyl group of the copolymer of =54/23/23 (mol%) was obtained by subjecting 0.4 equivalent of glycidyl methacrylate to addition reaction. The weight average molecular weight (Mw) of the alkali-soluble resin AR was 29,000.

(conductive particles)

In the following Examples and Comparative Examples, as the electroconductive particle, electroconductive particle A-1 and electroconductive particle A-2 were used as needed. The electroconductive particle A-1 was a silver particle (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the surface carbon coating layer of 1 nm and a primary particle diameter of 40 nm. The electroconductive particle A-2 was made into silver particle (made by Mitsui Metal Mining Co., Ltd.) with a primary particle diameter of 0.7 μm.

(First production example: Production of varnish for film-forming polyimide resin film)

In the first production example, a production example of a polyimide resin film-forming varnish (hereinafter abbreviated as "varnish" as appropriate) suitably used in the following examples and comparative examples will be described.

(Synthesis Example 1)

In Synthesis Example 1 of Varnish, ODPA (9.37 g (30.2 mmol)), TFMB (9.67 g (30.2 mmol)), and NMP (100 g) were placed in a 200 mL four-necked flask under a stream of dry nitrogen, and placed in a 200 mL four-necked flask at 60 Heating and stirring were carried out at °C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 1. The polyimide group concentration that can be produced using the varnish of Synthesis Example 1 was 23.5.

(Synthesis example 2)

In Synthesis Example 2 of Varnish, under a stream of dry nitrogen, CBDA (7.23 g (36.9 mmol)), TFMB (11.81 g (36.9 mmol)), and NMP (100 g) were put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 2. The imide group concentration of the polyimide that can be produced using the varnish of Synthesis Example 2 was 29.2.

(Synthesis example 3)

In Synthesis Example 3 of Varnish, ODPA (13.92 g (44.8 mmol)), CHDA (5.12 g (44.8 mmol)), and NMP (100 g) were put into a 200 mL four-necked flask under a stream of dry nitrogen, and placed in a 200 mL four-necked flask at 60 Heating and stirring were carried out at °C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 3. The polyimide group concentration that can be produced using the varnish of Synthesis Example 3 was 35.8.

(Synthesis example 4)

In Synthesis Example 4 of Varnish, BPDA (11.70 g (39.8 mmol)), BSAA (2.30 g (4.42 mmol)), CHDA (5.04 g (44.1 mmol)), and NMP (100 g) were placed under a stream of dry nitrogen. put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were performed for 8 hours, and thereafter, the heated stirring material was cooled to room temperature, and the varnish of Synthesis Example 4 was prepared. The polyimide group concentration that can be produced using the varnish of Synthesis Example 4 was 36.3.

(Synthesis Example 5)

In Synthesis Example 5 of Varnish, CBDA (6.68 g (34.1 mmol)), TFMB (9.27 g (28.9 mmol)), HFHA (3.09 g (5.11 mmol)) were mixed under a stream of dry nitrogen. mmol)) and NMP (100 g) were put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 5. The polyimide group concentration that can be produced using the varnish of Synthesis Example 5 was 27.7.

(Synthesis Example 6)

In Synthesis Example 6 of Varnish, ODPA (8.75 g (28.2 mmol)), TFMB (8.93 g (27.9 mmol)), X22-1660B-3 (1.36 g (0.309 mmol)), and NMP were mixed under a stream of dry nitrogen. (100 g) was put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature, and the varnish of Synthesis Example 6 was prepared. The imide group concentration of the polyimide that can be produced using the varnish of Synthesis Example 6 was 23.4.

(Synthesis Example 7)

In Synthesis Example 7 of Varnish, under a stream of dry nitrogen, ODPA (10.58 g (34.1 mmol)), 3,3'-DDS (8.46 g (34.1 mmol)), and NMP (100 g) were placed in a 200 mL four-hole The flask was heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 7. The polyimide group concentration that can be produced using the varnish of Synthesis Example 7 was 26.8.

(Synthesis Example 8)

In Synthesis Example 8 of Varnish, BPDA (13.72 g (46.6 mmol)), CHDA (5.32 g (46.6 mmol)), and NMP (100 g) were placed in a 200 mL four-necked flask under a stream of dry nitrogen, and placed in a 200 mL four-necked flask at 60 Heating and stirring were carried out at °C. heat the After stirring for 8 hours, the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 8. The polyimide group concentration that can be produced using the varnish of Synthesis Example 8 was 37.7.

(Synthesis Example 9)

In Synthesis Example 9 of Varnish, under dry nitrogen flow, put ODPA (7.95g (25.6mmol)), m-BAPS (11.09g (25.6mmol)) and NMP (100g) into a 200mL four-necked flask, Heating and stirring were performed at 60°C. The heating and stirring were carried out for 8 hours, after which the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 9. The polyimide group concentration that can be produced using the varnish of Synthesis Example 9 was 19.8.

