CN113474167B

CN113474167B - Substrate with conductive layer and touch panel

Info

Publication number: CN113474167B
Application number: CN202080016616.1A
Authority: CN
Inventors: 三井博子; 此岛阳平
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2019-04-02
Filing date: 2020-03-24
Publication date: 2023-02-21
Anticipated expiration: 2040-03-24
Also published as: TWI797437B; JPWO2020203447A1; JP6773258B1; WO2020203447A1; CN113474167A; TW202105419A

Abstract

The invention provides a base material with a conductive layer, which has good color tone and excellent migration resistance, and a touch panel using the same. A substrate with a conductive layer, which comprises at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1) and a first insulating layer (OC-1) on a substrate (S-1), wherein all of the following formulas (1) to (3) are satisfied when the b value of the substrate (S-1) is b (S-1), the b value of the first insulating layer (OC-1) is b (OC-1) and the b value of the entire substrate with a conductive layer is b (T) in accordance with the La b system specified by the International Commission on illumination in 1976. -4.3 ≤ b (T) ≤ 2.0 (1), 0.8 ≤ b (S-1) ≤ 5.0 (2), and 1.5 ≤ b (T) -b (OC-1) ≤ 5.5 (3).

Description

Substrate with conductive layer and touch panel

Technical Field

The present invention relates to a substrate with a conductive layer and a touch panel.

Background

In recent years, in touch panels for mobile devices, tablet devices, and the like, flexibility and thinning are desired from the viewpoint of design, convenience, and durability. 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 has a problem of cracking when it is made flexible because of its low bending resistance. Therefore, silver mesh wiring, silver nanowire wiring, and the like have attracted attention as touch wiring having both bending resistance and non-visibility and high conductivity.

The problem of the wiring using metal nanowires such as silver nanowires is high haze and easy coloring. To this end, for example, there are proposed: a substrate with a transparent electrode, comprising: a transparent substrate with an easy adhesion layer, a transparent electrode layer including metal nanowires and a transparent binder part formed on the easy adhesion layer, and a colored layer formed on the transparent electrode layer (for example, see patent document 1); an input device, comprising: a1 st base material having isogloss and having a1 st detection electrode provided on one surface thereof, a conductive shield layer made of a material having a negative chromaticity b provided on the 1 st base material on the surface on the side on which the 1 st detection electrode is provided in an electrically insulated state from the 1 st detection electrode, and a coated panel having isogloss and provided on the surface of the shield layer on the opposite side to the surface facing the 1 st base material (for example, see patent document 2).

On the other hand, as a touch panel having flexibility, for example, a touch panel including a portion in which a transparent layer, a first conductive layer, a first insulating layer, and a second conductive layer are sequentially stacked has been proposed (for example, see patent document 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2015-201023

Patent document 2: japanese patent laid-open publication No. 2017-156810

Patent document 3: international publication No. 2018/084067

Disclosure of Invention

Problems to be solved by the invention

The touch panel has a second electrode facing the first electrode with an insulating layer interposed therebetween, and for example, a touch panel structure in which a substrate with a transparent electrode disclosed in patent documents 1 to 2 is laminated as the first electrode and the second electrode is difficult to be thinned. Therefore, in recent years, as disclosed in patent document 3, a multilayer touch panel structure in which a plurality of conductive layers are laminated on one surface of a transparent layer has been studied. However, the multilayer touch panel disclosed in patent document 3 has a problem in terms of color tone because the substrate is yellowed by heating at the time of lamination. On the other hand, when the techniques disclosed in patent documents 1 to 2 are applied to the multilayer touch panel disclosed in patent document 3, the coloring agent reduces migration resistance of the colored layer and the insulating layer due to heating at the time of lamination, and thus there is a problem that silver migration is likely to occur between electrodes.

In view of the problems of the prior art described above, an object of the present invention is to provide a substrate with a conductive layer having good color tone and excellent migration resistance, and a touch panel using the substrate.

Means for solving the problems

The substrate with a conductive layer according to the present invention mainly has the following configuration.

(1) A substrate with a conductive layer, which comprises at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1) and a first insulating layer (OC-1) in this order on a substrate (S-1), wherein all of the following formulas (1) to (3) are satisfied when the b value of the substrate (S-1) is b (S-1), the b value of the first insulating layer (OC-1) is b (OC-1), and the b value of the entire substrate with a conductive layer is b (T) in accordance with the Lab-b color system specified in the International Commission on of illumination 1976.

-4.3≤b*(T)≤2.0 (1)

0.8≤b*(S-1)≤5.0 (2)

1.5≤b*(T)-b*(OC-1) ≤5.5 (3)

(2) A substrate with a conductive layer, which comprises a substrate (S-1) and, formed thereon, at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1) and a first insulating layer (OC-1) in this order, satisfies the following formulas (4) and (5) when b of the substrate (S-1) is b (S-1), b of the first insulating layer (OC-1) is b (OC-1) and b of the second insulating layer (OC-2) is b (OC-2) in accordance with the color system of La b a b prescribed by the International Commission on of illumination in 1976.

0.8≤b*(S-1)-b*(OC-1)≤8.0 (4)

0.5≤b*(OC-2)-b*(OC-1)≤7.0 (5)

(3) The substrate with a conductive layer according to (1) or (2), wherein the ratio ((OC-1)/(S-1)) of the film thickness of the first insulating layer (OC-1) to the film thickness of the substrate (S-1) is 0.05 to 0.5.

(4) The conductive-layer-provided substrate according to any one of (1) to (3), wherein the first insulating layer (OC-1) contains a colorant.

(5) The substrate with an electroconductive layer according to the above (4), wherein said coloring agent contains a metal complex.

(6) The substrate with an electroconductive layer according to (5), wherein the metal complex contains a phthalocyanine structure.

(7) The conductive-layer-provided substrate according to any one of (4) to (6), wherein the content of the colorant in the first insulating layer (OC-1) is 0.01 to 0.5 mass%.

(8) The substrate with a conductive layer according to any one of (1) to (7), wherein the substrate (S-1) has a total light transmittance at a wavelength of 400nm of 50 to 85%.

(9) The conductive-layer-provided substrate according to any one of (1) to (8), wherein the substrate (S-1) contains at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, and epoxy resin.

(10) The conductive-layer-provided substrate according to any one of (1) to (9), wherein the first conductive layer (A-1) and/or the second conductive layer (A-2) contains conductive particles having a coating layer.

(11) A touch panel comprising the base material with a conductive layer described in (1) to (10).

ADVANTAGEOUS EFFECTS OF INVENTION

The substrate with a conductive layer and the touch panel of the present invention are excellent in color tone and migration resistance.

Drawings

Fig. 1 is a cross-sectional view schematically showing one embodiment of a substrate with a conductive layer according to the present invention.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the substrate with a conductive layer of the present invention.

Detailed Description

The substrate with a conductive layer comprises a substrate (S-1) and, formed thereon, at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1), and a first insulating layer (OC-1) in this order. The substrate (S-1) functions as a support. The first conductive layer (A-1) and the second conductive layer (A-2) each function as an electrode in, for example, the orthogonal 2-direction. The first insulating layer (OC-1) and the second insulating layer (OC-2) have the function of insulating the first conductive layer (A-1) from the ambient atmosphere and the function of insulating the first conductive layer (A-1) from the second conductive layer (A-2), respectively. If a portion having such a laminated structure is present, the laminate may further have another layer or may have another structural portion. As one embodiment of the substrate with a conductive layer of the present invention, as shown in FIG. 1, a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1), and a first insulating layer (OC-1) are provided in this order on a substrate (S-1). As another embodiment of the substrate with a conductive layer of the present invention, as shown in FIG. 2, an insulating layer (OC-0), a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1), and a first insulating layer (OC-1) are provided in this order on a substrate (S-1). The above layers are explained.

