TW201347973A - Conductive film laminate, touch panel, wiring board, electronic device, transparent two-sided adhesive sheet, transparent adhesive sheet - Google Patents

Abstract

This invention provides a wiring board able to suppress Ag ion migration from an Ag-containing metallic wire and increase the reliability of insulation between the metallic wires. A conductive film laminate is provided, including a transparent substrate, an Ag-containing conductive film disposed on the transparent substrate, and a transparent two-sided adhesive sheet adhered on the conductive film. The content of Ag per unit area of the conductive film is 50 μ g/mm<SP>2</SP> or less, and the transparent two-sided adhesive sheet includes a transparent resin and at least one compound selected from a group consisting of compounds represented by formulas (1) to (3).

Description

Conductive film laminate, touch panel, wiring substrate, electronic device, Transparent double-sided adhesive sheet, transparent adhesive sheet

The present invention relates to a conductive film laminate, a touch panel, a wiring substrate, an electronic device, a transparent double-sided adhesive sheet, and a transparent adhesive sheet.

A wiring board in which metal wiring is disposed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements. As the metal constituting the metal wiring, silver or copper having high conductivity is often used, and these metals are liable to cause ion migration, and this problem is particularly apparent in silver.

As a method of preventing ion migration of such a metal, a method of introducing a compound that adsorbs metal ions into a polymer layer has been proposed (Patent Document 1).

However, in recent years, display devices such as liquid crystal displays (LCDs) or input devices used in combination with display devices such as touch panels have been widely used in various fields. In the manufacture of these display devices or input devices, an adhesive sheet is used for the purpose of bonding optical members.

As a trend of image display mode, the touch panel type image display mode has continued to receive attention, and in particular, the electrostatic capacitance type touch panel has been popularized. The capacitive touch panel has a structure in which a plurality of members are laminated, and an adhesive sheet is used for the purpose of bonding the members. For example, a capacitive touch panel having a laminate of a cover glass, an adhesive sheet, a conductive film, and a glass substrate can be cited.

As an adhesive sheet, for example, Patent Document 2 discloses an inclusion regulation. In the transparent adhesive sheet of the copolymer of the monomer component, it is described that when a hydroxyalkyl (meth)acrylate ((E) component) is contained as a monomer component of the copolymer, whitening can be prevented (paragraph 0040).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-192850

[Patent Document 2] Japanese Patent Laid-Open No. 2011-074308

On the other hand, in recent years, miniaturization of metal integrated circuits and wafer components has progressed in miniaturization of metal wiring. Therefore, the width and interval of the metal wiring in the wiring substrate are further narrowed, and the disconnection of the circuit due to ion migration is more likely to occur. Under such circumstances, the insulation reliability between the metal wirings including silver in the wiring substrate is required to be further improved.

The inventors of the present invention have placed a polymer layer containing a compound containing a thiol compound or the like and a metal ion-forming organometallic salt on a metal wiring containing silver, and studied the insulation reliability thereof. As a result, it is true in the metal wiring It is recognized that the resistance of the wiring closet is significantly reduced, and the ion migration suppression effect does not satisfy the current level, and further improvement is required.

In particular, in recent years, with the miniaturization of electronic components, it is highly desirable to further increase the total thickness of the metal wiring and to make the area of the wiring region of the metal wiring narrower. Under such circumstances, in the wiring design using a process such as screen printing, it becomes difficult to follow the integration, and it is necessary to select a printing step such as nanoparticle ink, or such as sputtering, ion plating, or the like. Such a film forming step is vacuum-deposited. However, in such a step of obtaining a high degree of integration, it is difficult to obtain a homogeneous thick film, or it is required to be industrially unacceptable, and thus the wiring thickness is thinned. As a result, in an environment in which ion migration occurs, it is easy to cause a resistance increase or a disconnection state in the wiring, which is a problem due to a lack of electrical reliability due to a short circuit between wirings.

Moreover, in recent years, small semiconductor integrated circuits or wafer parts, etc. The type and the miniaturization of metal wiring are constantly developing. Therefore, the width and interval of the metal wiring in the wiring substrate are further narrowed (specifically, the minimum distance (interval) between the metal wirings is less than 50 μm), and the circuit is broken due to ion migration. Conduction between lines or circuits. In particular, silver or copper having high conductivity is often used as the metal constituting the metal wiring. However, these metals have a problem that ion migration is likely to occur, and this problem is remarkably exhibited particularly in silver. Under such circumstances, the insulation reliability between the metal wirings including silver in the wiring substrate is required to be further improved.

The inventors of the present invention disclose a copolymer comprising the component (E) disclosed in Patent Document 1. The transparent adhesive sheet was attached to a substrate with a metal wiring having a minimum distance of less than 50 μm from the metal wiring line, and the insulation reliability of the metal wiring was investigated. As a result, it was confirmed that the resistance between the wirings was significantly lowered in the metal wiring, and the ion migration suppression effect did not satisfy the level required recently, and further improvement was required.

It is presumed that the reason is that a hydrophilic component such as the component (E) is contained in the copolymer. Therefore, when a copolymer containing no such component (E) is used, whitening occurs and the transparency of the adhesive layer is lost.

That is, in the prior art, the ion migration suppressing function has a trade off relationship with the prevention of whitening in many cases.

The purpose of the first embodiment of the present invention is to provide in view of the above facts. A wiring board that suppresses ion migration from silver containing metal wiring of silver and improves insulation reliability between metal wirings.

Further, an object of the first embodiment of the present invention is to provide a conductive film laminate including a transparent double-sided adhesive sheet, which can suppress ion migration from silver containing a conductive film containing silver and improve insulation reliability between conductive films.

Moreover, the second embodiment of the present invention aims at the above facts. Further, a wiring board which suppresses ion migration of silver in a metal wiring line containing silver, exhibits excellent insulation reliability between metal wiring lines, and is excellent in whitening resistance of a transparent adhesive layer is provided.

Further, an object of the second embodiment of the present invention is to provide a transparent adhesive sheet used in the above wiring board.

The inventors of the present invention conducted intensive research on the problems of the prior art, and concluded The dispersibility of the metal ion-absorbing compound containing a thiol compound or the like disclosed in Patent Document 1 in the polymer layer is affected. More specifically, the compound which adsorbs a metal ion such as a thiol compound disclosed in Patent Document 1 has low dispersibility due to its structure. Therefore, even if the compound for adsorbing metal ions is to be introduced into the polymer layer (resin layer), it is difficult to uniformly disperse the compound in the polymer layer, and electron migration inhibiting metal ions (especially silver ions) cannot be obtained. Effect. Further, when a large amount of the compound for adsorbing metal ions is to be introduced into the polymer layer, the compound which adsorbs the metal ions precipitates in the polymer layer, causing deterioration of the polymer and causing deterioration in electrical reliability. In addition, there are problems in that the diffusion of metal ions is accelerated, wiring damage, and the like are caused.

Based on the above knowledge, the inventors of the present invention have found that the above-described first embodiment can be solved by using a conductive film (or metal wiring) having a specific functional group and having a pair of metals. A compound that reduces the ability of ions and contains a defined amount of silver.

In other words, the inventors of the present invention have found that the above-described first embodiment can solve the problem of the first embodiment.

(1) A conductive film laminate which is a conductive film laminate including a transparent substrate, a conductive film containing silver disposed on the transparent substrate, and a transparent double-sided adhesive sheet bonded to the conductive film, the conductive film The amount of silver contained per unit area is 50 μg/mm ² or less, and the transparent double-sided adhesive sheet contains a transparent resin and a group selected from the group consisting of compounds represented by the formulas (1) to (3) described later. At least one compound.

(2) The conductive film laminate according to (1), wherein the compound is selected from the group consisting of compounds represented by the following formulas (4) to (6).

(3) The conductive film laminate according to (1) or (2), wherein the compound is selected from the group consisting of compounds represented by the formulas (5) to (6) which will be described later.

(4) The conductive film laminate according to any one of (1) to (3), wherein a mass ratio (A/C) of the total mass A of the compound to the total mass C of the transparent resin is 0.0001 to 0.1.

(5) The conductive film laminate according to any one of (1) to (4) wherein the conductive film contains a metal nanowire comprising silver or a silver alloy.

The conductive film laminate according to any one of (1), wherein the transparent resin contains an acrylic adhesive.

(7) A touch panel comprising the conductive film laminate according to any one of (1) to (6).

(8) A wiring board comprising an insulating substrate, a metal wiring including silver disposed on the insulating substrate, and a silver ion diffusion suppressing layer disposed on the metal wiring, wherein the amount of silver per unit area of the metal wiring is 50 In the μg/mm ² or less, the silver ion diffusion suppression layer contains at least one compound selected from the group consisting of compounds represented by the formulas (1) to (3) described later, and an insulating resin.

(9) The wiring board according to the item (8), wherein the compound is selected from the group consisting of compounds represented by the following formulas (4) to (6).

(10) The wiring board according to the item (8), wherein the compound is selected from the group consisting of compounds represented by the formulas (5) to (6) which will be described later.

The wiring board according to any one of (8) to (10), wherein the mass ratio (A/B) of the total mass A of the compound to the total mass B of the transparent resin is 0.0001 to 0.1.

(12) An electronic device comprising the wiring substrate according to any one of (8) to (11).

(13) A transparent double-sided adhesive sheet comprising a transparent resin and at least one compound selected from the group consisting of compounds represented by the formulas (1), (2) and (3) described later.

Moreover, the inventors of the present invention conducted intensive research on the problems of the prior art. As a result, it has been found that the above-described second embodiment can be solved by using a transparent adhesive sheet containing a compound exhibiting a predetermined oxidation-reduction potential and changing the haze over time in a predetermined environmental test. For a certain range.

In other words, the inventors of the present invention have found that the object of the second embodiment described above can be solved by the following configuration.

(14) A wiring board comprising: an insulating substrate; a plurality of metal wirings including silver disposed on the insulating substrate; and a transparent adhesive layer disposed in direct contact with the metal wiring on the metal wiring, and a distance between the adjacent metal wirings The minimum value is less than 50 μm, and the transparent adhesive layer contains a compound having an oxidation-reduction potential of 0.40 V to 1.30 V, and an adhesive. The transparent adhesive layer is in the environmental test described later, and the time X is 12 hours or less. Transparent adhesive layer.

(15) The wiring board according to (14), wherein the compound contains a phenol compound.

The wiring board according to the item (14), wherein the compound contains a phenol compound having an oxidation-reduction potential of 0.50 V to 1.20 V.

The wiring board according to any one of the aspects of the present invention, wherein the compound comprises at least one selected from the group consisting of compounds represented by the formulas (1) to (3) described later. Kind.

The wiring board according to any one of (14), wherein the time X is less than 6 hours.

The wiring board according to any one of (14), wherein a minimum value of a distance between adjacent metal wirings is less than 40 μm.

(20) A transparent adhesive sheet comprising at least a transparent adhesive layer comprising a compound having an oxidation-reduction potential of 0.40 V to 1.30 V and an adhesive, wherein the transparent adhesive layer is displayed in an environmental test described later in time X. Transparent adhesive layer for less than 12 hours.

(21) The transparent adhesive sheet according to (20), wherein the compound contains a phenol compound.

(22) The transparent adhesive sheet according to (20) or (21), wherein the compound comprises a phenol compound having an oxidation-reduction potential of 0.50 V to 1.20 V.

(23) The transparent adhesive sheet according to any one of (20) to (22), wherein the compound comprises a compound selected from the compounds represented by the formulas (1) to (3) described later. At least one of the groups.

The transparent adhesive sheet according to any one of (20) to (23) wherein the time X is less than 6 hours.

(25) A touch panel comprising the wiring substrate according to any one of (14) to (19).

According to the first embodiment of the present invention, it is possible to provide a wiring board capable of suppressing ion migration from silver containing metal wiring of silver and improving insulation reliability between metal wirings.

Further, according to the first embodiment of the present invention, it is possible to provide a conductive film laminate including a transparent double-sided adhesive sheet, which can suppress ion migration from silver containing a conductive film containing silver and improve insulation reliability between conductive films.

In addition, according to the second embodiment of the present invention, it is possible to provide a wiring board which is excellent in whitening resistance between the metal wirings, and excellent in whitening resistance of the transparent adhesive layer.

Moreover, according to the second embodiment of the present invention, the transparent adhesive sheet used in the wiring board described above can be provided.

10, 100‧‧‧ wiring substrate

12, 12a, 12b‧‧‧ insulating substrate

14, 14a, 14b‧‧‧ metal wiring

16, 16b‧‧‧Insulated substrate with metal wiring

18‧‧‧ Silver ion diffusion suppression layer

19‧‧‧Transparent adhesive layer

20‧‧‧Insulation

30‧‧‧Flexible circuit

32, 302‧‧‧ Transparent substrate

34‧‧‧Transparent electrode layer

36‧‧‧Lead wiring

38‧‧‧Active area

40‧‧‧Inactive area

42, 306, 306a, 306b‧‧‧ Transparent double-sided adhesive sheet

200‧‧‧Wiring substrate with insulating layer

300, 400, 600‧‧‧ conductive film laminate

304, 304a, 304b‧‧‧ conductive film

306c‧‧‧ surface

306d‧‧‧back

500‧‧‧Touch panel components

1 is a schematic cross-sectional view showing a preferred embodiment of a wiring board according to a first embodiment of the present invention.

2 is another suitable implementation of the wiring board according to the first embodiment of the present invention. A schematic cross-sectional view of the mode.

3 is a schematic cross-sectional view showing a preferred embodiment of a wiring board with an insulating layer according to the first embodiment of the present invention.

Fig. 4 is a schematic cross-sectional view showing an embodiment of a conductive film laminate according to a first embodiment of the present invention.

Fig. 5 is a schematic cross-sectional view showing another embodiment of the conductive film laminate according to the first embodiment of the present invention.

Fig. 6(A) is a partial plan view showing one end side of the touch panel member, and Fig. 6(B) is a schematic cross-sectional view taken along line A-A of Fig. 6(A).

Fig. 7 is a schematic cross-sectional view showing a preferred embodiment of a wiring board according to a second embodiment of the present invention.

Hereinafter, the first embodiment and the second embodiment of the present invention will be described in order.

<<First embodiment>>

Hereinafter, suitable embodiments of the wiring board and the conductive film laminate according to the first embodiment of the present invention will be described.

First, the feature points of the first embodiment of the present invention which are compared with the prior art will be described in detail.

As described above, in the first embodiment of the present invention, it is found that the compatibility of the compound having a reducing ability to metal ions (hereinafter also referred to as a reducing compound) and the resin of the dispersion reducing compound is controlled, and the conductive film is controlled. (or metal wiring) The amount of silver in the middle can achieve the desired effect. More specifically, by using a predetermined reducing compound, the dispersibility of the reducing compound in the resin can be improved to suppress deterioration of the resin, and the amount of silver in the conductive film (or metal wiring) can be made a predetermined value. The reduction characteristics of the predetermined reducing compound are further improved by the following. In particular, since the compound is well dispersed in the resin, the reduced silver is difficult to be localized, and as a result, it is difficult to absorb in the visible light region, and deterioration of coloring or haze can be suppressed.

Further, when the silver film or the silver nanowire is contained in the conductive film (or metal wiring), the specific surface area of the silver component in the conductive film is increased by controlling the amount of silver, and the reducing compound is further improved. The improvement effect brought by it.

In the following, the wiring board will be described in detail first. The conductive film laminate is described in detail in the following paragraph.

<Wiring board>

Next, a suitable form of the wiring board according to the first embodiment of the present invention will be described in detail with reference to the drawings.

1 is a schematic cross-sectional view showing an embodiment of a wiring board including an insulating substrate 12 including a metal wiring 14 and a metal wiring 14 disposed on an insulating substrate 12 and an insulating substrate 12; Silver ion diffusion suppression layer 18.

Hereinafter, each member (the insulating substrate 12, the metal wiring 14, and the silver ion diffusion suppression layer 18) will be described in detail.

[Insulating substrate]

The insulating substrate is insulative, and if it is a metal-supportable wiring, the type is not Special restrictions. For example, an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.

Further, the insulating substrate may have a structure in which at least two substrates selected from the group consisting of an organic substrate, a ceramic substrate, and a glass substrate are laminated.

The material of the organic substrate may be exemplified by a resin, and for example, it is preferred to use heat hardening. Resin, thermoplastic resin, or a mixture of these resins. Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy resin, an anthrone resin, a furan resin, and the like. A ketone resin, a xylene resin, a benzocyclobutene resin or the like. Examples of the thermoplastic resin include a polyimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, an aramid resin, a liquid crystal polymer, and the like.