(Synthesis Example 10)

In Synthesis Example 10 of Varnish, ODPA (3.97 g (12.8 mmol)), PMDA (2.79 g (12.8 mmol)), TFMB (8.11 g (25.3 mmol)), X22-1660B-3 ( 1.18 g (0.282 mmol)) and NMP (100 g) were put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, and thereafter, the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 10. The polyimide group concentration that can be produced using the varnish of Synthesis Example 10 was 25.4.

(Synthesis Example 11)

In Synthesis Example 11 of Varnish, ODPA (7.85 g (25.3 mmol)), X22-168-P5-B (1.18 g (0.282 mmol)), TFMB (8.20 g (25.6 mmol)), And NMP (100g) was put into a 200mL four-necked flask, Heating and stirring were performed at 60°C. The heating and stirring were carried out for 8 hours, and thereafter, the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 11. The polyimide group concentration that can be produced using the varnish of Synthesis Example 11 was 23.4.

(Synthesis Example 12)

In Synthesis Example 12 of Varnish, ODPA (3.97 g (12.8 mmol)), BPDA (3.77 g (12.8 mmol)), TFMB (8.11 g (25.3 mmol)), X22-1660B-3 ( 1.18 g (0.282 mmol)) and NMP (100 g) were put into a 200 mL four-necked flask, and heated and stirred at 60°C. The heating and stirring were carried out for 8 hours, and thereafter, the heated stirring material was cooled to room temperature to prepare a varnish of Synthesis Example 12. The polyimide group concentration that can be produced using the varnish of Synthesis Example 12 was 23.3.

(Second Production Example: Production of Conductive Composition)

In the second production example, the production of the conductive compositions AE-1 and AE-2 suitably used in the following examples and comparative examples will be described. In this second production example, conductive particles A-1 (80 g), surfactant "DISPERBYK" (registered trademark) 21116 (4.06 g) manufactured by DIC Corporation, PGMEA (98.07 g) and DPM (98.07 g) were mixed, and these mixtures were treated with a homogenizer at 1200 rpm for 30 minutes. Further, the treated mixture was dispersed using a high-pressure wet medium-less micronizing apparatus Nanomizer (manufactured by Nanomizer) to obtain a silver dispersion having a silver content of 40% by mass. L1. Moreover, except having used electroconductive particle A-2 instead of electroconductive particle A-1, carry out the same phase as the above The same operation was carried out to obtain silver dispersion L2.

Next, the alkali-soluble resin AR (20 g) as an organic compound, ALCH (0.6 g) as a metal chelate compound, NCI-831 (2.4 g) as a photopolymerization initiator, and PE-3A (12.0 g) PGMEA (132.6g) and DPM (52.6g) were added to what was mixed, and it stirred. Thereby, the organic liquid L3 for electroconductive composition was obtained. In addition, ALCH is a metal chelate compound (aluminum acetoacetate ethyl diisopropionate) manufactured by Kawaken Fine Chemical Co., Ltd. NCI-831 is a photopolymerization initiator manufactured by ADEKA. Then, the silver dispersion liquid L1, the silver dispersion liquid L2, and the organic liquid L3 obtained in the above-mentioned manner were mixed at the ratios shown in Table 1, respectively, thereby obtaining the conductive composition AE-1 and the conductive composition AE-2. .

(third production example: production of insulating composition)

In the third production example, the production of insulating compositions OA-1 and OA-2 suitably used in the following examples and comparative examples will be described. In this third production example, in the clean bottle, the above-mentioned two or more structural formula (10) V-259ME (50.0 g) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. as a cardo-based resin of the indicated structure, TAIC (18.0 g) manufactured by Nippon Kasei Co., Ltd. as a cross-linking monomer, and a cross-linking monomer M-315 (10.0 g) manufactured by Toagosei Co., Ltd., PG-100 (20.0 g) manufactured by Osaka Gas Chemical Co., Ltd. as an epoxy compound, and BASF (BASF) as a photopolymerization initiator OXE-01 (0.2 g) manufactured by the company was mixed, and the mixture was stirred for 1 hour. Thereby, insulating composition OA-1 was obtained. Moreover, except having used the alkali-soluble resin AR instead of the said cardo-type resin (V-259ME), the same operation as above was performed, and the insulating composition OA-2 was obtained by this.

(Fourth Production Example: Production of Polyimide Resin Film)

In the fourth production example, the production of the polyimide resin film T1 suitably used in the following examples and comparative examples will be described. In this fourth production example, a coating and developing device (Mark-7) manufactured by Tokyo Electron Co., Ltd. was used, and the film thickness after prebaking at a temperature of 140° C. for 4 minutes was 15±0.5 The varnish of the first fabrication example (any varnish from Synthesis Example 1 to Synthesis Example 12) was spin-coated on a 6-inch mirror silicon wafer as a substrate in the manner of μm. Then, about the coating film of this varnish, the prebaking process was performed at the temperature of 140 degreeC for 4 minutes using the hotplate of Mark-7. The prebaked film thus obtained was heated at a temperature of 3.5°C/min under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD) manufactured by Koyo Thermo Systems. The rate was ramped to 350°C and held for 30 minutes. Thereafter, the pre-baked film was cooled to 50° C. at a cooling rate of 5° C./min, thereby producing a polyimide resin film. T1. Next, the polyimide resin film T1 (in the state of being attached to the substrate) is dipped in hydrofluoric acid for 1 to 4 minutes to peel the polyimide resin film T1 from the substrate, and air-dried to obtain a polyimide resin film. Imide resin film T1 (monomer).