(base material (S-1))

As the substrate (S-1), a resin film having flexibility or the like is preferable. More preferably, the polymer contains a structure represented by the following general formula (1) and a structure represented by the following general formula (2). The polymer having a structure represented by the following general formula (1) and a structure represented by the following general formula (2) has high amorphousness and excellent transparency as compared with other polymers. Further, the structure represented by the general formula (1) and the structure represented by the general formula (2) have high ultraviolet light absorption ability, and the base material (S-1) absorbs external light, and has an effect of suppressing the occurrence of light degradation due to the ultraviolet light reaching other constituent parts. Further, since the polymer having the above structure has high heat resistance, yellowing caused by heating in a subsequent step is reduced, and the color tone can be further improved. Further, by including such a polymer in the base material (S-1), residue can be suppressed in the processing of the conductive layer (a-2) in the subsequent step, and therefore, a fine pattern can be formed, and the migration resistance of the base material with the conductive layer can be further improved.

[ chemical formula 1]

In the above general formulae (1) to (2), R ₁ And R ₂ Each independently represents a 1-valent organic group, and m and n each independently represent an integer of 0 to 4. m R ₁ And n R ₂ Each may be the same or different.

From the viewpoint of further improving the color tone, R ₁ And R ₂ Preferably an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, 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. The substituent for the substituted phenyl group is preferably fluorine, trifluoromethyl, an alkyl group having 1 to 10 carbon atoms, allyl, or an aryl group having 3 to 13 carbon atoms.

The 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 (4). The transparency can be further improved by including the structure represented by the following structural formula (3), and the elongation at break of the substrate (S-1) can be improved by including the structure represented by the following general formula (4).

[ chemical formula 2]

In the above general formula (4), R ₇ And R ₈ Each independently represents fluorine or a fluorine-containing group. Examples of the group containing fluorine include a trifluoromethyl group. R ₇ And R ₈ Preferably fluorine or trifluoromethyl. x and y each independently represent an integer of 1 to 4. x number of R ₈ And y of R ₇ Each may be the same or different.

Examples of the structure represented by the general formula (4) include structures represented by any of the following structural formulae (5) to (8).

[ chemical formula 3]

When the polymer contains a structure represented by the general formula (4), the content of the repeating unit having such a 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 further preferably 40 mol% or less, from the viewpoint of further improving the color tone.

The polymer preferably further contains a structure represented by the following structural formula (9). By including the structure represented by the following structural formula (9), the toughness of the transparent layer can be improved, and the yield in the subsequent step and the bending resistance of the substrate with the conductive layer can be greatly improved.

[ chemical formula 4]

When the polymer contains a structure represented by the general formula (9), the content of the repeating unit having such a structure is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more of all the 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 polymer having a structure represented by the general formula (1) and a structure represented by the general formula (2) is preferably a resin such as polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, or epoxy resin. It may contain 2 or more of them. By containing such a polymer, heat resistance can be further improved, and coloring due to heating 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, polyimide, polyimidesiloxane, polyethersulfone, and polybenzoxazole are more preferable. Further, polyimide, polyiminosiloxane, and polybenzoxazole are more preferable from the viewpoint of improving solvent resistance. Particularly preferred are polyimides and polyimidesiloxanes. Since polyimide and polyimide siloxane absorb ultraviolet light, ultraviolet light is prevented from reaching the insulating layer and the conductive layer, yellowing of the insulating layer and the conductive layer due to ultraviolet light can be reduced, a decrease in total light transmittance due to yellowing can be reduced, and light resistance can be remarkably improved.

The polyimide preferably has a structural unit represented by the following general formula (10).

[ chemical formula 5]

In the above general formula (10), R ₃ Represents an organic group having a valence of 4 to 10, R ₄ Represents an organic group having a valence of 2 to 8, R ₅ And R ₆ Each represents a 1-valent organic group, and may be the same or different. R is ₃ And/or R ₄ At least a part of (3) preferably includes a structure represented by the general formula (1) and a structure represented by the general formula (2). R is ₃ And/or R ₄ At least a part of (3) preferably further contains a structure represented by the general formula (4) and/or a structure represented by the structural formula (9). p and q each independently represent an integer of 0 to 6, and each represents a group having p R ₅ Having q of R ₆ 。R ₅ And/or R ₆ At least a part of (3) may include a structure represented by the general formula (1) and a structure represented by the general formula (2). R is ₅ And/or R ₆ May further include a structure represented by general formula (4) and/or a structure represented by structural formula (9).

In the general formula (10), R is preferably R from the viewpoint of further improving the heat resistance of the polyimide ₃ And R ₄ Is 50 mol% or more of an aromatic hydrocarbon group or a derivative thereof. More preferably R ₃ And R ₄ At least 80 mol% of (B) is an aromatic hydrocarbon group or a derivative thereof, and R is more preferably ₃ And R ₄ All of (A) are aromatic hydrocarbon groups or derivatives thereof.

The polyimide preferably has 5 to 100,000 structural units represented by the general formula (10) in one molecule of the polymer. By having 5 or more structural units represented by the general formula (10), the toughness of the substrate (S-1) can be improved. On the other hand, by having 100,000 or less structural units represented by the general formula (10), coatability can be maintained.

In the above general formula (10), R ₃ -(R ₅ ) _p Represents a residue of acid dianhydride. R ₃ Is an organic group having 4 to 10 valences, and among them, an organic group having 5 to 40 carbon atoms which contains an aromatic ring or a cyclic aliphatic group is preferable. R ₅ Preferably a phenolic hydroxyl group, a sulfonic acid group or a thiol group.

Examples of the acid dianhydride include an acid dianhydride having a structure represented by general formula (1), an acid dianhydride having a structure represented by general formula (2), and an acid dianhydride having a structure represented by general formula (3). More than 2 of them may be used.

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

Examples of the acid dianhydride having a structure represented by the general formula (2) include 3,3', 4' -diphenylethertetracarboxylic dianhydride (ODPA) and isomers thereof.

Examples of the acid dianhydride having a structure represented by the structural formula (3) include 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA), 4'- (hexafluoroisopropylidene) diphthalic anhydride, and 3,3' - (hexafluoroisopropylidene) diphthalic anhydride.

In the general formula (10), R ₄ -(R ₆ ) _q Represents the residue of a diamine. R ₄ Is an organic group having a valence of 2 to 8, and among them, preferably contains an aromatic ring or ringsAn organic group having 5 to 40 carbon atoms. R is ₆ Preferred examples thereof include a phenolic hydroxyl group, a sulfonic acid group and a thiol group, and these groups may be a single group or different groups may be present in combination.

Examples of the diamine include a diamine having a structure represented by general formula (1), a diamine having a structure represented by general formula (2), a diamine having a structure represented by general formula (3), a diamine having a structure represented by general formula (4), and a diamine having a structure represented by general formula (9). More than 2 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 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, bis [3- (3-aminophenoxy) phenyl ] sulfone, and isomers thereof.

Examples of the diamine having a structure represented by the general formula (2) include 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, and isomers thereof.

Examples of the diamine having a structure represented by the structural formula (3) include 2, 2-bis (4-aminophenyl) hexafluoropropane and the like.

Examples of the diamine having a structure represented by the general formula (4) 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. Of 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 the general formula (9) include 1,3, 5-tris (4-aminophenoxy) benzene and the like.

Examples of the method for producing polyimide include a method in which polyamic acid or 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 diester is obtained by reacting a tetracarboxylic dianhydride with an alcohol, and then reacted with an amine in the presence of a condensing agent; a method of obtaining a diester by reacting a tetracarboxylic dianhydride with an alcohol, then acylating-chlorinating the remaining dicarboxylic acid, and reacting with an amine; and so on.

The content of the polymer in the substrate (S-1) 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 substrate (S-1) may further contain a surfactant, a leveling agent, an adhesion improver, 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 substrate with a conductive layer, the thickness of the substrate (S-1) 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 suppressing yellowing and further improving the color tone, the substrate (S-1) preferably has a total light transmittance at a wavelength of 400nm of 50% or more, more preferably 60% or more. On the other hand, the substrate (S-1) preferably has a total light transmittance at a wavelength of 400nm of 85% or less, more preferably 80% or less, from the viewpoint of absorbing external light or the like and suppressing discoloration of the first insulating layer (OC-1) and the second insulating layer (OC-2) due to external light or the like. By applying a resin such as polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, or epoxy resin to the base material (S-1), absorption can be controlled and the above properties can be satisfied.