Further, as the material of the organic substrate, a glass woven fabric, a glass non-woven fabric, a polyarsenide woven fabric, a polyarylamine nonwoven fabric, an aromatic polyamide woven fabric, or a material in which the above resin is impregnated may be used.

[Metal wiring]

The metal wiring mainly contains silver. Silver may be contained in the form of a silver alloy. When the metal wiring contains a silver alloy, examples of the metal other than silver include tin, palladium, gold, nickel, chromium, and the like. In the metal wiring, a resin component such as a binder or a photosensitive compound may be contained in a range that does not impair the effects of the present invention, and other components may be further contained as needed.

Moreover, it is preferred that the metal wiring contains a metal nanowire containing silver or a silver alloy. In addition, the metal nanowire is described in detail in the latter stage.

The amount of silver contained per unit area of the metal wiring is 50 μg/mm ² or less. When the amount of silver is in the above range, the thickness and width of the metal wiring can be made small, and the high-density integrated product can be expected. If the amount of silver is too large, a short circuit easily occurs between the metal wirings. Among them, the amount of silver is preferably 30 μg/mm ² or less, more preferably 15 μg/mm ² or less. The lower limit is not particularly limited, and is preferably 0.001 μg/mm ² or more, and more preferably 0.005 μg/mm ² or more, from the viewpoint of further excellent electrical conductivity of the metal wiring.

In addition, when the amount of silver contained in the metal wiring is small, if ion migration occurs, silver which forms the metal wiring is eluted, and thus the disconnection of the metal wiring is likely to occur. However, in the present invention, by covering the metal wiring with the silver ion diffusion suppressing layer containing the predetermined compound, ion migration of silver can be suppressed, and disconnection of the metal wiring can be suppressed.

The method for measuring the amount of silver is not particularly limited, and a known method can be employed. example For example, the amount of silver can be determined by performing elemental analysis by observing a cross-sectional SEM photograph of a metal wiring. Further, the metal wiring can be brought into contact with a strong acid such as nitric acid to dissolve the silver in the metal wiring, and the amount of silver can be measured based on the amount dissolved. Further, when a metal wiring is produced by using a dispersion containing silver nanowires or silver nanoparticles, the silver in the metal wiring can be calculated by calculation based on the amount of the dispersion used in the production of the metal wiring. the amount.

Further, the unit area of the metal wiring is the unit area of the portion where the metal wiring is in contact with the insulating substrate. That is, the calculation of the amount of silver is performed based only on the area of the contact portion between the metal wiring and the insulating substrate. In other words, the area of the surface of the insulating substrate that is not in contact with the metal wiring (for example, the surface of the insulating substrate that is not in contact with the metal wiring between the metal wirings) is not considered in the calculation of the unit area of the above metal wiring. . Therefore, the amount of silver contained in the unit area of the metal wiring is the amount of silver contained in the unit area (mm ² ) in the contact portion between the metal wiring and the insulating substrate.

The width of the metal wiring is not particularly limited, and the height of the wiring substrate is ensured. The electrical reliability of the body portion and the lead wiring portion (lead wiring portion) is preferably 0.1 μm to 10000 μm, more preferably 0.1 μm to 300 μm, still more preferably 0.1 μm to 100. Μm, particularly preferably 0.2 μm to 50 μm.

The interval between the metal wirings is not particularly limited, and is preferably 0.1 μm to 1000 μm, more preferably 0.1 μm to 300 μm, still more preferably 0.1 μm from the viewpoint of high integration of the wiring substrate. 100 μm, particularly preferably 0.2 μm to 50 μm.

Further, the shape of the metal wiring is not particularly limited and may be any shape. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, etc. are mentioned. Moreover, the plurality of metal wires can be configured in a desired pattern (for example, stripe shape).

The thickness of the metal wiring is not particularly limited, and the integration of the wiring board is high. In view of the above, it is preferably 0.001 μm to 100 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.01 μm to 20 μm.

In FIG. 1, the metal wiring 14 may be provided only on one side of the insulating substrate 12. Can be set on both sides. That is, the insulating substrate 16 with the metal wiring may be a single-sided substrate, and may be a double-sided substrate. When the metal wiring 14 is present on both sides of the insulating substrate 12, the silver ion diffusion-tapped layer 18 may be provided on both sides.

Further, in FIG. 1, the wiring structure of one layer of the metal wiring 14 is taken as an example, and of course, it is not limited to this. For example, as shown in Figure 2, by using an interactive product The wiring board 100 having a plurality of metal wirings 14a, metal wirings 14b and insulating substrates 12a, and insulating substrates 16a (multilayer wiring substrates) to which metal wirings are attached is provided as a multilayer wiring structure.

Moreover, a through hole can be formed in the insulating substrate. Double-sided on the insulating substrate In the case of metal wiring, the metal wiring on both sides can be turned on by filling a metal (for example, silver or a silver alloy) in the through hole.

[Silver ion diffusion suppression layer]

The silver ion diffusion suppression layer is a layer that is disposed on the surface of the metal wiring side of the insulating substrate with the metal wiring, covers the surface of the metal wiring, and suppresses ion migration of silver between the metal wirings.

Further, it is preferable that the silver ion diffusion suppressing layer contains substantially no silver ions or metallic silver. When the silver ion diffusion suppressing layer contains excessive silver ions or metallic silver, the silver ion migration suppressing effect may be lowered.

In addition, the content of silver ions or metallic silver in the silver ion diffusion suppressing layer is preferably 1 μmol/l or less, more preferably 0.1 μmol/l or less, and most preferably 0 mol/l.

The thickness of the silver ion diffusion suppression layer is not particularly limited, and is diffused in silver ions. The ion transport inhibition ability of the suppression layer is more preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm.

The silver ion diffusion suppression layer contains an insulating resin and is selected from the formula (1), At least one compound of the compound group represented by the formula (2) and the formula (3).

Hereinafter, the insulating resin and the compound will be described in detail.

(insulating resin)

The insulating resin is coated with the insulating resin in the silver ion diffusion suppressing layer to cover the metal wiring, and the insulating property between the metal wirings is ensured by being disposed between the metal wirings.

The insulating resin to be used may be a known insulating resin, and it is preferable to use a curable insulating resin (for example, a thermosetting insulating resin and photocurability) in terms of facilitating formation of a layer of the silver ion diffusion inhibiting layer. Insulating resin) Hardened resin.

Examples of the thermosetting insulating resin include epoxy resin and bismaleimide. A triazine resin, a polyimide resin, an acrylic resin, a phenol resin, a melamine resin, an anthracene resin, an unsaturated polyester resin, a cyanate resin, an isocyanate resin, or a modified resin thereof.

Examples of the photocurable insulating resin include an unsaturated polyester resin, a polyester acrylate resin, an urethane urethane resin, an oxime acrylate resin, an epoxy acrylate resin, or a modified resin thereof.

Examples of other insulating resins include polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), polylactic acid, fluorine-containing resin, and polyether oxime. A thermoplastic resin such as a resin, a polyphenylene sulfide resin or a polyetheretherketone resin.

Among them, an epoxy resin or an acrylic resin is preferred in terms of being more excellent in compatibility with a compound to be described later.

Moreover, the insulating resin may be impregnated into the glass woven fabric or the glass woven fabric as needed. It is used in a heart material such as cloth or polyarsenide non-woven fabric. Specifically, a glass cloth epoxy resin, a glass cloth, a bismaleimide triazine resin, a glass cloth polyphenylene ether resin, or the like can be used. Polyarylamine non-woven fabric - epoxy resin, polyarylamine non-woven fabric - polyimine resin, and the like.

Further, when the insulating resin is a curable resin, a curing agent, a curing accelerator, or the like may be used in combination as needed.

Further, the insulating resin may be used in combination of two or more kinds of insulating resins.

(compound)

Further, silver can be further suppressed by containing at least one compound selected from the group consisting of compounds represented by formula (1), formula (2), and formula (3) (hereinafter also referred to simply as a reducing compound) in the silver ion diffusion inhibiting layer. Ion migration.

The reducing compound functions to reduce silver ions. That is, even if silver ions are eluted from the metal wiring, the silver ions are reduced to silver by the reducing compound, thereby suppressing ion migration. In addition, in the case of the reducing compound, the dispersibility in the silver ion diffusion inhibiting layer is excellent, and the localization of the reduced silver is suppressed, and as a result, the yellowing of the silver ion diffusion suppressing layer (absorption in the visible light region) can be suppressed. .

Further, two or more compounds represented by the formulae (1) to (3) may be contained in the silver ion diffusion inhibiting layer.

In the formula (1), R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom. Among them, a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a combination of these groups is preferred from the viewpoint of more excellent ion mobility inhibition ability.

The type of the hetero atom contained in the hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, from the viewpoint of excellent ion migration inhibition ability of silver, -Y ₁ -, -N(R _a )-, -C(=Y ₂ )-, -CON(R _b )-, -C(=Y ₃ )Y ₄ -, -SO _t -, -SO ₂ N(R _c )-, a halogen atom, or a combination of these groups.

Y ₁ to Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, oxygen atoms and sulfur atoms are preferred from the viewpoint of easier handling. t represents an integer from 1 to 3.

The hydrocarbon group which may have a hetero atom is preferably an aliphatic hydrocarbon group which may have an oxygen atom, an aromatic hydrocarbon group which may have an oxygen atom, or a combination of these groups, in terms of the effect of the present invention being more excellent. .

The number of carbon atoms in the hydrocarbon group is not particularly limited, and is preferably from 1 to 40, more preferably from 4 to 20, from the viewpoint of more excellent ion mobility inhibition ability. Further, the range of the number of carbon atoms which may be contained in the aliphatic hydrocarbon group having an oxygen atom, the aromatic hydrocarbon group which may have an oxygen atom, or the combination of these groups is also preferably in the above range.

In the formula (1), Z represents a hydrogen atom, a fluorenyl group or an RzOC(=O) group. Rz represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Among them, the ion migration inhibition ability is better In other respects, Z is preferably a hydrogen atom.

The number of carbon atoms contained in the fluorenyl group or the RzOC(=O) group is not particularly limited, and is preferably from 2 to 12, more preferably from 2 to 8, in terms of more excellent ion mobility inhibition ability.

Further, in the formula (1), the total number of carbon atoms contained in each of R ₁ to R ₅ is 4 or more. That is, at least one of R ₁ to R ₅ is a group containing a carbon atom (the above aliphatic hydrocarbon group, the above aromatic hydrocarbon group, or a combination of these groups).

When the total number of carbon atoms is in this range, ion migration of silver is suppressed, and insulation reliability between metal wirings is improved. Further, in terms of the effect being more excellent, the total number of counts is preferably 8 or more, and more preferably 10 or more. In addition, the upper limit is not particularly limited, and it is easier to synthesize from the synthesis, and the total number of the insulating resins is preferably 50 or less, and more preferably 40 or less.

Further, in the case where only one of R ₁ to R ₅ is a group containing a carbon atom (for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group), the number of carbon atoms in the group may be 4 or more.

Further, in the case where a plurality of groups in R ₁ to R ₅ are a group containing a carbon atom (for example, an alkyl group, an alkoxy group or the like), the total number of carbon atoms contained in each group is 4 More than that. For example, when R ₁ and R ₂ are an alkyl group and R ₃ to R ₅ are a hydrogen atom, the number of carbon atoms contained in the alkyl group of R _{1 and} the number of carbon atoms contained in the alkyl group of R ₂ are The total count is 4 or more.

Further, R ₁ to R ₅ may be bonded to each other to form a ring. The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring to a 6-membered ring structure.

In R ₁ to R ₅ , a known substituent may be further included as needed. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group, a decyloxy group, and an amine group. Mercaptooxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine, decylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, amine sulfonium Amino, alkyl or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo, alkyl or arylsulfinyl, alkyl or Arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethanyl, aryl or heterocyclic azo, quinone imine, phosphino, phosphinyl, phosphinyloxy , phosphinylamino, decyl.

In the formula (2), R ₆ to R ₈ each independently represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups.

The number of carbon atoms contained in the group in which the aliphatic hydrocarbon group, the aromatic hydrocarbon group or the combination of these groups is contained is not particularly limited, and is preferably from 1 to 40, more preferably from the viewpoint of more excellent ion mobility inhibition ability. It is 2~20.

In the formula (2), the total number of carbon atoms contained in each of R ₆ to R ₈ is 6 or more. When the total number of carbon atoms is in this range, ion migration of silver is suppressed, and insulation reliability between metal wirings is improved. Further, in terms of the effect being more excellent, the total number of counts is preferably 8 or more, and more preferably 10 or more. In addition, the upper limit is not particularly limited, and from the viewpoint of easier synthesis and more excellent dispersibility in the insulating resin, the total number is preferably 50 or less, more preferably 40 or less.

In the above-mentioned total, for example, when R ₆ to R ₈ are each an alkyl group, the number of carbon atoms contained in the alkyl group of R _{6 ,} the number of carbon atoms contained in the alkyl group of R ₇ , and R The total number of carbon atoms contained in the alkyl group of ₈ may be 6 or more.

Further, R ₆ to R ₈ may further contain a known substituent as needed. Examples of the substituent are the same as the substituents substituted for the above R ₁ to R ₅ .

Further, R ₆ to R ₈ may be bonded to each other to form a ring.

In the formula (3), R ₉ to R ₁₂ each independently represent an alkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, or a group in which these groups are combined.

The number of carbon atoms contained in the alkyl group or the aryl group is not particularly limited, and is preferably from 1 to 40, more preferably from 2 to 20, from the viewpoint of further excellent ion mobility inhibition ability.

Further, a hetero atom may be contained in the alkyl group or the aryl group. The type of the hetero atom to be contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, in terms of excellent ion mobility inhibition ability of silver, -X ₁ -, -N(R _a )-, -C(=X ₂ )-, -CON(R _b )-, -C(=X ₃ )X ₄ -, -SO _n -, -SO ₂ N(R _c )-, a halogen atom, or a combination of these groups.

X ₁ to X ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, an oxygen atom or a sulfur atom is preferred from the viewpoint of easier handling.

The above R _a , R _b and R _c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

n represents an integer from 1 to 3.

In the formula (3), the total number of carbon atoms contained in each of R ₉ to R ₁₂ is 6 or more. When the total number of carbon atoms is in this range, ion migration of silver is suppressed, and insulation reliability between metal wirings is improved. Further, in terms of the effect being more excellent, the total number of counts is preferably 8 or more, and more preferably 10 or more. In addition, the upper limit is not particularly limited, and it is easier to synthesize from the synthesis, and the total number of the insulating resins is preferably 50 or less, and more preferably 40 or less.

In the above-mentioned total, for example, when R ₉ to R ₁₂ are each an alkyl group, the number of carbon atoms contained in the alkyl group of R _{9 ,} the number of carbon atoms contained in the alkyl group of R ₁₀ , and R The total number of carbon atoms contained in the alkyl group of _{11 and} the number of carbon atoms contained in the alkyl group of R ₁₂ may be 6 or more.

Further, R ₉ to R ₁₂ may be bonded to each other to form a ring.

(suitable form)

Among the compounds represented by the above formulas (1) to (3), the compound represented by the formula (4) can be suitably used from the viewpoint of further excellent ion mobility inhibition ability.

In the formula (4), the definitions of Z, R ₁ , R ₂ and R _{3 are} the same as those of the groups in the formula (1).

In the formula (4), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom.

The hydrocarbon group is preferably an aliphatic hydrocarbon group which may contain an oxygen atom, an aromatic hydrocarbon group which may contain an oxygen atom, or a combination of these groups, in terms of the effect of the present invention being more excellent. Among them, an alkyl group containing a 3-stage carbon atom or a 4-stage carbon atom is preferred in terms of more excellent ion mobility-inhibiting ability.

Further, the number of carbon atoms in the hydrocarbon group which may have a hetero atom is not particularly limited as long as it satisfies the requirements described later, and is preferably from 1 to 40, more preferably from 2 to 20. Further, the range of the number of carbon atoms which may be an aliphatic hydrocarbon group having an oxygen atom, an aromatic hydrocarbon group which may have an oxygen atom, or a combination of these groups is also preferably in the above range.

Particularly preferably, R ₁₄ is an alkyl group having 1 to 5 carbon atoms, and R ₁₅ is an alkyl group having 10 to 20 carbon atoms.

The number of carbon atoms contained in at least one of R ₁ , R ₂ , R ₁₄ and R ₁₅ is from 1 to 40. When the number of carbon atoms is in the above range, the solubility in the insulating resin is improved, and the dispersibility of the compound in the silver ion diffusion inhibiting layer is improved, and as a result, the ion mobility inhibition ability of silver is improved. Among them, the number of carbon atoms is preferably from 8 to 40, more preferably from 10 to 30.