(Fifth production example: production of polyimide resin film with glass substrate)

In the fifth production example, the production of the polyimide resin film T2 suitably used in the following examples and comparative examples will be described. In this fifth production example, a spin coater (MS-A200) manufactured by Mikasa Co., Ltd. was used, and the film thickness after prebaking at a temperature of 140° C. for 4 minutes was 15±0.5 μm. The varnish of the first production example (any varnish of Synthesis Example 1 to Synthesis Example 12) was spin-coated on a glass substrate (TEMPAX) of 50 mm in length×50 mm in width×1.1 mm in thickness. Then, about the coating film of this varnish, the prebaking process was performed at the temperature of 140 degreeC for 4 minutes using the hotplate (D-SPIN) by Dainippon Screen. The pre-baked film thus obtained was heated to 350°C at a heating rate of 3.5°C/min under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD) manufactured by Koyo Thermo Systems. °C and hold for 30 minutes. Then, the polyimide resin film T2 in the state attached to the rectangular glass substrate was produced by cooling this prebaking film to 50 degreeC at the temperature-fall rate of 5 degreeC/min.

(Sixth Production Example: Production of Polyimide Resin Film with Glass Substrate)

In the sixth production example, the production of the polyimide resin film T3 suitably used in the following examples and comparative examples will be described. In this sixth production example, a spin coater (1H-360S) manufactured by Mikasa Co., Ltd. was used to carry out the process at a temperature of 140°C. After prebaking for 4 minutes, the varnish of the first production example (any varnish of Synthesis Example 1 to Synthesis Example 12) was spin-coated on a glass substrate with an outer diameter of 13 inches so that the film thickness became 15±0.5 μm. (AN-100 manufactured by Asahi Glass Co., Ltd.). Then, about the coating film of this varnish, the prebaking process was performed for 4 minutes at the temperature of 140 degreeC using a hotplate. The pre-baked film thus obtained was heated to 350°C at a heating rate of 3.5°C/min under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD) manufactured by Koyo Thermo Systems. °C and hold for 30 minutes. Then, the polyimide resin film T3 in the state attached to the circular glass substrate was produced by cooling this prebaking film to 50 degreeC at the temperature-fall rate of 5 degreeC/min.

(Seventh production example: production of polyimide resin film with silicon substrate)

In the seventh production example, the production of the polyimide resin film T4 suitably used in the following examples and comparative examples will be described. In this seventh production example, a spin coater (MS-A200) manufactured by Mikasa was used so that the film thickness after prebaking at a temperature of 140° C. for 4 minutes was 5±0.5 μm and spin-coating the varnish of the first production example (any varnish from Synthesis Example 1 to Synthesis Example 12) on a 4-inch silicon substrate cut to 1/4. Then, about the coating film of this varnish, the prebaking process was performed at the temperature of 140 degreeC for 4 minutes using the hotplate (D-SPIN) by Dainippon Screen. The prebaked film thus obtained was heated to 300°C at a heating rate of 3.5°C/min under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD) manufactured by Koyo Thermo Systems. °C and hold for 30 minutes. Thereafter, the prebaked film The polyimide resin film T4 in the state attached to the silicon substrate was produced by cooling to 50° C. at a cooling rate of 5° C./min.

(First measurement example: measurement of light transmittance (T))

In the first measurement example, the measurement of light transmittance appropriately used in the following Examples and Comparative Examples will be described. In this first measurement example, the light transmittance at a wavelength of 450 nm of the polyimide resin film T2 of the fifth production example was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500) manufactured by Shimadzu Corporation.

(Second measurement example: measurement of haze value)

In the second measurement example, the measurement of the haze value appropriately used in the following Examples and Comparative Examples will be described. In this second measurement example, the haze value (%) of the polyimide resin film T2 of the fifth production example was measured using a direct reading haze computer (HGM2DP, C light source) manufactured by Suka Testing Machine Co., Ltd. ). In addition, as this haze value, the average value of three measurements was used.