The substrate (S-1) can be molded, for example, from a resin composition containing a 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 conductive layer (A-1), second conductive layer (A-2))

The first conductive layer (a-1) (hereinafter, sometimes referred to as "conductive layer (a-1)") and the second conductive layer (hereinafter, sometimes referred to as "conductive layer (a-2)") preferably have a mesh structure formed of meshes having a line width of 0.1 to 9 μm. By having a mesh structure with a line width of 0.1 to 9 μm, both conductivity and non-visibility can be achieved. 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 non-visibility.

The thickness of the conductive layer (A-1) and the conductive layer (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 conductive layer (A-1) and the conductive layer (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 non-visibility.

The conductive layer (A-1) and/or the conductive layer (A-2) preferably contain conductive particles.

Examples of the conductive particles include metal particles containing a metal 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), or molybdenum (Mo). It may contain 2 or more of them. Among these, gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, and aluminum are more preferable, and silver particles are further preferable.

The conductive particles preferably have a coating layer on at least a part of the surface thereof. The presence of the coating layer on at least a part of the surface of the conductive particles can reduce the surface activity and suppress the reaction between the conductive particles or the reaction between the conductive particles and the organic component. In addition, in the case of using the photosensitive paste method, the wiring pattern can be processed with higher accuracy by suppressing scattering of exposure light by the conductive particles. On the other hand, the coating layer can be easily removed by heating at a high temperature of about 150 to 350 ℃, and sufficient conductivity can be exhibited. Preferably, the surfaces of the conductive particles are completely covered with the coating layer.

The coating layer more 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.

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

The average thickness of the coating layer is preferably 0.1 to 10nm. Within this range, the conductive particles are 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 average 1-order particle diameter of the conductive particles is preferably 10 to 60nm. The average 1-order particle diameter of the conductive particles can be calculated from the average particle diameter of 100 1-order particles randomly selected by using a scanning electron microscope. The particle diameter of each 1-time particle can be calculated by measuring the major axis and the minor axis of the 1-time particle and averaging the measured values.

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

The conductive layer (A-1) and/or the conductive layer (A-2) more preferably further contain an organic compound. Preferably, the organic compound is contained in an amount of 5 to 35 mass%. By containing the organic compound in an amount of 5 mass% or more, flexibility can be imparted to the conductive layer, and the bending resistance of the conductive layer can be improved. On the other hand, the conductive layer can have improved conductivity by containing 35 mass% or less of an organic compound.

As the organic compound, an alkali-soluble resin is preferable. As the alkali-soluble resin, a (meth) acrylic copolymer having a carboxyl group is more preferable. The (meth) acrylic copolymer is a copolymer of a (meth) acrylic monomer and another monomer. Examples of the (meth) acrylic monomer include methyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.

Examples of the other monomer include compounds having a carbon-carbon double bond, and examples thereof include aromatic vinyl compounds such as styrene and α -methylstyrene; amide-based unsaturated compounds such as (meth) acrylamide, and the like.

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

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 to 100,000. By setting the weight average molecular weight (Mw) to the above range, good coating characteristics are obtained, and solubility in a developer during pattern formation is also good. Herein, mw of the alkali-soluble resin means a polystyrene conversion value measured by Gel Permeation Chromatography (GPC).

The content of the alkali-soluble resin in the conductive layer (a-1) and/or the conductive layer (a-2) is preferably 5 to 30% by mass, respectively.

The conductive layer (A-1) and the conductive layer (A-2) may contain an organotin compound and/or a metal chelate compound. The conductive layer can further improve adhesion to the base material (S-1), the insulating layers (OC-1) and (OC-2) 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 provide 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 1 carbon atom bonded to a tin atom. Examples thereof include organic acid salts such as tin dilaurate; dibutyltin diacetate, dibutyltin dilaurate, dioctyltin maleate, dimethyltin dilaurate, dimethyltin maleate, allyltributyltin, allyltriphenyltin, diethyltin, and the like. It may contain 2 or more of them.

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 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 easiness of ligand desorption, 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) and magnesium bis (ethylacetoacetate); aluminum chelate compounds such as aluminum chelate compounds including ethyl aluminum acetylacetonate, aluminum tris (ethyl acetoacetate), alkyl aluminum diisopropyl acetoacetate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), and the like; titanium chelate compounds such as tetrakis (acetylacetonate) titanium; zirconium chelate compounds such as zirconium tetrakis (acetylacetonate) and zirconium tributoxymetastearate.

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

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

The conductive layer (A-1) and the conductive layer (A-2) can be formed using, for example, a conductive composition. As the conductive composition, a composition containing the conductive particles, an alkali-soluble resin, and a 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 required.

(first insulating layer (OC-1), second insulating layer (OC-2))

The conductive-layer-equipped substrate of the present invention has a second insulating layer (OC-2) (hereinafter, sometimes referred to as "insulating layer (OC-2)") between the conductive layer (a-1) and the conductive layer (a-2). The second insulating layer (OC-2) is used to provide insulation between the conductive layer (A-1) and the conductive layer (A-2). Further, a first insulating layer (OC-1) (hereinafter, sometimes referred to as "insulating layer (OC-1)") is provided on the upper surface of the conductive layer (A-1), that is, on the surface of the conductive layer (A-1) opposite to the surface thereof in contact with the insulating layer (OC-2). The insulating layer (OC-1) can prevent moisture in the atmosphere from reaching the conductive layer (A-1), thereby improving the migration resistance of the conductive layer (A-1).

The film thicknesses of the insulating layer (OC-1) and the insulating layer (OC-2) are preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of further improving the migration resistance. On the other hand, the film thickness of the insulating layer (OC-1) and the insulating layer (OC-2) is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less, from the viewpoint of further improving the transparency and the bending resistance.

The ratio ((OC-1)/(S-1)) of the film thickness of the insulating layer (OC-1) to the film thickness of the substrate (S-1) is preferably 0.05 to 0.5. By setting the film thickness ratio to 0.05 or more, the value b, which will be described later, can be easily adjusted, and variations in b can be suppressed. On the other hand, by setting the film thickness ratio to 0.5 or less, it is possible to suppress a decrease in the total light transmittance due to the insulating layer (OC-1) while further reducing the film thickness. Further, the decrease in bending resistance of the conductive base material due to becoming too rigid can be suppressed. The ratio of the film thickness is more preferably 0.3 or less. The film thickness can be measured using, for example, a stylus type height difference meter "SURFCOM (registered trademark)" 1400 (manufactured by tokyo co corporation). More specifically, the film thickness at random 3 positions was measured by a stylus type height difference meter (measurement length: 1mm, scanning speed: 0.3 mm/sec), and the average value was defined as the film thickness.

From the viewpoint of appearance, the variation of b is preferably within 1.5. More preferably within 1.0. The deviation b was evaluated by measuring 5 points in total, the center and 4 corners of the sample, and calculating the difference between the maximum value and the minimum value.

In the present invention, the insulating layer (OC-1) preferably contains a colorant in order to adjust b to a range described later. By containing the colorant, yellowing of the substrate with the conductive layer can be reduced, and the color tone can be further improved.

Examples of the colorant include pigments and dyes. Among them, pigments are preferable from the viewpoint of heat resistance and light resistance. From the viewpoint of adjusting b to the range described later, a blue colorant is preferable.

