KR20190134602A - Film with conductive layer, touch panel, manufacturing method of film with conductive layer and manufacturing method of touch panel - Google Patents

Abstract

It is a film with a conductive layer which has a conductive layer containing electroconductive particle on the resin film containing polyimide whose imide group density | concentration defined by following (I) formula is 20.0%-36.5% or less, These resin films and conductive layers The film with a conductive layer which has a gas barrier layer in between is provided. This conductive layer equipped film is applied to a touch panel, for example. The manufacturing method of this conductive layer equipped film is applied to the manufacturing method of a touch panel, for example.
(Molecular Weight of Imide Group Part) / (Molecular Weight of Repeating Unit of Polyimide) × 100 [%] (I)

Description

Film with conductive layer, touch panel, manufacturing method of film with conductive layer and manufacturing method of touch panel

TECHNICAL FIELD This invention relates to the manufacturing method of a film with a conductive layer, a touch panel, the film with a conductive layer, and the manufacturing method of a touch panel.

In recent years, in devices such as mobiles and tablets, in terms of design, convenience and durability, flexibility has been desired. However, there are various problems in flexibilization of the device, which has not yet reached practical use.

Especially, the main subject is improvement of the bending resistance, visibility, and electroconductivity of the film with a conductive layer used for an apparatus. Conventionally, as a film with a conductive layer, the thin film containing transparent conductive metals, such as ITO, was widely used from a viewpoint of visibility improvement. For example, Patent Documents 1 and 2 disclose a transparent conductive film in which a thin film containing ITO is formed on a polyimide film excellent in heat resistance. By pattern-processing the thin film by etching, the film with a conductive layer excellent in visibility and electroconductivity can be obtained. However, since ITO wiring is rigid and brittle, the bending resistance is low, and there existed a problem that a crack generate | occur | produced when it bends.

Therefore, various wiring techniques, such as metal mesh wiring, metal nanowire wiring, and carbon nanotube wiring, have been proposed as a transparent conductive layer instead of ITO. Among them, metal mesh wiring has attracted attention as a transparent conductive layer having both bending resistance, visibility, and high conductivity.

Metal mesh wiring is obtained by forming metal wiring in a mesh pattern so thin that it cannot be visually recognized. For example, wiring having good conductivity can be obtained by using a metal having a small electric resistance value such as gold, silver, or copper. In addition, pattern bending by photolithography is possible, and the bending resistance of the wiring can be improved by appropriately containing an organic component having excellent flexibility in the wiring. Such metal mesh wiring can fully respond to flexibility.

As a method of forming such a metal mesh wiring, for example, a method of patterning by screen printing, inkjet, photolithography, or the like using conductive metal particles (hereinafter, appropriately referred to as conductive particles) and a conductive paste containing an organic component. Can be mentioned. However, in order to form a fine pattern which cannot be visually recognized, it is necessary to make the particle diameter of electroconductive particle small to nano size. Such electroconductive particle had a problem that it was easy to fuse and aggregate at room temperature. Moreover, there existed a problem that the surface of electroconductive particle reacts with an organic component, and the storage stability of an electrically conductive paste falls. Moreover, when pattern-processing using photolithography, electroconductive particle has light reflectivity, and since this scatters exposure light, there existed a problem that it was difficult to form a fine pattern.

On the other hand, the method of solving the said problem is disclosed using the electroconductive particle which has a coating layer (for example, refer patent document 3). The surface layer of electroconductive particle can be reduced by a coating layer, and at least one of reaction of electroconductive particle and reaction of electroconductive particle and an organic component can be suppressed. Moreover, even when photolithography is used, scattering of exposure light can be suppressed and a wiring can be patterned with high precision. The coated electroconductive particle can be easily removed by heating at about 200 degreeC high temperature. Therefore, sufficient electroconductivity can be expressed in wiring.

Japanese Patent Laid-Open No. 2016-186936 Japanese Patent No. 5773090 Japanese Patent Publication No. 2013-196997

However, the technique disclosed in Patent Document 3 required 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 board | substrate, and only a glass substrate could be applied substantially. As a matter of course, it is difficult to cope with flexibility using a glass substrate. Moreover, even when the film excellent in heat resistance is used, the problem that a color tone falls by coloring of the film by heating in presence of oxygen, dimensional accuracy of a film falls, position shift arises, and the appearance defect called moire arises. There was a problem.

This invention is made | formed in view of the said situation, The objective is the manufacture of the film with a conductive layer, a touch panel, and the film with conductive layer which suppress yellowing at the time of conductive layer formation, and are excellent in the dimensional precision of a conductive layer. A method and a method for manufacturing a touch panel are provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, as for the structure which has a gas barrier layer between the resin film (polyimide resin film) containing the polyimide whose imide group concentration is a specific range, and a conductive layer, at the time of heating of a conductive layer, It was found that the polyimide resin film can be prevented from contacting with oxygen, and the drop in color tone and dimensional accuracy of the polyimide resin film can be suppressed.

That is, in order to solve the problem mentioned above and achieve the objective, the film with a conductive layer which concerns on this invention is a resin film containing the polyimide whose imide group density | concentration defined by following (I) formula is 20.0% or more and 36.5% or less. It is a film with a conductive layer which has a conductive layer containing electroconductive particle, and has a gas barrier layer between the said resin film and the said conductive layer, It is characterized by the above-mentioned.

(Molecular weight of imide group portion) / (molecular weight of repeating unit of polyimide) × 100 [%]. (I)

Moreover, in the said invention, the film with a conductive layer which concerns on this invention is characterized by the glass transition temperature of the said resin film being 250 degreeC or more.

Moreover, in the said invention, the film with a conductive layer which concerns on this invention is characterized by the said polyimide containing the structural unit represented by following General formula (1).

(In the formula ^(1), R 1 is a monocyclic or condensed polycyclic of from 4 to 40 carbons having an alicyclic structure in the alicyclic tetravalent organic group, or organic group having an alicyclic structure of the monocyclic group is directly or through a crosslinking structure A tetravalent organic group having 4 to 40 carbon atoms connected to each other.R ² represents a divalent organic group having 4 to 40 carbon atoms.)

Moreover, in the said invention, the film with a conductive layer which concerns on this invention is characterized by the said polyimide containing the structural unit represented by following General formula (2).

(In General Formula (2), R ³ represents a tetravalent organic group having 4 to 40 carbon atoms. R ⁴ is a divalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or Or a divalent organic group having 4 to 40 carbon atoms, or a divalent organic group represented by the following general formula (3), in which an organic group having a monocyclic alicyclic structure is connected to each other directly or through a crosslinked structure.)

(In general formula (3), X <^1> is a C1-C3 bivalent hydrocarbon group which may be substituted by the halogen atom. Ar <^1> and Ar <^2> are respectively independently C4-C40 divalent aromatic. Group.)

Moreover, in the film with a conductive layer which concerns on this invention, in the said invention, the said polyimide has a structural unit represented by following General formula (4) as a main component, and is represented by following General formula (5) It is characterized by including 5 mol% or more and 30 mol% or less of all the structural units.

(In general formula (4), (5), R <^1> is a C4-C40 tetravalent organic group which has a monocyclic or condensed polycyclic alicyclic structure, or the organic group which has a monocyclic alicyclic structure is directly or A tetravalent organic group having 4 to 40 carbon atoms connected to each other via a crosslinked structure, R ¹³ represents a divalent organic group represented by the following general formula (6): R ¹⁴ represents the following structural formula (7) or the following structural formula ( 8).

(In General formula (6), R <^15> -R <^22> respectively independently represents the C1-C3 monovalent organic group which may be substituted by the hydrogen atom, a halogen atom, or a halogen atom. X <^2> is a direct bond , An atom selected from an oxygen atom, a sulfur atom, a sulfonyl group, a halogen atom, a divalent organic group having 1 to 3 carbon atoms, an ester bond, an amide bond, and a sulfide bond.)

Moreover, in the film with a conductive layer which concerns on this invention, the said polyimide is a repeat represented by following General formula (9) in at least one of the acid dianhydride residue and diamine residue which comprise the said polyimide. It is characterized by containing a structure.

(In 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.)

Moreover, in the said invention, the film with a conductive layer which concerns on this invention is characterized by the said polyimide containing a triamine skeleton.

Moreover, in the film with a conductive layer which concerns on this invention, the said gas barrier layer contains at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride.

Moreover, in the film with a conductive layer which concerns on this invention, in the said invention, the said gas barrier layer is SiOxNy (x, y is 0 <x≤1, 0.55≤y≤1, and 0≤x / y≤1). It is a value which satisfies.

Moreover, in the said invention, the film with a conductive layer which concerns on this invention is an inorganic film laminated | stacked in two or more layers, The layer which contact | connects the said conductive layer among the said inorganic films is SiOz (z is 0.5 Is a value satisfying ≤ z ≤ 2.).

Moreover, in the film with a conductive layer which concerns on this invention, the said electroconductive particle is a silver particle, It is characterized by the above-mentioned.

Moreover, the film with a conductive layer which concerns on this invention is an insulation layer formed from alkali-soluble resin containing cardo resin which has two or more structures represented by following structural formula (10) on the said conductive layer in the said invention. Characterized in having a.

Moreover, the touch panel which concerns on this invention has the film with a conductive layer in any one of said invention, The said conductive layer is a wiring layer, It is characterized by the above-mentioned.

Moreover, the manufacturing method of the film with a conductive layer which concerns on this invention is the resin film formation process of forming the resin film containing polyimide on a support substrate, and the gas barrier layer formation which forms a gas barrier layer on the said resin film. A step, 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.

Moreover, in the manufacturing method of the film with a conductive layer which concerns on this invention, in the said invention, the said conductive layer formation process forms the said conductive layer using the electroconductive composition containing the electroconductive particle which has a coating layer in at least one part of the surface. Characterized in that.

Moreover, in the manufacturing method of the film with a conductive layer which concerns on this invention, the said resin film formation process is 300 degreeC or more and 500 degrees C or less for the polyimide resin composition on the said support substrate in the atmosphere whose oxygen concentration is 1000 ppm or less. Heating at a temperature of to form the resin film, and the conductive layer forming step heats the conductive composition on the gas barrier layer at a temperature of 100 ° C. or higher and 300 ° C. or lower in an atmosphere having an oxygen concentration of 15% or higher. It is characterized by forming a layer.

Moreover, the manufacturing method of the touchscreen which concerns on this invention is a manufacturing method of the touchscreen using the manufacturing method of the film with a conductive layer in any one of said invention, The said conductive layer formation process forms a wiring layer as said conductive layer. Characterized in that the process.

According to the present invention, it is possible to provide a conductive layer-containing film, a touch panel, a manufacturing method of a conductive layer-containing film, and a manufacturing method of a touch panel that suppress yellowing at the time of forming a conductive layer and are excellent in dimensional accuracy of the conductive layer. Exert.

1: is a schematic cross section which shows one structural example of the film with a conductive layer which concerns on embodiment of this invention.
It is a top view which shows the structural example of the touchscreen containing the film with a conductive layer which concerns on embodiment of this invention which concerns on embodiment of this invention.
FIG. 3: is a schematic cross section which shows an example of a structure of the touchscreen containing the film with a conductive layer which concerns on embodiment of this invention.
4 is a flowchart showing an example of a method of manufacturing a touch panel including a film with a conductive layer according to the embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, preferable embodiment is described in detail about the manufacturing method of the conductive layer equipped film, touch panel, the conductive layer equipped film, and the manufacturing method of a touch panel which concern on this invention. However, this invention is not limited to the following embodiment, It can variously change and implement according to an objective and a use.

<Film with conductive layer>

The film with a conductive layer which concerns on embodiment of this invention is a film with a conductive layer which has a conductive layer containing electroconductive particle on the resin film containing polyimide, and has a gas barrier layer between these resin films and a conductive layer. Have In this embodiment, this resin film is going to contain the polyimide whose imide group density | concentration defined by following formula (I) is 20.0% or more and 36.5% or less.

(Molecular weight of imide group portion) / (molecular weight of repeating unit of polyimide) × 100 [%]. (I)

1: is a schematic cross section which shows one structural example of the film with a conductive layer which concerns on embodiment of this invention. As shown in FIG. 1, this conductive film-containing film 11 includes a resin film 1, a gas barrier layer 2, and a conductive layer 3A. As described above, the resin film 1 is a polyimide resin film containing polyimide having an imide group concentration defined by formula (I) of 20.0% or more and 36.5% or less. 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 which has such a structure, the gas barrier layer 2 is interposed between the resin film 1 and 3 A of conductive layers, as shown in FIG. Thereby, the gas barrier layer 2 can prevent the oxygen at the time of heating and forming the conductive layer 3A from contacting the resin film 1. As a result, the fall of the color tone (for example, the fall of the color tone by yellowing) by the heating in oxygen presence is suppressed. Although not specifically shown in FIG. 1, the film with conductive layer 11 may further include an insulating layer on the conductive layer 3A.

It is a top view which shows the structural example of the touchscreen containing the film with a conductive layer which concerns on embodiment of this invention. FIG. 3: is a schematic cross section which shows an example of a structure of the touchscreen containing the film with a conductive layer which concerns on embodiment of this invention. FIG. 3 is a cross-sectional view of the touch panel 10 at the broken line II ′ in FIG. 2. This touch panel 10 is a touch panel containing the film 11 with a conductive layer which concerns on this embodiment. 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, and a second The wiring layer 5 and the second insulating layer 6 are provided.

