CN109891375B

CN109891375B - Touch panel and method for manufacturing touch panel

Info

Publication number: CN109891375B
Application number: CN201780066616.0A
Authority: CN
Inventors: 三井博子; 诹访充史; 山铺有香
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2016-11-01
Filing date: 2017-10-26
Publication date: 2022-04-12
Anticipated expiration: 2037-10-26
Also published as: WO2018084067A1; KR102338021B1; KR20190077363A; TWI736700B; CN109891375A; TW201824300A; JPWO2018084067A1; JP6933142B2

Abstract

A touch panel comprising a portion in which a transparent layer (OC-D), a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) are laminated in this order, wherein the transparent layer (OC-D) contains a heat-resistant polymer having a structure represented by the following chemical formula (1) and a structure represented by the following general formula (2). The present invention provides a touch panel which can be applied to a processing method with excellent dimensional accuracy, can suppress residues of a conductive composition, has excellent color tone and moist heat resistance, and can form a fine pattern and respond to flexibility. In the above general formulae (1) and (2), R₁And R₂Each independently represents a monovalent organic group. m and n each independently represent an integer of 0 to 4. m R₁And n R₂Each may be the same or different.

Description

Touch panel and method for manufacturing touch panel

Technical Field

The present invention relates to a touch panel and a method for manufacturing the touch panel.

Background

In recent years, in touch panels for mobile phones, tablet computers, and the like, flexibility is desired from the viewpoint of design, convenience, and durability. However, at present, there are various problems in the flexibility of the touch panel, and the flexibility is not yet practical. The main problem is the deficiency of touch panel technology, especially touch wiring technology. Conventionally, as a method for forming a touch wiring, the following methods have been widely used from the viewpoint of improving visibility: a thin film containing a transparent conductive metal such as ITO is formed on a substrate such as glass or a film, and patterning is performed by etching. However, ITO wiring is rigid and brittle, and therefore has low bending resistance, and there is a problem that cracks occur during bending. Therefore, as touch wiring instead of ITO, various technologies such as metal mesh wiring, metal nanowires, and carbon nanotubes have been proposed. Among them, the metal mesh wiring technology has attracted attention as a touch wiring having both bending resistance and visibility and high conductivity.

The metal mesh wiring is obtained by forming a metal wiring which is thin to an unrecognizable degree into a mesh pattern. For example, a wiring having good conductivity can be obtained by using a metal having a small resistance value such as gold, silver, or copper. Further, by containing a sufficiently designed organic component in an appropriate amount, the bending resistance can be improved, and the flexibility can be sufficiently coped with.

As a method of forming such a metal mesh wiring, for example, the following methods are given: a wiring pattern is formed by a method such as screen printing, ink jet, photolithography using a conductive paste containing conductive metal particles and an organic component (for example, see patent document 1). However, in order to form a fine pattern to an unrecognizable degree, it is necessary to miniaturize the particle diameter of the conductive particles to a nanometer size. Such conductive particles have a problem that they are easily fused and aggregated even at a low temperature such as room temperature. Further, the surface of the conductive particles reacts with an organic component, and there is a problem that storage stability is lowered. In addition, when patterning is performed by the photosensitive paste method, it is difficult to form a fine pattern because the conductive particles have light reflectivity and scatter light for exposure.

In view of the above, a method of solving the above problem by using conductive particles having a coating layer is disclosed (for example, see patent document 2). The coating layer reduces the surface activity of the conductive particles, and thus can suppress the reaction between the conductive particles and/or the reaction between the conductive particles and the organic component. In addition, even when the photosensitive paste method is used, scattering of light for exposure can be suppressed, and wiring can be patterned with high accuracy. On the other hand, the coating layer can be easily removed by heating at a high temperature of about 200 ℃, and sufficient conductivity is exhibited. By this technique, a metal mesh wiring can be formed.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2000-199954

Patent document 2: japanese laid-open patent publication No. 2013-196997

Disclosure of Invention

Problems to be solved by the invention

However, the technique disclosed in patent document 2 requires a high temperature of about 200 ℃ to remove the coating layer of the conductive particles, and therefore requires high heat resistance for an applicable substrate, and has a problem that the technique can be substantially formed only on a glass substrate. Of course, it is difficult to use a glass substrate to cope with flexibility. Further, even when a film having very excellent heat resistance is used as a substrate, there is a problem that: when the curing is repeated at a high temperature, the film is colored by thermal degradation to lower the color tone, or the dimensional accuracy is lowered to cause positional deviation, thereby causing appearance defects called moire. In addition, when a metal wiring is patterned on a film having excellent heat resistance by a photosensitive method using a conductive composition, the conductive composition in an unexposed portion is not sufficiently removed during development due to a strong interaction between the conductive composition and the film surface, and a residue is likely to be generated. On the other hand, if the developing conditions are increased to reduce the residue, the pattern is likely to be peeled off, and it is difficult to form a fine pattern. Further, there is a problem that the conductive composition is likely to migrate in a moist heat environment due to the residue thereof, and thus the moist heat resistance is insufficient.

The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a touch panel which is applicable to a processing method having excellent dimensional accuracy, has less residue of a conductive composition, is excellent in color tone and moist heat resistance, and can form a fine pattern and cope with flexibility.

Means for solving the problems

The present invention is a touch panel including a portion in which a transparent layer (OC-D), a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) are sequentially laminated, wherein the transparent layer (OC-D) contains a heat-resistant polymer including a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

[ chemical formula 1]

In the above general formulae (1) to (2), R₁And R₂Each independently represents a monovalent organic group, and m and n each independently represents an integer of 0 to 4. m R₁And n R₂Each may be the same or different.

Another aspect of the present invention is a method for manufacturing the touch panel, including the steps of:

a step for forming a transfer member by sequentially forming at least a transparent layer (OC-D), a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) on the temporary support;

bonding a surface of the transfer member opposite to the temporary support to the base via a transparent adhesive layer; and

a step of removing the temporary support body,

wherein the transparent layer (OC-D) has a release function and contains a polymer having a structure represented by the general formula (1) and a structure represented by the general formula (2).

Another embodiment of the present invention is a structure having a portion where a first wiring layer (a-1) is laminated on a transparent layer (OC-D), wherein the transparent layer (OC-D) contains a heat-resistant polymer having a structure represented by the general formula (1) and a structure represented by the general formula (2).

ADVANTAGEOUS EFFECTS OF INVENTION

The touch panel of the present invention can be applied to a processing method having excellent dimensional accuracy, and is excellent in color tone and moist heat resistance with little residue of the conductive composition. According to the present invention, a touch panel capable of forming a fine pattern and coping with flexibility can be provided.

Detailed Description

The touch panel of the present invention is characterized by having a portion in which a transparent layer (OC-D), a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) are sequentially laminated, wherein the transparent layer (OC-D) contains a heat-resistant polymer having a structure represented by the general formula (1) and a structure represented by the general formula (2). The above layers are explained.

(transparent layer (OC-D))

The transparent layer (OC-D) used in the present invention contains a heat-resistant polymer having a structure represented by the following general formula (1) and a structure represented by the following general formula (2). As a result of intensive studies, the inventors of the present application have found that by using a heat-resistant polymer containing both a structure represented by the following general formula (1) and a structure represented by the following general formula (2) in one molecule, the non-crystallinity can be improved and the coloration can be suppressed, and the transparency can be significantly improved, as compared with other polymers. Further, since the polymer having the above structure has high heat resistance, yellowing during heating in the subsequent step can be suppressed. Therefore, by applying the polymer to the transparent layer (OC-D), there is an effect of improving the color tone. Further, by including the polymer in the transparent layer (OC-D), it is possible to suppress the residue in the processing of the conductive layer (a-1) in the subsequent step, and therefore, it is possible to form a fine pattern and to improve the moist heat resistance of the obtained touch panel.

[ chemical formula 2]

From the viewpoint of further improving the color tone, R₁And R₂Preferably an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group, or a trifluoromethyl group. In addition, m and n are preferably 0 or 1, and more preferably 0, from the viewpoint of further improving the color tone. As the substituent of the substituted phenyl group, fluorine, trifluoromethyl, an alkyl group having 1 to 10 carbon atoms, allyl, or an aryl group having 3 to 10 carbon atoms is preferable.

The heat-resistant polymer preferably further contains fluorine, and the transparency can be further improved. The structure containing fluorine is preferably a structure represented by the following structural formula (3) or the following general formula (12). The transparent layer can have improved transparency by including the structure represented by the following structural formula (3), and the transparent layer can have improved elongation at break by including the structure represented by the following general formula (12).

[ chemical formula 3]

In the above general formula (12), R₇And R₈Each independently represents a fluorine atom or a group containing a fluorine atom. Examples of the group containing a fluorine atom include a trifluoromethyl group. R₇And R₈Preferably a fluorine atom or a trifluoromethyl group. x and y each independently represent an integer of 1 to 4. x number of R₈And y R₇Each may be the same or different.

Examples of the structure represented by the general formula (12) include structures represented by any one of the following structural formulae (14) to (17).

[ chemical formula 4]

When the heat-resistant polymer contains a structure represented by the general formula (12), the content of the repeating unit having the structure is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 8 mol% or more of the total repeating units, from the viewpoint of further improving the elongation at break. On the other hand, the content is preferably 50 mol% or less, more preferably 45 mol% or less, and still more preferably 40 mol% or less, from the viewpoint of further improving the color tone.

The heat-resistant polymer preferably further contains a structure represented by the following structural formula (13). By including the structure represented by the following structural formula (13), the toughness of the transparent layer can be improved, and the yield in the subsequent step and the bending resistance of the touch panel can be greatly improved.

[ chemical formula 5]

When the heat-resistant polymer contains a structure represented by the general formula (13), the content of the repeating unit having the structure is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more of the total repeating units in the polymer, from the viewpoint of further improving the elongation at break. On the other hand, the content is preferably 10 mol% or less, more preferably 3 mol% or less, and further preferably 2 mol% or less, from the viewpoint of further improving the color tone.

The heat-resistant polymer is preferably at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aromatic polyamide, epoxy resin, and sulfonamide. Two or more of them may be combined. By using these as a heat-resistant polymer, heat resistance can be further improved, and coloring in a subsequent step can be further suppressed, whereby a color tone can be further improved. From the viewpoint of further improving the heat resistance, at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, polyethersulfone, and polybenzoxazole is more preferable. Further, from the viewpoint of improving solvent resistance, at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, and polybenzoxazole is more preferable.

The polyimide preferably has a structural unit represented by the following general formula (4).

[ chemical formula 6]

In the above general formula (4), R₃Represents a 4-10 valent organic group, R₄Represents a 2-8 valent organic group, R₅And R₆The monovalent organic groups may be a single group or different groups may be present in combination. R₃And/or R₄At least a part of (3) includes a structure represented by the general formula (1) and a structure represented by the general formula (2). Preferably R₃And/or R₄At least a part of (a) further includes a structure selected from the group consisting of the structure represented by the above general formula (12) and the structure represented by the above structural formula (13). p and q each independently represent an integer of 0 to 6.