The colorant preferably contains a metal complex. By using the metal complex, yellowing of the substrate with the conductive layer can be further reduced by adding a trace amount. Examples of the metal complex include compounds in which a metal is coordinated to a phthalocyanine or a phthalocyanine having a substituent in at least a part thereof. Examples of the substituent include halogen such as chlorine, a sulfonic acid group, and an amino group. Examples of the coordinated metal include copper, zinc, nickel, cobalt, and aluminum. Two or more of these metal complexes may be contained. The metal complex is preferably a copper complex of phthalocyanine, which can suppress the reaction of the colorant with other organic components, and can further improve the color tone without discoloring at the time of high-temperature treatment in the process. More preferred are copper phthalocyanine sulfonic acid ammonium salts, copper phthalocyanine tertiary amine compounds, copper phthalocyanine sulfonic acid amide compounds. The coloring agent can be detected by MASS spectroscopy or the like of the insulating layer (OC-1).

Examples of the copper complexes of phthalocyanine include Pigment Blue 15, pigment Blue 15. Among them, copper phthalocyanine Blue pigments Pigment Blue 15 and Pigment Blue 15 having an epsilon-type and alpha-type structure are preferable from the viewpoint of improving light resistance, preventing discoloration even when exposed to sunlight, and maintaining good appearance.

The insulating layer (OC-1) may further contain a colorant having various hues, such as a red colorant, a yellow colorant, a green colorant, and the like, for the purpose of more finely adjusting hue.

Examples of the red colorant include anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, and the like. Examples of the color index (color index) include Pigment Red 48, pigment Red 57, pigment Red 122, pigment Red 168, pigment Red 170, pigment Red 177, pigment Red 188, pigment Red 202, pigment Red 206, pigment Red 207, pigment Red 209, pigment Red 221, pigment Red 242, pigment Violet 19, and Pigment Violet 42.

Examples of the yellow colorant include azo pigments, pyrazolone pigments, benzimidazolone pigments, quinoxaline pigments, azomethine pigments, and the like. Examples of the color index include Pigment Yellow 1, pigment Yellow 3, pigment Yellow 74, pigment Yellow 65, pigment Yellow 111, pigment Yellow 81, pigment Yellow 83, pigment Yellow 151, pigment Yellow 154, pigment Yellow 175, pigment Orange 13, and Pigment Orange 34.

Examples of the green colorant include phthalocyanine pigments and perylene pigments. Examples of the color index include Pigment Green 7, pigment Green 36, pigment Green 58, and Pigment Black 31.

The content of the colorant in the insulating layer (OC-1) is preferably 0.01 to 0.5 mass% of 100 mass% of the total solid content in the insulating layer (OC-1). By setting the content of the colorant to 0.01 mass% or more, the effect of the colorant can be sufficiently exerted, and the color tone of the base material with the conductive layer can be further improved. The content of the colorant is more preferably 0.05% by mass or more. Further, by setting the content of the colorant to 0.5% by mass or less, the absorption of the colorant can be suppressed and the total light transmittance can be improved. The content of the colorant is more preferably 0.4% by mass or less. The amount of the coloring agent can be quantified by means of TG-MASS.

The insulating layer (OC-1) and the insulating layer (OC-2) are preferably formed from a cured product of an insulating composition containing an alkali-soluble resin.

Examples of the alkali-soluble resin include the aforementioned (meth) acrylic copolymer and Cardo resin. Among them, from the viewpoint of increasing the crosslinking density and improving the light resistance, a (meth) acrylic copolymer is preferable, and a Cardo resin is preferable because the hydrophobicity can be increased and the migration resistance of the insulating layer can be further improved.

The Cardo resin is preferably a Cardo resin containing two or more structural units represented by the following chemical formula (11) and containing a polymerizable group and an alkali-soluble group.

[ chemical formula 6]

As the Cardo-based resin, commercially available products can be preferably used, and for example, "V-259ME" (trade name, manufactured by Nissan iron King chemical Co., ltd.) and the like can be suitably used.

The weight average molecular weight (Mw (A1)) of the (meth) acrylic copolymer and the weight average molecular weight (Mw (A2)) of the Cardo resin 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 in pattern formation. Here, the weight average molecular weight refers to a polystyrene conversion value 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 1.0 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 based on the desired film thickness and application, and is preferably 10 mass% or more and 70 mass% or less of 100 mass% of the total solid content.

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

The content of the hindered amine-based 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, if necessary. In the case of the insulating composition for forming the insulating layer (OC-1), the colorant described above is preferably contained. The colorant may be dispersed or dissolved in the insulating composition.

As shown in FIG. 2, the substrate with a conductive layer of the present invention may have an insulating layer (OC-0) between the substrate (S-1) and the second conductive layer (A-2). By forming the insulating layer (OC-0), the patterning properties of the second conductive layer (A-2) and the like can be improved.

As the insulating layer (OC-0), the above-mentioned insulating composition can be used, and an inorganic film can also be used. By using an inorganic film, the pattern processability of the second conductive layer (a-2) and the like after that can be further improved. Further, it is preferable to suppress migration of metal impurities, moisture, and the like from the substrate (S-1) to the second conductive layer (A-2) and to improve the reliability of the conductive layer.

Examples of the inorganic film include Si-based thin film, C-based thin film,Metal thin films, and the like. From the viewpoint of improving the subsequent patterning properties of the second conductive layer (a-2) and the like, an Si-based thin film is more preferable. Examples of the Si-based thin film include Si and SiO _x 、SiC _x 、SiN _x 、SiO _x Cy、SiO _x N _y 、SiO _x F _y And the like. The thickness of the inorganic film is preferably 5 to 20nm. By setting the thickness to 5nm or more, the movement of metal impurities, moisture, and the like from the base material (S-1) to the second conductive layer (A-2) can be sufficiently suppressed. By setting the thickness to 20nm or less, the bending resistance of the substrate with a conductive layer of the present invention is not impaired.

In the first aspect of the substrate with a conductive layer of the present invention, all of the following formulas (1) to (3) are satisfied when b is a value b (S-1) of the substrate (S-1), b is a value b (OC-1) of the first insulating layer (OC-1), and b is a value b (T) of the entire substrate with a conductive layer, in accordance with the L a b color system specified by the international commission on illumination in 1976.

-4.3≤b*(T)≤2.0 (1)

0.8≤b*(S-1)≤5.0 (2)

1.5≤b*(T)-b*(OC-1)≤5.5 (3)

In a second aspect, when the b value of the first insulating layer (OC-1) is denoted by b (OC-1) and the b value of the second insulating layer (OC-2) is denoted by b (OC-2) according to the color system L a b specified in the international commission on illumination 1976, the substrate with a conductive layer of the present invention satisfies the following formulas (4) and (5).

0.8≤b*(S-1)-b*(OC-1)≤8.0 (4)

0.5≤b*(OC-2)-b*(OC-1)≤7.0 (5)

As is well known, the values of L, a, b in the L, a, b color system represent lightness, a, and b values, hue and chroma. Specifically, the value a indicates a red hue if it is a positive value, and indicates a green hue if it is a negative value. The b value indicates a yellow hue if it is a positive value, and indicates a blue hue if it is a negative value. In both the a-value and the b-value, the larger the absolute value is, the more chromatic color of the color becomes, the more vivid the color becomes, and the smaller the absolute value is, the less chromatic color becomes. Since the measured value of b is neutral in the vicinity of 0, it is preferable that the color tone of the color image be visually recognized as colorless.

The formula (1) represents the color tone of the entire substrate with a conductive layer, and it is-4.3. Ltoreq. B.ltoreq.T.ltoreq.2.0. Blue discoloration is suppressed by setting b (T) to-4.3 or more, and yellow discoloration is suppressed by setting b (T) to 2.0 or less, and the entire color becomes colorless.

The formula (2) represents the color tone of the substrate (S-1), and it is 0.8. Ltoreq. B (S-1). Ltoreq.5.0. The bluing of the substrate (S-1) can be suppressed by setting b (S-1) to 0.8 or more, and the yellowing of the substrate (S-1) can be suppressed by setting b (S-1) to 5.0 or less. Therefore, the color tone of the entire substrate with the conductive layer can be easily adjusted.