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

As shown in FIGS. 2 and 3, the first wiring layer 3 is formed on the gas barrier layer 2 on the resin film 1 to form a desired wiring pattern. 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 of the first wiring layer 3. The second wiring layer 5 is a wiring layer different from the first wiring layer 3, and is formed on the first insulating layer 4 and the gas barrier layer 2 to form a desired wiring pattern. 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 is formed on the second wiring layer 5 and the first insulating layer 4 so as to cover other than the electrode portion of the second wiring layer 5.

(Resin film (polyimide resin film))

As for the resin film (for example, resin film 1 shown in FIG. 1) used for the film with a conductive layer which concerns on embodiment of this invention, the imide group density | concentration defined by Formula (I) mentioned above is 20.0% or more and 36.5%. The following polyimide is included.

Since a polyimide is obtained by making diamine and tetracarboxylic dianhydride react, when the molecular weight of each monomer (diamine and tetracarboxylic dianhydride) becomes large, the imide group concentration of the polyimide obtained will become small. When the imide group concentration is lower than 20.0%, the interaction between the polyimide molecules by the imide group is weakened, and the glass transition temperature (Tg) of the polyimide is lowered. In the film with a conductive layer, if the glass transition temperature of the resin film (polyimide resin film) used as a board | substrate is low, this resin film cannot endure the heat added at the time of formation of a gas barrier layer and a conductive layer. As a result, sufficient dimensional precision (for example, dimensional precision of a conductive layer) of a film with a conductive layer is not obtained. When the imide group concentration is greater than 36.5%, the interaction between the polyimide molecules by the imide group becomes too strong, so that the polyimide molecules crystallize in the resin film. As a result, the visibility of the film with a conductive layer deteriorates.

In this invention, the polyimide resin (polyimide which comprises the resin film of the film with conductive layer) with which heat resistance and transparency were balanced by making an imide group concentration into the density | concentration within the range of 20.0% or more and 36.5% or less can be obtained. The imide group concentration is a value calculated by the following method.

The molecular weight of an imide group part is a molecular weight of the (-CO-N-CO-) part contained in the repeating unit of a polyimide. The molecular weight per imide group is 70.03. In addition, the molecular weight of the repeating unit of a polyimide is the molecular weight of the part derived from the tetracarboxylic dianhydride and diamine which comprise one repeating unit. In this regard, the imide group concentration can be calculated based on the above-described formula (I). When two or more repeating units exist in a polyimide, after obtaining the imide group density | concentration of each repeating unit, the value which added together the product which multiplied the content rate of each repeating unit is made into the imide group concentration of polyimide.

For example, in the case of the polyimide represented by following structural formula (A), the molecular weight of an imide group part is a molecular weight of the location enclosed by the dotted line. In this case, the molecular weight of the imide group portion is 140.06 (= 70.03 × 2). In addition, the molecular weight of a repeating unit is 372.11. Therefore, an imide group concentration becomes 37.8% (= (140.06 / 372.11) * 100) based on Formula (I) mentioned above.

In addition, in the case of the polyimide represented by the following structural formula (B) in which a plurality of repeating units exist, the imide group concentration of the repeating unit G1 is 37.8% (= (140.06) based on the above-mentioned formula (I). / (372.11) x 100). The imide group concentration of the repeating unit G2 is 23.4% (= (140.06) / (598.66) × 100) based on the above-described formula (I). In addition, the number m of containing repeating unit G1 and the number n containing of repeating unit G2 have a relationship of m: n = 90: 10. Therefore, the imide group concentration of a polyimide becomes 36.4% (= 37.8% x 0.90 + 23.4% x 0.10).

In this invention, it is preferable that the glass transition temperature (Tg) of the resin film containing a polyimide is 250 degreeC or more. This is because the deformation of the resin film is suppressed in the heating step when forming the gas barrier layer or the conductive layer on the resin film, and as a result, the dimensional accuracy at the time of processing the conductive layer is further improved. As for the glass transition temperature of the resin film containing a polyimide, it is more preferable that it is 300 degreeC or more, and it is especially preferable that it is 350 degreeC or more.

As a measuring method of the glass transition temperature of a resin film, the measuring method (TMA method) using a thermomechanical analyzer is mentioned. In the present invention, a cylindrical sample having a thickness of 10 μm to 20 μm, a width of 15 mm, and a resin film small piece having a length of 30 mm is wound in the longitudinal direction, having a diameter of 3 mm and a height of 15 mm. The inflection point of the TMA curve when the sample is heated at a temperature rising rate of 5 ° C./min in the compression mode under nitrogen stream is taken as the glass transition temperature of the resin film.

In this invention, it is preferable that the polyimide used for the resin film of a film with a conductive layer contains the structural unit represented by following General formula (1).

In the formula ^(1), R 1 is, one another via a monocyclic or condensed polycyclic of from 4 to 40 carbons having an alicyclic structure in the alicyclic tetravalent organic group, or a monocyclic organic groups directly or cross-linked structure having an alicyclic structure of Connected tetravalent organic groups having 4 to 40 carbon atoms. R ² represents a divalent organic group having 4 to 40 carbon atoms.

When a polyimide contains the structural unit represented by General formula (1), the thermal expansion coefficient (CTE) of a polyimide becomes low. Therefore, when a polyimide is formed into a film on a support substrate for processes, such as a conductive layer formation, the curvature of a polyimide becomes small and can improve dimensional precision in the process of a conductive layer.

R ¹ in General formula (1) represents the structure of an acid component. In the alicyclic structure in R ¹ , some hydrogen atoms may be substituted with halogen. The acid dianhydride having an alicyclic structure is not particularly limited, but 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-cyclobutanetetra Carboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuranthtetracar Acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetra Hydro-1-naphthalenesuccinic dianhydride, 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] heptane tetracarboxylic dianhydride, bicyclo [2.2.1] heptan-5-carboxymethyl -2,3,6-tricarboxylic dianhydride, 7-oxabicyclo [2.2.1] heptane-2,4,6,8-tetracarboxylic dianhydride, octahydro naphthalene-1,2,6 , 7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-oxydicle Rohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, "lycaside" (Registered trademark) BT-100 (above, a brand name, the product made by Shin-Nihon Corporation), derivatives thereof, etc. are illustrated.

It is preferable that R <^1> in General formula (1) is one or more types chosen from six structures represented by the following structural formulas (11)-(16).

Among these six structures, R ¹ is more preferably a structure represented by the following structural formulas (17) to (19) from the viewpoint of being commercially available and readily available and the reactivity with the diamine compound. As an acid dianhydride which gives such a structure to R <^1> , it is 1S, 2S, 4R, 5R- cyclohexane tetracarboxylic dianhydride (for example, Wako Pure Chemical Industries Ltd., product name "PMDA- HH ''), 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride (for example, Wako Pure Chemical Industries, Ltd. product name "PMDA-HS"), 1,2,3,4-cyclobutanetetra Carboxylic acid dianhydride etc. are mentioned. In addition, these acid dianhydrides can be used individually or in combination of 2 or more types.

In General formula (1), R <^2> represents the structure of a diamine component. Although it does not specifically limit as a diamine compound used for R <^2> , An aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound is mentioned.

Although it does not specifically limit as an aromatic diamine compound, 1, 4-bis (4-amino phenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1, 5- naphthalenediamine, 2, 6- naphthalenediamine, Bis {4- (4-aminophenoxyphenyl)} sulfone, bis {4- (3-aminophenoxyphenyl)} sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy C) phenyl} ether, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 3-aminophenyl-4-aminobenzenesulfonate, 4-aminophenyl-4-aminobenzenesulfonate, or a part of the aromatic rings of these compounds is an alkyl group, an alkoxy group, a halogen atom The diamine compound substituted by these etc. are mentioned.

Although it does not specifically limit as alicyclic diamine compound, Cyclobutanediamine, isophorone diamine, bicyclo [2.2.1] heptanebismethylamine, 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'-diaminodicyclo Hexylmethane, 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'-diaminodicyclohexylether, 3,3', 5,5'-tetraethyl-4,4'-diaminodicyclohexylether , 3,5-die -3 ', 5'-dimethyl-4,4'-diaminodicyclohexylether, 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-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'-dia The diamine compound in which a part of the alibicyclohexane or the aliphatic ring of these compounds was substituted by the alkyl group, the alkoxy group, the halogen atom, etc. is mentioned.

Although it does not specifically limit as an aliphatic diamine compound, Ethylenediamine, 1, 3- diamino propane, 1, 4- diamino butane, 1, 5- diamino pentane, 1, 6- diamino hexane, 1, 7- dia Alkylenediamines such as minoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, Ethylene glycol diamines such as bis (3-aminopropyl) ether, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, Siloxane diamines, such as (omega) -bis (3-aminopropyl) polydimethylsiloxane, are mentioned.

These aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds can be used individually or in combination of 2 or more types.

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

In General formula (2), R <^3> represents the C4-C40 tetravalent organic group. R ⁴ is a C 4 to C 2 bivalent organic group having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure connected to each other directly or through a crosslinked structure. The organic group or the divalent organic group represented by the following general formula (3) is represented.

In General formula (3), X <^1> is a C1-C3 bivalent hydrocarbon group which may be substituted by the halogen atom. Ar ¹ and Ar ² each independently represent a divalent aromatic group having 4 to 40 carbon atoms.

When a polyimide contains the structural unit represented by General formula (2), the thermal expansion coefficient of a polyimide becomes low. Therefore, when a polyimide is formed into a film on a support substrate for processes, such as a conductive layer formation, the curvature of a polyimide becomes small and can improve dimensional precision in the process of a conductive layer.

R <^3> in General formula (2) shows the structure of an acid component. Although it does not specifically limit as acid dianhydride used for R <^3> , In addition to the acid dianhydride which has an alicyclic structure mentioned above, aromatic acid dianhydride and aliphatic acid dianhydride are mentioned.

The aromatic acid dianhydride is not particularly limited, but pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarb Acid dianhydrides, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydrides, 3,3', 4,4'-terphenyltetracarboxylic dianhydrides, 3,3 ', 4, 4'-oxyphthalic dianhydride, 2,3,3 ', 4'-oxyphthalic dianhydride, 2,3,2', 3'-oxyphthalic dianhydride, diphenylsulfone-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) ethane dianhydride , Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (1,3-di Oxo-1,3-dihydroisobenzfuran-5-carboxylic acid) 1,4-phenylene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10- Perylenetetracarboxylic 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-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-tree Fluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4-dicarboxy Phenoxy) biphenyl dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 4,4 '-((9H-flu Aromatic tetracarboxylic dianhydrides such as renyl) bis (4,1-phenyleneoxycarbonyl)) diphthalic dianhydride, "Licaside" (registered trademark) TMEG-100 (trade name, manufactured by Shin-Nihon Rika Corporation), and And derivatives thereof.

The aliphatic acid dianhydride is not particularly limited, but 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, derivatives thereof and the like can be given. Can be.

In General formula (2), R <^4> shows the structure of a diamine component. The diamine compound to be used for R ⁴ , that is, the diamine compound having an alicyclic structure, is not particularly limited but may be cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, 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'-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'-diaminodicyclohexylether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylether, 3,3', 5,5'-tetrae -4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis (4-aminocyclo Hexyl) propane, 2,2-bis (3-methyl-4-aminocyclohexyl) 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'-diaminodicyclohexyl) propane, 2,2'-bis (4-aminocyclohexyl) hexafluoropropane, 2,2'-dimethyl-4,4'-diaminobicyclohexane, 2,2'-bis (trifluoromethyl) -4,4'- diamino bicyclohexane, or the diamine compound which substituted a part of aliphatic rings of these compounds with the alkyl group, the alkoxy group, the halogen atom, etc. are mentioned.

Although it does not specifically limit as diamine which gives the structure represented by General formula (3), 2, 2-bis (3-aminophenyl) propane, 2, 2-bis [4- (4-amino phenoxy) 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 and the like.

In this invention, the polyimide used for the resin film of a film with a conductive layer has a structural unit represented by the following general formula (4) as a main component, and the polyimide is a structural unit represented by the following general formula (5). It is preferable to contain 5 mol% or more and 30 mol% or less of all the structural units of the mead.

In general formula (4) and (5), R <^1> is a C4-C40 tetravalent organic group which has a monocyclic or condensed polycyclic alicyclic structure, or the organic group which has a monocyclic alicyclic structure is directly or bridge | crosslinked. A tetravalent organic group having 4 to 40 carbon atoms connected to each other through the 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).

In General formula (6), R <^15> -R <^22> respectively independently represents the C1-C3 monovalent organic group which may be substituted by the hydrogen atom, a halogen atom, or 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 with a halogen atom, an ester bond, an amide bond, and a sulfide bond.

In addition, the oxazole ring in structural formula (8) is produced | generated by dehydration ring closing from the structure represented by structural formula (7).

Here, "having as a main component the structural unit represented by General formula (4)" means having 50 mol% or more of the structural unit represented by General formula (4) in the total amount of all the structural units of a polyimide. When a polyimide has a structural unit represented by General formula (4) as a main component, the thermal expansion coefficient of a polyimide becomes low. Therefore, when a polyimide is formed into a film on a support substrate for processes, such as a conductive layer formation, the curvature of a polyimide becomes small and can improve dimensional precision in the process of a conductive layer.

In addition, the total amount of all the structural units of a polyimide is specifically, the total amount (mol reference) of the structural unit represented by General formula (4) and General formula (5). When a polyimide contains structures other than the structural unit represented by General formula (4) and General formula (5), the said total amount is a structural unit represented by General formula (4) and General formula (5), It is the total amount (mol basis) with structures other than the structural unit represented by General formula (4) and General formula (5).

In this invention, it is more preferable that content of the structural unit represented by General formula (4) is 70 mol% or more of all the structural units of a polyimide.