In the general formula (4), R is preferably R from the viewpoint of further improving the heat resistance of the polyimide₃And R₄At least 50 mol% of the total amount of the aromatic hydrocarbon groups are aromatic hydrocarbon groups or derivatives thereof. More preferably R₃And R₄At least 80 mol% of (B) is an aromatic hydrocarbon group or a derivative thereof, and R is more preferably₃And R₄All of (A) are aromatic hydrocarbon groups or derivatives thereof.

The polyimide preferably has 5 to 100000 structural units represented by the above general formula (4) in one molecular polymer. By having 5 or more structural units represented by the above general formula (4), the toughness of the transparent layer can be improved. On the other hand, by having 100000 or less structural units represented by the above general formula (4), coatability can be maintained.

In the above general formula (4), R₃-(R₅)_pRepresents a residue of acid dianhydride. R₃Is a 4-to 10-valent organic group, and among them, those having 5 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group are preferableAn organic group. R₅Preferably, phenolic hydroxyl groups, sulfonic acid groups or thiol groups are used, and these groups may be present singly or in combination.

Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorenic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 3', aromatic tetracarboxylic acid dianhydrides such as 4, 4' -diphenylsulfone tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride and 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, and the like. Two or more of them may be used.

Examples of the acid dianhydride having the structure represented by the above general formula (1) include bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 4' - [ p-sulfonylbis (phenylene sulfide) ] diphthalic anhydride (DPSDA), and isomers thereof. Examples of the acid dianhydride having the structure represented by the above general formula (2) include 3,3 ', 4, 4' -diphenylethertetracarboxylic dianhydride (ODPA) and isomers thereof.

Examples of the acid dianhydride containing a fluorine atom include 5,5 ' - [2,2, 2-trifluoro-1- [3- (trifluoromethyl) phenyl ] ethylidene ] diphthalic anhydride, 5 ' - [2,2,3,3, 3-pentafluoro-1- (trifluoromethyl) propylidene ] diphthalic anhydride, 1H-difluoro [3,4-b:3 ', 4 ' -i ] xanthene-1, 3,7,9(11H) -tetraone, 5 ' -oxybis [4,6, 7-trifluoropyromellitic anhydride ], 3, 6-bis (trifluoromethyl) pyromellitic dianhydride, 4- (trifluoromethyl) pyromellitic dianhydride, 1, 4-difluoropyromellitic dianhydride, 1, 4-bis (3, 4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, and the like.

Among the acid dianhydrides containing a fluorine atom, examples of the acid dianhydride having a structure represented by the general formula (3) include 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4 '- (hexafluoroisopropylidene) diphthalic anhydride, 3' - (hexafluoroisopropylidene) diphthalic anhydride, and the like.

Among the acid dianhydrides containing a fluorine atom, examples of the acid dianhydride having a structure represented by the general formula (12) include 4,7 '-bis (trifluoromethyl) - (5, 5' -diisobenzofuran) -1,1 ', 3, 3' -tetraone, 4,7 '-difluoro- (5, 5' -diisobenzofuran) -1,1 ', 3, 3' -tetraone, and the like.

In the above general formula (4), R₄-(R₆)_qRepresents the residue of a diamine. R₅Is a 2-8 valent organic group, and among them, an organic group having 5-40 carbon atoms which contains an aromatic ring or a cyclic aliphatic group is preferable. R₆Preferably, phenolic hydroxyl groups, sulfonic acid groups or thiol groups are used, and these groups may be present singly or in combination.

Examples of the diamine include 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, and the like, 1, 4-bis (4-aminophenoxy) benzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl, 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 3,3 '-diethyl-4, 4' -diaminobiphenyl, 2 ', 3, 3' -tetramethyl-4, 4 '-diaminobiphenyl, 3, 3', 4,4 '-tetramethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 9-bis (4-aminophenyl) fluorene, 1,3, 5-tris (4-aminophenoxy) benzene or an aromatic ring thereof, at least a part of hydrogen atoms of which is substituted with an alkyl group, a substituted aryl group or a substituted aryl group, a substituted with a substituted aryl group, a substituted with a substituted aryl group, a substituted aryl group, Halogen atom-substituted compounds, aliphatic cyclohexanediamines, methylenebiscyclohexylamine, and the like. Two or more of them may be used.

These diamines may be used in the form of the corresponding diisocyanate compounds or trimethylsilylated diamines.

Examples of the diamine having a structure represented by the above general formula (1) include 4,4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, and isomers thereof. Examples of the diamine having a structure represented by the above general formula (2) include 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, and isomers thereof.

Examples of the diamine containing a fluorine atom include 2,2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 2,3,5, 6-tetrafluoro-1, 4-diaminobenzene, 2,4,5, 6-tetrafluoro-1, 3-diaminobenzene, 2,3,5, 6-tetrafluoro-1, 4-benzene (dimethylamine), 2 ' -difluoro- (1,1 ' -biphenyl) -4,4 ' -diamine, 2 ', 6,6 ' -tetrafluoro- (1,1 ' -biphenyl) -4,4 ' -diamine, 4 ' -diaminooctafluorobiphenyl, 2-bis (4-aminophenyl) hexafluoropropane, 4 ' -oxybis (2,3,5, 6-tetrafluoroaniline), 3 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) diphenyl ether, 1, 4-bis [ 4-amino-2- (trifluoromethyl) phenoxy ] benzene, 2-bis [4- [ 4-amino-2- (trifluoromethyl) phenoxy ] hexafluoropropane, 3, 5-diaminobenzotrifluoride, 4-diamino-2- (trifluoromethyl) diphenyl ether, and isomers thereof. Among these, examples of the diamine having a structure represented by the general formula (3) include 2, 2-bis (4-aminophenyl) hexafluoropropane and the like, and examples of the diamine having a structure represented by the general formula (12) include 2,2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 2 ' -difluoro- (1,1 ' -biphenyl) -4,4 ' -diamine, 2 ', 6,6 ' -tetrafluoro- (1,1 ' -biphenyl) -4,4 ' -diamine, 4 ' -diaminooctafluorobiphenyl, 4 ' -oxybis (2,3,5, 6-tetrafluoroaniline), 3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl and the like. Among these, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl is particularly preferable, and the elongation at break of the transparent layer can be further improved.

Examples of the amine having a structure represented by general formula (13) include 1,3, 5-tris (4-aminophenoxy) benzene and the like.

The polyimide can be produced by a method in which a polyamic acid or a polyamic acid ester is thermally cured. Examples of the method for producing polyamic acid or polyamic acid ester include: a method of reacting tetracarboxylic dianhydride with diamine at low temperature; a method in which a tetracarboxylic dianhydride and an alcohol are reacted to obtain a diester, and then the diester is reacted with an amine in the presence of a condensing agent; a method in which a tetracarboxylic dianhydride is reacted with an alcohol to obtain a diester, and then the remaining dicarboxylic acid is acid-chlorinated and reacted with an amine, and the like.

The content of the heat-resistant polymer in the transparent layer (OC-D) is preferably 50 to 100% by mass, and the transparency and heat resistance can be further improved. The content of the heat-resistant polymer is more preferably 75 to 100% by mass, and still more preferably 90 to 100% by mass.

The transparent layer (OC-D) may further contain a surfactant, a leveling agent, an adhesion modifier, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye, and the like.

From the viewpoint of enhancing the toughness of the touch panel, the thickness of the transparent layer (OC-D) is preferably 1 μm or more, more preferably 2 μm or more, and still more preferably 5 μm or more. On the other hand, from the viewpoint of further improving the transparency, the thickness is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less.

From the viewpoint of improving the image quality of the touch panel, the transmittance of the transparent layer (OC-D) at a wavelength of 550nm is preferably 85% or more. Further, the transparent layer (OC-D) after heat treatment at 150 to 350 ℃ preferably has a transmittance of 80% or more at a wavelength of 550 nm.

The transparent layer (OC-D) can be formed, for example, by using a transparent composition containing the heat-resistant polymer and, if necessary, an organic solvent, a surfactant, a leveling agent, an adhesion improver, a viscosity modifier, an antioxidant, an inorganic pigment, an organic pigment, a dye, or the like.

(first wiring layer (A-1), second wiring layer (A-2))

A touch panel of the present invention includes a first wiring layer (A-1) and a second wiring layer (A-2).

The wiring layers (A-1) and (A-2) preferably have a mesh structure formed by meshes having a line width of 0.1 to 9 μm. The conductive and visual recognition properties can be simultaneously realized by providing a mesh structure having a line width of 0.1 to 9 μm. From the viewpoint of conductivity, the line width of the mesh structure is more preferably 0.5 μm or more, and still more preferably 1 μm or more. On the other hand, the line width of the mesh structure is more preferably 7 μm or less, and still more preferably 6 μm or less, from the viewpoint of visibility.

The film thickness of the wiring layers (A-1) and (A-2) is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more, from the viewpoint of conductivity. On the other hand, the film thickness of the wiring layers (A-1) and (A-2) is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less, from the viewpoint of visibility.

The wiring layer (A-1) and/or the wiring layer (A-2) are preferably formed of conductive particles.

Examples of the conductive particles include metal particles made of metals such as gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc (Zn), palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), and molybdenum (Mo). Two or more of them may be used. Among these, metal particles containing gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum, and carbon are more preferable, and silver particles are still more preferable.

The conductive particles are more preferably conductive particles having a layer for coating the surface of the conductive particles (hereinafter referred to as a surface coating layer). By providing a surface coating layer on at least a part of the surface of the conductive particles, the surface activity can be reduced, and the reaction between the conductive particles or the reaction between the conductive particles and the organic component can be suppressed. In addition, when the photosensitive paste method is used, the wiring pattern can be processed with higher accuracy by suppressing scattering of exposure light by the conductive particles. On the other hand, the surface coating layer can be easily removed by heating at a high temperature of about 150 to 350 ℃, and sufficient conductivity is exhibited. Preferably, the surfaces of the conductive particles are completely covered with the surface coating layer.

The surface coating layer preferably contains carbon and/or a carbon compound. The dispersibility of the conductive particles can be further improved by containing carbon and/or a carbon compound.

As a method for forming a surface coating layer containing carbon and/or a carbon compound on the surface of conductive particles, for example, a method of bringing conductive particles into contact with a reactive gas when they are produced by a thermal plasma method (jp 2007-138287 a) and the like can be cited.

The average thickness of the surface coating layer is preferably 0.1 to 10 nm. Within this range, the conductive particles can be prevented from being fused with each other, and a finer pattern can be formed. In addition, by performing heat treatment at a temperature of 350 ℃ or lower, desired conductivity can be exhibited.