The expression (3) represents the relationship between the color tone of the entire substrate with a conductive layer and the color tone of the insulating layer (OC-1), and it is 1.5. Ltoreq. B (T) -b (OC-1). Ltoreq.5. The base material (S-1) tends to be colored yellow easily by heating at the time of lamination. In the first aspect of the present invention, the tone of the entire substrate with a conductive layer can be made nearly colorless by setting b of the substrate (S-1) that is easily colored yellow to the range of formula (2) and by making b of the insulating layer smaller (nearly negative). Here, as a method for reducing the b value of the insulating layer, there are a method for reducing the b value of the insulating layer (OC-1) and a method for reducing the b value of the insulating layer (OC-2). However, according to the studies of the inventors of the present application, it was found that when a blue colorant is contained in the insulating layer (OC-2) in order to reduce the b value of the insulating layer (OC-2), the blue colorant interacts with Ag ions, and when a voltage is applied between the conductive layer (a-1) and the conductive layer (a-2), the movement of Ag ions is accelerated, and the migration resistance is lowered. Therefore, in the first aspect of the present invention, the relation of the formula (3) is found focusing on reducing b-x value of the insulating layer (OC-1) instead of b-x value of the insulating layer (OC-2). By setting b (T) -b (OC-1) to 1.5 or more, the color tone of only the insulating layer (OC-1) in the entire base material with a conductive layer is approximated to bluish, and the entire base material is visually recognized as colorless. On the other hand, by setting b (T) -b (OC-1) to 5.5 or less, the color tone of the entire substrate with the conductive layer is close to the color tone of the insulating layer (OC-1), and the color tone of the insulating layer (OC-1) is suppressed from being excessively bluish to increase absorption.

Examples of the method for adjusting the color tone of the entire substrate with a conductive layer to the range of formulas (1) to (3) include a method in which an appropriate amount of colorant is added to the insulating layer (OC-1) to adjust the color tone of the insulating layer (OC-1).

The expression (4) represents the relationship between the color tone of the substrate (S-1) and the color tone of the insulating layer (OC-1), and the relationship is 0.8. Ltoreq. B (S-1) -b (OC-1). Ltoreq.8.0. By setting b (S-1) -b (OC-1) to 0.8 or more, yellowing of the entire substrate with a conductive layer can be suppressed. b (S-1) -b (OC-1) is more preferably 1.0 or more. By setting b (S-1) -b (OC-1) to 8.0 or less, the total light transmittance of the entire substrate with a conductive layer can be increased. b (S-1) -b (OC-1) is more preferably 5.0 or less.

The expression (5) represents the relationship between the color tone of the insulating layer (OC-1) and the color tone of the insulating layer (OC-2), and is 0.5. Ltoreq. B (OC-2) -b (OC-1). Ltoreq.7.0. As described above, according to the study of the inventors of the present application, it was found that when a blue colorant is contained in the insulating layer (OC-2) in order to reduce the b value of the insulating layer (OC-2), the migration resistance is lowered by heating at the time of forming the conductive layer (a-1) in the subsequent step. Therefore, in the second aspect of the present invention, the relationship of the formula (5) is found focusing on only reducing the b-x value of the insulating layer (OC-1). By setting b (OC-2) -b (OC-1) to 0.5 or more, yellowing of the entire substrate with a conductive layer can be suppressed, and migration resistance can be improved. b (OC-2) -b (OC-1) is more preferably 0.8 or more. On the other hand, by setting b (OC-2) -b (OC-1) to 7.0 or less, the total light transmittance of the entire substrate with a conductive layer can be improved. b (OC-2) -b (OC-1) is more preferably 5.0 or less.

Note that the reflection chromaticity b is a characteristic value defined by the colorimetric system. The L.a.b.color system is a color characterization method defined by the International Commission on illumination (CIE) in 1976, and the L.a., a.b.values in the present invention can be determined by a reflection-based measurement method in accordance with the method defined in JIS-Z8729: 1994. More specifically, the reflectance of total reflected light of each layer was measured by a spectrophotometer (CM-2600d, manufactured by KONICA MINOLTA, inc.), and the reflectance chromaticity b was measured to calculate the reflectance.

Next, a method for manufacturing the conductive layer-provided substrate of the present invention will be described. The method for producing a substrate with a conductive layer according to the present invention preferably includes a step of sequentially forming at least the substrate (S-1), the conductive layer (A-2), the insulating layer (OC-2), the conductive layer (A-1), and the insulating layer (OC-1) on the temporary support having a peeling function. By removing the temporary support, a substrate with a conductive layer can be obtained. The base material (S-1) preferably has a peeling function. The term "having a peeling function" means that the temporary support and the substrate with the conductive layer can be peeled off at the interface between the temporary support and the substrate (S-1).

Examples of the temporary support include a silicon wafer, a ceramic substrate, and an organic substrate. Examples of the ceramic substrate include a glass substrate made of glass such as soda-lime glass, alkali-free glass, borosilicate glass, and quartz glass; alumina substrates, aluminum nitride substrates, silicon carbide substrates, and the like. Soda-lime glass is easily available at low cost and is often used, and since alkali component is eluted from soda-lime glass, a trouble such as poor conductivity may occur, and for the purpose of suppressing elution of alkali component, it is preferable to form SiO on the surface ₂ And the like. Examples of the organic substrate include an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a polyimide film, and a polyester film. In the subsequent step described later, when a method of peeling the interface between the temporary support and the substrate (S-1) by laser irradiation is used, the temporary support is preferably used from the viewpoint of reducing the irradiation time of the laser light because the laser light transmittance of the temporary support is high.

First, a substrate is formed on a temporary support (S-1). The method for forming the base material (S-1) preferably includes: a coating step of coating the temporary support with the resin composition; a pre-baking step of drying the coated resin composition; and a curing step of curing the resin.

Examples of the method of applying the resin 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, drying under reduced pressure, 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 according to the composition of the resin composition and the film thickness of the coating film to be dried. The heating temperature is preferably 50 to 150 ℃ and the heating time is preferably 10 seconds to 30 minutes.

The atmosphere, temperature and time of the curing step may be appropriately set according to the composition of the resin composition and the film thickness of the coating film to be dried, and the curing is preferably performed in the air. 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 lower, more preferably 300 ℃ or lower, and still more preferably 245 ℃ or lower. 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 base material (S-1) formed in the above manner may be further subjected to surface treatment. By performing the surface treatment, the surface state of the base material (S-1) can be changed, and the deterioration of pattern processability caused by development residue in the subsequent forming step of the second conductive layer (A-2) 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.

Further, an insulating layer (OC-0) may be further formed on the formed substrate (S-1). By forming the insulating layer (OC-0), the pattern processability of the second conductive layer (A-2) and the like after the formation can be further improved even when the base material (S-1) is not subjected to the surface treatment. The forming method preferably has: a coating step of coating the insulating composition on a substrate (S-1); a pre-baking step of drying the coated insulating composition; and a curing step of curing the resin composition.

Next, a second conductive layer (A-2) is formed on the resulting substrate (S-1) or insulating layer (OC-0). The method for forming the second conductive layer (a-2) 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.

Examples of the method of applying the conductive composition to the surface of the substrate include a method exemplified as a method of applying a resin composition.

Examples of the method of drying in the pre-baking step and the curing step include a method exemplified as a method of drying a resin composition.

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 to 150 ℃ and the heating time is preferably 10 seconds to 30 minutes.

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

Examples of the developer used in the developing step include an alkaline aqueous solution obtained by dissolving in water the following alkaline substances:

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;

alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, and diethylaminoethanol;

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 and morpholine;

and so on.

To these, a water-soluble organic solvent such as ethanol, γ -butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone or the like may be added as appropriate.

In order to obtain a more favorable conductive pattern, it is also preferable to further add a surfactant such as a nonionic surfactant to the alkaline developer in an amount of 0.01 to 1% by mass based on 100% by mass of 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 deg.C, more preferably 200 to 300 deg.C. The heating time is preferably 5 minutes to 120 minutes.

Further, a second insulating layer (OC-2) is formed on the formed second conductive layer (A-2). The method of forming the second insulating layer (OC-2) preferably includes: a coating step of coating the conductive layer (A-2) with an insulating composition; 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 in the conductive layer (a-2).