In addition, when the polyimide contains 5 mol% or more and 30 mol% or less of the structural unit represented by General Formula (5), the thermal expansion coefficient of the polyimide can be kept low while improving the transparency of the resin film. Thereby, while maintaining the pattern workability of a conductive layer, the color tone of a film with a conductive layer (and further, a touch panel including this) can be improved. It is more preferable that content of the structural unit (repeated structural unit) represented by General formula (5) in a polyimide is 10 mol% or more and 25 mol% or less of all the structural units of a polyimide.

In the formula (4) and the formula (5) R ¹ is the same as R ¹ in the formula (1), and shows a structure of an acid component having an alicyclic structure. Preferable specific examples of R ¹ are as described above. R <^13> in General formula (4) and R <^14> in General formula (5) represent the structure of a diamine component.

Although it does not specifically limit as diamine which gives the structure represented by General formula (6) to R <^13> , 3,4'- diamino diphenyl ether, 4,4'- diamino diphenyl ether, 3,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) Hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'- Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, benzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2 , 2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2 ', 3,3'-tetramethylbenzidine, 4,4-diaminobenzanilide, 4-aminobenzoic acid-4-aminophenyl, 3, 4-diaminobenzanilide, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone, or room for these compounds Group unsubstituted alkyl part, there may be mentioned a diamine compound substituted by an alkoxy group, a halogen atom or the like.

R ¹³ is preferably one or more selected from four structures represented by the following structural formulas (20) to (23), from the viewpoints of availability, transparency and reduction of the coefficient of thermal expansion of the polyimide. .

In this invention, the polyimide used for the resin film of a film with a conductive layer may also contain another structural unit in the range which does not prevent the effect of this invention. As another structural unit, the polyimide which is a dehydration ring-closure of polyamic acid, the dehydration ring-closure polybenzoxazole of polyhydroxyamide, etc. are mentioned. As acid dianhydride used for another structural unit, the aromatic acid dianhydride or aliphatic acid dianhydride mentioned above is mentioned.

In addition, in this invention, the polyimide used for the resin film of a film with a conductive layer is a repeating structure represented by following General formula (9) in at least one of the acid dianhydride residue and diamine residue which comprise this polyimide. It is preferable to contain.

In General formula (9), R <^23> and R <^24> represents a C1-C20 monovalent organic group each independently. m is an integer of 3 to 200.

When the polyimide includes a structure represented by the general formula (9) in at least one of an acid dianhydride residue and a diamine residue, when the polyimide is formed on a support substrate for a process such as conductive layer formation, the poly The residual stress of the mid resin film is reduced. Therefore, the curvature of a polyimide becomes small and can improve dimensional precision in the process of a conductive layer.

By the way, in the film with a conductive layer, static electricity generate | occur | produces on a film and there exists a problem that the disconnection by electrostatic discharge (ESD) arises. On the other hand, since the polyimide containing the structure represented by General formula (9) has low dielectric constant, in the film with a conductive layer provided with the resin film containing such polyimide, electric charges accumulate in devices, such as a touch panel using this. It is hard to become, and ESD resistance becomes high. Therefore, it is preferable that the polyimide used for the resin film of a film with a conductive layer contains the repeating structure represented by General formula (9) as mentioned above.

Formula (9) in R ^23, and a monovalent group having 1 to 20 carbon atoms represented by R ²⁴ as the organic group, for example, a monovalent amino-alkyl group of monovalent hydrocarbon groups, having 1 to 20 carbon atoms having 1 to 20 carbon atoms, alkoxy A group, an epoxy group, etc. are mentioned.

As a C1-C20 monovalent hydrocarbon group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, etc. are mentioned. As a C1-C20 alkyl group, it is preferable that it is a C1-C10 alkyl group, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, t-butyl group, a pentyl group, and a hex Practical skills etc. are mentioned. As a C3-C20 cycloalkyl group, it is preferable that it is a C3-C10 cycloalkyl group, and a cyclopentyl group, a cyclohexyl group, etc. are mentioned specifically ,. As a C6-C20 aryl group, it is preferable that it is a C6-C12 aryl group, and a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned specifically ,.

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

Among these, it is preferable that R <^23> and R <^24> are a C1-C3 monovalent aliphatic hydrocarbon group or a C6-C10 aromatic group. This is because the heat resistance of the polyimide resin film obtained is higher and the residual stress is lower. Here, the C1-C3 monovalent aliphatic hydrocarbon group is particularly preferably a methyl group. The aromatic group having 6 to 10 carbon atoms is particularly preferably a phenyl group.

M in General formula (9) becomes like this. Preferably it is an integer of 10-200, More preferably, it is an integer of 20-150, More preferably, it is an integer of 30-100, Especially preferably, it is an integer of 35-80 to be. When m is 3 or more, the residual stress of a polyimide resin film tends to be reduced. When m is 200 or less, the turbidity of the varnish containing a polyimide precursor and a solvent which are compositions for obtaining a polyimide can be suppressed.

Although it does not specifically limit as a specific example of the acid dianhydride containing the repeating structure represented by General formula (9), X22-168AS (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-168A (made by Shin-Etsu Chemical Co., Ltd., Number average molecular weight 2,000), X22-168B (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-8 (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,200), DMS-Z21 (made by Gelest Corporation, Number average molecular weight 600-800) etc. are mentioned.

Although it does not specifically limit as a specific example of the diamine containing the repeating structure represented by General formula (9), Both terminal amino modified methylphenyl silicone (made by Shin-Etsu Chemical Co., Ltd .; X22-1660B-3 (number average molecular weight 4,400), X22-) 9409 (number average molecular weight 1,300)), both terminal amino-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), Toray Dow Corning Co., BY16-835U (number average molecular weight 900), Chisso Co., Ltd. silaplane FM3311 (number average molecular weight 1000), etc. are mentioned.

Moreover, in this invention, it is preferable that the polyimide used for the resin film of the film with a conductive layer contains a triamine skeleton. When a polyimide contains a triamine skeleton, the toughness of this polyimide can be improved and the yield of a subsequent process can be improved.

Specific examples of the triamine compound include 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (TAPOB), and tris as those having no aliphatic group. (4-aminophenyl) amine, 1,3,5-tris (4-aminophenyl) benzene, 3,4,4'-triaminodiphenyl ether, etc. are mentioned. Moreover, tris (2-aminoethyl) amine (TAEA), tris (3-aminopropyl) amine, etc. are mentioned as a thing which has an aliphatic as a specific example of a triamine compound. Among these, especially from a viewpoint of heat resistance improvement, it is preferable to use 2,4,4'- triamino diphenyl ether and 1,3, 5- tris (4-amino phenoxy) benzene.

It is preferable that it is 1 micrometer or more, and, as for the thickness of the resin film used for the film with a conductive layer of this invention from the viewpoint of improving the toughness (the toughness of a touch panel to advance), it is more preferable that it is 2 micrometers or more, It is more preferable that it is 5 micrometers or more. On the other hand, it is preferable that it is 50 micrometers or less, as for the thickness of a resin film from a viewpoint of improving the transparency of a film with a conductive layer further, it is more preferable that it is 40 micrometers or less, and it is still more preferable that it is 30 micrometers or less.

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

The resin film used for the film with a conductive layer of this invention is an organic solvent, surfactant, a leveling agent, an adhesion | attachment improver, a viscosity modifier, antioxidant, an inorganic pigment, an organic pigment, dye, etc. to the said polyimide or its precursor as needed. It can form using the resin composition which mixes.

One method of obtaining the resin film used for the film with a conductive layer of this invention is to imide-close the polyamic acid which is a precursor corresponding to the polyimide to obtain. It does not specifically limit as a method of imidation, Thermal imidation and chemical imidation are mentioned. Especially, thermal imidation is preferable from a viewpoint of the heat resistance of a polyimide resin film and transparency in visible region.

Polyimide precursors, such as a polyamic acid, a polyamic acid ester, and a polyamic acid silyl ester, can be synthesize | combined by the polymerization reaction of a diamine compound, an acid dianhydride, or its derivative (s). As a derivative of an acid dianhydride, the tetracarboxylic acid of an acid dianhydride, the monoester of this tetracarboxylic acid, diester, triester or tetraester, an acid chloride, etc. are mentioned. As a derivative of an acid dianhydride, the thing of the structure esterified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group etc. is mentioned specifically ,. There is no restriction | limiting in particular as long as the reaction method of the said polymerization reaction can manufacture the target polyimide precursor, A well-known reaction method can be used.

As a specific reaction method of the said polymerization reaction, after putting a predetermined amount of all diamine components and a solvent into a reactor, dissolving a diamine, a predetermined amount of acid dianhydride components are added, and it stirred at room temperature-80 degreeC for 0.5 to 30 hours. And the like can be mentioned.

In this invention, in order to adjust the molecular weight to a preferable range, the polyimide and polyimide precursor used for the resin film of a film with a conductive layer may seal both ends with a terminal sealant. Examples of the terminal sealant that reacts with the acid dianhydride include monoamines, monovalent alcohols, and the like. Moreover, as an end sealing agent which reacts with a diamine compound, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a mono active ester compound, bicarbonate ester, vinyl ether, etc. are mentioned. Moreover, various terminal groups can be introduced at both ends of the polyimide or polyimide precursor by reacting the end sealant as end groups. A well-known compound can be used for a terminal sealer.

It is preferable to exist in the range of 0.1-60 mol% with respect to an acid dianhydride component, and, as for the introduction ratio of the terminal sealant on the acid anhydride group side, it is more preferable to exist in the range which is 0.5-50 mol%. Moreover, it is preferable to exist in the range of 0.1-100 mol% with respect to a diamine component, and, as for the introduction ratio of the terminal sealer on the amino group side, it is more preferable to exist in the range which is 0.5-70 mol%. You may introduce | transduce a some other terminal group in these both ends by making several terminal sealing agent react with both ends of a polyimide or a polyimide precursor.

The terminal sealant introduced into the polyimide precursor or polyimide can be easily detected by the following method. For example, the polymer in which the terminal sealant is 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. By measuring these using gas chromatography (GC) or NMR, an end sealant can be detected easily. In addition, even if the polymer into which the terminal sealant is introduced is directly used for measurement such as pyrolysis gas chromatography (PGC), infrared spectrum, ¹ H NMR spectrum and ¹³ C NMR spectrum, the terminal sealant can be easily detected.

The composition for obtaining the resin film containing a polyimide (henceforth a "polyimide resin composition") may contain the suitable component other than a polyimide or a polyimide precursor. Although it does not specifically limit as a component which may be contained in the polyimide resin composition, A ultraviolet absorber, a thermal crosslinking agent, an inorganic filler, surfactant, an internal peeling agent, a coloring agent, etc. are mentioned. These can use well-known compounds, respectively.

In the present invention, for example, "a tetravalent organic group having 4 to 40 carbon atoms" means a tetravalent organic group having 4 to 40 carbon atoms. The same applies to the other groups that define the carbon number.

(Gas barrier layer)

The film with a conductive layer which concerns on embodiment of this invention has a gas barrier layer, as illustrated to the gas barrier layer 2 shown in FIG. The gas barrier layer in this invention is formed on the resin film used as a board | substrate, and means the layer which has a function which prevents the resin film and the gas in an environment from directly contacting. When forming the conductive layer containing electroconductive particle on a resin film, 200 degreeC or more high temperature is applied to a resin film in presence of oxygen. Therefore, if there is no gas barrier layer, yellowing by thermal oxidation will generate | occur | produce in a resin film, and this will deteriorate the color tone of the film with a conductive layer. By forming a gas barrier layer between the resin film and the conductive layer, it is possible to prevent the resin film from contacting with oxygen during heating in an oxygen atmosphere. Thus, the film with a conductive layer excellent in the 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 oxygen permeation during formation of the conductive layer, but an inorganic material is preferable from the viewpoint of oxygen barrier properties. Examples of the inorganic material include metal oxides, metal nitrides, metal oxynitrides, and metal carbonitrides. As metal elements contained in these, aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), niobium (Nb), for example. ), Molybdenum (Mo), tantalum (Ta), calcium (Ca) and the like.

In particular, the gas barrier layer preferably contains at least one of silicon oxide, silicon nitride, silicon oxynitride and silicon carbonitride. This is because by using these materials for the formation of the gas barrier layer, it is easy to obtain a uniform and dense gas barrier film, and the oxygen barrier property of the gas barrier layer is further improved.

In addition, it is preferable that a gas barrier layer contains the component represented by SiOxNy from a viewpoint of further improving oxygen barrier property. x and y are values satisfying 0 <x≤1, 0.55≤y≤1, and 0≤x / y≤1.

The gas barrier layer can be produced by, for example, a vapor deposition method in which a material is deposited from a vapor phase to form a film, such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method. Especially, it is preferable to use a sputtering method or the plasma CVD method from the point which can obtain a more uniform and high oxygen barrier property.

There is no restriction | limiting in the number of layers of a gas barrier layer, Only one layer may be sufficient and the multilayer of two or more layers may be sufficient. 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, the first layer contains SiON, and the second layer contains SiO. Can be mentioned.

In the present invention, the gas barrier layer is an inorganic film in which two or more layers are laminated, and among the inorganic films, the layer in contact with the conductive layer is represented by SiOz (z is a value satisfying 0.5 ≦ z ≦ 2.). It is preferred to be formed of components. This is because the chemical resistance of the gas barrier layer during the conductive layer processing (especially when developing with photolithography) is improved, and the effect of improving the pattern workability and dimensional accuracy of the conductive layer and suppressing the residue is obtained. For losing.