In order to form a fine conductive pattern having desired conductivity, the 1 st order particle diameter of the conductive particles is preferably 10 to 200nm, more preferably 10 to 60 nm. Here, the 1 st order particle diameter of the conductive particle can be calculated by an average value of particle diameters of 100 1 st order particles randomly selected by using a scanning electron microscope. The particle size of each 1 st order particle can be calculated from the average value of the major and minor diameters of the 1 st order particles measured.

The content of the conductive particles in the wiring layer (a-1) and the wiring layer (a-2) is preferably 20 mass% or more, more preferably 50 mass% or more, and still more preferably 65 mass% or more, from the viewpoint of improving conductivity. On the other hand, the content of the conductive particles is preferably 95% by mass or less, and more preferably 90% by mass or less, from the viewpoint of improving the pattern processability.

The wiring layers (A-1) and (A-2) preferably contain 0.1 to 80 mass% of an organic compound. By containing the organic compound in an amount of 0.1 mass% or more, flexibility can be imparted to the wiring layer, and the bending resistance of the wiring layer can be improved. The content of the organic compound is preferably 1% by mass or more, and more preferably 5% by mass or more. On the other hand, by containing 80 mass% or less of the organic compound, the conductivity of the wiring layer can be improved. The content of the organic compound is more preferably 50% by mass or less, and still more preferably 35% by mass or less.

As the organic compound, an alkali-soluble resin is preferable. As the alkali-soluble resin, a (meth) acrylic copolymer having a carboxyl group is preferable. The (meth) acrylic copolymer herein refers to a copolymer of a (meth) acrylic monomer and another monomer. Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 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-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, n-butoxy ethyl (meth) acrylate, butoxy triethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, butyl acrylate, and (meth) acrylate, n-butyl acrylate, and (meth) acrylate, wherein, Isobornyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethyl 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, benzylmercaptan (meth) acrylate, and the like.

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

Examples of the method for introducing a carboxyl group for imparting alkali solubility into an alkali-soluble resin include a method of copolymerizing (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and acid anhydrides thereof.

From the viewpoint of increasing the speed of the curing reaction, the (meth) acrylic copolymer preferably has a carbon-carbon double bond in a side chain or at a molecular terminal. Examples of the functional group having a carbon-carbon double bond include vinyl group, allyl group, and (meth) acrylic group

The carboxylic acid equivalent of the alkali-soluble resin is preferably 400 to 1,000 g/mol. The carboxylic acid equivalent of the acrylic resin can be calculated by measuring the acid value. In addition, in order to simultaneously achieve hardness and crack resistance at a high level, the alkali-soluble resin preferably has a double bond equivalent of 150 to 10,000 g/mol. The double bond equivalent of the acrylic resin can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000-100,000. When the weight average molecular weight (Mw) is in the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good. Here, Mw of the alkali-soluble resin refers to a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC).

The content of the alkali-soluble resin in the wiring layers (A-1) and (A-2) is preferably 5 to 30% by mass.

The wiring layers (A-1) and (A-2) may contain an organotin compound and/or a metal chelate compound. The wiring layer can further improve adhesion to the transparent layer (OC-D) and/or the insulating layer (OC-1) by containing an organotin compound and/or a metal chelate compound. The metal chelate compound is more preferable than the organotin compound because the metal chelate compound can obtain an effect of improving the adhesion without applying an environmental load.

The organotin compound means an organic acid salt of tin or a compound having at least one carbon atom bonded to a tin atom. Examples thereof include organic acid salts such as tin 2-ethylhexanoate and tin dilaurate; dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin bis (2-ethylhexyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dioctyltin diacetate, dioctyltin dilaurate, dioctyltin maleate, dimethyltin diacetate, dimethyltin dilaurate, dimethyltin maleate, diphenyltin diacetate, diphenyltin dilaurate, diphenyltin maleate, dibutyltin dichloride, dipropyltin dichloride, diethyltin dichloride, dimethyltin dichloride, butyltin trichloride, methyltin trichloride, diphenyltin dichloride, dibutyltin oxide, dimethyltin oxide, dioctyltin oxide, tetrabutyltin, tetramethyltin, tetraphenyltin, propadienyltributyltin, allyltributyltin, allyltriphenyltin, diethyltin, and the like. Two or more of them may be contained.

The metal chelate compound is a compound having a central metal and a ligand coordinated to the central metal at two or more sites. The metal chelate compound is easy to detach the ligand and forms a complex with the alkali-soluble functional group of the alkali-soluble resin, thereby improving the adhesion. Examples of the metal element of the metal chelate compound include Au (gold), Ag (silver), Cu (copper), Cr (chromium), Fe (iron), Co (cobalt), Ni (nickel), Bi (bismuth), Sn (tin), Pb (lead), Zn (zinc), Pd (palladium), In (indium), Pt (platinum), Mg (magnesium), Al (aluminum), Ti (titanium), Zr (zirconium), W (tungsten), and Mo (molybdenum). Among these, from the viewpoint of ease of ligand detachment, a metal selected from Mg (magnesium), Al (aluminum), Ti (titanium), and Zr (zirconium) is preferable, and from the viewpoint of stability of a complex with an alkali-soluble functional group, a metal selected from Al (aluminum) and Zr (zirconium) is more preferable.

Examples of the metal chelate compound include magnesium chelate compounds such as magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), magnesium isopropoxymono (acetylacetonate), and magnesium isopropoxymono (ethylacetoacetate); aluminum chelate compounds such as ethylaluminum diacetate, tris (ethylacetoacetate) aluminum, alkylaluminum diacetate, bis (ethylacetoacetate) aluminum monoacetylacetonate, and tris (acetylacetonate) aluminum; titanium chelate compounds such as tetrakis (acetylacetonate) titanium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonate) titanium, di-n-octyloxybis (octanedionato) titanium, diisopropoxybis (triethanolamine) titanium, bis (2-hydroxypropionate) dihydroxide titanium, and bis (2-hydroxypropionate) dihydroxide titanium ammonium salts; zirconium chelate compounds such as zirconium tetrakis (acetylacetonate), zirconium dibutoxybis (ethylacetoacetate), zirconium tributoxybis (acetylacetonate), zirconium tributoxybis (monostearate), and zirconium tributoxybis monostearate; gold chelate compounds such as bis (acetylacetonate) alloy and bis (ethylacetoacetate) alloy; silver chelate compounds such as bis (acetylacetonate) silver and bis (ethylacetoacetate) silver; copper chelate compounds such as bis (acetylacetonate) copper and bis (ethylacetoacetate) copper; chromium chelate compounds such as bis (acetylacetonato) chromium and bis (ethylacetoacetato) chromium; iron chelate compounds such as bis (acetylacetonate) iron and bis (ethylacetoacetate) iron; cobalt chelate compounds such as bis (acetylacetonate) cobalt and bis (ethylacetoacetate) cobalt; nickel chelate compounds such as bis (acetylacetonate) nickel and bis (ethylacetoacetate) nickel; bismuth chelate compounds such as bis (acetylacetonate) bismuth and bis (ethylacetoacetate) bismuth; tin chelate compounds such as tin bis (acetylacetonate) and tin bis (ethylacetoacetate); lead chelate compounds such as bis (acetylacetonate) lead and bis (ethylacetoacetate) lead; zinc chelate compounds such as bis (acetylacetonate) zinc and bis (ethylacetoacetate) zinc; palladium chelate compounds such as bis (acetylacetonate) palladium and bis (ethylacetoacetate) palladium; indium chelate compounds such as bis (acetylacetonate) indium and bis (ethylacetoacetate) indium; platinum chelate compounds such as bis (acetylacetonate) platinum and bis (ethylacetoacetate) platinum; tungsten chelate compounds such as bis (acetylacetonato) tungsten and bis (ethylacetoacetato) tungsten; molybdenum chelate compounds such as bis (acetylacetonate) molybdenum and bis (ethylacetoacetate) molybdenum.

From the viewpoint of further improving the substrate adhesion, the total content of the organotin compound and the metal chelate compound in the wiring layers (a-1) and (a-2) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. On the other hand, from the viewpoint of improving conductivity and forming a finer pattern, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 5% by mass or less.

The wiring layers (A-1) and (A-2) preferably further contain a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a solvent, a sensitizer, a pigment and/or dye that absorbs visible light, an adhesion improver, a surfactant, a polymerization inhibitor, and the like.

The wiring layers (A-1) and (A-2) may be made of the same material or different materials.

The wiring layers (A-1) and (A-2) can be formed using, for example, a conductive composition. As the conductive composition, a composition containing the conductive particles, the alkali-soluble resin, and the solvent can be used. The conductive composition may contain an organic tin compound, a metal chelate compound, a dispersant, a photopolymerization initiator, a monomer, a photoacid generator, a thermal acid generator, a sensitizer, a pigment and/or dye that absorbs visible light, an adhesion improver, a surfactant, a polymerization inhibitor, or the like, as necessary.

In another embodiment, the wiring layer (A-1) and/or (A-2) is preferably a transparent electrode. When a transparent electrode is used as the wiring layer (A-1) and/or (A-2), the wiring layer can be formed using existing production equipment without using expensive silver or the like. Examples of the material constituting the transparent electrode include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), Indium Zinc Tin Oxide (IZTO), Cadmium Tin Oxide (CTO), PEDOT (poly (3, 4-ethylenedioxythiophene)), Carbon Nanotubes (CNTs), and metal wires. Two or more of them may be used. Among these, Indium Tin Oxide (ITO) is preferable.

(insulating layer (OC-0), (OC-1), (OC-2))

In the touch panel, a first insulating layer (OC-1) is arranged between a first wiring layer (A-1) and a second wiring layer (A-2). Insulation between the first wiring layer (A-1) and the second wiring layer (A-2) can be ensured by the first insulating layer (OC-1).

Further, a second insulating layer (OC-2) may be further provided on the upper surface of the second wiring layer (A-2) (i.e., the surface opposite to the surface contacting the first insulating layer (OC-1)). By having the second insulating layer (OC-2), moisture in the atmosphere can be suppressed from reaching the second wiring layer (A-2), and the moist heat resistance of the touch panel can be further improved.

The insulating layer (OC-2) preferably has photosensitivity and adhesiveness. Here, photosensitivity refers to a property of causing a chemical change by irradiation of light. The term "adhesiveness" refers to a property of adhesion in a short time by a slight pressure at room temperature or under heating. By providing the insulating layer (OC-2) with photosensitivity, only the insulating layer (OC-2) on the connection portion with the external electrode can be removed with high accuracy, and the connection portion with the external electrode can be easily exposed. Further, the insulating layer (OC-2) has adhesiveness, and thus can be easily attached to other members such as a glass cover plate, a cover film, and an OLED substrate.