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

A first insulating layer (OC-1) may be further formed on the first conductive layer (A-1). By forming the first insulating layer (OC-1), moisture in the atmosphere can be prevented from reaching the conductive layer (A-1), and the moisture and heat resistance can be further improved.

In this case, the first insulating layer (OC-1) on the top of the lead-out portion of the electrode is preferably removed. 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 first insulating layer (OC-1). With such a configuration, the insulation property and the moist heat resistance can be further improved. The first insulating layer (OC-1) can be formed by the same method as the second insulating layer (OC-2).

In this way, a substrate with a conductive layer on the temporary support was obtained, in which the substrate with a conductive layer was formed on the temporary support.

Further, the surface of the substrate with the conductive layer on the side opposite to the temporary support is bonded to the opposing member via a transparent adhesive layer. The substrate (S-1) and the temporary support are peeled off from each other, and the substrate with the conductive layer having the opposing member can be obtained after the temporary support is removed. Among them, the counter member is preferably a glass substrate or a film substrate, and may be formed on a glass substrate or a film substrate. Specific examples of such opposing members include a cover glass, a cover film, a polarizing film, a color filter substrate, a display substrate, and the like.

Examples of the method for peeling the substrate (S-1) from the temporary support include a method of peeling the substrate (S-1) by irradiating the substrate (S-1) with a laser beam from the back surface of the temporary support, a method of peeling the temporary support provided with the substrate having the conductive layer 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 substrate (S-1) from the upper surface and mechanically peeling the substrate from the cut end face, and the like.

In another embodiment, the touch panel can be completed by performing the above-described peeling step on the conductive-layer-attached substrate with the temporary support to peel the conductive-layer-attached substrate from the temporary support, and then bonding the surface opposite to the temporary support to the counter member via the transparent adhesive layer. 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 to the first insulating layer (OC-1) of the conductive layer-equipped substrate with a temporary support. From the viewpoint of bonding accuracy, it is preferable to perform a peeling step after bonding the substrate with the conductive layer with the temporary support to a counter member such as a glass substrate.

As described above, the substrate with a conductive layer of the present invention is preferably produced by forming the substrate on a temporary support having excellent dimensional accuracy, and then peeling off and removing the temporary support. The manufacturing method can be applied to a processing method with excellent dimensional accuracy. The conductive layer-equipped substrate of the present invention contains the polymer having the above-described specific structure in the substrate (S-1), whereby the residue of the conductive composition can be suppressed, and the substrate is excellent in color tone and moist heat resistance. According to the present invention, a substrate with a conductive layer and a touch panel suitable for forming a fine pattern and flexibility can be provided.

Examples of applications of the substrate with a conductive layer of the present invention include a touch panel, a wiring of a curved display such as a micro LED, and various flexible sensors such as an RFID. Among them, the present invention is preferably used for a touch panel.

The touch panel of the present invention includes the base material with the conductive layer.

In the touch panel of the present invention, a touch module can be manufactured by mounting a flexible printed circuit board (FPC) on the base material with a conductive layer via an Anisotropic Conductive Film (ACF) and bonding the FPC to, for example, a cover glass via an optical adhesive sheet (OCA).

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' -diphenylethertetracarboxylic dianhydride (compound comprising a structure represented by the general formula (2)).

(diamine)

DDS: bis (3-aminophenyl) sulfone (compound comprising a structure represented by the general formula (1))

HFHA:2, 2-bis [3- (3-aminobenzamide) -4-hydroxyphenyl ] hexafluoropropane (compound containing a structure represented by structural formula (3))

TFMB:2,2' -bis (trifluoromethyl) benzidine (a compound comprising a structure represented by general formula (4)).

(triamine)

TAPOB:1,3, 5-tris (4-aminophenoxy) benzene (compound containing a structure represented by general formula (9)).

(solvent)

GBL: gamma-butyrolactone

PGMEA: propylene glycol monomethyl ether

And (3) DPM: dipropylene glycol monomethyl ether.

(alkali-soluble resin)

Alkali-soluble resin (a): the polymer was obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a (meth) acrylic copolymer containing 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 having an average thickness of 1nm and an average 1-order particle diameter of 40nm (manufactured by Nisshin Engineering Co., ltd.) as the surface carbon coating layer

A-2: silver particles having an average 1-order particle diameter of 0.7 μm (manufactured by Mitsui metals Co., ltd.).

(coloring agent)

color-1: copper phthalocyanine compound "Pigment Blue 15" (manufactured by DATAIJING CHEMICAL CO., LTD.

color-2: copper phthalocyanine compound "Pigment Blue 15" (manufactured by DATAIJING CHEMICAL CO., LTD.

color-3: sodium aluminum sulfosilicate (manufactured by Holiday Co., ltd.).

Production example 1: (Synthesis of polyimide solution-1 and polyimide solution-2)

(polyimide solution-1)

100 parts by mole of ODPA was dissolved in GBL under a stream of dry nitrogen gas to prepare a solution having a concentration of 10% by mass. 50 parts by mole of DDS and 48 parts by mole of TFMB as diamines and 2 parts by mole of TAPOB as triamines were added thereto, and the mixture was reacted at 20 ℃ for 1 hour and then at 50 ℃ for 2 hours. The concentration of the polyimide solution-1 after the completion of the reaction is 20 to 25 mass%.

(polyimide solution-2)

100 parts by mole of ODPA was dissolved in GBL under a dry nitrogen stream to prepare a solution having a concentration of 10% by mass. To this mixture, 45 parts by mole of DDS, 45 parts by mole of TFMB, 8 parts by mole of HFHA as diamine and 2 parts by mole of TAPOB as triamine were added, followed by reaction at 20 ℃ for 1 hour and then at 50 ℃ for 2 hours. The concentration of the polyimide solution-2 after the completion of the reaction is 20 to 25 mass%.

Production example 2: preparation of transparent compositions (s-1, s-2)

Into a clean bottle were added 1 100g of the polyimide solution prepared in production example 1 and 0.03g of a surfactant (F-477, manufactured by DIC Co., ltd.), and the mixture was stirred for 1 hour to obtain a transparent composition s-1. The same procedure was carried out using the polyimide solution-1 instead of the polyimide solution-2 to obtain a transparent composition s-2.

Production example 3: preparation of electroconductive compositions (a-1) and (a-2)

The conductive particles A-1 80g, 4.06g of a surfactant ("DISPERBYK (registered trademark)" 21116 (trade name, manufactured by DIC)), 98.07g of PGMEA, and 98.07g of DPM were mixed together, and mixed at 1200rpm for 30 minutes using a homogenizer. Thereafter, 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%.

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

The silver dispersion liquid 1 and the organic I liquid were mixed to obtain a conductive composition (a-1). In addition, using conductive particles A-2 instead of conductive particles A-1, get conductive composition (a-2).

Production example 4: preparation of insulating compositions (oc-0 to oc-11)

50.0g of Cardo resin (V-259 ME, manufactured by Nippon Tekken chemical Co., ltd.), 28.0g of monomer (PE-3A, manufactured by Kyoeisha chemical Co., ltd.), 20.0g of epoxy compound (PG-100, manufactured by Osaka Gas Chemicals Co., ltd.), and 0.2g of initiator (OXE-01, manufactured by BASF Co., ltd.) were added to the flask, and the mixture was stirred for 1 hour to obtain an insulating oc composition-0. Next, the colorants described in Table 1 were added to oc-0 to obtain oc-1 to oc-10, respectively. The Cardo-based resin was replaced with the alkali-soluble resin (A) to give oc-11. Then, 0.15% of a coloring agent was added to oc-0 to obtain oc-12. The "addition amount (% by mass)" is a mass% of an addition amount of the colorant with respect to 100% by mass of the total solid content in the insulating composition. The color tone b at each film thickness of 1.5 μm is shown in table 1.