It is preferable that it is 10 nm or more from a viewpoint of oxygen barrier property improvement, and, as for the thickness of the sum total of a gas barrier layer, it is more preferable that it is 50 nm or more. On the other hand, it is preferable that it is 1 micrometer or less, and, as for the thickness of the sum total of a gas barrier layer from a viewpoint of improving the bending tolerance of a film with a conductive layer, it is more preferable that it is 200 nm or less.

(Conductor Floor)

The film with a conductive layer which concerns on embodiment of this invention has a conductive layer containing electroconductive particle, as illustrated to 3 A of conductive layers shown in FIG. It is preferable that the conductive layer has a mesh structure having a line width of 0.1 to 9 µm. By having a conductive layer having a mesh structure having a line width of 0.1 to 9 µm, the conductivity and visibility of the conductive layer can be improved. As for the line width of the mesh structure of a conductive layer, it is more preferable that it is 0.5 micrometer or more, and it is still more preferable that it is 1 micrometer or more. On the other hand, it is more preferable that it is 7 micrometers or less, and, as for the line width of the mesh structure of a conductive layer, it is still more preferable that it is 6 micrometers or less.

Moreover, it is preferable that the film thickness of a conductive layer is 0.1 micrometer or more, It is more preferable that it is 0.2 micrometer or more, It is still more preferable that it is 0.3 micrometer or more. On the other hand, it is preferable that the film thickness of a conductive layer is 5 micrometers or less, It is more preferable that it is 3 micrometers or less, It is further more preferable that it is 1 micrometer or less.

As electroconductive particle contained in a conductive layer, gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc ( Metal particles such as Zn), palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), molybdenum (Mo), and metal particles having carbon. Metal particle | grains which have carbon are a composite of carbon black and a metal, for example. As this electroconductive particle, you may use two or more types of these. Among them, metal particles of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum or aluminum, and carbon particles are preferable, and silver particles are more preferable.

In order to form the fine conductive pattern which has desired electroconductivity, it is preferable that it is 10-200 nm, and, as for the primary particle diameter of electroconductive particle, it is more preferable that it is 10-60 nm. Here, the primary particle diameter of electroconductive particle is computed by observing the cross section of a conductive layer with a scanning electron microscope, randomly selecting 100 particle | grains, measuring the primary particle diameter of each particle, and taking those arithmetic mean values. . In addition, the particle diameter of the primary particle of each particle | grain is made into the arithmetic mean value of the longest part and the shortest part in a primary particle.

From the viewpoint of improving the 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 even more preferably 65% by mass or more. On the other hand, it is preferable that it is 95 mass% or less from a viewpoint of improving pattern workability, and, as for content of this electroconductive particle, it is more preferable that it is 90 mass% or less.

Moreover, it is preferable that a conductive layer contains 0.1-80 mass% of organic compounds. By containing 0.1 mass% or more of organic compounds, a conductive layer can provide flexibility to a conductive layer, and can improve the bending resistance of a conductive layer more. It is preferable that it is 1 mass% or more, and, as for content of the organic compound in a conductive layer, it is more preferable that it is 5 mass% or more. On the other hand, electroconductivity can be improved because a conductive layer contains 80 mass% or less of organic compounds. As for content of the organic compound in a conductive layer, it is more preferable that it is 50 mass% or less, and it is still more preferable that it is 35 mass% or less.

As an organic compound contained in a conductive layer, alkali-soluble resin is preferable. As 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, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, for example. sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, Butoxyethyl (meth) acrylate, Butoxytriethylene glycol (meth) acrylate, Cyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isobornyl (meth ) Acrylate, 2-hydroxypro (Meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate , Methoxydiethylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyethyl (meth) acrylate, stearyl (meth) acrylate, trifluoroethyl (meth) acrylate, (meth Acrylamide, aminoethyl (meth) acrylate, phenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, thiophenol (meth) acrylate, benzyl mercaptan (Meth) acrylate is mentioned.

As another monomer, the compound which has a carbon-carbon double bond is mentioned, For example, aromatic vinyl compounds, such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, (alpha) -methylstyrene, (meth Amide-based unsaturated compounds such as acrylamide, N-methylol (meth) acrylamide, and N-vinylpyrrolidone, (meth) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether and i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

In order to introduce a carboxyl group giving alkali solubility to alkali-soluble resin, (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, these acid anhydrides, etc. are copolymerized with the said (meth) acrylic-type monomer, for example. How to do this.

It is preferable that a (meth) acrylic-type copolymer has a carbon-carbon double bond in a side chain or a molecule terminal from a viewpoint of increasing the speed | rate of a hardening reaction. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, a (meth) acryl group, etc. are mentioned, for example.

It is preferable that the carboxylic acid equivalent of alkali-soluble resin is 400-1,000 g / mol. The carboxylic acid equivalent of acrylic soluble resin can be computed by measuring an acid value. Moreover, since the double bond equivalent of alkali-soluble resin can make compatible hardness and crack resistance at a high level, it is preferable that it is 150-10,000 g / mol. The double bond equivalent of acrylic soluble resin can be computed by measuring an iodine value.

It is preferable that the weight average molecular weight (Mw) of alkali-soluble resin is 1,000-100,000. By carrying out a weight average molecular weight in the said range, favorable application | coating characteristic of alkali-soluble resin is obtained, and the solubility of alkali-soluble resin with respect to the developing solution at the time of pattern-forming a conductive layer also becomes favorable. Here, the weight average molecular weight of alkali-soluble resin says the polystyrene conversion value measured by gel permeation chromatography (GPC).

In addition, the conductive layer may contain at least one of an organotin compound and a metal chelate compound. When the conductive layer contains at least one of an organic tin compound and a metal chelate compound, the adhesion between the conductive layer and the gas barrier layer can be further improved. In particular, the metal chelate compound is more preferable than the organotin compound in that an adhesive improvement effect is obtained without putting an environmental load. A well-known compound can be used for an organotin compound and a metal chelate compound.

From the viewpoint of further improving the substrate adhesiveness, the total content of the organic tin 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 even more preferably 0.1% by mass or more. Do. On the other hand, the total content of these organotin compounds and metal chelate compounds is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of improving the conductivity of the conductive layer and forming a finer pattern. It is more preferable that it is mass% or less.

The conductive layer contains, in addition, a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a solvent, a sensitizer, and at least one of pigments and dyes having absorption in visible light, adhesion improving agents, surfactants, polymerization inhibitors, and the like. It is desirable to.

In addition, the conductive layer in this invention can be formed using an electroconductive composition. As a component contained in this electrically conductive composition, it is an electroconductive particle, alkali-soluble resin, an organic tin compound, a metal chelate compound, a dispersing agent, a photoinitiator, a monomer, a photo-acid generator, a thermal acid generator, a solvent, a sensitizer, visible light, for example. At least one of the pigment and dye which have absorption, an adhesion improving agent, surfactant, a polymerization inhibitor, etc. are mentioned.

It is preferable that the electroconductive particle which an electroconductive composition contains has a coating layer in at least one part of the particle surface. Thereby, the surface activity of electroconductive particle is reduced, at least one of reaction of electroconductive particle and reaction of electroconductive particle and an organic component can be suppressed, and the dispersibility of electroconductive particle can be improved. Moreover, also when photolithography is used for the process of a conductive layer, scattering of exposure light can be suppressed and a conductive layer can be pattern-processed with high precision. On the other hand, the coating layer on the surface of this electroconductive particle can be easily removed by heating at high temperature about 150-350 degreeC in presence of oxygen. As a result, the electroconductive particle in a conductive composition can express the electroconductivity with which a conductive layer is sufficient.

It is preferable that the coating layer on the surface of electroconductive particle contains at least 1 among carbon and a carbon compound. When this coating layer contains at least one of carbon and a carbon compound, the dispersibility of the electroconductive particle in a conductive composition can be improved further.

As a method of forming the coating layer containing at least one of carbon and a carbon compound on the surface of electroconductive particle, the method of making the reactive particle which has carbon, such as methane gas, and electroconductive particle contact, for example by the thermal plasma method ( The method described in Unexamined-Japanese-Patent No. 2007-138287).

(Insulation layer)

It is preferable that the film with a conductive layer which concerns on embodiment of this invention has the insulating layer formed of alkali-soluble resin on a conductive layer. Alkali-soluble in this invention means melt | dissolving 0.1g or more at 25 degreeC with respect to 0.045 mass% potassium hydroxide aqueous solution (100g). Since the insulating layer formed of alkali-soluble resin can be pattern-processed by photolithography and can form the opening part for conduction of a conductive layer by this, it is preferable.

Moreover, it is preferable that the film with a conductive layer which concerns on embodiment of this invention has the insulating layer formed from alkali-soluble resin containing the above-mentioned (meth) acrylic-type copolymer on a conductive layer. This is because the flexibility of the insulating layer is increased by the (meth) acrylic copolymer in the alkali-soluble resin.

Moreover, the film with a conductive layer which concerns on embodiment of this invention has the insulating layer formed from alkali-soluble resin containing the cardo resin which has two or more structures represented by the following structural formula (10) on a conductive layer. It is preferable. This is because the cardo resin can increase the hydrophobicity of the insulating layer, thereby improving the insulation of the insulating layer.

Cardo resin can be obtained, for example by making the reactant of an epoxy compound and the organic acid containing a radically polymerizable group react with an acid dianhydride further. As a catalyst used for reaction of the organic compound containing an epoxy compound and a radically polymerizable group, and reaction of an epoxy compound and an acid dianhydride, an ammonium catalyst, an amine catalyst, a phosphorus catalyst, a chromium catalyst etc. are mentioned, for example. . As an ammonium catalyst, tetrabutylammonium acetate etc. are mentioned, for example. As an amine catalyst, 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine etc. are mentioned, for example. As a phosphorus catalyst, triphenyl phosphine etc. are mentioned, for example. As a chromium-type catalyst, acetylacetonate chromium, chromium chloride, etc. are mentioned, for example. Moreover, as an epoxy compound, the following compounds are mentioned, for example.

As an organic acid containing a radically polymerizable group, (meth) acrylic acid, mono succinate (2- (meth) acryloyloxyethyl), mono phthalate (2- (meth) acryloyloxyethyl), tetrahydro Phthalate mono (2- (meth) acryloyloxyethyl), p-hydroxy styrene, etc. are mentioned.

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-biphenyl Tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride, etc. are preferable. Moreover, in order to adjust the molecular weight of an acid dianhydride, what substituted the acid anhydride with a part of acid dianhydride can also be used.

Moreover, as a cardo resin which has two or more structures represented by Structural formula (10), a commercial item can be used preferably. As a commercial item of this cardo resin, "WR-301 (brand name)" (made by ADEKA company), "V-259ME (brand name)" (made by Shin-Nitetsu Sumikin Kagaku Corporation), "Ogsol CR-TR1 ( "Ogsol CR-TR2 (brand name)", "Ogsol CR-TR3 (brand name)", "Ogsol CR-TR4 (brand name)", "Ogsol CR-TR5 (brand name)", "Ogg Sol CR-TR6 (brand name) "(manufactured by Osaka Gas Chemical Co., Ltd.) and the like.

It is preferable that the weight average molecular weights of a (meth) acrylic-type copolymer and cardo resin are 2,000 or more from a viewpoint of improving application characteristics, respectively. Moreover, it is preferable that these weight average molecular weights are 200,000 or less from a viewpoint of improving the solubility of the insulating layer with respect to the developing solution in the pattern formation of an insulating layer, respectively. Here, a weight average molecular weight says the polystyrene conversion value measured by GPC.

When the insulating layer contains both the (meth) acrylic copolymer and cardo resin, the weight average molecular weight (Mw (A1)) of the (meth) acrylic copolymer and the weight average molecular weight (Mw (A2) of the cardo resin It is preferable that ratio (Mw (A2) / Mw (A1)) of)) is 0.14 or more from a viewpoint of suppressing layer separation and forming a uniform cured film. On the other hand, it is preferable that it is 1.5 or less, and, as for this ratio Mw (A2) / Mw (A1), suppressing layer separation and forming a uniform cured film, it is more preferable that it is 1.0 or less.

The insulating layer in this invention can be formed using the insulating composition containing alkali-soluble resin. Although content of alkali-soluble resin contained in this insulating composition can be arbitrarily selected according to desired film thickness and a use, it is common to set it as 10 mass parts or more and 70 mass parts or less with respect to 100 mass parts of solid content.

The said insulating composition may contain a hindered amine light stabilizer. When the said insulating composition contains a hindered amine light stabilizer, coloring of an insulating layer can be reduced more and the weather resistance of an insulating layer can be improved.

The said insulating composition may further contain additives, such as a polyfunctional monomer, a hardening | curing agent, a ultraviolet absorber, a polymerization inhibitor, an adhesion improving agent, a solvent, surfactant, a dissolution inhibitor, a stabilizer, and an antifoamer.

<Touch panel>

The touch panel which concerns on embodiment of this invention has a film with a conductive layer of this invention, as illustrated to the touch panel 10 shown in FIGS. In this invention, the conductive layer of the film with a conductive layer is a wiring layer (for example, the 1st wiring layer 3 shown in FIGS. 2 and 3) of a touch panel. 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 layer on the insulating layer. . The touch panel of this invention may further have a 2nd insulating layer in the side (namely, upper surface side) opposite to the surface which contact | connects the 1st insulating layer of the said 2nd wiring layer. By having the 2nd insulating layer in this way, the touchscreen of this invention can suppress that moisture | moisture content in air | atmosphere reaches a 2nd wiring layer. As a result, the reliability of the touch panel can be further improved.