Further, an insulating layer (OC-0) may be provided between the transparent layer (OC-D) and the first wiring layer (A-1). By providing the insulating layer (OC-0), the residue generated during processing of the first wiring layer (A-1) is further suppressed, and the moisture and heat resistance of the touch panel is further improved.

The insulating layers (OC-0), (OC-1), and (OC-2) may be made of the same material or different materials.

The thickness of the insulating layers (OC-1) and (OC-2) is preferably 0.1 μm or more, more preferably 0.5 μm or more, from the viewpoint of further improving the insulation properties. On the other hand, from the viewpoint of further improving the transparency, it is preferably 10 μm or less, and more preferably 3 μm or less.

The thickness of the insulating layer (OC-0) is preferably 0.05 μm or more, more preferably 0.1 μm or more, from the viewpoint of further suppressing the residue of the wiring layer (A-1). On the other hand, the thickness of the insulating layer (OC-0) is preferably 5 μm or less, more preferably 2 μm or less, from the viewpoint of further improving the transparency.

The insulating layers (OC-0), (OC-1) and (OC-2) are preferably formed from an insulating composition containing an alkali-soluble resin.

Examples of the alkali-soluble resin include the aforementioned (meth) acrylic copolymer and Cardo resin. The Cardo resin is preferable because it can improve the hydrophobicity and further improve the insulation property of the insulating layer.

The Cardo resin is preferably a Cardo resin containing two or more structural units represented by the following chemical formula (5) and containing a polymerizable group and an alkali-soluble group.

[ chemical formula 7]

The Cardo-based resin can be obtained, for example, by: the reaction product of the epoxy compound and the acid compound having a radical polymerizable group is further reacted with an acid dianhydride.

Examples of the catalyst used in the reaction of the epoxy compound with the acid compound having a radical polymerizable group and the reaction with the acid dianhydride include an ammonium catalyst such as tetrabutylammonium acetate, an amine catalyst such as 2,4, 6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine, a phosphorus catalyst such as triphenylphosphine, and a chromium catalyst such as chromium acetylacetonate or chromium chloride.

Examples of the epoxy compound include compounds having the following structures.

[ chemical formula 8]

Examples of the acid compound having a radical polymerizable group include (meth) acrylic acid, mono (2- (meth) acryloyloxyethyl succinate, mono (2- (meth) acryloyloxyethyl phthalate), mono (2- (meth) acryloyloxyethyl tetrahydrophthalate, and p-hydroxystyrene.

As the acid dianhydride, pyromellitic dianhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 2 ', 3,3 ' -biphenyltetracarboxylic dianhydride, and the like are preferable from the viewpoint of improving the chemical resistance of the insulating layer. In addition, the acid dianhydride may be used by replacing a part of the acid dianhydride with an acid anhydride for the purpose of adjusting the molecular weight.

Further, as the Cardo-based resin, commercially available products can be preferably used, and examples thereof include "WR-301 (trade name)" ((manufactured by ADEKA corporation), "V-259 ME (trade name)" (manufactured by seikagaku corporation), "OGSOL (registered trademark) CR-TR 1", "OGSOL (registered trademark) CR-TR2 (trade name)", "OGSOL (registered trademark) CR-TR 3", "OGSOL (registered trademark) CR-TR 4", "OGSOL (registered trademark) CR-TR 5", "OGSOL (registered trademark) CR-TR 6" (manufactured by Osaka Gas Chemicals, ltd).

The weight average molecular weight of the (meth) acrylic copolymer (Mw (a1)) and the weight average molecular weight of the Cardo resin (Mw (a2)) are preferably 2,000 or more from the viewpoint of improving coating properties, and preferably 200,000 or less from the viewpoint of improving solubility in a developer during pattern formation. Here, the weight average molecular weight refers to a value in terms of polystyrene measured by GPC. In addition, when the (meth) acrylic copolymer and the Cardo resin are contained, the ratio of Mw (a1) to Mw (a2) (Mw (a2)/Mw (a1)) is preferably 0.14 or more from the viewpoint of suppressing layer separation and forming a uniform insulating layer. On the other hand, Mw (a2)/Mw (a1) is preferably 1.5 or less, and more preferably 1 or less, from the viewpoint of suppressing layer separation and forming a uniform insulating layer.

The total content of the (meth) acrylic copolymer and the Cardo resin in the insulating composition may be arbitrarily selected depending on the desired film thickness and application, and is preferably 10 mass% or more and 70 mass% or less of 100 mass% of all solid components.

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

Examples of the hindered amine-based light stabilizer include compounds represented by the following formulae (7) to (11). Two or more of them may be contained. Among these, the compound represented by the chemical formula (7) or (8) is more preferable in view of high reactivity.

[ chemical formula 9]

Wherein in the general formulae (9) to (11), a, b, c and d each independently represent an integer of 0 to 15.

The content of the hindered amine light stabilizer in the insulating composition is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more, based on 100 mass% of the total solid content. The content of the hindered amine light stabilizer is preferably 10% by mass or less, and more preferably 5% by mass or less.

The insulating composition may further contain additives such as a polyfunctional monomer, a curing agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, and an antifoaming agent, as necessary.

(photosensitive adhesive layer (OC-R))

A photosensitive adhesive layer (OC-R) is preferably further disposed on the upper surface of the second insulating layer (OC-2). The moisture and heat resistance can be further improved by the photosensitive adhesive layer (OC-R). Further, by providing the photosensitive adhesive layer (OC-R) with photosensitivity, only the photosensitive adhesive layer (OC-R) at the connection portion with the external electrode can be removed with high accuracy, and the connection portion with the external electrode can be easily exposed. Further, by providing the photosensitive adhesive layer (OC-R) with adhesiveness, the insulating layer (OC-2) can be easily bonded to other members such as a glass cover plate, a cover film, and an OLED substrate even when it does not have adhesiveness.

As the photosensitive adhesive layer, a photosensitive adhesive composition containing an alkali-soluble resin and a photosensitive component can be preferably used. As the alkali-soluble resin, acrylic resin, silicone resin, urethane resin, and the like can be preferably used. From the viewpoint of transparency, acrylic resin or silicone resin is particularly preferable.

(light-shielding layer)

In the touch panel, a light shielding layer is preferably disposed below the first wiring layer (A-1) and below the second wiring layer (A-2), and/or above the first wiring layer (A-1) and above the second wiring layer (A-2). By providing the light-shielding layer, reflection of light by the wiring layer can be suppressed, and wiring appearance can be suppressed. In the touch panel, the lower portion refers to the side where the transparent layer (OC-D) is present, and the upper portion refers to the side where the second wiring layer (A-2) is present. When a light-shielding layer is disposed below the first wiring layer (A-1) and the second wiring layer (A-2), the appearance of wiring when viewed from the transparent layer (OC-D) side can be suppressed. In this case, one light-shielding layer may be provided below the first wiring layer (A-1) and one light-shielding layer may be provided below the second wiring layer (A-2), and a total of two or more light-shielding layers may be provided. On the other hand, when a light-shielding layer is disposed above the first wiring layer (A-1) and the second wiring layer (A-2), the appearance of wiring when viewed from the second wiring layer (A-2) side can be suppressed. In this case, it is preferable to provide only one light-shielding layer above the first wiring layer (A-1) and the second wiring layer (A-2) because the process can be omitted. Further, when a light-shielding layer is provided in both the lower portion of the first wiring layer (A-1) and the upper portion of the second wiring layer (A-2), the appearance of wiring on both sides can be suppressed.

The specific position for disposing the light-shielding layer is preferably any one of a position between the first wiring layer and the transparent layer (OC-D), a position directly above the second wiring layer (A-2), and a position directly above the second insulating layer (OC-2).

From the viewpoint of further suppressing the appearance of wiring, the optical density (hereinafter referred to as OD value) of the light-shielding layer is preferably 0.2 or moreAbove, more preferably 0.5 or more, and still more preferably 1.0 or more. For example, by forming the light-shielding layer from a preferable insulating composition described later, the OD value can be easily adjusted to be within the above range. The OD value of the light-shielding layer can be determined from the transmitted light intensity (I) and the incident light intensity (I) of the light-shielding layer measured by using a micro-spectroscope (Otsuka type MCPD2000)₀) And the following relational expression (a).

OD value log10 (I)₀/I) (a)

From the viewpoint of further suppressing the appearance of the wiring, the light-shielding layer preferably has a reflectance of 30% or less, more preferably 20% or less, and still more preferably 10% or less with respect to light having a wavelength of 550 nm. For example, by forming the light-shielding layer using a preferable insulating composition described later, the reflectance can be easily adjusted to the above range.

The light-shielding layer preferably has insulating properties. From the viewpoint of suppressing malfunction by improving the electrical characteristics of the touch panel, the surface resistance value of the light-shielding layer is preferably 10⁸Omega/□ or more, more preferably 10¹²Omega/□ or more, more preferably 10¹⁵Omega/□ or more. The surface resistance of the light-shielding layer was measured using Hiresta UP MCP-HT450 (manufactured by Mitsubishi Chemical Analyticch) under a condition of an applied voltage of 10V.

As a material for forming the light-shielding layer, a composition in which a light-shielding pigment is dispersed in the insulating composition exemplified above as a material for forming the insulating layer is preferable. Examples of the light-shielding pigment include organic pigments such as perylene black and aniline black; metal fine particles such as titanium oxynitride, titanium nitride, carbon black, graphite, cobalt oxide, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; inorganic pigments such as metal oxides, composite oxides, metal sulfides, metal nitrides, and metal carbides. Among these, carbon black or titanium nitride is more preferable from the viewpoint of light-shielding properties and reflective color characteristics.

From the viewpoint of improving light-shielding properties and insulating properties, the specific surface area of the light-shielding pigment measured by the nitrogen adsorption BET method is preferably 10m²A value of at least/g, more preferably 20m²More than g. On the other hand, from the viewpoint of suppressing aggregation of particles and improving dispersion stability, it is preferably 600m²A ratio of not more than 200 m/g, more preferably²A ratio of 100m or less per gram²The ratio of the carbon atoms to the carbon atoms is less than g.

In the case of using carbon black as the light-shielding pigment, carbon black having improved insulation properties by surface treatment is preferable. As surface treatments for improving insulation properties, for example, surface coating by a resin (japanese patent laid-open No. 2002-249678), wet oxidation treatment of the surface (japanese patent laid-open No. 4464081), surface modification by an organic group containing a non-polymer group (japanese patent laid-open No. 2008-517330), and the like are known.

In order to further improve the insulation properties, the atomic ratio of carbon on the surface of carbon black is preferably 95% or less, and more preferably 90% or less. Further, the higher the sulfur atom ratio on the surface of the carbon black, the more easily the alkali-soluble resin adsorbs to the carbon black, and the steric hindrance suppresses contact between the carbon blacks, thereby further improving the insulation properties of the light shielding layer. Therefore, the sulfur atom ratio on the surface of carbon black is preferably 0.5% or more, more preferably 1.0% or more.