(Third measurement example: measurement of glass transition temperature (Tg) and coefficient of linear expansion (CTE))

In the third measurement example, the measurement of the glass transition temperature and the coefficient of linear expansion, which are appropriately used in the following Examples and Comparative Examples, will be described. In this third measurement example, SII. A thermomechanical analyzer (EXSTAR 6000TMA/SS6000) manufactured by SII.NanoTechnology Co., Ltd. was used to measure the glass transition of the polyimide resin film T1 of the fourth production example in the compression mode under nitrogen flow. temperature and coefficient of linear expansion. As a sample for this measurement, a small piece of 15 mm in width x 30 mm in length was cut out from the polyimide resin film T1, and the small piece was along the longitudinal direction of the small piece. It was rolled up and made into a cylindrical shape through a platinum coil having a diameter of 3 mm and a height of 15 mm. The heating method is performed under the following conditions. In the first stage, the sample was heated to 150°C at a heating rate of 5°C/min to remove the adsorbed water of the sample. In the second stage, the samples were air-cooled to room temperature at a cooling rate of 5°C/min. In the third stage, the actual measurement of the sample is performed at a heating rate of 5° C./min, and the glass transition temperature of the polyimide resin film T1 is obtained. In addition, in the third stage, the average value of the linear expansion coefficients of the samples at 50° C. to 200° C. was obtained, and this was used as the linear expansion coefficient of the polyimide resin film T1 .

(Fourth Measurement Example: Measurement of Residual Stress)

In the fourth measurement example, the measurement of residual stress appropriately used in the following Examples and Comparative Examples will be described. In this fourth measurement example, the curvature radius r ₁ of a 6-inch silicon wafer having a thickness of 625 μm±25 μm was measured in advance using a residual stress measuring device (FLX-3300-T) manufactured by Toho Technology. On this silicon wafer, the film thickness after prebaking at a temperature of 140° C. for 4 minutes was 15±0.5 μm using a coating and developing device (Mark-7) manufactured by Tokyo Electron Co., Ltd. The varnish of the first preparation example (any varnish from Synthesis Example 1 to Synthesis Example 12) was spin-coated. Then, about the coating film of this varnish, the prebaking process was performed at the temperature of 140 degreeC for 4 minutes using the hotplate of Mark-7. The pre-baked film thus obtained was heated to 350°C at a heating rate of 3.5°C/min under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD) manufactured by Koyo Thermo Systems. °C and hold for 30 minutes. After that, the pre-baked film was cooled to 50° C. at a cooling rate of 5° C./min, thereby producing a silicon wafer with a polyimide resin film attached thereto. After drying the silicon wafer at 150° C. for 10 minutes, the curvature radius r ₂ of the silicon wafer was measured using the residual stress measuring device. Then, the residual stress σ (Pa) generated between the silicon wafer and the polyimide resin film was obtained by the following formula (II).

σ=Eh ² /6[(1/r ₂ )-(1/r ₁ )]t (II)

In the formula (II), E is the biaxial elastic coefficient (Pa) of the silicon wafer. h is the thickness (m) of the silicon wafer. t is the film thickness (m) of the polyimide resin film. r ₁ is the radius of curvature (m) of the silicon wafer before the polyimide resin film is formed. r ₂ is the radius of curvature (m) of the silicon wafer after the polyimide resin film is fabricated. Furthermore, the biaxial elastic modulus E of the silicon wafer was determined to be 1.805×10 ⁻¹¹ (Pa).

(Evaluation Example 1 to Evaluation Example 12)

In Evaluation Example 1 to Evaluation Example 12, about each varnish of Synthesis Example 1 to Synthesis Example 12, polyimide resin films T1 to polyimide resins were produced by the methods of the fourth preparation example to the seventh preparation example For the film T4, the light transmittance, the haze value, the glass transition temperature (Tg), the coefficient of linear expansion, and the residual stress were measured by the methods of the first measurement example to the fourth measurement example. Table 2 shows the results of Evaluation Example 1 to Evaluation Example 12.

[Table 2]

Next, the evaluation method of the touch panel performed in the following Example and a comparative example is demonstrated.

(Evaluation of Conductivity)

In the evaluation of the electrical conductivity of the touch panel, the surface resistance measuring machine ("Loresta" ("Loresta") (registered trademark)-FP, manufactured by Mitsubishi Oil & Chemical Co., Ltd.), the surface resistance value ρs (Ω/□) was measured, and the surface roughness profile measuring machine (“Surfcom” (registered trademark) 1400D, Tokyo Precision Co., Ltd. Production) The film thickness t (cm) of the wiring portion was measured, and the volume resistivity (μΩ·cm) was calculated by multiplying the two values. Using the obtained volume resistivity, the electrical conductivity of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as pass.

In the evaluation criteria for electrical conductivity evaluation, the volume resistivity is less than 60 μΩ. The case of cm is level 5. The volume resistivity is 60μΩ. cm above and less than 80μΩ. The case of cm is level 4. The volume resistivity is 80μΩ. cm above and less than 100μΩ. The case of cm is level 3. The volume resistivity is 100μΩ. cm above and less than 150μΩ. The case of cm is level 2. The volume resistivity is 150μΩ. If it is more than cm, it is level 1.

(Residue evaluation of conductive composition)

In the residue evaluation of the conductive composition of the touch panel, an ultraviolet-visible spectrophotometer (Shimadzu) was used for the unexposed portion of the substrate until the first wiring layer of the touch panel was fabricated in each Example and each Comparative Example. "MultiSpec-1500 (trade name)" manufactured by Seisakusho Co., Ltd.) measures the wavelength before and after the formation of the first wiring layer Transmission at 400nm. Then, when the transmittance before the formation of the first wiring layer is T0 and the transmittance after the formation of the first wiring layer is T, the transmittance change represented by the formula (T0-T)/T0 is calculated. Using the obtained value of the transmittance change, the residue of the conductive composition of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as pass.