Further, the total number of carbon atoms contained in each of R ₁ , R ₂ , R ₁₄ and R ₁₅ is 4 or more. When the total number of carbon atoms is in this range, ion migration of silver is suppressed, and insulation reliability between metal wirings is improved. Further, in terms of the effect being more excellent, the total number of counts is preferably 8 or more, and more preferably 10 or more. In addition, the upper limit is not particularly limited, and it is easier to synthesize from the synthesis, and the total number of the insulating resins is preferably 50 or less, and more preferably 40 or less.

Further, among the compounds represented by the above formulas (1) to (3), The compound represented by the formula (5) or the compound represented by the formula (6) is most preferable in terms of superior sub-migration inhibition ability.

In the formula (5), R ₃₁ to R ₃₈ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

A suitable example of the hydrocarbon group is -OR _a . R _a represents _a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom. These may be the same when there are multiple -OR _a cases.

The carbon number of the hydrocarbon group is preferably from 1 to 12, more preferably from 1 to 10, from the viewpoint of being more excellent in compatibility with the insulating resin.

More specifically, the hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups. The aliphatic hydrocarbon group may be linear, branched or cyclic By.

Further, the total molecular weight of each of R ₃₁ to R ₃₈ is 24 or more. Among them, it is preferably 35 or more. Further, the upper limit is not particularly limited, and is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less in terms of the effect of the present invention being more excellent. The total of the molecular weights of the above respective groups is a value obtained by calculating the molecular weight of each of R ₃₁ to R ₃₈ and summing these.

Further, R ₃₁ to R ₃₈ may be bonded to each other to form a ring.

Further, the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have a hetero atom represented by R ₁ to R ₅ described above.

The hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom represented by R ₃₁ to R ₃₆ is preferably selected from an aliphatic hydrocarbon group which may have an oxygen atom in terms of the effect of the present invention being more excellent ( For example, an alkyl group, an alkenyl group, or an alkynyl group, an aromatic hydrocarbon group (for example, a phenyl group) which may have an oxygen atom, and a group of groups in which these groups are combined have a carbon number of 1 to 20.

Further, it is preferred that R ₃₇ and R ₃₈ each independently represent a -CH ₂ -R ₄₀ group, a hydroxyl group, or an aliphatic hydrocarbon group which may have an oxygen atom. In terms of more excellent ion mobility inhibition ability, it is preferred that the aliphatic hydrocarbon group which may have an oxygen atom be a linear alkyl group. R ₄₀ represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups.

Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, or a cyclic chain.

R ₃₉ represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. The number of carbon atoms contained in the divalent aliphatic hydrocarbon group is preferably from 1 to 10. For example, a methylene group, an ethylene group, an isopropylidene group, a butylene group, an isodecylene group, or a cyclohexylene group may be mentioned, but the present invention is not limited thereto.

Further, the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have a hetero atom represented by R ₁ to R ₅ described above.

In the formula (6), R ₄₁ to R ₄₄ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

The suitable range of the hydrocarbon group represented by R ₄₁ to R ₄₄ is the same as the suitable range of the hydrocarbon group represented by the above R ₃₁ to R ₃₈ .

Further, the total molecular weight of each of R ₄₁ to R ₄₄ is 40 or more. Among them, it is preferably 50 or more. Further, the upper limit is not particularly limited, and is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less in terms of the effect of the present invention being more excellent.

Further, R ₄₁ to R ₄₄ may be bonded to each other to form a ring.

Further, the definition of the hetero atom is the same as the definition of the hetero atom in the hydrocarbon group which may have a hetero atom represented by R ₁ to R ₅ described above.

The hydrocarbon group having a carbon number of 1 to 20 which may be a hetero atom represented by R ₄₁ to R ₄₄ is preferably selected from an aliphatic hydrocarbon group which may have an oxygen atom in terms of the effect of the present invention being more excellent ( For example, an alkyl group, an alkenyl group, or an alkynyl group, an aromatic hydrocarbon group (for example, a phenyl group) which may have an oxygen atom, and a group of groups in which these groups are combined have a carbon number of 1 to 20.

Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, or a cyclic chain.

L represents a divalent or trivalent hydrocarbon group which may have a hetero atom, -S-, or these The basis of the combination.

Examples of the hydrocarbon group represented by L include an aliphatic hydrocarbon group which may have a divalent or trivalent oxygen atom, or a divalent or trivalent aromatic group which may have an oxygen atom, in terms of the effect of the present invention. Hydrocarbyl group.

The number of carbon atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group is not particularly limited, and the aliphatic hydrocarbon group is preferably from 1 to 40, more preferably from 2 to 20, and the aromatic hydrocarbon group is preferably from 6 to 40. More preferably, it is 6~20.

Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, or a cyclic chain.

n represents an integer of 2 or 3.

The compound represented by the formula (1) is exemplified by the following compounds.

[Chemical 4]

The compound represented by the formula (4) is exemplified by the following compounds.

[Chemical 5]

The compound represented by the formula (5) is exemplified by the following compounds.

The compound represented by the formula (6) is exemplified by the following compounds.

[Chemistry 7]

The compound represented by the formula (2) is exemplified by the following compounds.

The compound represented by the formula (3) is exemplified by the following compounds.

[11]

The above insulating resin in the silver ion diffusion suppressing layer and the above reductive The mass relationship of the compound is not particularly limited, and the mass ratio (A/B) of the total mass A of the reducing compound to the total mass B of the insulating resin is preferably 0.20 or less in terms of excellent ion migration inhibiting ability. More preferably, it is 0.10 or less. The lower limit is not particularly limited, and is preferably 0.0001 or more, and more preferably 0.0005 or more, from the viewpoint of obtaining a predetermined effect in the thin silver ion diffusion suppression layer.

Further, when the total mass A is two or more kinds of reducing compounds, the total mass of these compounds is shown. The total mass B indicates the total mass of these resins in the case where two or more kinds of insulating resins are contained.

[Wiring substrate]

The wiring board including the insulating substrate, the metal wiring, and the silver ion diffusion suppression layer can be used for various purposes and structures. For example, a panel substrate for a plasma display panel, a solar cell electrode substrate, a membrane wiring board, and a touch panel electrode substrate can be cited.

Further, the wiring board according to the first embodiment of the present invention preferably includes In an electronic device. The so-called electronic device refers to the touch panel or the diaphragm switch or carries this Televisions, mobile communication devices, personal computers, game devices, in-vehicle display devices, network communication devices, lighting, display light-emitting diodes (LEDs), electronic wiring devices related to solar cell control, A wireless communication device such as radio frequency identification (RFID) or a device for driving control by a semiconductor wiring substrate or an organic thin film transistor (TFT) wiring substrate.

(Manufacturing method of wiring board)

First, the method of forming the metal wiring on the insulating substrate is not particularly limited, and a known method can be employed. Typical examples include a subtractive method using an etching treatment, a semi-additive method using electrolytic plating, a method of producing a metal wiring using a silver paste (for example, a slurry containing silver nanoparticles or a silver nanowire), and a Japanese patent. A method of using a photosensitive material, a vacuum deposition method, a sputtering film formation method, an ion plating method, and the like disclosed in JP-A-2009-188360.

In addition, the silver paste is a conductive paste-like substance (slurry) obtained by dispersing silver particles having a predetermined particle diameter in a suitable solvent such as a resin binder, and is used for mounting a sample or conducting a conductive treatment. The commercial item is, for example, Peltron K-3424LB (trade name, manufactured by PELNOX Co., Ltd.).

The method of manufacturing the wiring board is not particularly limited, and for example, there are The composition for forming a silver ion diffusion suppression layer of the insulating resin, the reducing compound, and the solvent is applied onto an insulating substrate with metal wiring, and a solvent is removed to form a silver ion diffusion inhibiting layer. Further, a film for a silver ion diffusion suppression layer containing the above-mentioned insulating resin and the above compound is directly laminated on a metal wiring. A method on an insulating substrate.

From the viewpoint of easy adjustment of the thickness of the silver ion diffusion suppressing layer, it is preferred to use the above coating method.

Further, the composition for forming a silver ion diffusion suppression layer is coated with gold The method of the insulating substrate to be wired is not particularly limited, and a known method such as a dispensing method, a screen printing method, a curtain coating method, a roll coating method, a spin coating method, an inkjet method, or a dipping method can be employed. In terms of more easily controlling the amount of adhesion of the silver ion diffusion inhibiting layer, a dispensing method, a screen printing method, a spin coating method, or an ink jet method is preferred.

Further, when the insulating resin contained in the composition is a curable resin, after the composition is applied, heat treatment or exposure treatment may be performed as needed.

When the heat treatment is carried out, the heating temperature may be appropriately selected depending on the thermosetting resin to be used, and it is usually preferably from 100 ° C to 300 ° C, more preferably from 100 ° C to 250 ° C. Further, from the viewpoint of productivity, the heating time is preferably from 0.2 hours to 10 hours, more preferably from 0.5 hours to 5 hours.

Further, in the case of performing the exposure treatment, the light used for the exposure can be appropriately selected from the light of the most suitable wavelength depending on the photocurable resin to be used. For example, ultraviolet light, visible light, etc. are mentioned. From the viewpoint of productivity, the exposure time is preferably from 0.2 hours to 10 hours, more preferably from 0.5 hours to 5 hours.

[Wiring board with insulation layer]

Further, an insulating layer may be further provided on the surface of the wiring substrate on the side of the silver ion diffusion suppressing layer which is obtained as described above. By further providing an insulating layer on the silver ion diffusion suppressing layer, wiring can be further provided on the insulating layer to form a multilayer wiring board.

More specifically, the wiring layer 200 with the insulating layer may be provided with the insulating layer 20 on the silver ion diffusion suppression layer 18 as shown in FIG. 3 .

Hereinafter, the materials (insulating layers) to be used will be described, and the order of the manufacturing methods will be described later.

(Insulation)

As the material of the insulating layer, a known insulating material can be used. For example, an epoxy resin, a polyarylamine resin, a crystalline polyolefin resin, an amorphous polyolefin resin, a fluorine-containing resin (polytetrafluoroethylene, perfluoropolyimine, perfluoro amorphous resin, etc.), and a poly A quinone imine resin, a polyether oxime resin, a polyphenylene sulfide resin, a polyether ether ketone resin, an acrylate resin, or the like.

Further, as the insulating layer, a so-called optical transparent sheet (OCA) can be used. Commercially available products can be used for the OCA, and examples thereof include the 8171CL series and the 8146 series manufactured by 3M Co., Ltd.

Moreover, a so-called solder resist layer can be used for the insulating layer. A commercially available product can be used as the solder resist, and examples thereof include PFR800, PSR4000 (trade name) manufactured by Sun Ink Manufacturing Co., Ltd., and SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.

Among them, the insulating layer preferably contains a resin having an epoxy group or a (meth) acrylate group. This resin is easily bonded to the above-described silver ion diffusion suppressing layer, and as a result, the adhesion of the insulating layer is improved, and as a result, the effect of inhibiting the ion transport of silver is further improved.

Preferably, the resin is a main component of the insulating layer. The main component is that the total amount of the resin is 50% by mass or more based on the total amount of the insulating layer, and preferably 60. More than % by mass. Further, the upper limit is 100% by mass.

As the epoxy group-containing resin, a known epoxy resin can be used. For example, can be used A glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or the like.

As the resin having a (meth) acrylate group, a known resin can be used. For example, an acrylate resin, a methacrylate resin, or the like can be used.

(order of manufacture)

The method of forming the insulating layer on the wiring substrate is not particularly limited, and a known method can be employed. For example, a method of directly laminating an insulating layer film on a wiring board, a method of applying an insulating layer forming composition containing a component constituting the insulating layer to a wiring board, and immersing the wiring board in the formation of the insulating layer The method in the composition, and the like.

Further, the insulating layer forming composition may optionally contain a solvent. When the composition for forming an insulating layer containing a solvent is used, after the composition is placed on the wiring board, heat treatment may be performed as needed to remove the solvent.

Further, after the insulating layer is provided on the wiring substrate, energy can be applied to the insulating layer (for example, exposure or heat treatment) as needed.

The layer thickness of the formed insulating layer is not particularly limited, since the metal wiring layer From the viewpoint of insulation reliability, it is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm.

Moreover, it can be removed by drilling or laser processing. A portion of the insulating layer in the wiring substrate of the edge layer is packaged with a semiconductor wafer and used as a circuit board.

For example, when a solder resist is used as the insulating layer, a predetermined pattern mask is placed on the insulating layer, energy is applied to be cured, and the insulating layer in the region where no energy is applied is removed to expose the metal wiring. Next, the surface of the exposed metal wiring is cleaned (for example, by using sulfuric acid, a soft etchant, an alkali, or a surfactant) by a known method, and then the semiconductor wafer is packaged on the surface of the metal wiring.

Further, metal wiring can be further provided on the obtained insulating layer. form The method of the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, or the like) can be used.

In the first embodiment of the present invention, the substrate on which the metal wiring is further provided on the insulating layer disposed on the outermost layer of the obtained wiring layer with the insulating layer can be used as a new insulation with metal wiring. Substrate (inner substrate), several layers of insulating layers and metal wiring.

<Conductive film laminate>

Next, a suitable form of the conductive film laminate according to the first embodiment of the present invention will be described in detail with reference to the drawings.

4 is a schematic cross-sectional view showing an embodiment of a conductive film laminate. The conductive film laminate 300 includes a transparent substrate 302, a conductive film 304 containing silver or a silver alloy disposed on the transparent substrate 302, and a conductive film 304. A transparent double-sided adhesive sheet 306 is attached.

Each member (transparent substrate 302, conductive film 304, and transparent double-sided adhesive sheet 306) will be described in detail below.

[Transparent substrate]

The transparent substrate is not particularly limited as long as it is a substrate that supports a conductive film and a transparent double-sided adhesive sheet to be described later and is transparent to visible light.

As a material of the transparent substrate, for example, a polymer resin can be used in addition to glass. Examples of the polymer resin include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyether oxime, and poly Anthracene, polyarylate, cyclic polyolefin, polyimine, and the like.

The shape of the transparent substrate is not particularly limited, and examples thereof include a plate shape and a film shape.

The thickness of the transparent substrate is not particularly limited. When the conductive film laminate is applied to a touch panel, the thickness is preferably 0.01 mm to 3.0 mm, more preferably 0.05 mm to 1.5 mm.

The transparent substrate preferably has high transparency in the visible light region, and preferably has a total light transmittance of 80% or more.

In addition, the transparent substrate may include other functional layers such as an undercoat layer. Examples of the other functional layer include a matting agent layer, a protective layer, a solvent resistant layer, an antistatic layer, a smoothing layer, a adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, and an antifouling layer. Layer, printed layer, easy adhesion layer, and the like. These can be single layers and can be stacked in multiple layers.

[conductive film]

The conductive film is disposed on the transparent substrate and mainly contains silver. When applied to a touch panel, the conductive film can be used as a transparent electrode or a peripheral wiring (lead wiring) of the touch panel. In addition, a resin component such as a binder or a photosensitive compound may be contained in the conductive film in a range that does not impair the effects of the present invention, and may be further included as needed. Other ingredients.

Silver may be contained in the form of a silver alloy. When the conductive film contains a silver alloy, examples of the metal other than silver include tin, palladium, gold, nickel, chromium, and the like.

The pattern shape of the conductive film is not particularly limited, and as shown in FIG. 4, a portion of the surface of the transparent substrate may be a wiring (pattern-shaped conductive film) (in other words, a conductive thin wire may be used), or Set on the entire surface. Further, the pattern shape may be any pattern such as a stripe shape.

The amount of silver contained per unit area of the conductive film is 50 μg/mm ² or less. When the amount of silver is in the above range, the film thickness and width of the conductive film can be made small, and it is possible to cope with the high expectation of high-density integration. If the amount of silver is too large, it becomes easy to cause a short circuit between the conductive films. Among them, the amount of silver is preferably 30 μg/mm ² or less, more preferably 15 μg/mm ² or less. The lower limit is not particularly limited, and is preferably 0.001 μg/mm ² or more, and more preferably 0.005 μg/mm ² or more, from the viewpoint that the conductive property of the conductive film is more excellent.

Further, when the amount of silver contained in the conductive film is small, if ion migration occurs, silver which forms the conductive film is eluted, and disconnection of the conductive film is likely to occur. However, in the present invention, by adhering a transparent double-sided adhesive sheet containing a predetermined compound to a conductive film, ion migration of silver can be suppressed, and disconnection of the conductive film can be suppressed.