[ Table 1]

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

(1) Evaluation of color tone (b;)

In each of the examples and comparative examples, a spectrophotometer (CM-2600d, manufactured by KONICA MINOLTA, inc.) was used for each of the substrate (S-1), the first insulating layer (OC-1), the second insulating layer (OC-2), and the substrate with a conductive layer, and the measurement was performed using a glass substrate as a blank, and the results were measured in accordance with JIS-Z8729:1994, JIS-Z8781-4:2013 the reflectance of the total reflected light of each sample was measured from the glass substrate side, and the color characteristics b in CIE (L, a, b) color space were measured from 5 points at the center and 4 angles in total, and the average value thereof was evaluated as the color tone. The color tone of the substrate with the conductive layer was evaluated according to the following criteria. The product was judged to be acceptable if it was 2 or more.

5：-1.0≤b*(T)≤1.0

4: -2.0. Ltoreq. B (T) < -1.0 or 1.0. Ltoreq. B (T) < 1.5

3: -3.0 < b (T) < 2.0 or 1.5 < b (T) < 1.8

2: -4.3. Ltoreq. B (T) < -3.0 or 1.8. Ltoreq. B (T) ≦ 2.0

1: b (T) < -4.3 or 2.0 < b (T).

Note that the hue deviation is defined as the difference between the maximum value and the minimum value of b (hereinafter, referred to as b (MAX) -b (MIN)), and evaluated on the following basis. A pass rating of 2 or more was determined. As the light source, a D65 light source was used.

5：b*(MAX)-b*(MIN)≤1.0

4：1.0＜b*(MAX)-b*(MIN)≤1.5

3：1.5＜b*(MAX)-b*(MIN)≤2.0

2：2.0＜b*(MAX)-b*(MIN)≤2.5

1：2.5＜b*(MAX)-b*(MIN)。

(2) Evaluation of Total light transmittance

The total light transmittance at a wavelength of 400nm of the substrate (S-1) and the total light transmittance at a wavelength of 450nm of the substrate with the conductive layer were measured using an ultraviolet-visible spectrophotometer ("MultiSpec-1500 (product name, manufactured by Shimadzu corporation)") with respect to the substrate (S-1) and the substrates with the conductive layer prepared in the examples and comparative examples. The substrate with a conductive layer was evaluated for total light transmittance according to the following evaluation criteria. A pass rating of 2 or more was determined.

5: over 90 percent

4: more than 80 percent and less than 90 percent

3: at least 70% and less than 80% at least

2: more than 50 percent and less than 70 percent

1: less than 50%.

(3) Evaluation of bending resistance

The conductive layer-equipped base material produced in each of examples and comparative examples was cut to a width of 1cm from the upper surface, peeled from the glass substrate by the cut end face, subjected to a 180-degree bending test using metal rods having diameters of 2cm, 1cm, 0.5cm, and 0.3cm, respectively, and then observed for the presence or absence of crack generation using an optical microscope. The number of tests was set to 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 0.3cm diameter

4: no crack was generated when the diameter was 0.5cm, and crack was generated when the diameter was 0.3cm

3: no cracks occurred at a diameter of 1cm, and cracks occurred at a diameter of 0.5cm

2: no cracks occurred when the diameter was 2cm, and cracks occurred when the diameter was 1cm

1: cracks occurred with a diameter of 2 cm.

(4) Evaluation of migration resistance

The moist heat resistance of the conductive layer-equipped substrates prepared in the examples and comparative examples was evaluated by the following method. For the measurement, the insulation deterioration characteristic evaluation system "ETAC SIR13" (trade name, manufactured by nanchu chemical industries, ltd.) was used. Electrodes were attached to the terminal portions of the conductive layer (A-1) and the conductive layer (A-2), respectively, and the laminated substrate was placed in a high-temperature and high-humidity chamber set at 85% RH at 85 ℃. After 5 minutes had elapsed from the time when the in-cell environment had stabilized, a voltage was applied between the electrodes of the conductive layer (A-1) and the conductive layer (A-2), and the change in insulation resistance with time was measured. A voltage of 10V was applied to the conductive layer (A-1) as a positive electrode and the conductive 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 is 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.

(5) Evaluation of light resistance

For the purpose of management of each entityThe laminated substrates prepared in examples and comparative examples were evaluated for light resistance by the following method. An irradiation amount at 340nm was 0.60W/m in an environment of 45 ℃ using a light resistance tester ("Q-SUN Xenon Test Chamber Model Xe-1 (trade name, manufactured by Q-Lab Corporation)") ² After the irradiation with light was continued for 24 hours, the amount of change in b (hereinafter, referred to as Δ b) was evaluated according to the following evaluation criteria.

5：Δb*≤2.0

4：2.0＜Δb*≤4.0

3：4.0＜Δb*≤6.0

2：6.0＜Δb*≤8.0

1：8.0＜Δb*。

(example 1)

< formation of substrate (S-1) >

The transparent composition (S-1) was spin-coated on a glass substrate having a length of 210mm × a width of 297mm as a temporary support at 600rpm for 10 seconds using a spin coater "1H-360S (trade name, manufactured by Mikasa)", and then pre-baked at 100 ℃ for 2 minutes using a hot plate "SCW-636 (trade name, manufactured by Dainippon Screen Manufacturing)", to prepare a pre-baked film. The prepared substrate with the pre-baked film was cured in air at 240 ℃ for 50 minutes using an oven "IHPS-222 (trade name, manufactured by ESPEC Corporation)", to form a base material (S-1). The film thickness measured by using a stylus level difference meter was 10 μm. When the color tone and the total light transmittance of the substrate (S-1) were measured, b was 1.0, and the total light transmittance at 400nm was 75%.

< formation of second conductive layer (A-2) >

After the conductive composition (a-1) was spin-coated on the glass substrate on which the base material (S-1) was formed using a spin coater ("trade name" manufactured by Mikasa corporation) at 300rpm, 10 seconds, 500rpm, and 2 seconds, the substrate was prebaked at 100 ℃ for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Manufacturing corporation) to prepare a prebaked 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 220 ℃ for 30 minutes using an oven, to form a second conductive layer (a-2). The line width of the formed second conductive layer (A-2) was averaged by 5-point measurement using a digital microscope ("VHX-5000 (trade name, manufactured by Keyence Corporation)"), and as a result, the line width was 3.8. Mu.m. The film thickness measured by using a stylus level difference meter was 0.5 μm.

< formation of second insulating layer (OC-2) >

The insulating composition shown in table 2 was spin-coated on the glass substrate on which the second conductive layer (a-2) was formed using a spin coater at 650rpm for 5 seconds, and then pre-baked for 2 minutes at 100 ℃ using a hot plate, thereby producing a pre-baked film. The pre-baked film was exposed to light through a desired mask using a parallel light type mask aligner and an ultra-high pressure mercury lamp as a light source. 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 220 ℃ for 50 minutes using an oven to form a second insulating layer (OC-2).

< first conductive layer (A-1) >

The first conductive layer (a-1) was formed on the insulating layer using the conductive composition (a-1) in the same manner as in the formation of the "second conductive layer (a-2)". Further, the line width was measured in the same manner as in the second conductive layer (A-2), and the line width was 4.1. Mu.m. The film thickness was measured and found to be 0.5. Mu.m.

< formation of first insulating layer (OC-1) >

The insulating composition shown in Table 2 was used to form a first insulating layer (OC-1) on the first conductive layer (A-1) in the same manner as in the formation of the second insulating layer (OC-2), thereby producing a substrate with a conductive layer. The results of the evaluation by the above-described method are shown in table 2. The degree of yellowing was slightly increased, and b × (T) was evaluated as "3", but was a range that could be used without problems. The color tone deviation, bending resistance, migration resistance and light resistance of "5", is good.

(examples 2 to 5)

The same operation as in example 1 was performed, except that the insulating composition used in the first insulating layer (OC-1) was changed as described in table 2. Since the amount of coloring added is increased, the hue approaches neutrality.