In the touch panel of this invention, the 1st insulating layer and the 2nd insulating layer may be respectively comprised from the same material, and may be comprised from different materials. In addition, it is preferable that it is 0.1 micrometer or more, and, as for the film thickness of a 1st insulating layer and a 2nd insulating layer, from a viewpoint of improving insulation more, it is more preferable that it is 0.5 micrometer or more. On the other hand, it is preferable that it is 10 micrometers or less, and, as for the film thickness of a 1st insulating layer and a 2nd insulating layer, from these viewpoints to improve these transparency more, it is more preferable.

It is preferable that the thickness of the conductive layer equipped film (namely, the conductive layer equipped film which concerns on embodiment of this invention) applied to such a touch panel is 1-40 micrometers. By setting the thickness of the conductive layer-containing film to be within this range, problems such as tearing and warping in the manufacturing process of the conductive layer-containing film are suppressed, and the yield of the conductive layer-containing film (to improve the yield of the touch panel) is improved. You can. Moreover, the followability of the shape with respect to bending when the touch panel of this invention is used as a flexible touch panel improves remarkably. In this invention, it is more preferable that it is 3 micrometers or more, and, as for the thickness of a touch panel, it is still more preferable that it is 5 micrometers or more. On the other hand, it is more preferable that it is 30 micrometers or less, and, as for the thickness of a touch panel, it is still more preferable that it is 25 micrometers or less.

As for the film with a conductive layer which concerns on embodiment of this invention, it is preferable that the value of b * by L * a * b * color system prescribed | regulated to the International Illumination Commission 1976 is -5-5. By setting the value of b * 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 display can be further improved. In this invention, it is more preferable that it is -4-4, and, as for the value of b *, it is still more preferable that it is -3-3.

<The manufacturing method of the touch panel containing the film with conductive layer>

The manufacturing method of the touchscreen containing the conductive layer equipped film which concerns on embodiment of this invention uses the manufacturing method of this conductive layer equipped film. This manufacturing method of 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. A resin film formation process is a process of forming the resin film containing a polyimide on a 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. A peeling process is a process of peeling the resin film after the said gas barrier layer, a conductive layer, etc. are formed from this support substrate. In this invention, the manufacturing method of a touchscreen includes a wiring layer formation process as a conductive layer formation process in the manufacturing method of the film with a conductive layer. 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 flowchart showing an example of a method of manufacturing a touch panel including a film with a conductive layer according to the embodiment of the present invention. In the manufacturing method of the touch panel in this embodiment, a resin film forming process, a gas barrier layer forming process, a 1st wiring layer forming process, a 1st insulating layer forming process, a 2nd wiring layer forming process, and a 2nd The insulating layer forming step and the peeling step are sequentially performed in this order.

In detail, first, in the resin film formation process, as shown to the state S1 of FIG. 4, the resin film 1 containing the polyimide mentioned above is formed on the support substrate 7. Next, in the gas barrier layer forming step, as shown in state S2 of 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 of FIG. 4, the first wiring layer 3 is formed on the gas barrier layer 2. Subsequently, in the first insulating layer forming step, as shown in state S4 of 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 of FIG. 4, on the first insulating layer 4 (in the present embodiment, on the gas barrier layer 2 and the first insulating layer 4). The second wiring layer 5 is formed in this. Next, in the second insulating layer forming step, as shown in state S6 of 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 process, as shown to the state S7 of FIG. 4, the laminated structure of the resin film 1 and the gas barrier layer 2 is cut in the cut end surface 8 thereof. Subsequently, the resin film 1 of this laminated structure is mechanically peeled 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)

The resin film forming step is a step of forming the resin film 1 containing the polyimide on the support substrate 7 as described above. This resin film formation process is a coating process which apply | coats the polyimide resin composition mentioned above on the support substrate 7, the prebaking process which dries the polyimide resin composition on this support substrate 7, and the poly after this drying It is preferable to include the curing process of curing a mid resin composition.

As the support substrate 7, a silicon wafer, a ceramic substrate, an organic substrate, etc. are mentioned, for example. As a ceramic substrate, glass substrates, such as a soda glass, an alkali free glass, a borosilicate glass, a quartz glass, an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, etc. are mentioned, for example. As an organic board | substrate, an epoxy board | substrate, a polyetherimide resin board | substrate, a polyether ketone resin board | substrate, a polysulfone-type resin board | substrate, a polyimide film, a polyester film, etc. are mentioned suitably, for example.

As a method of apply | coating a polyimide resin composition on the support substrate 7, For example, application | coating using a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a calender coater, a meniscus coater, screen printing, Spray coating, dip coating, and the like.

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

What is necessary is just to determine the prebaking temperature and time of the polyimide resin composition in a prebaking process suitably according to the composition of the polyimide resin composition made into object, and the film thickness of the coating film (coating film of a polyimide resin composition) to dry. . For example, in the prebaking process in this invention, it is preferable to heat a coating film in 10 second-30 minutes in the temperature range of 50-150 degreeC.

What is necessary is just to determine suitably the cure atmosphere, temperature, and time of the polyimide resin composition in a cure process according to the composition of the polyimide resin composition made into object, and the film thickness of the coating film (coating film of a polyimide resin composition) to cure. . From this viewpoint of suppressing the yellowing of the film by heating, in this cure process, the coating film of the polyimide resin composition on the support substrate 7 is 5-180 at the temperature of 300 degreeC or more and 500 degrees C or less in the atmosphere whose oxygen concentration is 1000 ppm or less. It is preferable to form the resin film 1 by heating for minutes.

(Gas Barrier Layer Forming Step)

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

Since the polyimide resin preferably used for the resin film 1 in the present invention has a high glass transition temperature, it is also possible to increase the substrate temperature (temperature of the supporting substrate 7) when the gas barrier layer 2 is formed. Do. As the substrate temperature is higher, the crystallinity of the gas barrier layer 2 is improved, so that the gas barrier performance is improved. 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 will fall. From these viewpoints, as a minimum of the film forming temperature of the gas barrier layer 2, 80 degreeC or more is preferable and 100 degreeC or more is more preferable. Moreover, as an upper limit of the film forming temperature of the gas barrier layer 2, 400 degrees C or less is preferable, and 350 degrees C or less is more preferable.

(1st wiring layer forming process)

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 includes a coating step of applying the above-described conductive composition on the gas barrier layer 2, a prebaking step of drying the coating film of the conductive composition, and the dried coating film (prebaking film). It is preferable to include the process (exposure process and image development process) of exposing and developing and forming a mesh pattern, and the curing process of curing this pattern-formed prebaking film.

In particular, in the first wiring layer forming step, it is preferable to form the first wiring layer 3 by using a conductive composition containing conductive particles having a coating layer on at least part of the surface. This is because the electroconductive particle which has a coating layer in at least one part of the surface suppresses scattering of exposure light in an exposure process, and can pattern-process the wiring of the 1st wiring layer 3 by high precision by this.

In the first wiring layer forming step, as the method for applying the conductive composition onto the gas barrier layer 2 and the drying method in the prebaking step and the curing step for the coating film of the conductive composition, the above-described resin film forming step The method illustrated by the polyimide resin composition of this is mentioned.

As a light source used at the exposure process of the coating film of an electroconductive composition, j line | wire, i line | wire, h line | wire, and g line | wire of a mercury lamp are preferable, for example. As a developing solution used at the coating film developing process of an electroconductive composition, a well-known developing solution can be used. For example, as this developing solution, the aqueous alkali solution which melt | dissolved alkaline substances, such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (TMAH), in water is mentioned. This developer may be suitably added water-soluble organic solvents such as ethanol, gamma -butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone to these developers. In addition, in order to obtain a better conductive pattern than the coating film of a conductive composition by this developing process, in addition to these alkaline developing solutions, surfactant, such as a nonionic surfactant, content in a developing solution is 0.01-1 mass% It is also preferable to add as much as possible.

The atmosphere, temperature, and time of the cure of the coating film (prebaked film forming a pattern shape) of the conductive composition in the curing process depend on the composition of the conductive composition and the film thickness of the coating film (coating film of the conductive composition) to cure. You may decide appropriately. In this cure process, it is preferable to heat the coating film of an electroconductive composition for 5 to 120 minutes in the temperature range of 100-300 degreeC in air, for example. 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, in this curing step, a gas barrier layer ( It is preferable to form the 1st wiring layer 3 by heating the coating film of the electroconductive composition of 2) on the temperature of 100 degreeC or more and 300 degrees C or less in the atmosphere whose oxygen concentration is 15% or more.

In particular, in order to obtain the touch panel 10 with less yellowing and excellent conductivity, in the method for manufacturing the touch panel 10, the polyimide resin composition is heated at a temperature of 300 ° C. or more and 500 ° C. or less under an atmosphere having an oxygen concentration of 1000 ppm or less. The conductive film is heated at a temperature of 100 ° C. or more and 300 ° C. or less in a resin film forming step of forming the resin film 1 containing the polyimide and in an atmosphere having an oxygen concentration of 15% or more, thereby forming a wiring layer (for example, a first wiring layer ( It is preferable to include the wiring layer forming process of forming 3)).

(First Insulation Layer Forming Step)

As described above, the first insulating layer forming step is a step of forming the first insulating layer 4 so as to cover the first wiring layer 3 on the gas barrier layer 2. This 1st insulating layer formation process is a coating process which apply | coats the insulating composition mentioned above on the 1st wiring layer 3, the prebaking process which dries the coating film of this insulating composition, and this dry coating film (prebaking film) It is preferable to include the process (exposure process, image development process) which forms a pattern by exposing and developing this, and the curing process which cures this pattern-prebaked film (insulating film). Each step included in the first insulating layer forming step can be performed in the same manner as in the first wiring layer forming step described above.

(2nd wiring layer forming process, 2nd insulating layer forming process)

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 in the same manner 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 this second insulating layer forming step, the second insulating layer 6 can be formed in the same manner as the first insulating layer 4 described above.

In the manufacturing method of the touch panel 10, although it is not necessary to form the 2nd insulating layer 6 on the 2nd wiring layer 5, it is preferable to form the 2nd insulating layer 6 as mentioned above. Do. This is because by forming the second insulating layer 6, it is possible to suppress the moisture in the air from reaching the second wiring layer 5, thereby improving the moisture and heat resistance of the touch panel 10.

(Peeling process)

The peeling process is a process of peeling the resin film 1 from the support substrate 7 as mentioned above. As a method of peeling the resin film 1 containing a polyimide from the support substrate 7 in this peeling process, it is peeled by irradiating a laser beam to the resin film 1 from the back surface of the support substrate 7, for example. 10 seconds to 10 hours in a solvent and purified water maintained at 0 to 80 ° C. in the support substrate 7 (hereinafter, referred to as a touch panel support substrate) before taking out the touch panel 10. And the method of peeling, the resin film 1 is cut from the upper surface, and the method of mechanical peeling from the cut end surface 8, etc. are mentioned. Especially, in consideration of the influence on the reliability of the touch panel 10, the method of mechanically peeling from the cut end surface 8 is preferable.

In addition, the above-mentioned peeling process may be performed directly to a touchscreen support substrate, and may be performed after bonding a protective film and a transparent adhesive layer (OCA: Optical Clear Adhesive) to a touchscreen support substrate. Furthermore, after bonding a touch panel supporting substrate to members, such as a display substrate, through OCA, peeling (that is, taking out the touch panel 10) of the resin film 1 from this touch panel supporting substrate is also performed. It is preferable from a viewpoint of joining precision.

In the touch panel which concerns on embodiment of this invention, since the yellowing of the resin film containing polyimide at the time of wiring layer formation is suppressed by the gas barrier layer, visibility is good. Moreover, since the dimensional change of the resin film at the time of wiring layer formation is suppressed by the gas barrier layer, a touch panel excellent in dimensional accuracy can be provided. The touch panel which concerns on embodiment of this invention is used suitably as a display member, such as a smartphone and a tablet terminal.

<The manufacturing method of the film with a conductive layer>

The manufacturing method of the film with a conductive layer which concerns on embodiment of this invention contains a resin film formation process, a gas barrier layer formation process, a conductive layer formation process, and a peeling process at least. Among these processes, the resin film forming step, the gas barrier layer forming step, and the peeling step are the same as those of the above-described method for manufacturing the touch panel, as illustrated in states S1, S3, and S7 of FIG. 4. The conductive layer forming step is a step of forming a conductive layer on the gas barrier layer. This conductive layer formation process is the same as the process of replacing the 1st wiring layer of the 1st wiring layer formation process in the manufacturing method of a touchscreen mentioned above with a conductive layer. In this invention, it is preferable that this conductive layer formation process is a process of forming a conductive layer using the electroconductive composition containing the electroconductive particle which has a coating layer in at least one part of the surface. Moreover, it is preferable that this conductive layer formation process is a process of heating the electrically conductive composition on a gas barrier layer at the temperature of 100 degreeC or more and 300 degrees C or less in the atmosphere whose oxygen concentration is 15% or more, and forming a conductive layer.

Moreover, the manufacturing method of the film with a conductive layer may include the insulating layer formation process of forming an insulating layer so that a conductive layer may be covered on a gas barrier layer. This insulation layer formation process can be performed by the method similar to the 1st insulation layer formation process in the manufacturing method of a touchscreen mentioned above, for example. By forming an insulating layer on a conductive layer by this insulating layer formation process, it can suppress that moisture | moisture content in air | atmosphere reaches a conductive layer, and can improve the moisture-heat resistance of the film with a conductive layer by this.

Example

Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by the following Example. First, the material used in the following example and the comparative example, the measurement, and evaluation which were performed are demonstrated.