The method for measuring the amount of silver is not particularly limited, and a known method can be employed. example For example, the amount of silver can be determined by performing elemental analysis by observing a cross-sectional SEM photograph of the conductive film. Further, the conductive film can be brought into contact with a strong acid such as nitric acid to dissolve the silver in the conductive film, and the amount of silver can be measured according to the amount of dissolution. Moreover, the use of silver nanowires or silver nanoparticles When a conductive film is produced by using a dispersion liquid, the amount of silver in the conductive film can be calculated by calculation based on the amount of the dispersion used in the production of the conductive film.

Further, the unit area of the conductive film is the unit area per unit area of the contact portion of the conductive film with the transparent substrate. That is, the calculation of the amount of silver is performed based only on the area of the contact portion of the conductive film and the transparent substrate. In other words, when the conductive film is patterned, the area of the transparent substrate surface that is not in contact with the conductive film (for example, the surface of the transparent substrate that is not in contact with the conductive film between the conductive films) is not considered in the above. The calculation per unit area of the conductive film. Therefore, the amount of silver contained in the unit area of the conductive film is the amount of silver contained per unit area (mm ² ) indicating the contact portion of the conductive film and the transparent substrate.

The thickness of the conductive film is not particularly limited since the application of the conductive film laminate In terms of the touch panel, it is preferably 0.05 μm to 100 μm, more preferably 0.1 μm to 20 μm, still more preferably 0.1 μm to 10 μm.

When the conductive film is applied to the transparent electrode of the touch panel, it is preferable to have high transparency in the visible light region, and it is preferable that the total light transmittance is 80% or more.

When the conductive film is in the shape of a pattern (conductive thin wire), the conductive film The width is not particularly limited. From the viewpoint of applying the conductive film laminate to the touch panel, it is preferably 0.1 μm to 100,000 μm, more preferably 1 μm to 20,000 μm, still more preferably 1 μm. ~10000 μm, particularly preferably 10 μm~300 μm.

When the conductive film is in the shape of a pattern (conductive thin wire), the interval between the conductive films is not particularly limited. From the viewpoint of applying the conductive film laminate to the touch panel, the narrowest portion is preferably 0.1. Mm~500 μm, more preferably 0.1 μm ~100 μm, especially from the viewpoint of visibility, particularly preferably 0.1 μm to 20 μm.

The method for forming the conductive film is not particularly limited, and examples thereof include vapor deposition and sputtering. Method for forming a silver film containing silver nanoparticles or silver nanowires by a chemical vapor deposition method such as a physical film formation method or a chemical vapor deposition (CVD) method, or a Japanese patent The method of using a silver salt disclosed in Japanese Laid-Open Patent Publication No. 2009-188360, and the like.

In addition, when the conductive film is applied to a transparent electrode such as a touch panel, Preferably, the conductive film contains a metal nanowire containing silver or a silver alloy (hereinafter also referred to as a metal nanowire). By using the metal nanowire, a conductive film can be formed at a low temperature to provide a transparent electrode having high transmittance and low resistance.

(metal nanowire)

The metal nanowire contains silver or a silver alloy. The types of silver alloys are as described above.

The metal nanowire refers to a shape having conductivity and having a sufficiently long length in the long axis direction as compared with the diameter (length in the short axis direction). It can be a solid fiber and can be a hollow fiber.

In terms of excellent electrical conductivity, the material of the metal nanowire is particularly good. Silver, or an alloy of silver with other metals.

Examples of other metals used in the alloy with silver include platinum, rhodium, palladium, iridium, tin, iridium, nickel, and the like. These can be used alone or in combination of two or more.

The average minor axis length of the metal nanowire (sometimes referred to as "average short axis diameter" and "average diameter") is preferably 5 nm to 50 nm, more preferably 5 nm to 25 nm, and further excellent. It is 5 nm to 20 nm.

When the average minor axis length is less than 5 nm, the oxidation resistance is deteriorated and the durability is deteriorated. On the other hand, when the average minor axis length exceeds 50 nm, the scattering of the metal nanowire becomes large, and the haze value of the conductive film becomes large. In particular, by making the average minor axis length 25 nm or less, the scattering of the metal nanowire can be reduced, and the haze value of the conductive film can be greatly improved (reduced). The touch panel using the conductive film with small haze can eliminate the pattern appearance of the conductive film (skeletal appearance) and improve the visibility of the touch panel.

The average short axis length of the metal nanowire can be transmitted using a transmission electron microscope (Transmission electron microscope, TEM; manufactured by JEOL Ltd., JEM-2000FX), 300 metal nanowires were observed, and the average minor axis length of the metal nanowires was determined from the average value. Further, in the case where the short axis of the metal nanowire is not circular, the short axis length is the longest one.

Average long axis length of metal nanowires (sometimes referred to as "average length") It is preferably 5 μm or more, more preferably 5 μm to 40 μm, still more preferably 5 μm to 30 μm.

If the average major axis length is less than 5 μm, it is difficult to form a dense network, and sufficient conductivity cannot be obtained. If it exceeds 40 μm, the metal nanowire is too long to be entangled during manufacturing. The phenomenon of condensate formation.

For the average long axis length of the metal nanowire, for example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX) can be used to observe 300 metal nanowires, based on the average value thereof. Find the average long axis length of the metal nanowire. In addition, when the metal nanowire is bent, consider the circle which is the arc, and calculate it according to its radius and curvature. The value is taken as the length of the long axis.

The manufacturing method of the metal nanowire is not particularly limited, and may be by any means. The method is preferably produced by reducing a metal ion in a solvent in which a halogen compound and a dispersing agent are dissolved. Further, from the viewpoint of self-dispersibility and temporal stability of the conductive film, it is preferred to carry out desalting treatment by a usual method after forming a metal nanowire.

In addition, Japanese Laid-Open Patent Publication No. 2009-215594, Japanese Patent Laid-Open No. 2009-242880, Japanese Patent Laid-Open No. 2009-299162, and Japanese Patent Laid-Open No. 2010-84173 The method described in Japanese Laid-Open Patent Publication No. 2010-86714, and the Japanese Patent Publication No. 2009-505358.

As the aspect ratio of the metal nanowire, it can be selected as needed, if 10 or more is not particularly limited, and more preferably 50 or more, still more preferably 100 or more, still more preferably 5,000 or more, and particularly preferably 10,000 to 100,000. The aspect ratio generally indicates the ratio of the long side to the short side of the fibrous material (the ratio of the average major axis length to the average minor axis length).

The method for measuring the aspect ratio is not particularly limited, and may be appropriately selected as necessary, and examples thereof include a method of measuring by an electron microscope or the like.

When the aspect ratio of the metal nanowire is measured by an electron microscope, it can be confirmed in the field of view of the electron microscope. Moreover, the aspect ratio of the entire metal nanowire can be estimated by measuring the average major axis length and the average minor axis length of the metal nanowires one by one.

Further, when the metal nanowire is tubular, the outer diameter of the tube is used as the diameter for calculating the aspect ratio.

(Conductive film containing a metal nanowire containing silver or a silver alloy)

The method for forming the conductive film containing the metal nanowire containing silver or a silver alloy is not particularly limited, and it is preferred to use at least the following composition as a matrix component together with the above metal nanowire: (1) at least a binder A photosensitive composition of the agent and the photopolymerizable composition, (2) a sol-gel cured product, or (3) a composition containing at least a polymer.

In addition, the mass of the matrix component (all components other than the metal nanowire and the solvent contained in the conductive film) and the quality of the metal nanowire are preferably 0.5 to 15 (more preferably 1.0 to 12, Particularly good is 2.0~10). When the mass ratio is less than 0.5, the binder component is small, the adhesion of the metal nanowire to the substrate surface is weak, and the film strength is weak. When the mass ratio exceeds 15, the surface resistance value of the conductive film increases.

The materials used as the matrix component are detailed below.

(adhesive)

The binder may have at least one base which promotes alkali solubility (for example, a carboxyl group) in a molecule (preferably an acrylic copolymer or a styrene copolymer-based molecule) as a linear organic high molecular polymer. An alkali-soluble resin such as a phosphoric acid group or a sulfonic acid group is suitably selected.

Preferred among these are those which are soluble in an organic solvent and are soluble in an aqueous alkaline solution, and particularly preferably have an acid dissociable group and an acid dissociable group due to an acid A binder that becomes soluble in alkali when dissociated.

Here, the acid dissociable group means a functional group which can be dissociated in the presence of an acid.

In the manufacture of a binder, for example, a known radical polymerization can be suitably used. Method of law. The polymerization conditions such as the temperature, the pressure, the kind and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally determined. .

The linear organic high molecular polymer preferably has a carboxylic acid group in a side chain. Compound.

As a polymer having a carboxylic acid in a side chain, there are, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japanese Patent Publication No. Sho 54-25957 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, and a Malay described in each of Japanese Patent Laid-Open Publication No. SHO 59-53836 An acid copolymer, a partially esterified maleic acid copolymer, an acid cellulose derivative having a carboxylic acid in a side chain, or an acid anhydride added to a polymer having a hydroxyl group, and the like may further be exemplified in the side chain (A) A polymer based on acrylonitrile is preferred.

Particularly preferred among these are benzyl (meth)acrylate/(meth)acrylic acid copolymerization. A multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer.

Further, it may be further exemplified by a high molecular polymer having a (meth) acrylonitrile group in a side chain or a multicomponent copolymer containing (meth)acrylic acid/glycidyl (meth)acrylate/other monomer. As a useful polymer. The polymer can be used in any amount by mixing.

In addition to the above, the linear organic high molecular polymer can be exemplified by Japanese patents. 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-benzene acrylate described in Kaiping No. 7-140654 Oxypropyl propyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methacrylic acid Ester/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

The specific structural unit in the alkali-soluble resin is suitably (meth) propylene. An acid, and other monomers copolymerizable with the (meth)acrylic acid.

Other monomers copolymerizable with (meth)acrylic acid may, for example, be (meth) propyl An alkyl olefinate, an aryl (meth) acrylate, a vinyl compound, or the like. The alkyl and aryl hydrogen atoms of these compounds may be substituted by a substituent.

Examples of the alkyl (meth)acrylate or the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Ester, tolyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate And dicyclopentenyloxyethyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, polymethyl methacrylate macromonomer, and the like. These compounds may be used alone or in combination of two or more.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and CH ₂ =CR ⁸ R ^{9 .} [wherein R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁹ represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms]. These compounds may be used alone or in combination of two or more.

The weight of the adhesive is flat in terms of alkali dissolution rate, film properties, and the like. The average molecular weight is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, still more preferably from 5,000 to 200,000.

Here, the weight average molecular weight can be measured by gel permeation chromatography and determined using a standard polystyrene calibration curve.

As the content of the binder, photopolymerization including the aforementioned metal nanowire The total mass of the solid matter of the composition is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, still more preferably 20% by mass to 80% by mass based on the total mass. When it is in the above range, both the developability and the conductivity of the metal nanowire can be considered.

(Photopolymerizable composition)

The photopolymerizable composition represents a function of imparting an image by exposure of a conductive film or providing a starting point. A photopolymerization initiator containing (a) an addition polymerizable unsaturated compound and (b) a radical generated by irradiation with light is contained as a basic component.

(a) Addition of polymerizable unsaturated compounds

The addition polymerizable unsaturated compound (hereinafter also referred to as "polymerizable compound") of the component (a) is an addition polymerization reaction in the presence of a radical, and is polymerized. The compound is usually used for a compound having at least one, more preferably two or more, still more preferably four or more, and still more preferably six or more ethylenically unsaturated double bonds at the molecular terminal.

These compounds have chemical forms such as monomers, prepolymers, i.e., dimers, trimers or oligomers, or mixtures of these.

Such a polymerizable compound is known as various compounds which can be used as the component (a).

Among them, as a particularly preferred polymerizable compound, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylic acid are particularly preferable from the viewpoint of film strength. Ester, dipentaerythritol penta (meth) acrylate.

As the content of the component (a), the light is contained in the above-mentioned metal nanowire The total mass of the solid matter of the conjugate composition is preferably from 2.6 mass% to 37.5% by mass, more preferably from 5.0 mass% to 20.0 mass%.

(b) Photopolymerization initiator

The photopolymerization initiator of the component (b) is a compound which generates a radical when irradiated with light. Examples of such a photopolymerization initiator include a compound which generates an acid radical which eventually becomes an acid by light irradiation, a compound which generates another radical, and the like. Hereinafter, the former is referred to as "photoacid generator", and the latter is referred to as "photoradical generator".

- Photoacid generator -

The photoacid generator can be suitably selected and used as a photoinitiator photoinitiator, a photoradical polymerization photoinitiator, a dye photochromic agent, a photochromic agent, or a micro resist. Used by irradiating actinic rays or radiation Known compounds which produce acid free radicals and mixtures thereof.

The photoacid generator is not particularly limited and may be appropriately selected as needed. For example, triazine having at least one dihalomethyl group or trihalomethyl group, 1,3,4-oxadiazole, naphthoquinone-1,2-diazido-4-sulfonyl halide, heavy Nitrogen salts, cerium salts, cerium salts, cerium salts, sulfhydrazine sulfonates, sulfonium sulfonates, diazo dihydrazide, diterpene, o-nitrobenzoyl sulfonate, and the like. Particularly preferred among these are sulfimine sulfonate, oxime sulfonate, o-nitrobenzoyl sulfonate which are compounds which produce sulfonic acid.

Further, a compound in which a radical or a compound which generates an acid radical by irradiation with actinic rays or radiation is introduced into a main chain or a side chain of a resin, for example, a specification of U.S. Patent No. 3,849,137 and a specification of German Patent No. 3914407 can be used. Japanese Patent Laid-Open No. 63-26653, Japanese Patent Laid-Open No. Sho 55-164824, Japanese Patent Laid-Open No. Sho 62-69263, Japanese Patent Laid-Open No. Sho 63-146038, Japanese Patent Laid-Open No. 63-163452, A compound described in each of JP-A-62-153853, JP-A-63-146029, and the like.

Further, the compounds described in the respective specifications of U.S. Patent No. 3,779,778 and European Patent No. 126,712 can be used as an acid radical generating agent.

The above triazine-based compound can be, for example, a Japanese patent A compound described in Japanese Patent Laid-Open Publication No. 2011-254046.

In the present invention, it is preferred to produce a sulfonic acid compound in the photoacid generator. The oxime sulfonate compound shown below is particularly preferable from the viewpoint of high sensitivity.

[化12]

As a photoacid generator, if a compound having 1,2-diazide naphthoquinone group is used The object has high sensitivity and good developability.

From the viewpoint of high sensitivity, among the photoacid generators, those in which D is independently a hydrogen atom or a 1,2-diazepinenaphthyl group are preferable.

[Chemistry 13]

-Photoradical generator -

The photoradical generator is a compound having a function of directly absorbing light or generating photo-sensitization to generate a decomposition reaction or a hydrogen abstraction reaction to generate a radical. The photoradical generator is preferably a compound having absorption at a wavelength of from 300 nm to 500 nm.

A plurality of compounds are known, and examples thereof include a triazine compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, and an organic compound described in JP-A-2008-268884. A peroxidic compound, an azo compound, a coumarin compound, an azide, a metallocene compound, a hexaaryldiimidazole compound, an organoboronic acid compound, a disulfonic acid compound, an oxime ester compound, a mercaptophosphine (oxide) compound. These compounds can be suitably selected as needed. Particularly preferred among these compounds are a benzophenone compound, an acetophenone compound, a hexaaryldiimidazole compound, an oxime ester compound, or a mercaptophosphine (oxide) compound from the viewpoint of exposure sensitivity.

The photoradical generator can be, for example, Japanese Patent Laid-Open No. 2011-018636 The photoradical generator described in Japanese Laid-Open Patent Publication No. 2011-254046.

The photopolymerization initiator may be used alone or in combination of two or more. The amount is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, based on the total mass of the solid matter of the photopolymerizable composition containing the metal nanowire, and further preferably It is 1% by mass to 20% by mass. In such a numerical range, when a pattern including a conductive region and a non-conductive region to be described later is formed on the conductive film, good sensitivity and pattern formation property are obtained.

Other additives other than the above components may, for example, be a chain transfer agent, cross-linking Various additives such as agents, dispersants, solvents, surfactants, antioxidants, vulcanization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, etc.

(chain transfer agent)

The chain transfer agent is used to increase the exposure sensitivity of the photopolymerizable composition. Examples of such a chain transfer agent include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxime. Oxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6 a mercapto compound having a heterocyclic ring such as (1H, 3H, 5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyrate) An aliphatic polyfunctional thiol compound such as decyloxy)butane or the like. These compounds may be used alone or in combination of two or more.