In the evaluation criteria of the residue evaluation of the conductive composition, a case where the value of the transmittance change was less than 1% was regarded as level 5. The case where the value of the transmittance change was 1% or more and less than 2% was the level 4. The case where the value of the transmittance change was 2% or more and less than 3% was regarded as level 3. The case where the value of the transmittance change was 3% or more and less than 4% was regarded as level 2. The case where the value of the transmittance change was 4% or more was regarded as level 1.

(Evaluation of Hue (b*))

In evaluation of the color tone (b*) of the touch panel, the color tone of the laminated substrate was evaluated by the following method using the substrate until the second insulating layer of the touch panel was produced in each Example and each Comparative Example.

The reflectance of total reflection light was measured from the glass substrate side using a spectrophotometer (CM-2600d, manufactured by Konica Minolta) for the substrates up to and including the second insulating layer of the touch panel. The color properties b* are determined in the International Commission on Illumination (Commission Internationale de L'Eclairage, CIE) (L*, a*, b*) color space. Using the obtained color characteristics b*, the color tone of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as pass. In addition, a D65 light source was used as a light source.

In the evaluation criteria for color tone evaluation, the color characteristic b* is -2≦b*≦2 The situation is level 5. The case where the color characteristic b* is -3≦b*<-2 or 2<b*≦3 is the level 4. The case where the color characteristic b* is -4≦b*<-3 or 3<b*≦4 is the level 3. The case where the color characteristic b* is -5≦b*<-4 or 4<b*≦5 is the level 2. The case where the color characteristic b* is b*<-5 or 5<b* is the level 1.

(Evaluation of heat and humidity resistance)

In the evaluation of the wet heat resistance of the touch panel, the wet heat resistance was evaluated by the following method about the touch panel produced in each Example and each comparative example.

The insulation deterioration characteristic evaluation system "ETAC SIR13" (manufactured by Kusumoto Chemical Co., Ltd.) was used for the measurement of the heat-and-moisture resistance. Electrodes were attached to each end of the first wiring layer and the second wiring layer of the touch panel, respectively, and the touch panel was placed in a high-temperature, high-humidity tank set at 85° C. and 85% RH. After 5 minutes elapsed after the environment in the tank was stabilized, a voltage was applied between the electrodes of the first wiring layer and the second wiring layer, and the change in insulation resistance with time was measured. The first wiring layer was set as the positive electrode and the second wiring layer was set as the negative electrode, a voltage of 10 V was applied, and the resistance value was measured for 500 hours at intervals of 5 minutes. When the measured resistance value was 10 to the fifth power or less, it was judged as a short circuit due to poor insulation, the application of the voltage was stopped, and the test time until then was defined as the short circuit time. Using the obtained short-circuit time, the humidity and heat resistance of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as pass.

In the evaluation criteria of the moist heat resistance evaluation, the case where the short-circuit time is 1000 hours or more is the level 5. The case where the short-circuit time is 500 hours or more and less than 1000 hours is the level 4. The case where the short-circuit time was 300 hours or more and less than 500 hours was the level 3. The case where the short-circuit time was 100 hours or more and less than 300 hours was the level 2. When the short-circuit time is less than 100 hours, it is level 1.

(Evaluation of Dimensional Accuracy)

In the evaluation of the dimensional accuracy of the touch panel, the dimensional accuracy was evaluated by the following method with respect to the touch panel produced in each Example and each Comparative Example.

In the design portion in which the mesh intersection of the first wiring layer and the mesh intersection of the second wiring layer overlapped at the center of the build-up substrate, the offset in the horizontal direction was measured. Using the obtained measurement value of "shift", the dimensional accuracy of the touch panel was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or higher was regarded as pass.

In the evaluation criteria for dimensional accuracy evaluation, a case where the deviation is less than 1 μm is a level 5. When the deviation is 1 μm or more and less than 2 μm, it is level 4. When the deviation is 2 μm or more and less than 3 μm, it is level 3. When the deviation is 3 μm or more and less than 5 μm, it is level 2. The case where the offset is 5 μm or more is the level 1.

(ESD (Electrostatic Discharge) Resistance Evaluation)

In the ESD resistance evaluation of the touch panel, an ESD tester (Compact ESD Simulator) HCE-5000 was used for the substrates up to the first wiring layer of the touch panel in each Example and each Comparative Example. , manufactured by Hanwa Electronics Co., Ltd.) to evaluate ESD resistance. Specifically, electrodes were attached to the ends of the first wiring layer, and a voltage was continuously applied from 100V in steps/times of 100V. Regarding the resistance value of the leakage current after the voltage application, when the resistance value increased by 10% or more compared with that before the application, it was regarded as a disconnection of the wiring layer, and the voltage after the disconnection was lower than 100V as the voltage ESD withstand voltage.