The content of the light-shielding pigment in the light-shielding layer is preferably 40% by mass or more, and more preferably 60% by mass or more, from the viewpoint of improving the light-shielding property. On the other hand, the content is preferably 80 mass% or less, more preferably 75 mass% or less, from the viewpoint of improving the adhesion between the light-shielding layer and the substrate and the patterning property.

From the viewpoint of enhancing the strength of the touch panel, the thickness of the touch panel is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. On the other hand, from the viewpoint of further improving the bending resistance, it is preferably 40 μm or less, more preferably 30 μm or less, and still more preferably 25 μm or less.

The touch panel preferably has a b value of-5 to 5 based on the L a b color system specified by the international commission on illumination in 1976. By setting the range to this range, excessive chromaticity adjustment is not required, and visibility of the display can be further improved. The value of b is more preferably-4 to 4, and still more preferably-3 to 3. Note that b-value of the touch panel can be calculated as follows: the reflectance of all reflected light was measured from the glass substrate side using a spectrophotometer (CM-2600 d; manufactured by KONICA MINOLTA, Inc.) to measure a color characteristic b in CIE (L, a, b) color space.

Next, a method for manufacturing a touch panel of the present invention will be described. The method for manufacturing a touch panel of the present invention includes the steps of: a step of forming at least the transparent layer (OC-D), the first wiring layer (A-1), the first insulating layer (OC-1), and the second wiring layer (A-2) in this order on a temporary support to produce a transfer member; bonding a surface of the transfer member opposite to the temporary support to the base via a transparent adhesive layer; and removing the temporary support. The transparent layer (OC-D) has a peeling function. Here, the transfer member means: and a member in which at least the transparent layer (OC-D), the first wiring layer (A-1), the first insulating layer (OC-1), and the second wiring layer (A-2) are laminated in this order. The term "having a peeling function" means that the temporary support and the transfer member can be peeled at the interface between the temporary support and the transparent layer (OC-D). Specific examples of the peeling method include: a method of mechanical lift-off at the interface of the temporary support and the transparent layer (OC-D); a method of peeling the interface between the temporary support and the transparent layer (OC-D) by immersing the temporary support in hot water, a chemical solution such as an organic solvent, or the like; or a method of irradiating the temporary support with a laser beam having a wavelength of 300 to 400nm from the temporary support side to thereby peel off the interface between the temporary support and the transparent layer (OC-D); and so on.

Examples of the temporary support include a silicon wafer, a ceramic substrate, and an organic substrate. Examples of the ceramic substrate include glass substrates made of glass such as soda lime glass, alkali-free glass, borosilicate glass, and quartz glass; alumina substrate, aluminum nitride substrate, silicon carbide substrate. Examples of the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a polyimide film, and a polyester film.

First, a transparent layer (OC-D) is formed on a temporary support. The method of forming the transparent layer (OC-D) preferably includes: a coating step of coating the transparent composition on a temporary support; a pre-baking step of drying the coated transparent composition; and a curing step of curing the resin composition.

Examples of the method of applying the transparent composition to the temporary support include coating using a spin coater, a bar coater, a knife coater, a roll coater, a die coater, a roll coater, a meniscus coater, screen printing, spray coating, dip coating, and the like.

Examples of the drying method in the pre-baking step and the curing step include heat drying, reduced pressure drying, vacuum drying, and infrared irradiation. Examples of the heating and drying device include a hot plate and a hot air dryer (oven).

The temperature and time of the preliminary baking step can be appropriately set depending on the composition of the transparent composition and the film thickness of the coating film to be dried. The heating temperature is preferably 50-150 ℃, and the heating time is preferably 10 seconds-30 minutes.

The atmosphere, temperature and time of the curing step may be appropriately set depending on the composition of the transparent composition and the film thickness of the coating film to be dried, and curing in air is preferred. The heating temperature is preferably 150 ℃ or higher, and more preferably 180 ℃ or higher, from the viewpoint of sufficiently performing curing. On the other hand, from the viewpoint of further suppressing yellowing by heating and further improving the color tone, the heating temperature is preferably 350 ℃ or less, more preferably 300 ℃ or less, and further preferably 245 ℃ or less. From the viewpoint of sufficient curing, the heating time is preferably 5 minutes or more, and more preferably 20 minutes or more. On the other hand, the heating time is preferably 120 minutes or less, more preferably 80 minutes or less, from the viewpoint of further suppressing yellowing due to heating and further improving the color tone.

The transparent layer (OC-D) formed in the above manner may be further subjected to surface treatment. By performing the surface treatment, the surface state of the transparent layer (OC-D) can be changed, and the deterioration of pattern processability due to development residue in the subsequent step of forming the first wiring layer (A-1) and the like can be suppressed. Preferable examples of the surface treatment method include corona discharge treatment, plasma treatment, and UV ozone treatment. From the viewpoint of further reducing the residue by modifying the surface state while suppressing the surface deterioration, corona discharge treatment or plasma treatment is preferable, and plasma treatment is more preferable. On the other hand, from the viewpoint of simplicity of the apparatus, corona discharge treatment or UV ozone treatment is preferable, and UV ozone treatment is more preferable.

In addition, an insulating layer (OC-0) may be further formed on the formed transparent layer (OC-D). By forming the insulating layer (OC-0), the pattern processability of the first wiring layer (A-1) and the like after the formation can be further improved even when the transparent layer (OC-D) is not subjected to the surface treatment described above.

The insulating layer (OC-0) can be formed using the insulating composition. The forming method preferably has: a coating step of coating the insulating composition on an insulating layer (OC-0); a pre-baking step of drying the coated insulating composition; and a curing step of curing the resin composition.

In addition, an inorganic film is also preferably formed as the insulating layer (OC-0). By forming the inorganic film, the pattern processability of the first wiring layer (a-1) and the like after that can be further improved. In addition, it is preferable to suppress the migration of metal impurities, moisture, etc. from the transparent layer (OC-D) to the first wiring layer (A-1) and to improve the reliability of the wiring layer.

Examples of the inorganic film include an Si-based thin film, a C-based thin film, and a metal thin film. Examples of the Si-based thin film include Si and SiO_x、SoC_x、SiN_x、SiO_xCy、SiO_xN_y、SiO_xF_yAnd so on. Examples of the C-based thin film include DLC (a-C: H), N-DLC, Si-DLC, F-DLC, Metal-DLC, and graphene. Examples of the metal thin film include TiO_x、SnO_x、AlO_xW, etc. The Si-based thin film is more preferable from the viewpoint of improving the pattern processability of the first wiring layer (A-1) and the like.

Next, a first wiring layer (A-1) is formed on the resulting transparent layer (OC-D) or insulating layer (OC-0). The method of forming the first wiring layer (a-1) preferably includes: a coating step of coating the conductive composition on a substrate surface; a pre-baking step of drying the coated conductive composition; a step of forming a grid pattern by exposing and developing the pattern (an exposure step and a development step); and a curing step of curing the obtained mesh pattern.

As a method of applying the conductive composition to the surface of the substrate, a method exemplified as a method of applying the transparent composition can be cited.

As a drying method in the pre-baking step and the curing step, a method exemplified as a method for drying a transparent composition can be cited.

The temperature and time of the prebaking may be appropriately set depending on the composition of the conductive composition and the film thickness of the coating film to be dried. The heating temperature is preferably 50-150 ℃, and the heating time is preferably 10 seconds-30 minutes.

As the light source used in the exposure step, for example, j-line, i-line, h-line, and g-line of a mercury lamp are preferable.

Examples of the developer used in the developing step include an alkaline aqueous solution obtained by dissolving an alkaline substance in water, the alkaline substance being: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH); quaternary ammonium salts such as choline; alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and the like; organic bases such as cyclic amines including pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, 1, 5-diazabicyclo [4,3,0] -5-nonane, morpholine and the like; and so on. To these, a water-soluble organic solvent such as ethanol, γ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added as appropriate.

In order to obtain a more favorable conductive pattern, it is also preferable to further add 0.01 to 1 mass% of a surfactant such as a nonionic surfactant to the alkaline developer.

The atmosphere, temperature and time of the curing step may be appropriately set according to the composition of the conductive composition and the film thickness of the coating film to be dried, and curing in air is preferred. The heating temperature is preferably 100 to 300 ℃, and more preferably 200 to 300 ℃. The heating time is preferably 5 minutes to 120 minutes.

Further, a first insulating layer (OC-1) is formed on the formed wiring layer (A-1). The method of forming the first insulating layer (OC-1) preferably includes: a coating step of coating the insulating composition on the wiring layer (A-1); a pre-baking step of drying the coated insulating composition; a step of forming a pattern by exposing and developing the resist (exposure step and development step); and a curing step of curing the obtained pattern. Each step can be performed in the same manner as the wiring layer (A-1).

Next, a second wiring layer (A-2) is formed on the first insulating layer (OC-1). The second wiring layer (A-2) can be formed by the same method as the first wiring layer (A-1).

A second insulating layer (OC-2) may be further formed on the second wiring layer (A-2). By forming the second insulating layer (OC-2), moisture in the atmosphere can be prevented from reaching the wiring layer (A-2), and the moist heat resistance can be further improved.

In this case, the second insulating layer (OC-2) is preferably removed from the upper portion of the electrode lead-out portion. By removing this portion precisely in advance, the subsequent connection to the external electrode can be easily performed.

In addition, a photosensitive adhesive layer is also preferably formed on the second insulating layer (OC-2). With this configuration, the insulation property and the moist heat resistance can be further improved. The second insulating layer (OC-2) can be formed by the same method as that used for the first insulating layer (OC-1).

Preferably, the method further comprises a step of forming a light-shielding layer. Examples of the method for forming the light-shielding layer include: (i) a method of forming a light-shielding layer on the transparent layer (OC-D), patterning the light-shielding layer so as to have the same shape as the first wiring layer (A-1) and the second wiring layer (A-2), and then forming the first wiring layer (A-1), the first insulating layer (OC-1), and the second wiring layer (A-2); (ii) a method of forming a first light-shielding layer (B-1) on the transparent layer (OC-D), patterning the first light-shielding layer so as to have the same shape as the first wiring layer (A-1), then forming the first wiring layer (A-1) and the first insulating layer (OC-1), then forming a second light-shielding layer (B-2) on the first insulating layer (OC-1), patterning the second light-shielding layer so as to have the same shape as the second wiring layer (A-2), and then forming the second wiring layer (A-2); (iii) a method of forming a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) on a transparent layer (OC-D), and then forming a light-shielding layer on the second wiring layer (A-2), and patterning the light-shielding layer so as to have the same shape as the first wiring layer (A-1) and the second wiring layer (A-2); and so on.