The content of the chain transfer agent is a photopolymerizable group containing the aforementioned metal nanowire The total mass of the solid matter of the product is preferably from 0.01% by mass to 15% by mass, more preferably from 0.1% by mass to 10% by mass, even more preferably from 0.5% by mass to 5% by mass.

(crosslinking agent)

The crosslinking agent is a compound which forms a chemical bond by a radical, an acid, or a heat to harden the conductive film, and examples thereof include at least one selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group. a substituted melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a phenol compound or a phenol ether compound, an epoxy compound, a propylene oxide compound, a sulfur epoxy compound, an isocyanate compound, An azide-based compound or a compound having an ethylenically unsaturated group such as a methacryl oxime group or an acryl fluorenyl group. Among these, epoxy compounds, propylene oxide compounds, and compounds having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.

Further, the propylene oxide resin may be used singly or in combination with an epoxy resin. In particular, when it is used in combination with an epoxy resin, it is preferable from the viewpoint of high reactivity and improvement in film physical properties.

Further, in the case where a compound having an ethylenically unsaturated double bond group is used as the crosslinking agent, the crosslinking agent is also contained in the polymerizable compound, and the content thereof is considered to be contained in the content of the polymerizable compound of the present invention.

When the total mass of the solid matter containing the photopolymerizable composition of the metal nanowire is 100 parts by mass, the content of the crosslinking agent is preferably from 1 part by mass to 250 parts by mass, more preferably 3 parts by mass to 200 parts by mass.

(Dispersant)

The dispersing agent serves to prevent the aforementioned metal nanowires in the photopolymerizable composition from agglomerating and dispersing. The dispersing agent is not particularly limited as long as it can disperse the metal nanowire, and may be appropriately selected as needed. For example, a commercially available dispersant can be used as the pigment dispersant, and a polymer dispersant having a property of adsorbing on a metal nanowire is particularly preferable. Examples of such a polymer dispersant include polyvinylpyrrolidone, BYK series (manufactured by BYK Chemie Co., Ltd.), Solsperse series (manufactured by Lubrizol Co., Ltd.), and Ajisper series (Ajinomoto). Manufacturing company, etc.).

Further, in the case where a polymer dispersant as a dispersing agent is further added in addition to the user in the production of the metal nanowire, the polymer dispersing agent is also contained in the binder, and the content thereof should be considered to be included in the aforementioned bonding. In the content of the agent.

The content of the dispersant is preferably from 0.1 part by mass to 50 parts by mass, more preferably from 0.5 part by mass to 40 parts by mass, based on 100 parts by mass of the binder. It is 1 part by mass to 30 parts by mass.

When the content of the dispersant is 0.1 part by mass or more, aggregation of the metal nanowires in the dispersion can be effectively suppressed, and by setting the content of the dispersant to 50 parts by mass or less, stable formation can be achieved in the coating step. The liquid film is preferred because it suppresses the occurrence of coating unevenness.

(solvent)

The solvent is a component for forming a coating liquid containing the composition of the metal nanowire and the photopolymerizable composition to form a film on the surface of the substrate, and may be appropriately selected as needed. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy-2-propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate, and the like. The solvent may also serve as at least a part of the solvent of the dispersion of the aforementioned metal nanowire. These solvents may be used alone or in combination of two or more.

The solid content concentration of the coating liquid containing such a solvent is preferably contained in the range of 0.1% by mass to 20% by mass.

(metal corrosion inhibitor)

Preferred are metal corrosion inhibitors which previously contain a metal nanowire. The metal corrosion inhibitor is not particularly limited and may be appropriately selected as needed. For example, mercaptans, azoles and the like are suitable.

By containing a metal corrosion inhibitor, the rust-preventing effect can be exhibited, and the decrease in conductivity and transparency caused by the passage of the conductive material over time can be suppressed. Metal corrosion inhibition The agent may be added to the photosensitive layer-forming composition in a state of being dissolved in a suitable solvent or in the form of a powder, or may be applied by immersing it in a metal corrosion inhibitor bath after the conductive film is formed.

When a metal corrosion inhibitor is added, it is preferably contained in an amount of 0.5% by mass to 10% by mass based on the metal nanowire.

As another substrate, a polymer compound as a dispersing agent used in the production of the above-mentioned metal nanowire can be used as at least a part of a component constituting the matrix.

In the formation of the transparent conductive film, a composition containing at least a sol-gel cured product can be used as a matrix component together with the metal nanowire.

Hereinafter, the sol-gel cured product will be described in detail.

(sol-gel cured)

The sol-gel cured product is subjected to hydrolysis and polycondensation of an alkoxide compound (hereinafter also referred to as "specific alkoxide compound") selected from the group consisting of Si, Ti, Zr, and Al, and further If necessary, heat and dry.

The specific alkoxide compound is preferably a compound represented by the following formula (X) in terms of ease of obtaining.

M ¹ (OR ²⁰ ) _a R ²¹ _4-a (X)

(In the formula (X), M ¹ represents an element selected from the group consisting of Si, Ti and Zr, and R ²⁰ and R ²¹ each independently represent a hydrogen atom or a hydrocarbon group, and a represents an integer of 2 to 4)

The respective hydrocarbon groups of R ²⁰ and R ²¹ in the formula (X) are preferably an alkyl group or an aryl group.

The number of carbon atoms in the case of indicating an alkyl group is preferably from 1 to 18, more preferably from 1 to 8, and still more preferably from 1 to 4. Further, in the case of expressing an aryl group, a phenyl group is preferred.

The alkyl group or the aryl group may have a substituent, and examples of the substituent which may be introduced include a halogen atom, an amine group, an alkylamine group, a fluorenyl group and the like.

Further, the compound represented by the formula (X) is a low molecular compound, and preferably has a molecular weight of 1,000 or less.

Specific examples of the compound represented by the general formula (X), for example, in Japan Patent Publication No. 2010-064474 and the like are described.

In the present invention, a sol-gel cured product is used as a substrate for a conductive film. In the case of a shape, it is preferred to use the ratio of the specific alkoxide compound to the aforementioned metal nanowire, that is, the specific alkoxide compound/metal nanowire mass ratio is 0.25/1 to 30/1. . When the mass ratio is less than 0.25/1, the conductive film is inferior in transparency and at least one of abrasion resistance, heat resistance, moist heat resistance, and flex resistance; on the other hand, in the above mass ratio When it is larger than 30/1, it becomes a conductive film which is inferior in conductivity and flexibility.

If the above mass ratio is more preferably in the range of 0.5/1 to 20/1, further preferably 1/1 to 15/1, and most preferably in the range of 2/1 to 8/1, it is stable. A conductive material having high conductivity and high transparency (total light transmittance and haze) and excellent in abrasion resistance, heat resistance, and moist heat resistance and excellent in flex resistance is preferable.

Moreover, in the formation of the conductive film, it can be used together with the metal nanowire to A composition containing a small amount of a polymer is used as a matrix component.

The polymer used will be described in detail below.

The polymer contains a synthetic polymer or a natural polymer, and the synthetic polymer can be listed. Polyester, polyimine, polyacryl, polyvinylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, methacrylic resin, fluorine resin, phenol resin, Melamine resin, fluorenone resin, synthetic rubber or latex of these. Examples of the natural polymer include a cellulose resin or a natural rubber.

A protective layer containing a protective coating material may be disposed on the conductive film as needed.

For the protective coating material forming the protective layer, for example, those described in Japanese Laid-Open Patent Publication No. 2011-167848 can be applied.

The protective coating material may include a crosslinking agent, a polymerization initiator, a stabilizer (for example, an antioxidant and a UV stabilizer for prolonging the life of the product, and a polymerization inhibitor for improving storage), a surfactant, And those with the same effect. Moreover, the protective coating material may further comprise a corrosion inhibitor that prevents corrosion of the metal nanowire.

As a method of forming a protective layer, if it is a well-known wet coating method, There are no special restrictions. Specific examples thereof include spraying, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, and the like.

Forming a protective layer by impregnating a transparent conductive film with a protective layer coating When the film thickness of the protective layer after application and drying is too thin with respect to the conductive film before coating, the functions of the protective layer such as abrasion resistance, abrasion resistance, and weather resistance are lowered; Then, the contact resistance as a conductor increases.

The protective layer coating is applied to the conductive film to a film thickness of 50 to 150 nm. When the range is formed, the film thickness after application and drying is preferably from 30 nm to 150 nm, and the film thickness of the conductive film can be adjusted so that the surface resistivity and the haze can be adjusted to a predetermined value. Among them, 40 nm to 175 nm is preferable, and 50 nm to 150 nm is particularly preferable. The film thickness after drying of the coating material for a protective layer depends on the film thickness of the transparent conductive film. However, when the film thickness is 30 nm or more, the protective function of the protective layer is more favorably exhibited, and the thickness is preferably 150 nm or less. The film thickness has a tendency to ensure better electrical conductivity.

The conductive film can be patterned into a desired shape depending on the use.

The method of patterning the conductive film is not particularly limited, and for example, the conductive film can be exposed and developed. More specifically, it includes a step of pattern exposure, a development step, and further includes other steps as needed.

In the case where the substrate of the conductive film is non-photosensitive, it is preferred to Patterning was carried out by the following methods (1) to (2).

(1) A photoresist layer is provided on the conductive film, and the photoresist layer is subjected to a desired pattern exposure and development to form the patterned resist (etch mask), which is etched by etching. A patterning method in which a liquid is subjected to a wet process for treating a conductive film or a dry process such as reactive ion etching to etch a conductive film in a region not protected by a resist to break or disappear. This method is described, for example, in Japanese Patent Laid-Open Publication No. 2010-507199 (particularly paragraphs 0212 to 0217).

(2) The photocurable resin is provided on the pattern in a desired region on the conductive film by an inkjet method or a screen printing method, and the photocurable resin layer is applied to the photocurable resin layer. Desirable exposure, after forming the patterned resist (etching mask), immersing the conductive film in an etchable etching solution, or spraying the etching solution to make a conductive film in a region not protected by the resist A patterning method that breaks or disappears.

In the case of using the method of the above (1) or (2), it is preferred that the resist on the conductive film is removed by a usual method after the patterning is completed.

The method of imparting the etching mask is not particularly limited, and for example, coating is exemplified. Method, printing method, inkjet method, etc.

The coating method is not particularly limited, and examples thereof include roll coating, bar coating, dip coating, spin coating, casting, die coating, knife coating, bar coating, and gravure coating. , curtain coating method, spraying method, blade coating method, and the like.

Examples of the printing method include a letterpress (blade) printing method, a stencil printing method, an offset printing method, a gravure printing method, and the like. In addition, the resist layer formed in this step may be a positive resist layer or a negative resist layer. In the case of a positive resist layer, the patterned exposed regions become soluble, forming a patterned resist layer in the unexposed regions (undissolved regions); in the case of a negative resist layer, exposure The region is a hardened resist layer, and a resist layer which is an unexposed portion, that is, an uncured portion is removed by applying a solution to form a patterned resist layer.

The material for forming a resist layer used in the method of the above (1) The class is not particularly limited, and any of a negative type, a positive type, and a dry film type can be used.

In the formation of the resist layer, a commercially available alkali-soluble photoresist can be suitably used. For example, the color mosaic series manufactured by Fujifilm, FILS series, FIOS series, FMES series, FTENS series, FIES series, positive and negative photoresist series for semiconductor process, Fuji Resist series manufactured by Fuji Pharmaceuticals (including FR series, FPPR series, FMR series, FDER series, etc.) And a series of photoresists manufactured by AZ Electronic Materials (including RFP series, TFP series, SZP series, HKT series, SFP series, SR series, SOP series, SZC series) , CTP series, ANR series, P4000 series, TPM606, 40XT, nXT series, etc.), various photoresists manufactured by JSR, etc. can be widely used in high-resolution type to low-resolution type.

The dry film resist includes a photosensitive film for a printed wiring board manufactured by Hitachi Chemical Co., Ltd., a photosensitive dry film SUNFORT series manufactured by Asahi Kasei E-materials, and a FXG series manufactured by DuPont MRC dry film. These dry film resists can be suitably used in the FXR series, FX900 series, JSF100 series, SA100 series, LDI series, FRA series, CM series, and Transer series manufactured by Fujifilm.

These resist layer forming materials may be appropriately selected depending on the resolution of the pattern formed in the conductive film or the like.

When a dry film type resist layer forming material is used in the formation of the resist layer, the photosensitive resist layer of the dry film resist prepared in advance may be transferred onto the surface of the formed conductive film. .

The exposure step can be performed using an etch mask comprising a photopolymerization initiator The exposure was carried out at an oxygen concentration of 5% or less.

Moreover, the transfer material can be used to pattern on the target substrate by transfer A conductive film is formed.

Further, as described in [0147] to [0148] of JP-A-2011-167848, a pattern of a removing agent (etching liquid) can be applied to a conductive film by screen printing to perform a conductive film. Patterned.

[Transparent double-sided adhesive sheet]

The transparent double-sided adhesive sheet is transparent and has an adhesive sheet on the front and back sides. The sheet is laminated on the conductive film in such a manner that one of the adhesive surfaces is attached to the conductive film. In other words, the transparent double-sided adhesive sheet is attached to the side of the conductive film of the transparent substrate with the conductive film on the transparent substrate and the conductive film disposed thereon.

More specifically, in FIG. 4, the surface 306c and the back surface 306d of the transparent double-sided adhesive sheet 306 are adhesive, and the transparent double-sided adhesive sheet 306 is disposed on the conductive film 304 in such a manner that the surface 306c is attached to the conductive film 304. on.

If the transparent double-sided adhesive sheet contains at least an adhesive layer, it may be included in The type of the substrate on which the adhesive layer is disposed on both sides of the substrate (the transparent double-sided adhesive sheet with the substrate) may be of a type including only the adhesive layer and not including the substrate (transparent transparent substrate without substrate) Adhesive film). Among them, from the viewpoint of film formation of a product using a transparent double-sided adhesive sheet, a transparent double-sided adhesive sheet having no substrate is preferable.

The above-mentioned reducing compound is contained in the transparent double-sided adhesive sheet. Contained Suitable forms of the original compound are as described above.

Further, in the case where the transparent double-sided adhesive sheet is a transparent double-sided adhesive sheet to which a substrate is attached, the reducing compound may be contained in any one of the substrate or the adhesive layer. It can be included in both the substrate and the adhesive layer.

Further, when the above-mentioned reducing compound is contained in the adhesive layer of the double-sided adhesive sheet, the dispersibility of the reducing compound in the adhesive is more excellent, and therefore, even when the conductive film laminate is placed in a high-temperature and high-humidity environment, The adhesion of the adhesive layer was also not found to decrease.

The content of the reducing compound in the transparent double-sided adhesive sheet is not particularly limited. Further, the precipitation of the reducing compound in the transparent resin is further suppressed, and the transparency of the sheet is further improved, and the precipitation of the reducing compound in the vicinity of the surface of the sheet is further suppressed, and the adhesion between the sheet and the adherend is further improved, and the electrical property is further improved. In view of reliability, the mass ratio (A/C) of the total mass A of the reducing compound to the total mass C of the transparent resin is preferably 0.20 or less, more preferably 0.10 or less. The lower limit is not particularly limited, and is preferably 0.0001 or more, and more preferably 0.0005 or more, in that a thin transparent double-sided adhesive sheet can obtain a predetermined effect.

Further, when the total mass A is two or more kinds of reducing compounds, the total mass of these is shown. The total mass C indicates the total mass of these when it contains two or more types of transparent resins.

The thickness of the transparent double-sided adhesive sheet is not particularly limited, since the conductive film is laminated In terms of the touch panel, it is preferably 5 μm to 150 μm, more preferably 20 μm to 100 μm.

By making the thickness of the transparent double-sided adhesive sheet 20 μm or more, the effect of covering the step or the unevenness of the attached substrate can be obtained, and the thickness of the transparent double-sided adhesive sheet can be sufficiently ensured by 100 μm or less. The effect of the transparency of the transparent double-sided adhesive sheet.

The transparent double-sided adhesive sheet is a transparent double-sided adhesive sheet with a substrate attached thereto. In the shape, the adhesive layer is provided on both sides of the substrate. The type of the substrate to be used is not particularly limited, and a transparent substrate is preferably used. Examples of the transparent substrate include polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane, and diethylcellulose. Membrane, triacetyl cellulose membrane, ethylene glycol cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, Polycarbonate film, polymethylpentene film, polyfluorene film, polyether ether ketone film, polyether ruthenium film, polyether phthalimide film, polyimine film, fluororesin film, nylon film, acrylic film Wait.