(Example 1)

<Formation of Polyimide Resin Film>

In Example 1, the polyimide resin film T3 was produced by the method of the sixth production example using the varnish of the synthesis example 1 produced in the first production example.

<Formation of Gas Barrier Layer>

In Example 1, on the polyimide resin film T3 obtained as described above, sputtering was performed in an argon atmosphere using a target containing SiO ₂ to form a gas barrier layer containing SiO ₂ with a film thickness of 100 nm. As sputtering conditions at this time, the pressure was set to 2×10 ⁻¹ Pa, the substrate temperature was set to 150° C., and the power supply was set to an AC power supply of 13.56 MHz.

<Formation of First Wiring Layer>

In Example 1, a spin coater (“1H-360S (trade name)” manufactured by Mikasa Corporation) was used to coat the conductive material produced in the second production example under the conditions of 10 seconds at 300 rpm and 2 seconds at 500 rpm. The synthetic composition AE-1 was spin-coated on the substrate on which the polyimide resin film T3 and the gas barrier layer were formed. Then, the coating film of this conductive composition AE-1 was heated at 100° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Manufacturing Co., Ltd.). Prebake to make a prebake film. Next, using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon), an ultra-high pressure mercury lamp is used as a light source, and a desired mask is interposed. The prebaked film is exposed to light. Then, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), the pre-baked film was subjected to shower development for 60 seconds with a 0.045 mass % potassium hydroxide aqueous solution, followed by a water shower. Wash for 30 seconds and proceed Pattern processing. The patterned substrate was cured in air (oxygen concentration: 21%) at 250° C. for 30 minutes using an oven to form a first wiring layer.

<Formation of First Insulating Layer>

In Example 1, the insulating composition OA-1 produced in the third production example was spin-coated at 650 rpm for 5 seconds on the substrate on which the first wiring layer was formed using a spin coater. Then, about the coating film of this insulating composition OA-1, prebaking was performed at 100 degreeC for 2 minutes using a hotplate, and a prebaking film was produced. Next, an exposure machine is aligned with a parallel mask, an ultra-high pressure mercury lamp is used as a light source, and the prebaked film is exposed through a desired mask. Then, using an automatic developing apparatus, the pre-baked film was subjected to shower development with a 0.045 mass % potassium hydroxide aqueous solution for 60 seconds, and was then rinsed with water for 30 seconds to perform patterning. The patterned substrate was cured in air (oxygen concentration: 21%) at 250° C. for 60 minutes using an oven to form a first insulating layer.

<Formation of Second Wiring Layer>

In Example 1, on the substrate on which the first insulating layer was formed as described above, the second wiring layer was formed by the same method as the first wiring layer.

<Formation of Second Insulating Layer>

In Example 1, on the substrate on which the second wiring layer was formed as described above, the second insulating layer was formed by the same method as the first insulating layer.

Finally, using a single blade, the periphery of the region where the first wiring layer and the second wiring layer are formed is cut from the upper surface, and mechanical peeling is performed from the cut end face, using This obtained the touch panel of Example 1. The obtained touch panel of Example 1 was evaluated for electrical conductivity, residue of the conductive composition, color tone (b*), heat and humidity resistance, dimensional accuracy, and ESD withstand voltage by the methods described above. The evaluation result of Example 1 is shown in Table 3 mentioned later.

(Example 2)

In Example 2, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 2 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 2, since the polyimide contained in the polyimide resin film has a structural unit of the general formula (1), the dimensional accuracy is improved, and the level of the evaluation results is improved. is "5". The color tone was slightly deteriorated due to yellowing at the time of wiring processing, and the level of the evaluation result was "3", but it was a range that could be used without problems.

(Example 3)

In Example 3, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 3 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 3, since the polyimide contained in the polyimide resin film has a structural unit of the general formula (2), the dimensional accuracy is improved, and the level of the evaluation results is improved. is "4". The color tone was slightly deteriorated due to yellowing at the time of wiring processing, and the level of the evaluation result was "3", but it was a range that could be used without problems.

(Example 4)

In Example 4, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 4 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 4, the polyimide resin film contained in the Since imide has a structural unit of the general formula (2), the dimensional accuracy is improved, and the level of the evaluation result is "5". The color tone was slightly deteriorated due to yellowing at the time of wiring processing, and the level of the evaluation result was "3", but it was a range that could be used without problems.

(Example 5)

In Example 5, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 5 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 5, the polyimide contained in the polyimide resin film is mainly composed of the structural unit represented by the general formula (4), and contains all the structural units Since the structural unit represented by the general formula (5) accounts for 5 mol % or more and 30 mol % or less, the dimensional accuracy is improved, and the level of the evaluation result is "5".

(Example 6)

In Example 6, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 6 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 6, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved, and the evaluation results The level is "5". In addition, the ESD withstand voltage was improved to 1200V.