(Mountain dianhydride)

In the following Examples and Comparative Examples, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 3,3 ', 4,4'-biphenyltetracarboxylic acid as acid dianhydride Dianhydride (BPDA), 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride (BSAA), 3,3 ', 4,4'-diphenylethertetracarboxylic acid Both dianhydride (ODPA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), and both terminal acid anhydride modified methylphenylsilicone oils (X22-168-P5-B) manufactured by Shin-Etsu Chemical Co., Ltd. Used accordingly.

(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) sulfone (3,3'-DDS), bis [4- (3-aminophenoxy Phenyl] sulfone (m-BAPS) and the both terminal amine modified methylphenyl silicone oil (X22-1660B-3) by Shin-Etsu Chemical Co., Ltd. are used as needed.

(solvent)

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

(Alkali-soluble resin)

In the following examples and comparative examples, alkali-soluble resin AR is used as necessary. Alkali-soluble resin AR adds and reacts 0.4 equivalent glycidyl methacrylate with respect to the carboxyl group of the copolymer containing methacrylic acid / methyl methacrylate / styrene = 54/23/23 (mol%). The weight average molecular weight (Mw) of this alkali-soluble resin AR is 29,000.

(Conductive particles)

In the following Example and a comparative example, electroconductive particle A-1 and A-2 are used as needed as electroconductive particle. The electroconductive particle A-1 was 1 nm in average thickness of the surface carbon coating layer, and set it as the silver particle (made by Nisshin Engineering Co., Ltd.) whose primary particle diameter is 40 nm. Electroconductive particle A-2 was set to the silver particle (made by Mitsui Kinzoku Kogyo Co., Ltd.) whose primary particle diameter is 0.7 micrometer.

(1st production example: preparation of the varnish for polyimide resin film forming)

In a 1st preparation example, the preparation example of the polyimide resin film forming varnish (henceforth abbreviated as "varnish" suitably) used for the following Example and comparative example is demonstrated.

Synthesis Example 1

In Synthesis Example 1 of the varnish, ODPA (9.37 g (30.2 mmol)), TFMB (9.67 g (30.2 mmol)), and NMP (100 g) were added to a 200 mL four-necked flask under a dry nitrogen stream at 60 ° C. It stirred by heating. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 1. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 1 is 23.5.

Synthesis Example 2

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

Synthesis Example 3

In Synthesis Example 3 of the varnish, ODPA (13.92 g (44.8 mmol)), CHDA (5.12 g (44.8 mmol)), and NMP (100 g) were added to a 200 mL four-necked flask under a dry nitrogen stream at 60 ° C. It stirred by heating. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 3. The imide group concentration of the polyimide which can be produced using the varnish of this Synthesis Example 3 is 35.8.

Synthesis Example 4

In Synthesis Example 4 of the varnish, BPDA (11.70 g (39.8 mmol)), BSAA (2.30 g (4.42 mmol)), CHDA (5.04 g (44.1 mmol)) and 200 mL four-necked flasks under dry nitrogen stream , NMP (100 g) was added thereto, and the mixture was heated and stirred at 60 ° C. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 4. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 4 is 36.3.

Synthesis Example 5

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

Synthesis Example 6

In Synthesis Example 6 of the varnish, in a 200 mL four-necked flask under a dry nitrogen stream, ODPA (8.75 g (28.2 mmol)), TFMB (8.93 g (27.9 mmol)), and X22-1660B-3 (1.36 g (0.309) mmol)) and NMP (100 g) were added thereto, and the resulting mixture was heated and stirred at 60 ° C. This heating stirring was performed for 8 hours, after which the heating and stirring were cooled to room temperature, and it was set as the varnish of the synthesis example 6. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 6 is 23.4.

Synthesis Example 7

In Synthesis Example 7 of the varnish, 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-necked flask under a dry nitrogen stream. It put and stirred at 60 degreeC by heating. This heating stirring was performed for 8 hours, after which the heating and stirring were cooled to room temperature, and it was set as the varnish of the synthesis example 7. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 7 is 26.8.

Synthesis Example 8

In Synthesis Example 8 of the varnish, BPDA (13.72 g (46.6 mmol)), CHDA (5.32 g (46.6 mmol)), and NMP (100 g) were added to a 200 mL four-necked flask under a dry nitrogen stream at 60 ° C. It stirred by heating. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 8. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 8 is 37.7.

Synthesis Example 9

In Synthesis Example 9 of the varnish, ODPA (7.95 g (25.6 mmol)), m-BAPS (11.09 g (25.6 mmol)), and NMP (100 g) were added to a 200 mL four-necked flask under a dry nitrogen stream. It stirred by heating at ° C. This heating stirring was performed for 8 hours, after which the heating and stirring were cooled to room temperature, and it was set as the varnish of the synthesis example 9. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 9 is 19.8.

Synthesis Example 10

In Synthesis Example 10 of the varnish, in a 200 mL four-necked flask under dry nitrogen stream, ODPA (3.97 g (12.8 mmol)), PMDA (2.79 g (12.8 mmol)), TFMB (8.11 g (25.3 mmol)) and , X22-1660B-3 (1.18 g (0.282 mmol)) and NMP (100 g) were added thereto, and the resulting mixture was heated and stirred at 60 ° C. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 10. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 10 is 25.4.

Synthesis Example 11

In Synthesis Example 11 of the varnish, in a 200 mL four-necked flask under dry nitrogen stream, ODPA (7.85 g (25.3 mmol)), X22-168-P5-B (1.18 g (0.282 mmol)), and TFMB (8.20 g) (25.6 mmol)) and NMP (100 g) were added, and the mixture was heated and stirred at 60 ° C. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 11. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 11 is 23.4.

Synthesis Example 12

In Synthesis Example 12 of the varnish, in a 200 mL four-necked flask under dry nitrogen stream, ODPA (3.97 g (12.8 mmol)), BPDA (3.77 g (12.8 mmol)), TFMB (8.11 g (25.3 mmol)) and , X22-1660B-3 (1.18 g (0.282 mmol)) and NMP (100 g) were added thereto, and the mixture was heated and stirred at 60 ° C. This heating stirring was carried out for 8 hours, after which the heating and stirring were cooled to room temperature to obtain a varnish of Synthesis Example 12. The imide group concentration of the polyimide which can be produced using the varnish of Synthesis Example 12 is 23.3.

(2nd production example: preparation of a conductive composition)

In a 2nd preparation example, preparation of the electroconductive composition AE-1 and AE-2 used suitably by the following example and the comparative example is demonstrated. In this 2nd preparation example, electroconductive particle A-1 (80g), surfactant "DISPERBYK" (trademark) 21116 (4.06g) by DIC Corporation, PGMEA (98.07g), and DPM (98.07g) are mixed. Then, these mixtures were treated with a homogenizer for 1200 rpm for 30 minutes. Moreover, the mixture after this process was disperse | distributed using the high pressure wet medialess atomizer nanomizer (manufactured by Nanomizer company), and the silver dispersion liquid L1 whose silver content is 40 mass% was obtained. In addition, except having used electroconductive particle A-2 instead of electroconductive particle A-1, operation similar to the above was performed and the silver dispersion liquid L2 was obtained by this.

Subsequently, 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) were mixed. PGMEA (132.6 g) and DPM (52.6 g) were added and stirred. This obtained the organic liquid L3 for electroconductive compositions. In addition, ALCH is a metal chelate compound (ethylacetoacetate aluminum diisopropylate) by Kawaken Fine Chemicals. NCI-831 is a photoinitiator made by ADEKA Corporation. Then, the silver dispersion liquid L1, L2 and organic liquid L3 which were obtained as mentioned above were mixed in the ratio shown in Table 1, respectively, and thereby, electroconductive compositions AE-1 and AE-2 were obtained.

(3rd Production Example: Production of Insulating Composition)

In 3rd manufacture example, preparation of insulating composition OA-1 and OA-2 used suitably by the following example and the comparative example is demonstrated. In this third production example, V-259ME (50.0 g) manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd. as a cardo resin having two or more structures represented by Structural Formula (10) in a clean bottle, and a crosslinkable monomer TAIC (18.0g) by Nihon Kasei Co., Ltd. M-315 (10.0g) by Toagosei Co., Ltd. as a crosslinkable monomer, PG-100 (20.0g) by Osaka Gas Chemical Co., Ltd. as an epoxy compound, and BASF as a photoinitiator Commercial OXE-01 (0.2 g) was mixed, and these mixtures were stirred for 1 hour. This obtained insulating composition OA-1. In addition, operation similar to the above was performed except having used alkali-soluble resin AR instead of the said cardo resin (V-259ME), and thereby insulating composition OA-2 was obtained.

(Fourth Production Example: Preparation of Polyimide Resin Film)

In a 4th preparation example, preparation of the polyimide resin film T1 used suitably by the following example and the comparative example is demonstrated. In this fourth production example, the film thickness after 4 minutes of prebaking at a temperature of 140 ° C. was applied to a 6-inch mirror silicon wafer as a substrate using a coating and developing apparatus (Mark-7) manufactured by Tokyo Electron Corporation. The varnish (varnish in any one of the synthesis examples 1-12) of the 1st production example was spin-coated so that it might become micrometer. Then, the prebaking process of 4 minutes was performed on the coating film of this varnish using the Mark-7 hot plate at the temperature of 140 degreeC. The prebaked membrane obtained by this was heated up to 350 degreeC by the temperature increase rate of 3.5 degree-C / min under nitrogen stream (oxygen concentration of 20 ppm or less) using the inner oven (INH-21CD) by the Koyo Thermo Systems company, and 30 minutes Maintained. Then, this prebaking film was cooled to 50 degreeC by the temperature-fall rate of 5 degreeC / min, and the polyimide resin film T1 was produced by this. Subsequently, the polyimide resin film T1 (in the state affixed to the substrate) is immersed in hydrofluoric acid for 1 to 4 minutes, the polyimide resin film T1 is peeled off from the substrate, and air-dried to form the polyimide resin film T1 (single). Got it.

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

In a 5th production example, preparation of the polyimide resin film T2 used suitably by the following example and the comparative example is demonstrated. In this 5th production example, it is free for 4 minutes at the temperature of 140 degreeC using the Mikasa Corporation spin coater (MS-A200) for the glass substrate (tempax) of 50 mm in length x 50 mm in width x 1.1 mm in thickness. The varnish (varnish in any one of the synthesis examples 1-12) of the 1st production example was spin-coated so that the film thickness after baking might be 15 +/- 0.5 micrometer. Thereafter, the coating film of this varnish was subjected to prebaking for 4 minutes at a temperature of 140 ° C using a hot plate (D-SPIN) manufactured by Dainippon Screen. The prebaked membrane obtained by this was heated up to 350 degreeC by the temperature increase rate of 3.5 degree-C / min under nitrogen stream (oxygen concentration of 20 ppm or less) using the inner oven (INH-21CD) by the Koyo Thermo Systems company, and 30 minutes Maintained. Then, this prebaking film was cooled to 50 degreeC by the temperature-fall rate of 5 degree-C / min, and the polyimide resin film T2 of the state affixed on the rectangular glass substrate was produced by this.

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

In a 6th production example, preparation of the polyimide resin film T3 used suitably by the following example and the comparative example is demonstrated. In the sixth production example, the film after prebaking for 4 minutes at a temperature of 140 ° C. was used on a glass substrate having an outer diameter of 13 inches (AN-100, manufactured by Asahi Glass, Inc.) using a spin coater (1H-360S) manufactured by Mikasa Co., Ltd. The varnish (varnish in any one of the synthesis examples 1-12) of the 1st production example was spin-coated so that thickness might be 15 +/- 0.5 micrometer. Then, the prebaking process of 4 minutes was performed at the temperature of 140 degreeC with respect to the coating film of this varnish using a hotplate. The prebaking film obtained by this was heated up to 350 degreeC by the temperature increase rate of 3.5 degree-C / min under nitrogen stream (oxygen concentration 20 ppm or less) using the inner oven (INH-21CD) by Koyo Thermo Systems, Inc., and 30 minutes Maintained. Then, this prebaking film was cooled to 50 degreeC by the temperature-fall rate of 5 degree-C / min, and the polyimide resin film T3 of the state affixed on the circular glass substrate was produced by this.

(Seventh Production Example: Fabrication of Polyimide Resin Film with Silicon Substrate)

In the seventh production example, the preparation of the polyimide resin film T4 suitably used in the examples and the comparative examples below will be described. In the sixth production example, the film thickness after 4 minutes of prebaking at a temperature of 140 ° C. was used for a 4-inch silicon substrate cut in quarters using a Mikasa spin coater (MS-A200). The varnish (varnish in any one of the synthesis examples 1-12) of the 1st production example was spin-coated so that it might become 0.5 micrometer. Thereafter, the coating film of this varnish was subjected to prebaking for 4 minutes at a temperature of 140 ° C using a hot plate (D-SPIN) manufactured by Dainippon Screen. The prebaked membrane obtained by this was heated up to 300 degreeC by the temperature increase rate of 3.5 degree-C / min under nitrogen stream (oxygen concentration 20 ppm or less) using the inner oven (INH-21CD) by the Koyo Thermo Systems company, and 30 minutes Maintained. Then, this prebaking film was cooled to 50 degreeC by the temperature-fall rate of 5 degreeC / min, and the polyimide resin film T4 of the state affixed on the silicon substrate was produced by this.

(First Measurement Example: Measurement of Light Transmittance (T))

In a 1st measurement example, the measurement of the light transmittance suitably used by the following example and the comparative example is demonstrated. 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 (MultiSpec1500) manufactured by Shimadzu Corporation.