The material of the adhesive layer of the transparent double-sided adhesive sheet is not particularly limited, and Use well-known materials. For example, various transparent resin adhesives such as a rubber-based adhesive, an acrylic adhesive, an anthrone-based adhesive, and a urethane-based adhesive can be used, and the transparency is more excellent and the compatibility with the above-mentioned reducing compound is excellent. In terms of this, an acrylic adhesive is preferred.

The acrylic adhesive will be a monomer unit of alkyl (meth)acrylate. The acrylic polymer of the main skeleton serves as a base polymer. Further, (meth) acrylate means acrylate and/or methacrylate. The average carbon number of the alkyl group of the (meth)acrylic acid alkyl ester constituting the main skeleton of the acrylic polymer is preferably about 1 to 12, and specific examples of the (meth)acrylic acid alkyl ester can be exemplified (methyl). Methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.

Moreover, the transparent double-sided adhesive sheet is preferably at 60 ° C, 90% RH strip The total light transmittance after standing for 100 hours is 80% or more (more preferably 85%) Further, it is more preferably 90% or more), and the haze is 1.0% or less (more preferably 0.7% or less).

Further, the water absorption rate of the transparent double-sided adhesive sheet is preferably 2.0% or less (more preferably 1.25% or less, still more preferably 1.0% or less) after standing for 100 hours under conditions of 60 ° C and 90% RH. ).

The method for measuring the water absorption rate is based on the method described in JP-A-2012-11637.

The above transparent double-sided adhesive sheet can be produced by a known method. For example, In the case of a substrate-free transparent double-sided adhesive sheet, a transparent double-sided adhesive sheet can be produced by coating an adhesive composition containing a reducing compound in a manner to have a thickness after drying to a predetermined thickness. After the coating layer of the adhesive composition is provided on a member (liner), the coating layer is dried and, if necessary, cured to form an adhesive layer.

Further, in the case of a transparent double-sided adhesive sheet to which a substrate is attached, an adhesive layer (direct printing method) may be provided by directly applying an adhesive composition containing a reducing compound to the surface of the substrate to be dried. An adhesive layer containing a reducing compound is formed on the separator in the same manner as described above, and then the substrate is transferred (bonded) to form an adhesive layer on the substrate (transfer method).

Further, as another manufacturing method, for example, a method in which an adhesive composition is applied to a surface of a substrate containing a reducing compound to form an adhesive layer, and a transparent double-sided adhesive sheet with a substrate is produced is exemplified.

In addition, in FIG. 4, one surface of the transparent substrate 302 is provided. The conductive film 304 and the transparent double-sided adhesive sheet 306 are provided, but the shape is not limited thereto.

For example, a conductive film 304a, a conductive film 304b, a transparent double-sided adhesive sheet 306a, and a transparent double-sided adhesive sheet 306b may be provided on both surfaces of the transparent substrate 302 as in the conductive film laminate 400 shown in FIG. 5. Further, as with the conductive film 304a and the conductive film 304b, the pattern shapes of the two may be different. Further, the conductive films 304a and 304b are both thin and linear, and they are arranged in an orthogonal manner.

<Conductive film laminate>

As described above, the conductive film laminate of the first embodiment of the present invention includes a transparent substrate, a conductive film containing silver disposed on the transparent substrate, and a transparent double-sided adhesive sheet bonded to the conductive film.

Further, it is also possible to further bond another member (for example, a protective substrate to be described later) to the surface on which the transparent double-sided adhesive sheet is exposed to exhibit adhesiveness.

Conductive in terms of further inhibiting ion migration between conductive films The film laminate can be widely applied to, for example, a touch panel, an electrode for a display, an electromagnetic wave mask, an electrode for an organic or inorganic electroluminescence (EL) display, an electronic paper, an electrode for a flexible display, or an integrated solar body. In batteries, display elements, various other components, and the like. Particularly preferred of these are the lead wiring portions of the touch panel. Hereinafter, the form of the lead wiring portion of the touch panel will be described in detail.

[suitable form]

When the above-mentioned conductive film laminate is used in a touch panel, ion migration between the conductive films is further suppressed, so that the performance can be maintained even after being left for a long time in a severe environment.

In recent years, the touch panel has been promoted for use in a small information terminal device, and in order to secure a wide input area, the width of the edge portion is required to be narrow (narrow edge). In general, the lead wiring (peripheral wiring) is disposed on the edge portion of the touch panel, and in order to achieve narrow edge, it is necessary to narrow the width of the lead wiring and the distance between the lead wirings. On the other hand, when such a narrowing is performed, it becomes easy to disconnect the lead wire or short-circuit between the lead wires.

On the other hand, when the conductive film laminate is applied to the lead wiring portion (that is, when the conductive film of the conductive film laminate is applied as a lead wiring), the transparent double-sided adhesive sheet containing the reducing compound is used. The function is to further suppress the disconnection of the lead wiring (metal wiring) or the short circuit between the lead wirings.

This will be described in more detail below with reference to the drawings.

Fig. 6(A) is a plan view schematically showing a part of the touch panel member, and Fig. 6(B) is a schematic cross-sectional view taken along line A-A. The touch panel member 500 shown in FIG. 6A is configured by a flexible circuit 30 in which a conductive film laminate 600 for a touch panel and a conductive film laminate 600 for a touch panel are bonded to each other at a predetermined position.

In the conductive film laminate 600 for a touch panel, a transparent electrode layer 34 (for example, an ITO layer or a silver-containing layer) and a transparent double-sided adhesive sheet 42 are provided on one side of one surface of the transparent substrate 32. Further, the transparent electrode layer 34 is formed by connecting a plurality of diamond shapes arranged on the transparent substrate 32 in a linear pattern in one direction. A plurality of lead wires 36 electrically connected to each other are provided on the transparent electrode layer 34. A conductor (not shown) is provided at the end of the lead wiring 36, and is electrically connected to a terminal (not shown) of the flexible circuit 30.

On the transparent substrate 32, in the region where the transparent electrode layer 34 is provided, an active area 38 that functions as a sensing unit (sensor portion) that can be detected by the touch panel user and can detect the touch position is formed. The outer side becomes an inactive area 40. The edge portion of the touch panel is equivalent to the inactive area 40. Usually, the lead wiring 36 or the flexible circuit 30 is present in the inactive area 40 as described above. By disposing the transparent double-sided adhesive sheet 42 so as to cover the lead wiring 36 on the lead wiring 36, the disconnection of the lead wiring 36 and the short circuit between the lead wirings 36 can be further suppressed.

In other words, one of the suitable embodiments of the conductive film laminate includes a conductive film laminate for a touch panel: a transparent substrate; an electrode pattern portion that functions as a sensor disposed on the transparent substrate; One end of the substrate is connected to the electrode of the electrode pattern portion, and the other end is connected to a terminal connected to the external control circuit, and includes a terminal wiring portion including silver lead wiring; and the transparent double-sided adhesive sheet disposed on at least the lead wiring. In addition, the amount of silver contained in the lead wiring per unit area is 50 μg/mm ² or less, and the transparent double-sided adhesive sheet contains the transparent resin and the reducing compound.

<<2th embodiment>>

Hereinafter, suitable embodiments of the wiring board and the transparent adhesive sheet according to the second embodiment of the present invention will be described.

First, the feature points of the second embodiment of the present invention compared with the prior art will be described in detail.

As described above, it has been found that in the second embodiment of the present invention, by using A desired adhesive layer can be obtained by a compound having a predetermined oxidation-reduction potential and a transparent adhesive layer whose haze changes within a predetermined range in a predetermined environmental test. By using a compound having an oxidation-reduction potential within a predetermined range, silver ions in the transparent adhesive layer can be reduced to metallic silver, and as a result, ion migration can be suppressed. Further, in the environmental test described later, the transparent adhesive layer exhibiting predetermined characteristics is more likely to interact with moisture, and as a result, whitening is suppressed, and the dispersibility of the compound is also excellent. As a result, ion migration inhibition ability and whitening resistance which were previously in a trade-off relationship can be achieved at a higher level.

In particular, when the compound is a phenol compound, the hydroxyl group in the compound easily interacts with the material (adhesive) constituting the transparent adhesive layer, and the dispersibility in the transparent adhesive layer is more excellent. As a result, ion mobility inhibition ability and whitening resistance can be achieved at a higher level.

First, a suitable shape of the transparent adhesive sheet of the second embodiment of the present invention State is detailed.

The transparent adhesive sheet contains at least a compound having a redox potential of 0.40 V to 1.30 V and a transparent adhesive layer of an adhesive.

Hereinafter, each component contained in the transparent adhesive layer will be described in detail first.

(A compound with an oxidation-reduction potential of 0.40 V to 1.30 V)

The transparent adhesive layer of the transparent adhesive sheet contains a compound having an oxidation-reduction potential of 0.40 V to 1.30 V (hereinafter also referred to as a reducing compound). The reducing compound is a so-called electron transport inhibitor (electron migration inhibitor) which reduces silver ions in the transparent adhesive layer to metal by including the reducing compound in the transparent adhesive layer. Silver, thereby suppressing ion migration.

The redox potential of the reducing compound is 0.40 V to 1.30 V, and more preferably 0.50 V to 1.20 V, more preferably 0.55 V to 1.1 V, more preferably in terms of ion mobility inhibition ability. It is 0.55 V~1.0 V.

When the redox potential of the reducing compound is less than 0.40 V or exceeds 1.30 V, the ion migration inhibiting ability is poor.

Further, the method for measuring the oxidation-reduction potential of the reducing compound used in the second embodiment of the present invention can be measured by a method described in a number of documents, and in the present invention, the value defined by the following method is defined. It is an oxidation-reduction potential.

After 5 minutes of Ar foaming of a reducing compound 1 mM, a tetrabutylammonium perchlorate 0.1 M DMF as a supporting electrolyte, a potentiostat (ALS-604A of BAS Co., Ltd.) was used. Cyclic voltammetry measurements were performed. The oxidation-reduction potential of the working electrode was measured using glassy carbon (Glassy Carbon), the counter electrode was Pt, and the reference electrode was a saturated calomel electrode.

The type of the reducing compound does not satisfy the above oxidation-reduction potential. Specific examples thereof include a phenol compound, an amine compound, a sulfur compound, and a phosphorus compound. When the redox potential of the reducing compound in the second embodiment of the present invention is within a predetermined range, it is oxidized instead of silver oxidation, and the intended effect is obtained.

Among them, a phenol compound is preferred in terms of excellent dispersibility in the transparent adhesive layer and superior ion mobility inhibition ability. In more detail, the adhesion layer comparison Since the hydrophilic property is exhibited, the hydroxyl group in the phenol compound easily interacts with the adhesive constituting the adhesive layer, and the dispersibility of the phenol compound in the adhesive is excellent, and as a result, the ion migration inhibiting ability is improved.

There is no special type of phenolic compound if it meets the above redox potential. The limitation is, for example, DL-α-tocopherol or the like.

(suitable form)

A suitable form of the phenol compound is a compound represented by the following formula (1A) to formula (3A). When it is this compound, it is excellent in compatibility with an adhesive agent, and it is excellent in the ion migration suppression ability.

R _11a to R _15a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

A suitable example of the hydrocarbon group is -OR _31a . R _31a represents a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom. These may be the same when there are multiple -OR _31a cases.

The carbon number of the hydrocarbon group is better in terms of being more compatible with the adhesive. It is 1~12, and more preferably 1~10.

More specifically, the hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group.

Further, the total molecular weight of each of R _11a to R _15a is 21 or more. Among them, it is preferably 35 or more. Further, the upper limit is not particularly limited, and is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less in terms of the effect of the present invention being more excellent. The total of the molecular weights of the above respective groups is a value indicating the molecular weight of each of the groups of R _11a to R _{15a and} the total of these molecular weights.

Further, R _11a to R _15a may be bonded to each other to form a ring. For example, two groups such as R _11a and R _12a , R _12a and R _13a , R _13a and R _14a , or R _14a and R _15a may be bonded to each other to form a ring. The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring to a 6-membered ring structure.

The type of the hetero atom contained in the hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, in terms of excellent ion mobility inhibition ability of silver, -Y ₁ -, -N(R _a )-, -C(=Y ₂ )-, -CON(R _b )-, -C(=Y ₃ )Y ₄ -, -SO _t -, -SO ₂ N(R _c )-, a halogen atom, or a combination of these groups.

Y ₁ to Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, an oxygen atom or a sulfur atom is preferred in terms of ease of handling. t represents an integer from 1 to 3.

In the formula (1A), R _11a and R _15a each independently represent a hydrogen atom or a hydrocarbon group having an oxygen atom and having 1 to 20 carbon atoms. The carbon number of the hydrocarbon group is preferably from 1 to 8, more preferably from 1 to 4, in terms of being more excellent in compatibility with the adhesive.

More specifically, the hydrocarbon group which may contain an oxygen atom may be an aliphatic hydrocarbon group which may contain an oxygen atom, an aromatic hydrocarbon group which may contain an oxygen atom, or a combination of these groups. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group.

Further, an oxygen atom may be contained in the hydrocarbon group. In the case of containing an oxygen atom, it may be contained in the form of a linking group such as -O- or -COO-.

It is preferred that R _12a and R _14a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may include an oxygen atom. The carbon number of the hydrocarbon group is preferably from 2 to 9, more preferably from 3 to 8, in terms of being more excellent in compatibility with the adhesive.

It is preferred that R _13a represents a hydroxyl group or a hydrocarbon group having a carbon number of 1 to 20 which may contain an oxygen atom (for example, -OR _a ). R _a represents _a hydrocarbon group having 1 to 20 carbon atoms. The carbon number of the hydrocarbon group represented by R _13a and R _a is preferably from 1 to 18, more preferably from 1 to 15, in terms of being more excellent in compatibility with the adhesive.

R _11a to R _15a may be bonded to each other to form a ring. That is, any two of R _11a to R _15a may be bonded to each other to form a ring. For example, two groups such as R _11a and R _12a , R _12a and R _13a , R _13a and R _14a , or R _14a and R _15a may be bonded to each other to form a ring.

The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring to a 6-membered ring structure.

In the formula (2A), R _16a to R _23a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

The suitable range of the hydrocarbon group represented by R _16a to R _23a is the same as the suitable range of the hydrocarbon group represented by the above R _11a to R _15a .

Further, the total molecular weight of each of R _16a to R _23a is 24 or more. Among them, it is preferably 35 or more. Further, the upper limit is not particularly limited, and is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less in terms of the effect of the present invention being more excellent. Further, R _16a to R _23a may be bonded to each other to form a ring.

R _24a represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

In the formula (2A), R _16a , R _23a and R _24a each independently represent a hydrogen atom or a hydrocarbon group having an oxygen atom and having 1 to 20 carbon atoms. The suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _16a , R _23a and R _24a is the same as the suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _11a and R _15a described above.

It is preferred that R _17a , R _{19a ,} R _20a and R _22a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom. The suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _17a , R _{19a ,} R _20a and R _22a is the same as the suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _12a and R _14a described above.

R _18a and R _21a each independently represent a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms (for example, -OR _a ) which may include an oxygen atom. R _a represents _a hydrocarbon group having 1 to 20 carbon atoms. Suitable same appropriate range R _18a and R _21a are represented by the above-described hydrocarbon groups of R _13a and the hydrocarbon group represented by R _a scope.

In the formula (3A), R _25a to R _28a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom.

The suitable range of the hydrocarbon group represented by R _25a to R _28a is the same as the suitable range of the hydrocarbon group represented by the above R _11a to R _15a .

Further, the total molecular weight of each of R _25a to R _28a is 40 or more. Among them, it is preferably 50 or more. Further, the upper limit is not particularly limited, and is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less in terms of the effect of the present invention being more excellent.

Further, R _25a to R _28a may be bonded to each other to form a ring.

L represents a divalent or trivalent hydrocarbon group which may have a hetero atom, -S-, or a combination of these groups. The carbon number of the divalent hydrocarbon group is preferably from 1 to 12, more preferably from 1 to 10, in terms of being more excellent in compatibility with the insulating resin.

m represents an integer of 2 or 3.

In the formula (3A), it is preferred that R _25a to R _28a each independently represent a hydrogen atom or a hydrocarbon group having an oxygen atom and having 1 to 20 carbon atoms. The suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _25a to R _28a is the same as the suitable range of the hydrocarbon group which may contain an oxygen atom represented by R _11a and R _15a described above.

Preferably, L represents a divalent or trivalent hydrocarbon group which may have an oxygen atom, -S-, or a combination of these groups. The number of carbon atoms contained in the hydrocarbon group is not particularly limited, and is preferably from 1 to 40, more preferably from 2 to 20. The hydrocarbon group may be any of a linear form, a branched form, a cyclic form, or an aromatic form, and examples thereof include an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the oxygen atom may be contained in the above hydrocarbon group in the form of a linking group such as -O- or -COO-.