In general, the above-described embodiment can provide a temporary support with a transfer member, in which the transfer member is formed on the temporary support.

Then, the surface of the transfer member opposite to the temporary support is bonded to the base via the transparent adhesive layer, and then the transparent layer (OC-D) of the temporary support with the transfer member is peeled off from the temporary support, and only the temporary support is removed, thereby completing the touch panel. Here, the base material is preferably a glass substrate or a film substrate, and a member may be formed on the glass substrate or the film substrate. Specific examples of such a substrate include a glass cover plate, a cover film, a polarizing film, a color filter substrate, a display substrate, and the like.

Examples of the method for peeling the transparent layer (OC-D) from the temporary support include a method of peeling the transparent layer (OC-D) by irradiating the transparent layer (OC-D) with laser light from the back surface of the temporary support, a method of peeling the temporary support with the touch panel by immersing the temporary support in a solvent and/or purified water maintained at 0 to 80 ℃ for 10 seconds to 10 hours, a method of cutting the transparent layer (OC-D) from the upper surface and mechanically peeling the transparent layer from the cut end face, and the like.

In another embodiment, after the transfer member is separated from the temporary support by performing the above-described separation step on the temporary support with the transfer member, the surface of the transfer member opposite to the temporary support is bonded to the substrate via the transparent adhesive layer, thereby completing the touch panel. The bonding step and the peeling step may be performed after a protective film and a transparent adhesive layer (hereinafter referred to as OCA) are bonded onto the second wiring layer (a-2) of the temporary support with the transfer member. From the viewpoint of bonding accuracy, it is more preferable to perform the peeling step after bonding the temporary support with the transfer member to a substrate such as a glass substrate.

As described above, the touch panel of the present invention is manufactured by forming the temporary support having excellent dimensional accuracy on the temporary support and then peeling and removing the temporary support, and therefore, the touch panel can be applied to a processing method having excellent dimensional accuracy. In the touch panel of the present invention, the transparent layer (OC-D) contains the heat-resistant polymer having the above-described specific structure, whereby the residue of the conductive composition can be suppressed, and the touch panel is excellent in color tone and moist heat resistance. According to the present invention, a touch panel capable of forming a fine pattern and having flexibility can be provided.

The present invention can be applied to a structure having wiring other than a touch panel. Examples of the structure include a curved display such as a micro LED, and various flexible sensors such as an RFID.

The structure of the present invention is a structure having a portion where a first wiring layer (A-1) is laminated on a transparent layer (OC-D), wherein the transparent layer (OC-D) contains a heat-resistant polymer having a structure represented by the following general formula (1) and a structure represented by the following general formula (2).

[ chemical formula 10]

In the above general formulae (1) and (2), R₁And R₂Each independently represents a monovalent organic group; m and n each independently represent an integer of 0 to 4; m R₁And n R₂Each may be the same or different.

Examples

Hereinafter, examples of the present invention will be described. First, materials used in examples and comparative examples will be described.

(acid dianhydride)

ODPA: 3,3 ', 4, 4' -Diphenyl Ether tetracarboxylic dianhydride (Compound comprising the Structure represented by the general formula (2))

And (3) PMDA: 1,2,4, 5-benzenetetracarboxylic dianhydride

PMDA-HS: 1,2,4, 5-cyclohexane tetracarboxylic dianhydride.

(diamine)

DDS: bis (4-aminophenyl) sulfone (compound having a structure represented by the general formula (1))

m-BAPS: bis [4- (3-aminophenoxy) phenyl ] sulfone (compound having a structure represented by general formulae (1) and (2))

BAHF: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (compound having a structure represented by general formula (3))

TFMB: 2, 2' -bis (trifluoromethyl) benzidine (compound having a structure represented by the general formula (12))

FDA: 9, 9' -bis (4-aminophenyl) fluorene

HFHA: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (compound having a structure represented by general formula (3))

TAPOB: 1,3, 5-tris (4-aminophenoxy) benzene (a compound having a structure represented by general formula (13)).

(solvent)

GBL: gamma-butyrolactone

PGMEA: propylene glycol monomethyl ether

DPM: dipropylene glycol monomethyl ether.

(alkali-soluble resin)

Alkali-soluble resin (a): obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate with a carboxyl group of a copolymer of methacrylic acid/methyl methacrylate/styrene (54/23/23 mol%) (weight average molecular weight (Mw): 29,000).

(others)

PE-3A: pentaerythritol triacrylate

(conductive particles)

A-1: silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of 1nm and a 1-order particle diameter of 40nm for the carbon coating layer on the surface

A-2: 1 silver particle (manufactured by Mitsui metals Co., Ltd.) having a primary particle diameter of 0.7 μm.

Production example 1: polymer (Synthesis of P-1 to P-7, P-9 to P-15)

Acid dianhydride shown in table 1 was dissolved in GBL under a dry nitrogen flow to prepare a solution having a concentration of 10 mass%. To this was added the diamine shown in Table 1, and the reaction was carried out at 20 ℃ for 1 hour, followed by 50 ℃ for 2 hours. The concentration of the polymerization solution after the completion of the reaction is 20 to 25 mass%.

[ Table 1]

(Heat-resistant Polymer)

P-8: polyether sulfone resin ("SUMIKAEXCEL" (registered trademark) 5003PS, manufactured by Sumitomo chemical Co., Ltd.).

Production example 2: preparation of transparent compositions (OP-1 to OP-15)

20g of the heat-resistant polymer shown in Table 2, 70g of GBL and 0.03g of a surfactant (F-477 manufactured by DIC Co., Ltd.) were added to a clean bottle and stirred for 1 hour to obtain transparent compositions OP-1 to OP-15.

[ Table 2]

[ TABLE 2]

Transparent composition	Heat-resistant polymer
		OP-1	P-1
OP-2	P-2
		OP-3	P-3
OP-4	P-4
		OP-5	P-5
OP-6	P-6
		OP-7	P-7
OP-8	P-8
		OP-9	P-9
OP-10	P-10
		OP-11	P-11
OP-12	P-12
		OP-13	P-13
OP-14	P-14
		OP-15	P-15

Production example 3: preparation of electroconductive compositions (AE-1 to AE-4)

The conductive particles A-180g, surfactant ("DISPERBYK" (registered trademark) 21116, DIC) 4.06g, PGMEA 98.07g and DPM 98.07g were mixed, and mixed at 1200rpm for 30 minutes using a homogenizer. Then, dispersion treatment was further performed using a high-pressure wet type media-free micronizer (Nanomizer, ltd.) to obtain a silver dispersion 1 having a silver content of 28.6 mass%.

Silver dispersion 2 was obtained in the same manner as described above, except that conductive particles a-2 were used instead of conductive particles a-1.

20g of an alkali-soluble resin (A) as an organic compound, 0.6g of ethyl aluminum acetoacetate diisopropyl ester (ALCH: Kawaken Fine Chemical Co., Ltd.), 2.4g of a photopolymerization initiator (NCI-831 (manufactured by ADEKA Co., Ltd.), and 12.0g of PE-3A were mixed, and 132.6g of PGMEA and 52.6g of DPM were added thereto and stirred to obtain an organic I liquid for conductive compositions.

The silver dispersion liquid and the organic I liquid were mixed at the ratios shown in table 3, respectively, to obtain conductive compositions (AE-1 to AE-4).

[ Table 3]

[ TABLE 3] in parts by mass

Conductive composition	AE-1	AE-2	AE-3	AE-4
					Silver Dispersion 1	1.88	2.41	0.38	-
Silver dispersion liquid 2	-	-	-	1.88
					Organic I liquid	0.71	0.10	2.43	0.71
Amount of Ag	83	97.7	22	83
					Amount of organic component	17	2.3	78	17

In the table, the amount of Ag and the amount of organic component represent the mass ratio of the silver particles and the organic component (excluding the solvent) contained in the conductive composition.

Production example 4: preparation of insulating composition (OA-1)

A Cardo resin (V-259ME, manufactured by Nippon iron Sumitomo chemical Co., Ltd.) 50.0g, a monomer (TAIC, manufactured by Nippon chemical Co., Ltd.) 18.0g, a monomer (M-315, manufactured by Toyo Synthesis Co., Ltd.) 10.0g, an epoxy compound (PG-100, manufactured by Osaka Gas Chemicals, Ltd.) 20.0g, and an initiator (OXE-01, manufactured by BASF corporation) 0.2g were added to the clean bottle and stirred for 1 hour to obtain an insulating composition OA-1.

Production example 5: preparation of light-shadability composition (b-1)

50.0g of an insulating composition (OA-1) and 8.0g of carbon black ("M-100" (registered trademark) manufactured by Mitsubishi chemical corporation) as a light-shielding pigment were added to a clean bottle and dispersed for 1 hour using an Ultra Apex Mill to obtain a light-shielding composition (b-1).

Next, the evaluation methods performed in examples and comparative examples will be described.

(1) Evaluation of Fine Pattern processability

In examples 1 to 11, 13, 15 to 22 and comparative examples, the conductive compositions used in examples and comparative examples were spin-coated on the transparent layer (OC-D), and on the insulating layer (OC-0) using a spin coater ("1H-360S (trade name)" manufactured by Mikasa corporation) at 300rpm × 10 seconds and 500rpm × 2 seconds, respectively. Next, the substrate coated with the conductive composition was prebaked at 100 ℃ for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Manufacturing, Ltd.) to obtain a prebaked film having a film thickness of 0.9. mu.m. The prebaked film was exposed to light through a mask having a line-and-space pattern using an ultra-high pressure mercury lamp as a light source using a parallel light type mask aligner ("PLA-501F (trade name)" manufactured by Canon corporation). Then, the plate was subjected to spray development with a 0.045 mass% aqueous solution of potassium hydroxide for 60 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.), followed by rinsing with water for 30 seconds to perform patterning. After exposure and development, the exposure amount at which a line-and-space pattern of 5 μm in width was formed with a width of 1: 1 was set as the optimum exposure amount. The exposure amount was measured using an I-line luminometer. Then, the minimum pattern size after development at the optimum exposure amount was measured, and the fine pattern processability was evaluated according to the following evaluation criteria, and 2 or more was regarded as a pass.

5: less than 3 μm

4: 3 μm or more and less than 4 μm

3: 4 μm or more and less than 5 μm

2: 5 μm or more and less than 6 μm

1: 6 μm or more.