(Example 7)

In Example 7, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 7 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 7, since the Tg of the polyimide resin film was slightly low (refer to Evaluation Example 7 in Table 2), the dimensional accuracy was deteriorated, and the evaluation result was rated as "2" ”, but is a usable range.

(Example 8)

In Example 8, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 10 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 8, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved, and the evaluation results The level is "5". In addition, the ESD withstand voltage was improved to 1200V.

(Example 9)

In Example 9, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 11 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 9, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved, and the evaluation results The level is "5". In addition, the ESD withstand voltage was improved to 1200V.

(Example 10)

In Example 10, the same operation as Example 1 was repeated except that the varnish of Synthesis Example 12 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 10, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved, and the evaluation results The level is "5". In addition, the ESD withstand voltage was improved to 1100V.

(Example 11)

In Example 11, the same operation as in Example 5 was repeated except that the target material at the time of forming the gas barrier layer was changed to a target material containing SiON. As shown in Table 3, in the touch panel of Example 11, the color was changed by changing the gas barrier layer. The rating of the evaluation result is "5". On the other hand, the chemical resistance was lowered by changing the gas barrier layer. Therefore, the residues of the conductive composition and the dimensional accuracy were slightly deteriorated, respectively, and the level of the evaluation result was "4", but they were all within the usable range.

(Example 12)

In Example 12, when forming the gas barrier layer, first, using a target material containing SiON, sputtering was performed in an argon atmosphere to form a gas barrier layer containing SiON with a film thickness of 80 nm. Next, using a target material containing SiO ₂ , sputtering was performed in an argon atmosphere to form a gas barrier layer containing SiO ₂ with a film thickness of 20 nm. Except for the above, the same operations as in Example 5 were repeated. As shown in Table 3, in the touch panel of Example 12, by using SiON as the gas barrier layer on the polyimide resin film side, yellowing at the time of wiring processing was suppressed, and as a result, the color tone was improved. Evaluation The level of the result is "5". In addition, since the barrier property of the gas barrier layer was improved, the heat and humidity resistance was improved, and the evaluation result was rated as "5". Furthermore, when the gas barrier layer on the wiring layer side was made of SiO ₂ , the level of the evaluation results of the conductive composition residue and dimensional accuracy remained unchanged at "5", which was favorable.

(Example 13)

In Example 13, the same operation as in Example 5 was repeated except that the conductive composition was changed from the conductive composition AE-1 to the conductive composition AE-2. As shown in Table 3, in the touch panel of Example 13, the conductive particles (metal fine particles) contained in the conductive composition AE-2 were not coated, and the metal fine particles were not uniformly aggregated in the wiring layer. Therefore, the electrical conductivity was deteriorated, and the level of the evaluation result was "3", but it was within the usable range. In addition, the residue of the conductive composition and the dimensional accuracy are slightly deteriorated, The level of the evaluation results was "4", but it was in the range where there was no problem in use.

(Example 14)

In Example 14, the same operation as Example 5 was repeated except that the insulating composition was changed from insulating composition OA-1 to insulating composition OA-2. As shown in Table 3, in the touch panel of Example 14, since the insulating layer did not have the predetermined cardo-based resin, the moisture and heat resistance was greatly deteriorated, and the evaluation result was rated as "2", but it was usable. scope. The conductivity, the residue of the conductive composition, and the dimensional accuracy were slightly deteriorated, and the level of the evaluation result was "4", but it was a range that could be used without problems.

(Example 15)

In Example 15, when the wiring layer was formed, the patterned substrate was subjected to nitrogen gas flow (oxygen concentration: 14%) using an inert oven (INH-21CD manufactured by Koyo Thermo Systems). Except for heating, the same operation as in Example 5 was repeated. As shown in Table 3, in the touch panel of Example 15, the color tone was improved due to the change of the oxygen concentration at the time of formation of the wiring layer, and the level of the evaluation result was "5". On the other hand, the electrical conductivity was significantly deteriorated, and the level of the evaluation result was "2", but it was within the usable range. The dimensional accuracy is slightly worse, and the evaluation result has a level of "4", but it is in the range where there is no problem in use.

(Example 16)

In Example 16, the same operation as in Example 11 was repeated except that the varnish of Synthesis Example 6 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 16, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the dimensional accuracy is improved, The level of the evaluation result was "5". In addition, the ESD withstand voltage was improved to 1300V.

(Example 17)

In Example 17, the same operation as in Example 12 was repeated except that the varnish of Synthesis Example 6 was used as the varnish for polyimide resin film formation. As shown in Table 3, in the touch panel of Example 17, since the polyimide contained in the polyimide resin film has a repeating structure represented by the general formula (9), the ESD withstand voltage is improved and is 1300V.

(Comparative Example 1)

In Comparative Example 1, the same operation as in Example 5 was repeated except that the gas barrier layer was not formed and the first wiring layer was directly formed on the polyimide resin film. In the touch panel of Comparative Example 1, the residues of the conductive composition, the color tone, and the heat-and-moisture resistance were significantly reduced, and were at a level not usable (level 1).