(example 6)

The same operation as in example 1 was performed, except that the insulating composition used in the first insulating layer (OC-1) was changed as described in table 2. When the amount of the coloring added was further increased, the blue color was enhanced, the color tone evaluation was "2", and the total light transmittance was decreased, and the evaluation was "3", but the range was usable without any problem.

(example 7)

The same operation as in example 1 was performed, except that the insulating composition used for the first insulating layer (OC-1) was changed as described in table 2.

(example 8)

The same operation as in example 1 was performed, except that the insulating composition used for the first insulating layer (OC-1) was changed as described in table 3. The evaluation of light fastness was "3" because the light fastness of the colorant was lowered, but the evaluation was within a range that could be used without any problem.

(example 9)

The same operation as in example 6 was carried out, except that the coating conditions for the substrate (S-1) were changed and the film thickness was changed as described in table 3. The variation of b becomes large, and the evaluation becomes "4". Further, the total light transmittance decreased in accordance with the portion where the thickness of the substrate (S-1) was increased, and the evaluation was changed to "2", but the range was usable without any problem.

(example 10)

The same operation as in example 9 was carried out, except that the coating conditions for the substrate (S-1) were changed and the film thickness was changed as described in table 3. The variation of b becomes larger, and the evaluation becomes "3", but the range is usable without any problem.

(example 11)

The same operation as in example 4 was performed, except that the film thickness of the first insulating layer (OC-1) was changed as described in table 3. The first insulating layer (OC-1) becomes too rigid and the bending resistance decreases, and the evaluation value becomes "4", but the range is usable without any problem.

(example 12)

The same operation as in example 11 was performed, except that the film thickness of the first insulating layer (OC-1) was changed as described in table 3. The first insulating layer (OC-1) further becomes too rigid and the bending resistance decreases, and the evaluation value becomes "3", but it is within a range that can be used without problems.

(example 13)

The same operation as in example 7 was carried out, except that the transparent composition (s-2) was used in place of the transparent composition (s-1). When the color tone and the total light transmittance of the substrate (S-1) were measured, b was 0.8, and the total light transmittance at 400nm was 77%. The substrate (S-1) formed using the transparent composition (S-2) had good transparency and b was low, and the total light transmittance of the substrate with a conductive layer was evaluated as "5".

(example 14)

The same operation as in example 5 was carried out, except that PET (Heat-resistant PET film, "Lumiror" manufactured by Toray corporation, 50 μm in thickness) was used instead of the transparent composition (s-1). PET has a high total light transmittance at 400nm of 82%, and when light resistance test light is passed through it, the insulating layer is colored, and the light resistance is evaluated as "3". The water permeability is high and the migration resistance is "2", but the range is usable without any problem.

(example 15)

The same operation as in example 8 was performed, except that the insulating compositions used for the first insulating layer (OC-1) and the second insulating layer (OC-2) were changed as shown in table 2. Since the (meth) acrylic copolymer of the alkali-soluble resin (a) has low absorbance and good light resistance, the light resistance was evaluated as "5" and was good.

(example 16)

The same operation as in example 4 was carried out, except that the conductive composition (a-2) was used instead of the conductive composition (a-1). The second conductive layer (A-2) was formed to have a line width of 8.8 μm and a film thickness of 1.2. Mu.m, and the first conductive layer (A-1) had a line width of 8.4 μm and a film thickness of 1.2. Mu.m. The evaluation of the total light transmittance was "2" due to the large line width, and the evaluation of the warpage was "4" due to the large film thickness, but the evaluation was within a range that can be used without any problem.

Comparative example 1

The same operation as in example 1 was performed, except that the insulating composition used for the first insulating layer (OC-1) was changed as described in table 4. Since b of the first insulating layer (OC-1) largely becomes 0.5, the evaluation of the color tone becomes "1", which is an unusable level.

Comparative example 2

The same operation as in example 1 was performed, except that the insulating composition used for the first insulating layer (OC-1) was changed as described in table 4. Since b of the first insulating layer (OC-1) largely becomes 0.4, the evaluation of the color tone becomes "1", which is an unusable level.

Comparative example 3

The same operation as in example 1 was performed, except that the insulating composition used for the first insulating layer (OC-1) was changed as described in table 4. Since b of the first insulating layer (OC-1) largely becomes-7.2, the evaluation of the color tone becomes "1", which is an unusable level. In addition, since the amount of the colorant added is large, the variation of b becomes large, and the total light transmittance decreases.

Comparative example 4

The same operation as in example 5 was performed, except that the insulating composition used for the first insulating layer (OC-1) and the film thickness thereof, and the insulating composition used for the second insulating layer (OC-2) were changed as shown in table 4. The colorant in the second insulating layer had decreased migration resistance and was evaluated to become "1" at an unusable level.

Comparative example 5

The same operation as in example 10 was carried out, except that the film thicknesses of the base material (S-1) and the insulating layer (OC-1) were changed. The value of b (T) -b (OC-1) becomes large, and the total light transmittance of the substrate with a conductive layer decreases accordingly.

The evaluation results of the examples and comparative examples are shown in tables 2 to 4.

[ Table 2]

[ Table 3]

[ Table 4]

Industrial applicability

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

Description of the reference numerals

1. First insulating layer (OC-1)

2. First conductive layer (A-1)

3. Second insulating layer (OC-2)

4. Second conductive layer (A-2)

5. Insulating layer (OC-0)

6. Substrate (S-1)

Claims

1. A substrate with a conductive layer, which comprises a substrate (S-1) and, formed thereon, at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1), and a first insulating layer (OC-1) in this order, wherein all of the following formulas (1) to (3) are satisfied when the b value of the substrate (S-1) is b (S-1), the b value of the first insulating layer (OC-1) is b (OC-1), and the b value of the entire substrate with a conductive layer is b (T) in accordance with the La b system defined by the International Commission on of illumination in 1976,

-4.3≤b*(T)≤2.0 (1)

0.8≤b*(S-1)≤5.0 (2)

1.5≤b*(T)-b*(OC-1)≤5.5 (3)。

2. a substrate with a conductive layer, which comprises a substrate (S-1) and, successively disposed thereon, at least a second conductive layer (A-2), a second insulating layer (OC-2), a first conductive layer (A-1), and a first insulating layer (OC-1), wherein when b of the substrate (S-1) is b (S-1), b of the first insulating layer (OC-1) is b (OC-1), and b of the second insulating layer (OC-2) is b (OC-2) according to the color system of La.ab.prescribed by the International Commission on illumination in 1976, the following formulas (4) and (5) are satisfied,

0.8≤b*(S-1)-b*(OC-1)≤8.0 (4)

0.5≤b*(OC-2)-b*(OC-1)≤7.0 (5)。

3. the substrate with a conductive layer according to claim 1 or 2, wherein a ratio ((OC-1)/(S-1)) of a film thickness of the first insulating layer (OC-1) to a film thickness of the substrate (S-1) is 0.05 to 0.5.

4. The conductive-layer-provided substrate according to any one of claims 1 to 3, wherein the first insulating layer (OC-1) contains a colorant.

5. The substrate with a conductive layer according to claim 4, wherein the colorant contains a metal complex.

6. The substrate with a conductive layer according to claim 5, wherein the metal complex contains a phthalocyanine structure.

7. The conductive-layer-provided substrate according to any one of claims 4 to 6, wherein the content of the colorant in the first insulating layer (OC-1) is 0.01 to 0.5 mass%.

8. The substrate with an electrically conductive layer according to any one of claims 1 to 7, wherein the substrate (S-1) has a total light transmittance at a wavelength of 400nm of 50 to 85%.

9. The substrate with a conductive layer according to any one of claims 1 to 8, wherein the substrate (S-1) contains at least one polymer selected from the group consisting of polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, and epoxy resin.

10. The conductive-layer-provided substrate according to any one of claims 1 to 9, wherein the first conductive layer (a-1) and/or the second conductive layer (a-2) contains conductive particles having a coating layer.

11. A touch panel comprising the substrate with a conductive layer according to any one of claims 1 to 10.