(2) Evaluation of conductivity of conductive composition

In examples 1 to 11, 13, 15 to 22 and comparative examples, a prebaked film having a film thickness of 0.9 μm was formed on the transparent layer (OC-D), on the insulating layer (OC-0), in example 12, example 14 and example 23, by the method described in the above (1) using the conductive composition used in each example and comparative example. The prebaked film was exposed to light through a mask having a volume resistivity evaluation pattern using an ultra-high pressure mercury lamp as a light source using a parallel light type mask aligner ("PLA-501F (trade name)" manufactured by Canon corporation). Then, the plate was subjected to spray development with a 0.045 mass% aqueous solution of potassium hydroxide for 60 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.), followed by rinsing with water for 30 seconds to perform patterning. Then, a volume resistivity evaluation pattern was obtained by post-baking in an oven ("IHPS-222"; manufactured by ESPEC corporation) at 230 ℃ for 30 minutes in air.

The volume resistivity (μ Ω · cm) was calculated by measuring the surface resistance ρ s (Ω/□) of the obtained volume resistivity evaluation pattern by using a surface resistance measuring instrument ("Loresta" (registered trademark) -FP; manufactured by mitsubishi oil corporation), measuring the film thickness t (cm) by using a surface roughness shape measuring instrument ("SURFCOM" (registered trademark) 1400D (manufactured by tokyo precision corporation), multiplying the two values, and the conductivity was evaluated according to the following evaluation criteria, and 2 or more was regarded as being acceptable.

5: less than 60 mu omega cm

4: 60 [ mu ] omega cm or more and less than 80 [ mu ] omega cm

3: 80 [ mu ] omega cm or more and less than 100 [ mu ] omega cm

2: 100 [ mu ] omega cm or more and less than 150 [ mu ] omega cm

1: 150 mu omega cm or more.

(3) Evaluation of residue of conductive composition

The transmittance at 400nm before and after film formation was measured using an ultraviolet-visible spectrophotometer ("MultiSpec-1500 (trade name)", manufactured by Shimadzu corporation) for the unexposed portion of the substrate on which the volume resistivity evaluation pattern obtained by the method (2) was formed. Then, the transmittance change represented by the formula (T0-T)/T0 was calculated when the transmittance before film formation was T0 and the transmittance after film formation was T, and the residue was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more.

5: less than 1%

4: more than 1 percent and less than 2 percent

3: more than 2 percent and less than 3 percent

2: more than 3 percent and less than 4 percent

1: more than 4% and less than 5%.

(4) Evaluation of color tone (b;)

In examples 1 to 12, 15 to 21, and 23 and comparative examples, regarding the substrate laminated to the conductive layer (a-2), and in examples 13 to 14 and 22, regarding the substrate laminated to the transparent layer (OC-2), the reflectance of all reflected light of the laminated substrate was measured from the glass substrate side using a spectrophotometer (CM-2600 d; manufactured by KONICA MINOLTA corporation), the color characteristic b in CIE (L, a, b) color space was measured, and the color tone was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more. As the light source, a D65 light source was used.

5：-2≤b*≤2

4: -3 -2 or 2 < 3

3: -4 -3 or 3 -4

2: -5 -4 or 4 -5

1: b < -5 or 5.

(5) Evaluation of bending resistance

Only the transparent layer (OC-D) of the glass substrate with the transparent layer (OC-D) produced in each of examples and comparative examples 1 to 3 was cut to a width of 1cm, peeled from the glass substrate, subjected to a 180-degree bending test using metal rods having diameters of 10cm, 5cm, 3cm and 1cm, respectively, and then observed for the presence or absence of crack generation using an optical microscope. In comparative example 4, the PET film was cut out to a width of 1cm, subjected to a 180-degree bending test in the same manner, and then observed for the presence of cracks using an optical microscope. The number of tests was 1. The bending resistance was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more.

5: no crack generation at a diameter of 1cm

4: no cracks occurred at a diameter of 3cm, and cracks occurred at a diameter of 1cm

3: no cracks occurred at a diameter of 5cm, and cracks occurred at a diameter of 3cm

2: no cracks occurred at a diameter of 10cm, and cracks occurred at a diameter of 5cm

1: when the diameter is 10cm, cracks are generated.

(5) Evaluation of Wet Heat resistance

The laminated substrates produced in the examples and comparative examples were evaluated for wet heat resistance by the following methods. For the measurement, the insulation deterioration characteristic evaluation system "ETAC SIR 13" (manufactured by nanchu cheng ji (r.k.)) was used. Electrodes are mounted on terminal portions of the wiring layer (A-1) and the wiring layer (A-2), respectively, and the laminated substrate is placed in a high-temperature and high-humidity chamber set to 85 ℃ and 85% RH. After 5 minutes had elapsed from the time when the in-cell environment had stabilized, a voltage was applied between the electrodes of the wiring layer (A-1) and the wiring layer (A-2), and the change in insulation resistance with time was measured. A voltage of 10V was applied to the wiring layer (A-1) as a positive electrode and the wiring layer (A-2) as a negative electrode, and the resistance value was measured at 5 minute intervals for 500 hours. When the measured resistance value reaches 5 th power or less of 10, it is determined that short-circuiting is caused by insulation failure, and the voltage application is stopped, and the test time up to this point is referred to as a short-circuiting time. The moist heat resistance was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more.

5: short circuit time of more than 1000 hours

4: short circuit time is more than 500 hours and less than 1000 hours

3: short-circuit time of 300 hours or more and less than 500 hours

2: short-circuit time of 100 hours or more and less than 300 hours

1: the short circuit time is less than 100 hours.

(6) Evaluation of dimensional accuracy

The laminated substrates produced in the examples and comparative examples were evaluated for dimensional accuracy by the following method. At a portion designed so that a mesh intersection of a wiring layer (A-1) and a mesh intersection of a wiring layer (A-2) overlap at the center of a laminated substrate, the horizontal direction deviation of the mesh intersection of the wiring layer (A-1) and the mesh intersection of the wiring layer (A-2) is measured, and dimensional accuracy is evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more.

5: offset less than 1 μm

4: the offset is 1 μm or more and less than 2 μm

3: the offset is 2 μm or more and less than 3 μm

2: the offset is 3 μm or more and less than 5 μm

1: the offset is 5 μm or more.

(7) Evaluation of elongation at Break

Only the transparent layer (OC-D) of the glass substrate with the transparent layer (OC-D) produced in each of examples and comparative examples 1 to 3 was cut into a long strip having a width of 1cm and a length of about 9cm, and then peeled from the glass substrate to obtain a sample for measuring elongation at break. In comparative example 4, the PET film was cut into a long piece having a width of 1cm and a length of about 9cm, and the piece was used as a sample for measuring elongation at break. The tensile test was carried out at a tensile rate of 50 mm/min by setting the sample for elongation at break to Tensilon RTM-100 manufactured by ORIENTEC, Inc. at an initial sample length of 50 mm. The measurement was performed 12 times, and the average value of the first 5 points of the obtained elongation at break was taken as the elongation at break of the transparent layer (OC-D), and the elongation at break was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more.

5: over 30 percent

4: more than 15 percent and less than 30 percent

3: more than 5 percent and less than 15 percent

2: more than 1 percent and less than 5 percent

1: less than 1%

(8) Evaluation of wiring appearance

In examples 1 to 12, 15 to 21, and 23 and comparative examples, the wiring layer was visually observed from the transparent layer (OC-D) side under green light and fluorescent light for the substrates laminated on the conductive layer (a-2) and examples 13 to 14 and 22, and the wiring appearance was evaluated according to the following evaluation criteria. The product was judged to be acceptable if it was 2 or more. As the light source, a D65 light source was used.

5: completely unrecognizable under green light

4: can be identified under green light

3: completely unrecognizable under fluorescent lamp

2: identifiable under fluorescent lamp according to angle

1: recognizable under fluorescent light.

(example 1)

< formation of transparent layer (OC-D) >

The transparent compositions shown in Table 4 were spin-coated on a glass substrate having a longitudinal length of 210mm × a transverse length of 297mm at 600rpm × 10 seconds by using a spin coater ("trade name" manufactured by Mikasa corporation), and then pre-baked at 100 ℃ for 2 minutes by using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Manufacturing corporation), thereby forming pre-baked films. The substrate with the prebaked film thus prepared was cured in air at 230 ℃ for 30 minutes in an oven ("IHPS-222 (trade name)" manufactured by ESPEC corporation), to form a transparent layer (OC-D).

< formation of first Wiring layer (A-1) >

The conductive compositions shown in Table 4 were spin-coated on a substrate having a transparent layer formed thereon by using a spin coater ("trade name" manufactured by Mikasa corporation) at 300 rpm.times.10 seconds and 500 rpm.times.2 seconds, and then pre-baked at 100 ℃ for 2 minutes by using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Manufacturing corporation) to prepare a pre-baked film. The prebaked film was exposed to light through a desired mask using an ultra-high pressure mercury lamp as a light source using a parallel light type mask aligner ("PLA-501F (trade name)" manufactured by Canon corporation). Then, the pre-baked film was subjected to pattern processing by spray development with 0.045 mass% aqueous solution of potassium hydroxide for 60 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.), followed by rinsing with water for 30 seconds.

The patterned substrate was cured in air at 230 ℃ for 30 minutes using an oven, to form a first wiring layer (a-1).

< formation of insulating layer (OC-1) >

The insulating composition shown in table 4 was spin-coated on the substrate on which the first wiring layer (a-1) was formed using a spin coater at 650rpm × 5 seconds, and then pre-baked at 100 ℃ for 2 minutes using a hot plate to prepare a pre-baked film. The pre-baked film was exposed to light through a desired mask using an ultra-high pressure mercury lamp as a light source using a parallel light type mask aligner. Then, the substrate was subjected to spray development with a 0.045 mass% aqueous solution of potassium hydroxide for 60 seconds and then rinsed with water for 30 seconds using an automatic developing apparatus, thereby patterning.

The patterned substrate was cured in air at 230 ℃ for 60 minutes using an oven to form an insulating layer, thereby obtaining a laminated substrate.

< second wiring layer (A-2) >

A second wiring layer (a-2) was formed on the insulating layer in the same manner as in < formation of the first wiring layer (a-1) > described above using the conductive compositions shown in table 4.

The results of evaluation by the above-described methods are shown in table 4. Fine pattern processability, conductivity, color tone, bending resistance and dimensional accuracy were "5", good. The residue and the moist heat resistance of the conductive composition are "4", but they are within the range that can be used without any problem. The elongation at break is "2", but is a range that can be used without problems.

(example 2)

The same operations as in example 1 were carried out, except that the transparent composition, the curing temperature and the film thickness were changed as described in table 4. Since the curing temperature is low, the conductivity is slightly lowered to "4", but the range is usable without any problem.

(example 3)

The same operations as in example 1 were carried out, except that the transparent composition, the curing temperature and the film thickness were changed as described in table 4. Since the curing temperature was high, the color tone was slightly lowered to "4", but the range was usable without any problem.

(example 4)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 4. The evaluation results were not changed.