(Comparative Example 2)

In Comparative Example 2, the same operation as in Example 5 was repeated except that the varnish of Synthesis Example 8 was used as the varnish for polyimide resin film formation. In the touch panel of Comparative Example 2, the polyimide group concentration of the polyimide contained in the polyimide resin film was high, clouding occurred after the resin film was formed, and visibility was greatly impaired. Therefore, the polyimide resin film in Comparative Example 2 cannot be used as a substrate of a touch panel.

(Comparative Example 3)

In Comparative Example 3, the same operation as in Example 5 was repeated, except that the varnish of Synthesis Example 9 was used as the varnish for forming a polyimide resin film. In the touch panel of Comparative Example 3, the polyimide resin contained in the polyimide resin film Since the amine group concentration was low and the Tg of the polyimide resin film was lowered (see Evaluation Example 9 in Table 2), the dimensional accuracy was greatly lowered and the level was unusable (Level 1). The evaluation results of Comparative Examples 1 to 3 are shown in Table 3 together with the evaluation results of Examples 1 to 17.

[table 3]

[Industrial Availability]

As described above, the film with a conductive layer, the touch panel, the method for producing a film with a conductive layer, and the method for producing a touch panel of the present invention are suitable for suppressing yellowing of the resin film during formation of the conductive layer and ensuring electrical conductivity A film with a conductive layer with high dimensional accuracy of layers, a touch panel, a method for producing a film with a conductive layer, and a method for producing a touch panel.

1: Resin film

2: Gas barrier layer

3A: Conductive layer

11: Film with conductive layer

Claims (10)

A film with a conductive layer having a conductive layer containing conductive particles on a resin film containing a polyimide having an imide group concentration of 20.0% or more and 36.5% or less defined by the following formula (I), The film with a conductive layer is characterized by having a gas barrier layer between the resin film and the conductive layer; (molecular weight of imide moiety)/(molecular weight of repeating unit of polyimide)×100 [%] (1); The polyimide has a structural unit represented by the following general formula (4) as a main component, and contains the following general formula ( 5) the structural unit represented,

In general formula (4) and general formula (5), R ¹ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic structure The tetravalent organic group of carbon number 4~40 that the organic group is connected to each other directly or via a cross-linking structure; R ¹³ represents a divalent organic group represented by the following general formula (6); R ¹⁴ is the following structural formula (7) or the structure represented by the following structural formula (8);

In general formula (6), R ¹⁵ ～R ²² independently represent a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 3 carbon atoms that can be substituted by a halogen atom; X ² is selected from a direct bond, an oxygen atom , structure in sulfur atom, sulfonyl group, divalent organic group with 1 to 3 carbon atoms that can be substituted by halogen atom, ester bond, and amide bond;

A film with a conductive layer having a conductive layer containing conductive particles on a resin film containing a polyimide having an imide group concentration of 20.0% or more and 36.5% or less defined by the following formula (I), The film with a conductive layer is characterized by having a gas barrier layer between the resin film and the conductive layer; (Molecular weight of imide moiety)/(Molecular weight of repeating unit of polyimide)×100[%] (I); the polyimide contains a triamine skeleton. A film with a conductive layer having a conductive layer containing conductive particles on a resin film containing a polyimide having an imide group concentration of 20.0% or more and 36.5% or less defined by the following formula (I), The film with a conductive layer is characterized by having a gas barrier layer between the resin film and the conductive layer; (molecular weight of imide moiety)/(molecular weight of repeating unit of polyimide)×100 [%] (I); On the conductive layer, there is an insulating layer formed of an alkali-soluble resin containing a cardo-based resin having two or more of the following structural formula (10) structure,

The film with a conductive layer according to any one of claims 1 to 3, wherein the resin film has a glass transition temperature of 250° C. or higher. The film with a conductive layer according to any one of claims 1 to 3, wherein the polyimide is in acid dianhydride residues and diamine residues constituting the polyimide At least one of , contains a repeating structure represented by the following general formula (9),

In the general formula (9), R ²³ and R ²⁴ each independently represent a monovalent organic group having 1 to 20 carbon atoms; m is an integer of 3 to 200. The film with a conductive layer according to any one of items 1 to 3 of the claimed scope, wherein the gas barrier layer comprises at least one of silicon oxide, silicon nitride, silicon oxynitride and silicon carbonitride one. The film with a conductive layer according to any one of claims 1 to 3, wherein the gas barrier layer comprises SiOxNy (x, y satisfy 0<x≦1, 0.55≦y≦1 and 0 < value of x/y≦1). The film with a conductive layer according to any one of claims 1 to 3, wherein the gas barrier layer is an inorganic film formed by laminating two or more layers, and the inorganic film is connected to the conductive layer. The adjoining layers are made of SiOz (z is 0.5 ≦z≦2 value) represented by the composition. The film with a conductive layer according to any one of claims 1 to 3, wherein the conductive particles are silver particles. A touch panel is characterized by comprising the film with a conductive layer according to any one of items 1 to 3 of the patent application scope, wherein the conductive layer is a wiring layer.

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