(2nd measurement example: measurement of haze value)

In a 2nd measurement example, the measurement of the haze value suitably used by the following example and the comparative example is demonstrated. In this 2nd measurement example, the haze value (%) of the polyimide resin film T2 of the 5th production example was measured using the direct reading haze computer (HGM2DP, C light source) by the Shiga Corporation. In addition, as this haze value, the average value of 3 times measurement was used.

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

In a 3rd measurement example, the measurement of the glass transition temperature and linear expansion coefficient used suitably by the following example and a comparative example is demonstrated. In this third measurement example, the glass transition temperature and the linear expansion coefficient of the polyimide resin film T1 of the fourth production example were compressed using a thermomechanical analyzer (EXSTAR6000TMA / SS6000) manufactured by SII Nanotechnology Co., Ltd. under a nitrogen stream. Measured at About the sample of this measurement, the small piece of width 15mm x length 30mm is cut out from polyimide resin film T1, this small piece is wound in the longitudinal direction, and it passes through a platinum coil of diameter 3mm and height 15mm, and is cylindrical. What was used was used. The temperature raising method was performed on condition of the following. In a 1st step, the sample was heated up to 150 degree | times at the temperature increase rate of 5 degree-C / min, and the adsorption water of the sample was removed. In the second step, the sample was air cooled to room temperature at a temperature drop rate of 5 ° C / min. In the 3rd step, this measurement of the sample was performed at the temperature increase rate of 5 degree-C / min, and the glass transition temperature of polyimide resin film T1 was calculated | required. In addition, in the 3rd step, the average value of the linear expansion coefficient of the sample in 50-200 degreeC was calculated | required, and this was made into the linear expansion coefficient of polyimide resin film T1.

(Example 4 Measurement: Measurement of Residual Stress)

In a 4th measurement example, the measurement of the residual stress used suitably by the following example and the comparative example is demonstrated. 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 apparatus (FLX-3300-T) manufactured by Toho Technologies. Varnish of the first production example (synthesis example) using a coating and developing apparatus (Mark-7) manufactured by Tokyo Electron Co., Ltd. on the silicon wafer so that the film thickness after prebaking for 4 minutes at a temperature of 140 ° C. was 15 ± 0.5 μm. Varnish of any of 1 to 12) was spin applied. Then, the prebaking process of 4 minutes was performed on the coating film of this varnish using the Mark-7 hot plate at the temperature of 140 degreeC. The prebaked membrane obtained by this was heated up to 350 degreeC by the temperature increase rate of 3.5 degree-C / min under nitrogen stream (oxygen concentration of 20 ppm or less) using the inner oven (INH-21CD) by the Koyo Thermo Systems company, and 30 minutes Maintained. Then, this prebaking film was cooled to 50 degreeC by the temperature-fall rate of 5 degree-C / min, and the silicon wafer with a polyimide resin film was produced by this. After the drying for 10 minutes in a silicon wafer 150 ℃, using the above-mentioned residual stress measurement device to measure the radius of curvature r ₂ of the silicon wafer. And the residual stress (sigma) (Pa) which generate | occur | produced between this silicon wafer and a polyimide resin film was calculated | required by following formula (II).

^{σ = Eh 2/6 [(} 1 / r 2) - (1 / r 1)] t (II)

In Formula (II), E is a biaxial elastic modulus (Pa) of a silicon wafer. h is the thickness m of a silicon wafer. t is the film thickness (m) of a polyimide resin film. r ₁ is the curvature radius m of the silicon wafer before polyimide resin film preparation. r <_2> is the curvature radius m of the silicon wafer after polyimide resin film preparation. In addition, the biaxial elastic modulus E of the silicon wafer was calculated | required as 1.805x10 <^-11> (Pa).

(Evaluation Examples 1 to 12)

In the evaluation examples 1-12, about the varnish of the synthesis examples 1-12 mentioned above, polyimide resin film T1-T4 is produced by the method of the 4th production example-the 7th production example, and the 1st measurement example-the 4th measurement The light transmittance, haze value, glass transition temperature (Tg), linear expansion coefficient, and residual stress were measured by the example method. The results of Evaluation Examples 1 to 12 are shown in Table 2.

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

(Conductivity Evaluation)

In the electroconductivity evaluation of a touch panel, in each Example and each comparative example, with respect to the board | substrate which the touch panel produced to the 1st wiring layer, to the surface resistance measuring instrument ("Loresta" (trademark) -FP, Mitsubishi Yuka Corporation make) The surface resistance value ρs (Ω / □) was measured, and the film thickness t (cm) of the wiring portion was measured by a surface roughness shape measuring instrument ("Surcomm" (registered trademark) 1400D, manufactured by Tokyo Seimitsu Co., Ltd.). By multiplying the values, the volume resistivity (μΩ · cm) was calculated. Using the obtained volume resistivity, the electroconductivity of the touch panel was evaluated in accordance with the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or more was made into the pass.

In the evaluation criteria of the electrical conductivity evaluation, when the volume resistivity is less than 60 µΩ · cm, it is level 5. When volume resistivity is 60 microohm * cm or more and less than 80 microohm * cm, it is level 4. When the volume resistivity is 80 μΩ · cm or more and less than 100 μΩ · cm, it is level 3. When the volume resistivity is 100 µΩ · cm or more and less than 150 µΩ · cm, it is level 2. When the volume resistivity is 150 μΩ · cm or more, it is level 1.

(Residue Evaluation of Conductive Composition)

In the residue evaluation of the electroconductive composition of a touch panel, in each Example and each comparative example, the transmittance | permeability in wavelength 400nm before and behind 1st wiring layer formation with respect to the unexposed part of the board | substrate produced to the 1st wiring layer of a touch panel. Was measured using an ultraviolet visible spectrophotometer ("MultiSpec-1500 (trade name) manufactured by Shimadzu Seisakusho Corporation). And when the transmittance before 1st wiring layer formation was made into T0, and the transmittance after 1st wiring layer formation was made into T, the transmittance | permeability change represented by Formula (T0-T) / T0 was computed. The residue of the electroconductive composition of a touchscreen was evaluated according to the following evaluation criteria using the obtained value of the transmittance | permeability change. In this evaluation, the case where the evaluation result was level 2 or more was made into the pass.

In the evaluation criteria of the residue evaluation of an electrically conductive composition, when the value of the transmittance | permeability change is less than 1%, it is level 5. When the value of the transmittance change is 1% or more and less than 2%, it is level 4. When the value of the transmittance change is 2% or more and less than 3%, it is level 3. When the value of the transmittance change is 3% or more and less than 4%, it is level 2. When the value of the transmittance change is 4% or more, it is level 1.

(Tint (b *) evaluation)

In hue (b *) evaluation of a touch panel, in each Example and each comparative example, the hue of the laminated substrate was evaluated by the following method using the board | substrate produced even to the 2nd insulating layer of a touch panel.

About the board | substrate produced to the 2nd insulating layer of a touchscreen, the reflectance of total reflection light is measured from the glass substrate side using the spectrophotometer (CM-2600d, the product made by Konica Minolta), and CIE (L *, a *, b) *) Color properties b * were measured in the color space. The color tone of the touch panel was evaluated in accordance with the following evaluation criteria using the obtained color characteristic b *. In this evaluation, the case where the evaluation result was level 2 or more was made into the pass. As the light source, a D65 light source was used.

In the evaluation criteria of color tone evaluation, when color characteristic b * is -2 <= b * <= 2, it is level 5. When the color characteristic b * is -3≤b * <-2 or 2 <b * ≤3, it is level 4. When color characteristic b * is -4 <= b * <-3 or 3 <b * <= 4, it is level 3. When the color characteristic b * is -5≤b * <-4 or 4 <b * ≤5, it is level 2. When the color characteristic b * is b * <-5 or 5 <b *, it is level 1.

(Moisture heat resistance evaluation)

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

Insulation deterioration characteristic evaluation system "ETAC SIR13" (made by Kusumoto Kasei Co., Ltd.) was used for the measurement of moisture-heat resistance. Electrodes were provided in each end of the 1st wiring layer and the 2nd wiring layer of a touch panel, respectively, and the touch panel was put in the high temperature, high humidity tank set on 85 degreeC and 85% RH conditions. After 5 minutes had elapsed since 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 over time of the insulation resistance was measured. With the first wiring layer as the positive electrode and the second wiring layer as the negative electrode, a voltage of 10 V was applied and the resistance value for 500 hours was measured at 5 minute intervals. When the measured resistance value reached 5 or less of 10, it judged that it was a short circuit because of insulation failure, the pressure was stopped, and the test time to it was made into the short circuit time. Using the obtained short time, the heat and moisture resistance of the touch panel was evaluated in accordance with the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or more was made into the pass.

In the criteria for evaluating moisture and heat resistance evaluation, when the short time is 1000 hours or more, the level is level 5. When short time is 500 hours or more and less than 1000 hours, it is level 4. When short time is 300 hours or more and less than 500 hours, it is level 3. When short time is 100 hours or more and less than 300 hours, it is level 2. When short time is less than 100 hours, it is level 1.

(Dimension Accuracy Evaluation)

In dimensional precision evaluation of a touch panel, the dimensional precision was evaluated with the following method about the touch panel produced in each Example and each comparative example.

The shift | offset | difference of the horizontal direction was measured in the design part where the laminated board | substrate is the center and the mesh intersection part of a 1st wiring layer and the mesh intersection part of a 2nd wiring layer overlap. Using the obtained measurement value of "deviation", the dimensional precision of a touchscreen was evaluated according to the following evaluation criteria. In this evaluation, the case where the evaluation result was level 2 or more was made into the pass.

In the evaluation criteria of the dimensional accuracy evaluation, when the deviation is less than 1 µm, it is level 5. When a deviation is 1 micrometer or more and less than 2 micrometers, it is level 4. When a deviation is 2 micrometers or more and less than 3 micrometers, it is level 3. When a deviation is 3 micrometers or more and less than 5 micrometers, it is level 2. When a deviation is 5 micrometers or more, it is level 1.

(ESD (Electrostatic Discharge) Immunity Assessment)

In the ESD resistance evaluation of a touch panel, in each Example and each comparative example, an ESD test apparatus (Compact ESD Simulator HCE-5000, manufactured by Hanwa Denshi Kogyo Co., Ltd.) was used for a substrate on which the touch panel was made up to the first wiring layer. ESD tolerance was evaluated. Specifically, an electrode was provided at the end of the first wiring layer, and started from 100V, and voltage was continuously applied once at 100V steps. When the resistance value of the leakage current after voltage application showed a rise of a resistance value of 10% or more compared with before application, it was regarded as disconnection of the wiring layer, and the voltage of 100 V lower than the disconnected voltage was regarded as the 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 Synthesis Example 1 produced in the first production example.

<Formation of Gas Barrier Layer>

In Embodiment 1, to form a polyimide resin film by using the target containing SiO ₂ in the T3, subjected to sputtering in an argon atmosphere, the gas barrier layer comprises a film of SiO ₂ 100㎚ thickness obtained as above . As sputtering conditions at this time, pressure was 2x10 <^-1> Pa, board | substrate temperature was 150 degreeC, and the power supply was 13.56 MHz AC power supply.

<Formation of first wiring layer>

In Example 1, the spin coater ("1H-360S (brand name) by Mikasa Co., Ltd.) by the electrically conductive composition AE-1 produced by the 2nd production example on the board | substrate with which the said polyimide resin film T3 and the gas barrier layer were formed. Was spin-coated under conditions of 10 seconds at 300 rpm and 2 seconds at 500 rpm. Then, the coating film of this electroconductive composition AE-1 was prebaked at 100 degreeC for 2 minutes using a hotplate ("SCW-636 (brand name) by Dainippon Screen Seizo Corporation), and the prebaking film was produced. Subsequently, using the parallel light mask aligner ("PLA-501F" (brand name) by Canon Corporation), this prebaking film was exposed through the desired mask using the ultrahigh pressure mercury lamp as a light source. Subsequently, using the automatic developing apparatus ("AD-2000 (trade name) made by Takizawa Sangyo Co., Ltd.), this prebaked film was shower-developed for 60 seconds with 0.045 mass% potassium hydroxide aqueous solution, and then rinsed with water for 30 seconds. The pattern processing was performed. The substrate processed in this manner was cured at 250 ° C. for 30 minutes in air (oxygen concentration 21%) using an oven to form a first wiring layer.

<Formation of First Insulation 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 a substrate on which the first wiring layer was formed using a spin coater. Then, the coating film of this insulating composition OA-1 was prebaked at 100 degreeC for 2 minutes using a hotplate, and the prebaking film was produced. Subsequently, the ultra-high pressure mercury lamp was used as a light source using the parallel light mask aligner, and this prebaking film was exposed through the desired mask. Thereafter, the prebaked film was shower-developed with 0.045% by mass of potassium hydroxide aqueous solution for 60 seconds using an automatic developing device, and then rinsed with water for 30 seconds to perform pattern processing. The substrate processed in this manner was cured at 250 ° C. for 60 minutes in air (oxygen concentration 21%) using an oven to form a first insulating layer.

<Formation of Second Wiring Layer>

In Example 1, the 2nd wiring layer was formed on the board | substrate with which the 1st insulating layer was formed as mentioned above by the method similar to this 1st wiring layer.

<Formation of Second Insulation Layer>

In Example 1, the 2nd insulating layer was formed on the board | substrate with which the 2nd wiring layer was formed as mentioned above by the method similar to the said 1st insulating layer.