(example 5)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 4. The heat-resistant polymer has a small proportion of the structure represented by the general formula (1), and therefore, the heat resistance is slightly lowered and the color tone is lowered, but the heat-resistant polymer is in a usable range. Since the structure represented by the general formula (12) is introduced into the heat-resistant polymer, the elongation at break is improved.

(example 6)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 4. The heat-resistant polymer has a small proportion of the structure represented by the general formula (2), and therefore, the heat resistance is slightly lowered and the color tone is lowered, but the heat-resistant polymer is in a usable range.

(example 7)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 4. Since the proportion of the structure represented by the general formula (2) in the heat-resistant polymer is small and the proportion of the aromatic ring is small, the heat resistance is lowered and the color tone is lowered. In addition, the conductive composition residues are generated, but all of them are in the usable range.

(example 8)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 4. The use of polyethersulfone instead of polyimide reduces the fine pattern processability and color tone, but both are in usable ranges.

(example 9)

The same operation as in example 1 was performed, except that the conductive composition was changed as shown in table 4. Since the amount of the organic compound in the conductive composition is small, the fine pattern processability is lowered, and a residue is generated. Further, the bending resistance is also lowered, but all of them are in a usable range.

(example 10)

The same operation as in example 1 was performed, except that the conductive composition was changed as shown in table 4. Since the conductive composition contains a large amount of organic compounds, the conductivity is lowered, but the range is usable.

(example 11)

The same operation as in example 1 was performed, except that the conductive composition was changed as shown in table 4. Since the metal fine particles are not coated, fine pattern processability, conductivity, and moist heat resistance are lowered, and residue and wiring are generated, but all of them are in a usable range.

(example 12)

The same operation as in example 1 was performed, except that the insulating layer (OC-0) was formed on the transparent layer (OC-D) as shown in table 5. The residue of the conductive composition is improved by the insulating layer (OC-0), but the color tone is slightly lowered. To the extent that there is no problem in use.

(example 13)

The same operation as in example 1 was carried out, except that the insulating layer (OC-2) was formed on the wiring layer (A-2) as shown in Table 5. The insulating layer (OC-2) is formed in the same manner as the insulating layer (OC-1). The moisture and heat resistance is improved by the insulating layer (OC-2), but the color tone is slightly lowered. To the extent that there is no problem in use.

(example 14)

The same operation as in example 1 was carried out, except that the insulating layer (OC-0) was formed on the transparent layer (OC-D) and the insulating layer (OC-2) was formed on the wiring layer (A-2) as shown in Table 5. The residue of the conductive composition is improved by the insulating layer (OC-0), and the moist heat resistance is improved by the insulating layer (OC-2), but the color tone is slightly lowered. To the extent that there is no problem in use.

(example 15)

The same operation as in example 1 was performed, except that the curing temperature was changed as shown in table 5. Since the curing temperature is low, the conductivity and the moist heat resistance are reduced to "2", but both ranges are usable.

(example 16)

The same operation as in example 1 was performed, except that the curing temperature was changed as shown in table 5. Since the curing temperature is high, the color tone, flexibility and wiring appearance are reduced, and they are "2", "3" and "2", respectively, but all of them are in usable ranges.

(example 17)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 5. Since the structure represented by the general formula (12) is introduced into the heat-resistant polymer, the elongation at break is improved.

(example 18)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 5. Since the proportion of the structure represented by the general formula (12) in the heat-resistant polymer was increased as compared with example 17, the elongation at break was further improved.

(example 19)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 5. Since the structure represented by the structural formula (13) is introduced into the heat-resistant polymer, the elongation at break is improved.

(example 20)

The same operation as in example 1 was performed, except that the transparent composition was changed as shown in table 5. Since the proportion of the structure represented by the structural formula (13) in the heat-resistant polymer was increased as compared with example 17, the color tone was decreased.

(example 21)

The same operation as in example 1 was performed, except that the light-shielding layer (B-1) was formed on the transparent layer (OC-D) as described in table 5. The wiring appearance viewed from the transparent layer (OC-D) side is reduced by the light shielding layer (B-1). The method for forming the light-shielding layer (B-1) is described below.

< formation of light-shielding layer (B-1) >

The light-shielding composition (b-1) was spin-coated at 750rpm × 10 seconds using a spin coater, and then pre-baked at 100 ℃ for 2 minutes using a hot plate to prepare a pre-baked film. The pre-baked film was exposed to light through a desired mask using an ultra-high pressure mercury lamp as a light source using a parallel light type mask aligner. Then, the substrate was subjected to spray development with a 0.045 mass% aqueous solution of potassium hydroxide for 60 seconds and then rinsed with water for 30 seconds using an automatic developing apparatus, thereby patterning.

The patterned substrate was cured in air at 230 ℃ for 60 minutes using an oven to form a light-shielding layer (B-1).

(example 22)

The same operation as in example 21 was performed, except that the light-shielding layer (B-1) was formed on the second insulating layer (OC-2) as described in table 5. The appearance of wiring viewed from the second insulating layer (OC-2) side is reduced by the light-shielding layer (B-1).

(example 23)

Except that SiO was formed on the transparent layer (OC-D) by sputtering to a thickness of 30nm as shown in Table 5₂The same operation as in example 1 was carried out except for the film. By SiO₂The film improved the residue of the conductive composition and the color tone was not changed.

Comparative example 1

The same operation as in example 1 was performed except that the heat-resistant polymer was changed as shown in table 5. Since the heat-resistant polymer does not contain any of the structures represented by the general formulae (1) and (2), the fine pattern processability, residue, color tone, and moist heat resistance are greatly reduced to an unusable level.

Comparative example 2

The same operation as in example 1 was performed except that the heat-resistant polymer was changed as shown in table 5. Since the heat-resistant polymer does not contain the structure represented by the general formula (2), the fine pattern processability, residue, color tone and moist heat resistance are greatly reduced to an unusable level.

Comparative example 3

The same operation as in example 1 was performed except that the heat-resistant polymer was changed as shown in table 5. Since the heat-resistant polymer does not contain the structure represented by the general formula (1), the fine pattern processability, residue, color tone and moist heat resistance are greatly reduced to an unusable level.

Comparative example 4

The same operation as in example 1 was carried out, except that a PET film (manufactured by Toray corporation, registered trademark) having a film thickness of 50 μm was used instead of the glass substrate coated with the transparent layer (OC-D). Since the heat resistance of the PET film is low, the fine pattern processability, residue, color tone and moist heat resistance are greatly reduced, and thus the PET film cannot be used. Further, due to the deformation of the film, the pattern is displaced, and the dimensional accuracy is also greatly reduced to an unusable level.

The evaluation results of the examples and comparative examples are shown in tables 4 to 5.

[ Table 4]

[ Table 5]

Industrial applicability

The touch panel of the present invention can be applied not only to a conventional flat panel display but also to a flexible display.

Claims

1. A touch panel comprising a portion in which a transparent layer (OC-D), a first wiring layer (A-1), a first insulating layer (OC-1), and a second wiring layer (A-2) are sequentially laminated, wherein the transparent layer (OC-D) comprises a heat-resistant polymer having a structure represented by general formula (1) and a structure represented by general formula (2), and the heat-resistant polymer is at least one selected from the group consisting of polyimide, polyimidesiloxane, and polybenzoxazole,

[ chemical formula 1]

In the general formula (1) and the general formula (2), R₁And R₂Each independently represents a monovalent organic group; m and n each independently represent an integer of 0 to 4; m R₁And n R₂Each may be the same or different.

2. The touch panel according to claim 1, wherein the heat-resistant polymer further comprises a structure represented by the following general formula (12),

[ chemical formula 2]

In the general formula (12), R₇And R₈Each independently represents a fluorine atom or a group containing a fluorine atom; x and y each independently represent an integer of 1 to 4; x number of R₈And y R₇Each may be the same or different.

3. The touch panel according to claim 1 or 2, wherein the heat-resistant polymer further comprises a structure represented by the following structural formula (13),

[ chemical formula 3]

4. The touch panel according to claim 1 or 2, wherein the first wiring layer (a-1) and/or the second wiring layer (a-2) has a mesh structure with a line width of 0.1 to 9 μm.

5. The touch panel according to claim 1 or 2, wherein the first wiring layer (a-1) and/or the second wiring layer (a-2) contains conductive particles having a surface coating layer.

6. Touch panel according to claim 1 or 2, wherein the first wiring layer (a-1) and/or the second wiring layer (a-2) are transparent electrodes.

7. The touch panel according to claim 1 or 2, further provided with a second insulating layer (OC-2) on an upper surface of the second wiring layer (a-2).

8. The touch panel according to claim 7, wherein the second insulating layer (OC-2) has photosensitivity and adhesiveness.

9. The touch panel according to claim 7, further comprising a photosensitive adhesive layer (OC-R) disposed on an upper surface of the second insulating layer (OC-2).

10. Touch panel according to claim 1 or 2, further provided with an insulating layer (OC-0) between the transparent layer (OC-D) and the first wiring layer (a-1).

11. The touch panel according to claim 1 or 2, further provided with a light shielding layer at a lower portion of the first wiring layer (a-1) and a lower portion of the second wiring layer (a-2), and/or at an upper portion of the first wiring layer (a-1) and an upper portion of the second wiring layer (a-2).

12. The touch panel according to claim 1 or 2, wherein the first wiring layer (a-1) and/or the second wiring layer (a-2) contains 0.1 to 80 mass% of an organic compound.

13. Touch panel according to claim 1 or 2, wherein the first wiring layer (a-1) and/or the second wiring layer (a-2) comprise silver particles.

14. The touch panel according to claim 1 or 2, having a thickness of 1 to 40 μm.

15. A method for manufacturing a touch panel, comprising the steps of:

a step of removing the temporary support body,

wherein the transparent layer (OC-D) has a release function, and contains a heat-resistant polymer having a structure represented by the following general formula (1) and a structure represented by the following general formula (2), the heat-resistant polymer being at least one selected from the group consisting of polyimide, polyimidesiloxane, and polybenzoxazole,

[ chemical formula 4]

16. The method for manufacturing a touch panel according to any one of claims 1 to 14, comprising the steps of:

a step of removing the temporary support body,

[ chemical formula 5]

17. The method for manufacturing a touch panel according to claim 15 or 16, wherein the base material is a glass substrate or a film substrate.

18. The method of manufacturing a touch panel according to claim 17, wherein the substrate is a glass substrate having an OLED element.

19. The method of manufacturing a touch panel according to claim 16, wherein the step of forming the transparent layer (OC-D) includes a step of heating at 150 to 350 ℃.

20. A structure having a portion where a first wiring layer (A-1) is laminated on a transparent layer (OC-D) containing a heat-resistant polymer having a structure represented by general formula (1) and a structure represented by general formula (2), wherein the heat-resistant polymer is at least one selected from the group consisting of polyimide, polyimidesiloxane, and polybenzoxazole,

[ chemical formula 6]