A suitable form of R _13a in the formula (1A) and R _18a and R _21a in the formula (2A) is a group represented by the formula (4).

Formula (4A)*-CH ₂ -R _32a

R _32a represents a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms. The carbon number of the hydrocarbon group represented by R _32a is preferably from 1 to 15, more preferably from 1 to 12, in terms of being more excellent in compatibility with the adhesive. * indicates the bonding position.

Among the reducing compounds, the ion migration inhibition ability is more excellent. In other words, a compound represented by the formula (5) can be suitably used.

In the formula (5A), the definitions of R _11a , R _14a and R _{15a are} the same as those of the group in the formula (1A).

In the formula (5A), R _40a and R _41a each independently represent a hydrogen atom, a hydroxyl group, an aliphatic hydrocarbon group which may contain an oxygen atom, and an aromatic hydrocarbon group which may contain an oxygen atom. Among them, an alkyl group containing a 3-stage carbon atom or a 4-stage carbon atom is preferred in terms of more excellent ion mobility-inhibiting ability.

The number of carbon atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group is not particularly limited, and more preferably 2 to 20. Particularly preferably, R _40a is an alkyl group having 1 to 5 carbon atoms, and R _41a is an alkyl group having 10 to 20 carbon atoms.

It is preferred that at least one of R _11a , R _15a , R _40a and R _41a has 1 to 20 carbon atoms. When the number of carbon atoms is within the above range, the solubility in the adhesive is improved, and the dispersibility of the compound is improved, and as a result, the ion mobility inhibition ability of silver is improved. Among them, the number of carbon atoms is preferably from 8 to 20, more preferably from 10 to 18.

Further, it is preferred that the total number of carbon atoms contained in each of R _11a , R _15a , R _40a and R _41a is 4 or more. When the total number of carbon atoms is in this range, ion migration of silver is suppressed, and insulation reliability between metal wirings is improved. Further, in terms of the effect being more excellent, the total number of counts is preferably 8 or more, and more preferably 10 or more. In addition, the upper limit is not particularly limited, and it is easier to synthesize from the synthesis, and the total number of the adhesives is preferably 50 or less, and more preferably 40 or less.

(adhesive)

The adhesive is not particularly limited, and a known material can be used as a material exhibiting adhesiveness (for example, an adhesive resin). For example, various adhesives such as a rubber-based adhesive, an acrylic adhesive, an anthrone-based adhesive, and a urethane-based adhesive can be used, and the transparency is more excellent and the compatibility with the reducing compound is more excellent. In other words, an acrylic adhesive is preferred.

The acrylic adhesive will be a monomer unit of alkyl (meth)acrylate. The acrylic polymer of the main skeleton serves as a base polymer. Further, (meth) acrylate means acrylate and/or methacrylate. The main skeleton constituting the acrylic polymer The average carbon number of the alkyl group of the (meth)acrylic acid alkyl ester is preferably about 1 to 12, and specific examples of the alkyl (meth)acrylate may be exemplified by methyl (meth) acrylate and (methyl). Ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.

The transparent adhesive sheet may be a substrate containing only a transparent adhesive layer. Type (transparent adhesive sheet without substrate), which may be a type comprising a substrate with a transparent adhesive layer disposed on at least one main surface of the substrate (a transparent adhesive sheet with a substrate attached thereto, for example, on both sides of the substrate) A transparent double-sided adhesive sheet with a substrate attached to the adhesive layer, and a transparent single-sided adhesive sheet with an adhesive layer only on one side of the substrate. Among them, from the viewpoint of film formation of a product using an adhesive sheet, a transparent double-sided adhesive sheet having no substrate is preferable.

When the transparent adhesive sheet is a transparent adhesive sheet with a substrate attached thereto, The type of the substrate to be used is not particularly limited, and a transparent substrate is preferably used. Examples of the transparent substrate include a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyethylene film, a polypropylene film, a cellophane, and a second film. Cellulose film, triethylene glycol film, ethylene glycol cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polyphenylene a vinyl film, a polycarbonate film, a polymethylpentene film, a polyfluorene film, a polyether ether ketone film, a polyether ruthenium film, a polyether quinone film, a polyimide film, a fluororesin film, a nylon film, Acrylic resin film, etc.

The transparent adhesive layer contained in the transparent adhesive sheet is tested in the following environment. The medium time X shows a transparent adhesive layer of less than 12 hours. Among them, in terms of the ion mobility inhibition ability of the transparent adhesive layer being more excellent, it is preferable that the above time X is insufficient. 6 hours.

When the above time X exceeds 12 hours, the ion migration inhibiting ability is poor.

As an environmental test, a transparent adhesive layer (length 5 cm × width 4 cm × thickness 50 μm) containing the above-mentioned reducing compound and a predetermined adhesive was first placed on a glass substrate, and a PET substrate (50 μm) was placed on the transparent adhesive layer. ) An evaluation sample was produced. Thereafter, the evaluation sample was allowed to stand under the conditions of 65 ° C and 95% RH for 72 hours. Thereafter, the evaluation sample was taken out and placed in an environment of 23 ° C and 50% RH. Then, the haze of the transparent adhesive layer in the evaluation sample was measured using "HR-100 type" manufactured by Murakami Color Research Laboratory, and the time X until the haze reached 3% or less was measured.

The quality (A) of the above-mentioned reducing compound in the transparent adhesive layer and the above The mass ratio (A/B) of the mass (B) of the adhesive is not particularly limited, and is preferably 0.0001 to 0.20, more preferably in terms of ion mobility inhibition ability and whitening resistance of the adhesive layer. It is 0.0005~0.10.

The total light transmittance of the transparent adhesive sheet is not particularly limited, and it is preferably 80%. Upper (more preferably 85% or more, and even more preferably 90% or more).

In addition, the total light transmittance can be measured using "HR-100 type" manufactured by Murakami Color Technology Research Institute.

The thickness of the transparent adhesive layer in the transparent adhesive sheet is not particularly limited, and The adhesive sheet is preferably used in the touch panel of 5 μm to 250 μm, more preferably 20 μm to 200 μm.

Coverage can be obtained by making the thickness of the transparent adhesive layer 20 μm or more The effect of the step or the unevenness of the substrate; the effect of sufficiently ensuring the transmittance of the transparent adhesive sheet can be obtained by making the thickness of the transparent adhesive layer 250 μm or less.

The above transparent adhesive sheet can be produced by a known method. For example, without base In the case of a transparent double-sided adhesive sheet, a transparent double-sided adhesive sheet can be produced by coating an adhesive composition containing the above-mentioned reducing compound and an adhesive in a manner to have a thickness after drying to a predetermined thickness. After the coating layer of the adhesive composition is placed on the separator (release liner), the coating layer is dried and, if necessary, cured to form a transparent adhesive layer.

Further, in the case of the transparent double-sided adhesive sheet to which the substrate is attached, the transparent adhesive layer can be provided by directly applying the adhesive composition containing the above-mentioned reducing compound and the adhesive to the surface of the substrate to be dried. In the same manner as described above, a transparent adhesive layer containing the above compound is formed on the separator, and then transferred (bonded) to the substrate to form a transparent adhesive layer on the substrate (transfer method). Further, after being applied to the separator (release liner), it can be cured by irradiating ultraviolet rays by attaching a separator to the coated surface. In this case, a photopolymerization initiator is generally added.

[Wiring substrate]

Next, a suitable form of the wiring board according to the second embodiment of the present invention will be described in detail with reference to the drawings.

FIG. 7 is a schematic cross-sectional view showing an embodiment of a wiring board including an insulating substrate 12, a metal wiring 14 disposed on the insulating substrate 12, and a transparent adhesive layer 19 covering the metal wiring 14. Further, the insulating substrate 12 and the metal wiring 14 constitute an insulating substrate 16 to which metal wiring is attached.

Hereinafter, each member (the insulating substrate 12, the metal wiring 14, and the transparent adhesive layer 19) will be described in detail.

(insulated substrate)

The insulating substrate is insulative, and the type of the insulating substrate is not particularly limited. For example, an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.

Further, the insulating substrate may have a structure in which at least two substrates selected from the group consisting of an organic substrate, a ceramic substrate, and a glass substrate are laminated.

The material of the organic substrate may be exemplified by a resin, and for example, it is preferred to use heat hardening. Resin, thermoplastic resin, or a mixture of these resins. Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy resin, an anthrone resin, a furan resin, and the like. A ketone resin, a xylene resin, a benzocyclobutene resin or the like. Examples of the thermoplastic resin include a polyimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a polyarylamine resin, a liquid crystal polymer, and the like.

Further, as the material of the organic substrate, a glass woven fabric, a glass nonwoven fabric, a polyarsenide woven fabric, a polyarylamine nonwoven fabric, an aromatic polyamide woven fabric, or a material in which the above resin is impregnated may be used.

(metal wiring)

The metal wiring mainly contains silver. Silver may be contained in the form of a silver alloy. When the metal wiring contains a silver alloy, examples of the metal other than silver include tin, palladium, gold, nickel, chromium, and the like. In addition, in the metal wiring, a resin component such as a binder or a photosensitive compound may be contained in a range that does not impair the effects of the present invention. Further ingredients are included as needed.

Moreover, it is preferred that the metal wiring contains a metal nanowire containing silver or a silver alloy. In addition, the metal nanowire is described in detail in the latter stage.

The method of forming the metal wiring is not particularly limited, and examples thereof include a vapor deposition method and a sputtering method. A physical film forming method such as a plating method, or a chemical vapor phase method such as a CVD method, or a method of applying a silver paste containing silver nanoparticles or a silver nanowire, and disclosed in Japanese Patent Laid-Open Publication No. 2009-188360 The method of using silver salt and the like.

Having a plurality of metal wirings disposed on the insulating substrate, adjacent to the metal wiring The minimum distance (interval) is less than 50 μm. In other words, a portion (region) having a distance of at least one or more adjacent metal wirings of less than 50 μm. By setting the distance between the metal wirings to the above range, it is possible to manufacture a wiring board in which metal wiring is formed at a higher density. Among them, from the viewpoint of further increasing the total thickness of the metal wiring, it is preferable that the minimum value (distance) between the adjacent metal wirings is less than 40 μm.

Further, the minimum value of the distance between the metal wirings may satisfy the above range, and may be a distance (interval) of 50 μm or more.

The average interval between the metal wiring closets is not particularly limited, and the height of the wiring board is high. In terms of integration, it is further preferably 0.1 μm to 60 μm, and particularly preferably 0.2 μm to 50 μm. In addition, the average interval here is a value obtained by arithmetically averaging the intervals between the metal wirings at arbitrary positions of 20 or more.

It is preferable that the amount of silver contained per unit area of the metal wiring is 50 μg/mm ² or less. By setting the amount of silver to the above range, the film thickness and width of the metal wiring can be made small, and the high-density integrated product can be expected. Among them, the amount of silver is preferably 30 μg/mm ² or less, more preferably 15 μg/mm ² or less. The lower limit is not particularly limited, and is preferably 0.001 μg/mm ² or more, and more preferably 0.005 μg/mm ² or more, from the viewpoint of further excellent electrical conductivity of the metal wiring.

In addition, when the amount of silver contained in the metal wiring is small, if ion migration occurs, silver which forms the metal wiring is eluted, and thus the disconnection of the metal wiring is likely to occur. In the second embodiment of the present invention, the metal wiring is covered with a transparent resin layer containing a predetermined reducing compound, whereby ion migration of silver can be suppressed, and disconnection of the metal wiring can be suppressed.

The method for measuring the amount of silver is not particularly limited, and a known method can be employed. example For example, the amount of silver can be determined by performing elemental analysis by observing a cross-sectional SEM photograph of a metal wiring. Further, the metal wiring can be brought into contact with a strong acid such as nitric acid to dissolve the silver in the metal wiring, and the amount of silver can be measured based on the amount dissolved. Further, when a metal wiring is produced by using a dispersion containing silver nanowires or silver nanoparticles, the silver in the metal wiring can be calculated by calculation based on the amount of the dispersion used in the production of the metal wiring. the amount.

Further, the unit area of the metal wiring is, in other words, the unit area of the contact portion of the metal wiring with the insulating substrate. That is, the calculation of the amount of silver is performed based only on the area of the contact portion between the metal wiring and the insulating substrate. In other words, the area of the surface of the insulating substrate that is not in contact with the metal wiring (for example, the surface of the insulating substrate that is not in contact with the metal wiring between the metal wirings) is not considered in the calculation of the unit area of the above metal wiring. . Therefore, the amount of silver contained in the unit area of the metal wiring is the amount of silver contained in the unit area (mm ² ) in the contact portion between the metal wiring and the insulating substrate.

The width of the metal wiring is not particularly limited, and the height of the wiring substrate is ensured. The electrical reliability of the body portion and the lead wiring portion (lead wiring portion) is preferably 0.1 μm to 10000 μm, more preferably 0.1 μm to 300 μm, still more preferably 0.1 μm to 100 μm. Particularly preferred is 0.2 μm to 50 μm.

Further, the shape of the metal wiring is not particularly limited and may be any shape. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, etc. are mentioned. Further, the arrangement (pattern) of the metal wiring is not particularly limited, and examples thereof include a stripe shape.

In addition, in FIG. 1, two metal wirings 14 are provided, and the number is not specifically limited. Usually, a plurality of metal wirings are provided.

The thickness of the metal wiring is not particularly limited, and the integration of the wiring board is high. In view of the above, it is preferably 0.001 μm to 100 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.01 μm to 20 μm.

In FIG. 7, the metal wiring 14 may be provided only on one side of the insulating substrate 12. Can be set on both sides. That is, the insulating substrate 16 with the metal wiring may be a single-sided substrate, and may be a double-sided substrate. When the metal wiring 14 is present on both sides of the insulating substrate 12, the transparent adhesive layer 19 may be provided on both sides.

Further, in FIG. 7, the metal wiring 14 is exemplified by a wiring structure of one layer, and of course, it is not limited thereto. For example, a wiring board having a multilayer wiring structure can be formed by using an insulating substrate (multilayer wiring substrate) having a plurality of metal wirings and an insulating substrate with metal wiring interposed therebetween.

Further, a through hole can be formed in the insulating substrate. Double-sided on the insulating substrate In the case of metal wiring, the through hole may be filled with a metal such as silver or silver. The alloy) turns on the metal wiring on both sides.

(metal nanowire)

The metal nanowire contains silver or a silver alloy. The types of silver alloys are as described above.

The metal nanowire refers to a shape having conductivity and having a sufficiently long length in the long axis direction as compared with the diameter (length in the short axis direction). It can be a solid fiber and can be a hollow fiber.

In terms of excellent electrical conductivity, the material of the metal nanowire is particularly good. Silver, or an alloy of silver with other metals. Examples of other metals used in the alloy with silver include platinum, rhodium, palladium, iridium, tin, iridium, nickel, and the like. These can be used alone or in combination of two or more.

Average short axis length of metal nanowires (sometimes referred to as "average short axis diameter") It is 5 nm to 50 nm, more preferably 5 nm to 25 nm, and further preferably 5 nm to 20 nm.

It is preferable to increase the oxidation resistance by making the average minor axis diameter 5 nm or more, and it is preferable to reduce the scattering of the metal nanowire by making the average minor axis diameter 50 nm or less. In particular, by making the average minor axis length 25 nm or less, it is preferable to reduce the scattering of the metal nanowire to a large extent.

The average short-axis diameter of the metal nanowire can be observed by a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX), and the short axis diameters of 300 metal nanowires are observed. The average value of the metal nanowires was determined as the average minor axis diameter. Further, the short axis diameter when the cross section of the metal nanowire is not circular is the shortest diameter.

Average long axis length of metal nanowires (sometimes referred to as "average long axis diameter") It is preferably 5 μm or more, more preferably 5 μm to 40 μm, still more preferably 5 μm to 30 μm.

By making the average major axis diameter 5 μm or more, the metal nanowires are brought into contact with each other to easily form a conductive mesh, and the average long axis diameter is 40 μm or less, and the metal nanowire is used. The possibility of entanglement with each other at the time of manufacture becomes lower and is preferable.

For example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX) can be used to observe the long axis diameter of 300 metal nanowires. The average major axis diameter of the metal nanowires was determined from the average value. Further, in the case where the metal nanowire is bent, it is considered that the value calculated from the radius and the curvature is the major axis diameter.