Finally, the touch panel of Example 1 was obtained by cutting the periphery of the area | region which formed the 1st wiring layer and the 2nd wiring layer from the upper surface to one blade, and mechanically peeling from the cut end surface. About the obtained touchscreen of Example 1, electroconductivity, the residue of a conductive composition, color tone (b *), moisture heat resistance, dimensional accuracy, and ESD voltage resistance were evaluated by the method mentioned above. The evaluation result of Example 1 was shown in Table 3 mentioned later.

(Example 2)

In Example 2, operation similar to Example 1 was repeated except having used the varnish of the synthesis example 2 as a varnish for polyimide resin film forming. As shown in Table 3, in the touch panel of Example 2, since it has the structural unit of General formula (1) in the polyimide contained in a polyimide resin film, dimensional precision improves and the level of an evaluation result is "5. It became. Although the color tone deteriorated slightly due to yellowing at the time of wiring processing, and the level of the evaluation result became "3", it was a range which can be used without a problem.

(Example 3)

In Example 3, operation similar to Example 1 was repeated except having used the varnish of the synthesis example 3 as a varnish for polyimide resin film forming. As shown in Table 3, in the touch panel of Example 3, since it has the structural unit of General formula (2) in the polyimide contained in a polyimide resin film, dimensional precision improves and the level of an evaluation result is "4. It became. Although the color tone deteriorated slightly due to yellowing at the time of wiring processing, and the level of the evaluation result was "3", it was a range which can be used without a problem.

(Example 4)

In Example 4, operation similar to Example 1 was repeated except having used the varnish of the synthesis example 4 as a varnish for polyimide resin film forming. As shown in Table 3, in the touch panel of Example 4, since it has the structural unit of General formula (2) in the polyimide contained in a polyimide resin film, dimensional precision improves and the level of an evaluation result is "5. It became. Although the color tone deteriorated slightly due to yellowing at the time of wiring processing, and the level of the evaluation result became "3", it was a range which can be used without a problem.

(Example 5)

In Example 5, operation similar to Example 1 was repeated except having used the varnish of the synthesis example 5 as a varnish for polyimide resin film forming. As shown in Table 3, in the touch panel of Example 5, the polyimide contained in a polyimide resin film has a structural unit represented by General formula (4) as a main component, and is represented by General formula (5) Since 5 mol% or more and 30 mol% or less of a structural unit are included, dimensional precision improved and the level of the evaluation result became "5".

(Example 6)

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

(Example 7)

In Example 7, the same operation as in Example 1 was repeated except that the varnish of Synthesis Example 7 was used as the varnish for polyimide resin film forming. As shown in Table 3, in the touch panel of Example 7, the Tg of the polyimide resin film was slightly low (see Evaluation Example 7 in Table 2), so that the dimensional accuracy deteriorated and the level of the evaluation result became "2". , Available range.

(Example 8)

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

(Example 9)

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

(Example 10)

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

(Example 11)

In Example 11, operation similar to Example 5 was repeated except having changed the target into the target containing SiON at the time of gas barrier layer formation. As shown in Table 3, in the touch panel of Example 11, color tone improved by changing a gas barrier layer, and the level of the evaluation result became "5". On the other hand, chemical resistance fell by changing a gas barrier layer. Thereby, although the electrically conductive composition residue and dimensional precision deteriorated slightly each, and the level of the evaluation result became "4", it was the range which can all be used.

(Example 12)

In Example 12, at the time of forming a gas barrier layer, first, using the target containing SiON, sputtering was performed in argon atmosphere, and the gas barrier layer containing SiON of 80 nm in thickness was formed. Subsequently, using a target containing SiO ₂ , sputtering was carried out in an argon atmosphere to form a gas barrier layer containing SiO ₂ having a film thickness of 20 nm. Other than this, the same operation as in Example 5 was repeated. As shown in Table 3, in the touch panel of Example 12, when the gas barrier layer on the polyimide resin film side is SiON, yellowing at the time of wiring processing is suppressed. As a result, color tone is improved and the level of the evaluation result is improved. It became "5." Moreover, since the barrier property of the gas barrier layer improved, the moisture heat resistance improved and the level of the evaluation result became "5". In addition, by setting the gas barrier layer on the wiring layer side to SiO ₂ , the conductive composition residue and dimensional accuracy were satisfactory without changing the level of the evaluation result to “5”.

(Example 13)

In Example 13, the same operation as in Example 5 was repeated except that the conductive composition was changed from conductive composition AE-1 to conductive composition AE-2. As shown in Table 3, in the touch panel of Example 13, the electroconductive particle (metal microparticles | fine-particles) contained in electroconductive composition AE-2 were not coat | covered, and metal microparticles | fine-particles agglomerated unevenly in the wiring layer. Therefore, although electroconductivity worsened and the level of evaluation result became "3", it was a range which can be used. In addition, although the electrically conductive composition residue and the dimensional precision deteriorated slightly and the level of the evaluation result became "4", respectively, it was a range without a problem in use.

(Example 14)

In Example 14, operation similar to Example 5 was repeated except having changed the insulating composition 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 moist heat resistance significantly deteriorated and the level of the evaluation result was "2", but it was a range which can be used. . Although the electroconductivity, the electrically conductive composition residue, and the dimensional precision deteriorated slightly and the level of the evaluation result became "4", respectively, it was a possible range without a problem in use.

(Example 15)

In Example 15, at the time of formation of a wiring layer, the patterned board | substrate was heated with nitrogen stream (14% of oxygen concentration) using the inert oven (INH-21CD by Koyo Thermo Systems Co., Ltd.) except Example 5 and The same operation was repeated. As shown in Table 3, in the touch panel of Example 15, color tone improved by the change of the oxygen concentration at the time of wiring layer formation, and the level of the evaluation result became "5". On the other hand, although the electroconductivity deteriorated greatly and the level of the evaluation result became "2", it was a range which can be used. Although the dimensional accuracy deteriorated slightly and the level of the evaluation result became "4", it was a range without a 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 forming. As shown in Table 3, in the touch panel of Example 16, since it has a repeating structure represented by General formula (9) in the polyimide contained in a polyimide resin film, dimensional precision improves and the level of an evaluation result is improved. It became "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 forming. As shown in Table 3, in the touch panel of Example 17, since it had a repeating structure represented by General formula (9) in the polyimide contained in a polyimide resin film, ESD withstand voltage improved and it became 1300V.

(Comparative Example 1)

In the comparative example 1, operation similar to Example 5 was repeated except having formed the 1st wiring layer directly on the polyimide resin film, without forming a gas barrier layer. In the touch panel of the comparative example 1, the electrically conductive composition residue, color tone, and heat-and-moisture resistance fell significantly, and was the level (level 1) which cannot be used.

(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 forming. In the touch panel of the comparative example 2, the imide group concentration of the polyimide contained in a polyimide resin film was high, haze generate | occur | produced after resin film formation, and visibility was largely impaired. For this reason, the polyimide resin film in the comparative example 2 was not applicable as a board | substrate of a touch panel.

(Comparative Example 3)

In the comparative example 3, operation similar to Example 5 was repeated except having used the varnish of the synthesis example 9 as a varnish for polyimide resin film forming. In the touch panel of the comparative example 2, since the imide group density | concentration of the polyimide contained in a polyimide resin film was low, and Tg of the polyimide resin film fell (refer to evaluation example 9 of Table 2), dimensional precision fell drastically. It became the level (level 1) which was unavailable. Each evaluation result of these Comparative Examples 1-3 was shown in Table 3 with each evaluation result of Examples 1-17 mentioned above.

As described above, the method for producing a conductive layer-containing film, a touch panel, a film with a conductive layer, and a method for manufacturing a touch panel according to the present invention suppress yellowing of the resin film at the time of forming the conductive layer and provide high dimensional accuracy of the conductive layer. It is suitable for the manufacturing method of a conductive layer equipped film, a touch panel, the film with a conductive layer, and the manufacturing method of a touch panel which can be ensured.

1: resin film
2: gas barrier layer
3: first wiring layer
3A: conductive layer
4: first insulating layer
5: second wiring layer
6: second insulating layer
7: support substrate
8: cut end face
10: touch panel
11: Film with conductive layer

Claims (17)

It is a film with a conductive layer which has a conductive layer containing electroconductive particle on the resin film containing the polyimide whose imide group density | concentration defined by following (I) formula is 20.0% or more and 36.5% or less,
Having a gas barrier layer between the resin film and the conductive layer
The film with a conductive layer characterized by the above-mentioned.
(Molecular weight of imide group portion) / (molecular weight of repeating unit of polyimide) × 100 [%]. (I) The glass transition temperature of the said resin film is 250 degreeC or more.
The film with a conductive layer characterized by the above-mentioned. The said polyimide contains the structural unit represented by following General formula (1).
The film with a conductive layer characterized by the above-mentioned.

(In the formula ^(1), R 1 is a monocyclic or condensed polycyclic of from 4 to 40 carbons having an alicyclic structure in the alicyclic tetravalent organic group, or organic group having an alicyclic structure of the monocyclic group is directly or through a crosslinking structure A tetravalent organic group having 4 to 40 carbon atoms connected to each other.R ² represents a divalent organic group having 4 to 40 carbon atoms.) The said polyimide is a structural unit as described in any one of Claims 1-3 containing the structural unit represented by following General formula (2).
The film with a conductive layer characterized by the above-mentioned.

(In General Formula (2), R ³ represents a tetravalent organic group having 4 to 40 carbon atoms. R ⁴ is a divalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or Or a divalent organic group having 4 to 40 carbon atoms, or a divalent organic group represented by the following general formula (3), in which an organic group having a monocyclic alicyclic structure is connected to each other directly or through a crosslinked structure.)

(In general formula (3), X <^1> is a C1-C3 bivalent hydrocarbon group which may be substituted by the halogen atom. Ar <^1> and Ar <^2> are respectively independently C4-C40 divalent aromatic. Group.) The said polyimide has a structural unit represented by the following general formula (4) as a main component, and the structural unit represented by the following general formula (5) is a whole structure in any one of Claims 1-4. 5 mol% or more and 30 mol% or less of a unit are included
The film with a conductive layer characterized by the above-mentioned.

(In general formula (4), (5), R <^1> is a C4-C40 tetravalent organic group which has a monocyclic or condensed polycyclic alicyclic structure, or the organic group which has a monocyclic alicyclic structure is directly or A tetravalent organic group having 4 to 40 carbon atoms connected to each other via a crosslinked structure, R ¹³ represents a divalent organic group represented by the following general formula (6): R ¹⁴ represents the following structural formula (7) or the following structural formula ( 8).

(In General formula (6), R <^15> -R <^22> respectively independently represents the C1-C3 monovalent organic group which may be substituted by the hydrogen atom, a halogen atom, or a halogen atom. X <^2> is a direct bond , An atom selected from an oxygen atom, a sulfur atom, a sulfonyl group, a halogen atom, a divalent organic group having 1 to 3 carbon atoms, an ester bond, an amide bond, and a sulfide bond.)

The said polyimide contains the repeating structure represented by following General formula (9) in at least one of the acid dianhydride residue and diamine residue which comprise the said polyimide. doing
The film with a conductive layer characterized by the above-mentioned.

(In 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 polyimide of claim 1, wherein the polyimide comprises a triamine skeleton.
The film with a conductive layer characterized by the above-mentioned. The gas barrier layer of claim 1, wherein the gas barrier layer comprises at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride.
The film with a conductive layer characterized by the above-mentioned. The gas barrier layer has a value satisfying SiO x N y (x, y is 0 <x≤1, 0.55≤y≤1 and 0≤x / y≤1). Containing ingredients indicated by
The film with a conductive layer characterized by the above-mentioned. The gas barrier layer according to any one of claims 1 to 9, wherein the gas barrier layer is an inorganic film laminated in two or more layers,
The layer in contact with the conductive layer in the inorganic film is formed of a component represented by SiOz (z is a value satisfying 0.5 ≦ z ≦ 2).
The film with a conductive layer characterized by the above-mentioned. The said electroconductive particle is a silver particle in any one of Claims 1-10.
The film with a conductive layer characterized by the above-mentioned. The insulating layer according to any one of claims 1 to 11, having an insulating layer formed of an alkali-soluble resin containing a cardo resin having two or more structures represented by the following structural formula (10) on the conductive layer.
The film with a conductive layer characterized by the above-mentioned.

It has a film with a conductive layer in any one of Claims 1-12,
The conductive layer is a wiring layer
Touch panel, characterized in that. A resin film forming step of forming a resin film containing a polyimide on a support substrate,
A gas barrier layer forming step of forming a gas barrier layer on the resin film;
A conductive layer forming step of forming a conductive layer on the gas barrier layer,
Peeling process of peeling the said resin film from the said support substrate
The manufacturing method of the film with a conductive layer characterized by including at least. The said conductive layer formation process of Claim 14 which forms the said conductive layer using the electroconductive composition containing the electroconductive particle which has a coating layer in at least one part of the surface.
The manufacturing method of the film with a conductive layer characterized by the above-mentioned. The said resin film formation process of Claim 14 or 15 heats the polyimide resin composition on the said support substrate at the temperature of 300 degreeC or more and 500 degrees C or less in the atmosphere whose oxygen concentration is 1000 ppm or less, and forms the said resin film. and,
In the conductive layer forming step, the conductive composition on the gas barrier layer is heated at a temperature of 100 ° C or more and 300 ° C or less in an atmosphere having an oxygen concentration of 15% or more to form the conductive layer.
The manufacturing method of the film with a conductive layer characterized by the above-mentioned. As a manufacturing method of the touchscreen using the manufacturing method of the film with a conductive layer of any one of Claims 14-16,
The conductive layer forming step is a step of forming a wiring layer as the conductive layer.
The manufacturing method of the touch panel characterized by the above-mentioned.

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