The manufacturing method of the metal nanowire is not particularly limited, and may be by any means. The method is preferably produced by reducing a metal ion in a solvent in which a halogen compound and a dispersing agent are dissolved. Further, from the viewpoint of self-dispersibility and temporal stability of the conductive film, it is preferred to carry out desalting treatment by a usual method after forming a metal nanowire.

In addition, Japanese Laid-Open Patent Publication No. 2009-215594, Japanese Patent Laid-Open No. 2009-242880, Japanese Patent Laid-Open No. 2009-299162, and Japanese Patent Laid-Open No. 2010-84173 The method described in Japanese Laid-Open Patent Publication No. 2010-86714, and the Japanese Patent Publication No. 2009-505358.

As the aspect ratio of the metal nanowire, it can be selected as needed, if 10 or more is not particularly limited, and more preferably 50 or more, still more preferably 100 or more, still more preferably 5,000 or more, and particularly preferably 10,000 to 100,000. The aspect ratio generally indicates the ratio of the long side to the short side of the fibrous material (ratio of the average major axis diameter to the average minor axis diameter).

The method for measuring the aspect ratio is not particularly limited, and may be appropriately selected as necessary, and examples thereof include a method of measuring by an electron microscope or the like.

When the aspect ratio of the metal nanowire is measured by an electron microscope, it can be confirmed in the field of view of the electron microscope. Further, the aspect ratio of the entire metal nanowire can be estimated by measuring the average major axis diameter and the average minor axis diameter of the metal nanowires, respectively.

Further, when the metal nanowire is tubular, the outer diameter of the tube is used as the diameter for calculating the aspect ratio.

(transparent adhesive layer)

The transparent adhesive layer is disposed on the surface of the metal wiring side of the insulating substrate with the metal wiring, and is a layer covering the surface of the metal wiring to suppress ion migration of silver between the metal wirings. In other words, the transparent adhesive layer corresponds to a silver ion diffusion inhibiting layer.

Further, it is preferred that the transparent adhesive layer contains substantially no silver ions or metallic silver. If excessive silver ions or metallic silver are contained in the transparent adhesive layer, there is a case where the ion migration suppressing effect is lowered.

In addition, the term "substantially free of silver ions or metallic silver" means that the content of silver ions or metallic silver in the transparent adhesive layer is 1 μmol/l or less, more preferably 0.1 μmol/l. The best is 0 mol/l.

The above-mentioned reducing compound and adhesive are contained in the transparent adhesive layer. each The definition of the ingredients is as described above. Further, the mass ratio of the reducing compound to the adhesive in the transparent adhesive layer is the same as the mass ratio of the reducing compound to the adhesive in the transparent adhesive sheet, and the same applies to the embodiment.

The thickness of the transparent adhesive layer is not particularly limited, and the ion migration inhibiting ability In a more excellent aspect, it is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm.

The total light transmittance of the transparent adhesive layer is not particularly limited, and it is preferably 80%. Upper (more preferably 85% or more, and even more preferably 90% or more).

In addition, the total light transmittance can be measured using "HR-100 type" manufactured by Murakami Color Technology Research Institute.

The manufacturing method of the transparent adhesive layer is not particularly limited, for example, there is a package The adhesive layer-forming composition containing a reducing compound and an adhesive is applied onto an insulating substrate with a metal wiring, and a solvent is removed as necessary to form a transparent adhesive layer. Further, a method in which a transparent adhesive sheet containing a reducing compound and an adhesive is directly laminated (attached) to an insulating substrate with metal wiring is exemplified.

It may be required to be on the surface of the transparent adhesive layer of the wiring substrate obtained above. Further provide an insulating layer. By further providing an insulating layer on the resin layer, a metal wiring can be further provided on the insulating layer to form a multilayer wiring board.

In terms of further inhibiting ion migration between metal wiring lines, The wire substrate can be widely applied to, for example, a touch panel, an electrode for a display, and an electromagnetic Wave mask, electrode for organic or inorganic EL display, electronic paper, electrode for flexible display, integrated solar cell, display element, various other elements, and the like. Among these, the touch panel is particularly good. That is, the wiring substrate is preferably used in a touch panel application. More specifically, it is preferable that the metal wiring in the wiring board is a lead-out wiring that is connected to the touch panel electrode portion. In addition, the touch panel electrode portion is, for example, a sensing electrode portion that senses a change in electrostatic capacitance in a capacitive touch panel.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to these examples.

<<First embodiment>>

<Example 1>

(Manufacture of transparent double-sided adhesive sheet)

Preparation of acrylic copolymer: 91.5 parts by mass of n-butyl acrylate, 0.5 parts by mass of 2-hydroxyethyl acrylate, acrylic acid in a reaction vessel having a stirrer, a cold flow condenser, a thermometer, a dropping funnel and a nitrogen inlet 8.0 parts by mass and 0.2 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator were dissolved in 100 parts by mass of ethyl acetate, and subjected to nitrogen substitution, followed by polymerization at 80 ° C for 8 hours to obtain mass. An acrylic copolymer (1) having an average molecular weight of 800,000.

Then, the acrylic copolymer (1) (98 parts by mass) and the tocopherol (2 parts by mass) were diluted with ethyl acetate to obtain an adhesive composition having a resin solid content of 30%.

To 100 parts by weight of the above-mentioned adhesive composition, 0.7 parts by weight of an isocyanate-based crosslinking agent (CORONATE L-45 manufactured by Nippon Polyurethane Industry Co., Ltd., 45% of solid content) was added for 15 minutes. After stirring, the film was applied to a PET film having a thickness of 50 μm which was subjected to a release treatment on one side by an oxime compound after drying to a thickness of 25 μm, and dried at 75 ° C for 5 minutes. A PET film having a thickness of 38 μm which was subjected to a release treatment on one side by an anthrone compound was attached to the obtained adhesive sheet. Thereafter, aging was carried out at 23 ° C for 5 days to obtain a transparent double-sided adhesive sheet (adhesive sheet without substrate) S-1 having a thickness of 25 μm. The adhesive sheet had a total light transmittance of 90.8%, a haze of 0.6%, and a water absorption of 1.24%. The method of measuring the total light transmittance, haze, and water absorption rate is based on the method described in Japanese Laid-Open Patent Publication No. 2012-11637. More specifically, the measurement is carried out by the method described in the following paragraph.

Further, the content of the tocopherol in the transparent double-sided adhesive sheet was 2% by mass based on the total mass of the transparent double-sided adhesive sheet.

(Total transmittance and haze measurement of transparent double-sided adhesive sheets)

The obtained transparent double-sided adhesive sheet S-1 was allowed to stand under the conditions of 60 ° C and 90% RH for 100 hours, and then a PET film and glass were laminated in this order to prepare test samples. The total light transmittance and haze (%) of the prepared sample were measured using "HR-100 type" manufactured by Murakami Color Technology Research Co., Ltd.

(Measurement of water absorption of transparent double-sided adhesive sheets)

After placing the 100 mm × 100 mm double-sided adhesive sheet at 60 ° C and 90% RH for 100 hours, immediately peel off the single-sided release film of the transparent double-sided adhesive sheet. The weight was measured by subtracting the other peeling film from the pre-weighed 150 mm × 150 mm stainless steel mesh (#250) (the weight minus the weight of the stainless steel mesh was taken as W1). This was dried at 105 ° C for 2 hours, and then weighed (the weight from the weight minus the weight of the stainless steel mesh was taken as W2). The water absorption rate of the double-sided adhesive sheet was calculated by the following formula.

Water absorption rate of double-sided adhesive sheet (%) = (W1-W2) / W2 × 100

<Example 2>

A copper-clad laminate (MCL-E-679F manufactured by Hitachi Chemical Co., Ltd., substrate: glass epoxy substrate) is used to produce a metal with a silver wiring of L/S = 200 μm / 200 μm by screen printing. Insulating substrate A of wiring. The insulating substrate A with metal wiring was produced by the following method.

After the copper foil of the copper-clad laminate was peeled off by an etching process, the conductive silver paste (FA-451 manufactured by Fujikura Kasei Co., Ltd.) was patterned on the substrate by a metal mask using a screen printing apparatus.

Thereafter, heat treatment was performed at 150 ° C for 30 minutes to cure the silver wiring, and a comb-type silver wiring substrate having a pattern of silver wiring of L/S = 200 μm / 200 μm (an insulating substrate with metal wiring) was obtained. A).

The silver wiring cross section formed by screen printing is a trapezoidal shape in which the lower side (corresponding to the side where the wiring is in contact with the substrate) is slightly longer than the upper side. The average thickness near the center of the wiring portion is 16 μm, and the amount of silver component in the conductive silver paste used is 70 wt%, which is included in the unit area of the silver wiring itself in the contact portion between the silver wiring and the insulating substrate. The amount of silver was set to be 10.5 g/cm ^{3 in terms} of the specific gravity of silver, and was calculated to be about 24.2 μg/mm ² . Further, when calculating the amount of silver contained in each unit area, the area of the portion where the silver wiring is in contact with the insulating substrate is calculated, and the surface of the insulating substrate which is not in contact with the silver wiring is not considered (for example, The area of the insulating substrate surface of the silver wiring between the silver wiring contacts.

Further, the amount of silver can be calculated from the elemental analysis result of the SEM photograph of the cross section of the metal wiring. Further, the amount of silver calculated based on the total area of the equivalent diameter of the silver particles observed by the SEM observation and the sectional area ratio of the wiring, and the amount of the conductive silver paste used were calculated. The value of silver is roughly the same.

(Manufacture of wiring board)

On the insulating substrate A with the metal wiring obtained, the peeling film on one of the single sides of the transparent double-sided adhesive sheet S-1 corresponding to the silver ion diffusion suppressing layer is peeled off, and the surface of one of the adhesive faces is displayed. The film was laminated as a laminate, and the release film on the other side of the transparent double-sided adhesive sheet S-1 was further peeled off, and a PET film (film thickness: 50 μm) was bonded to the surface on the other side where adhesion was exhibited. The wiring board is obtained. Thereafter, the obtained wiring substrate was subjected to autoclave treatment at 45 ° C and 0.5 MPa for 20 minutes. Thereby, the wiring substrate T-1 is obtained.

The following life measurement was performed about the obtained wiring board T-1.

(Evaluation method 1 (life extension effect measurement))

Use the resulting wiring substrate at a humidity of 90%, a temperature of 60 degrees, and a voltage of Life measurement was carried out under conditions of 10 V (the device used was EHS-221MD manufactured by ESPEC Co., Ltd.).

As the evaluation method, the transparent double-sided adhesive sheet S-0 was first produced in the order of the above-described Example 1 without using tocopherol. The transparent double-sided adhesive sheet S-0 does not contain tocopherol. Then, on the insulating substrate A with the metal wiring, the release film on one side of one of the transparent double-sided adhesive sheets S-0 is peeled off, and the surface on which one of the adhesiveness is displayed is attached as a layer. Further, the release film on the other side of the other of the transparent double-sided adhesive sheets was further peeled off, and a PET film (having a film thickness of 50 μm) was bonded to the other surface on which adhesiveness was exhibited to obtain a comparative wiring substrate. Using the obtained comparative wiring board, the life measurement was performed under the above conditions, and the time X until the resistance value between the silver wirings was less than 1 × 10 ⁵ Ω was measured.

Next, the life of the wiring board T-1 was measured under the above conditions, and the time Y until the resistance value between the silver wirings was less than 1 × 10 ⁵ Ω was measured.

The life improvement effect (Y/X) was calculated using the obtained time X and time Y. The results are shown in Table 1.

<Example 3>

An insulating substrate B with a metal wiring including a silver wiring of L/S = 50 μm / 50 μm is manufactured by the method described in paragraphs [0108] to [0120] of JP-A-2009-188360. Further, the amount of silver contained per unit area of the metal wiring was 8.7 μg/mm ² .

In the same manner as in the first embodiment and the second embodiment, the insulating substrate B with the metal wiring is used instead of the insulating substrate A with the metal wiring. The evaluation of the above evaluation method 1 was carried out on the wire substrate T-2. The results are shown in Table 1.

<Example 4>

(Manufacture of transparent substrate with conductive film)

A transparent substrate including a PET substrate (thickness: 125 μm) corresponding to a transparent substrate was prepared, and a silver-containing conductive film of a comb-shaped electrode pattern (L/S = 200 μm/200 μm) was formed on the transparent substrate in the following order. The amount of silver contained in the unit area of the conductive film can be calculated by measuring the concentration of the silver nitrate aqueous solution obtained by immersing the wiring board in nitric acid and dissolving it in an ICP-MS, and is 0.014 μg/mm ² . Further, the PET substrate also corresponds to an insulating substrate.

(Production of water dispersion of silver nanowire)

-Preparation of silver nanowire dispersion (1) -

A silver nitrate solution 101 was prepared by dissolving 60 g of silver nitrate powder in 370 g of propylene glycol. 72.0 g of polyvinylpyrrolidone (molecular weight: 55,000) was added to 4.45 kg of propylene glycol, and the temperature was raised to 90 ° C while introducing nitrogen gas into the gas phase portion of the vessel. This liquid was used as the reaction solution 101. To the vigorously stirred reaction solution 101, 2.50 g of a silver nitrate solution 101 was added while maintaining nitrogen gas, and the mixture was heated and stirred for 1 minute. Further, a solution of 11.8 g of tetrabutylammonium chloride dissolved in 100 g of propylene glycol was added to the solution to prepare a reaction solution 102.

200 g of the silver nitrate solution 101 was added to the reaction solution 102 which was kept at 90 ° C and stirred at a stirring speed of 500 rpm at an addition rate of 50 cc / min. The stirring speed was reduced to 100 rpm, the nitrogen gas was stopped, and heating and stirring was carried out for 15 hours. In the liquid which was kept at 90 ° C and stirred at a stirring speed of 100 rpm, 220 g of silver nitrate solution 101 was added at an addition rate of 0.5 cc/min, and heating and stirring were continued for 2 hours after the end of the addition. The stirring was changed to 500 rpm, 1.0 kg of distilled water was added, and the mixture was cooled to 25 ° C to prepare a charging liquid 101.

Ultrafiltration was carried out as described below using an ultrafiltration module having a molecular weight cutoff of 150,000. A mixed solution of distilled water and 1-propanol (volume ratio of 1 to 1) was repeatedly added to the charging liquid 101 and the concentration of the liquid 101 was repeated to make the conductivity of the finally obtained filtrate 50 μS/cm. the following. Concentration was carried out to obtain a silver nanowire dispersion (1) having a metal content of 0.45%.

The silver nanowire of the obtained silver nanowire dispersion (1) was measured as described above, and the average short axis length and the average major axis length were measured.

As a result, the average minor axis length was 28.5 nm, and the average major axis length was 15.2 μm. Hereinafter, when it is described as "silver nanowire dispersion (1)", the silver nanowire dispersion obtained by the above method is shown.

(Production of conductive film)

A solution of the alkoxide compound having the following composition was stirred at 60 ° C for 1 hour to confirm uniformity. The weight average molecular weight (Mw) of the obtained sol-gel solution was measured by GPC (polystyrene conversion), and the Mw was 4,400. 2.24 parts of the sol-gel solution and 17.76 parts of the silver nanowire dispersion (1) prepared above were mixed, and further diluted with distilled water and 1-propanol to obtain a silver nanowire coating liquid (1). The solvent ratio of the obtained coating liquid was distilled water: 1-propanol = 60:40. The silver nanowire coating liquid (1) was applied to a PET substrate (thickness 125 μm) by a bar coating method in such a manner that the amount of silver became 0.015 g/m ² and the total solid coating amount was 0.120 g/m ² . Then, it was dried at 120 ° C for 1 minute to form a conductive film 1 containing silver nanowires.

<Solution of alkoxide compound>

. Tetraethoxydecane 5.0 parts

(KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)

(patterning of conductive film)

A photoresist (TMSMR-8900LB; manufactured by Tokyo Ohka Co., Ltd.) was applied onto the electroconductive film 1 by spin coating, and calcination was carried out at 90 ° C for 60 seconds. Next, pattern exposure was performed using a photomask (exposure amount: 12 mW/cm ² , 20 seconds), and development was carried out by a developing solution (NMD-W; manufactured by Tokyo Chemical Industry Co., Ltd.), washed with water, and dried, and then dried at 120 Calcination was carried out for 60 seconds at ° C to form a patterned photoresist on the conductive film 1.

Then, after immersing in a silver etching solution (SEA-2; manufactured by Kanto Chemical Co., Ltd.) for 30 seconds, it was washed with water and dried, and the silver nanowire was etched to form a non-conductive portion on the conductive film 1. Thereafter, the photoresist was peeled off using a neutral peeling liquid (PK-SFR8120; manufactured by Parker Corporation), and then washed with water and dried to prepare a pattern of a comb-shaped electrode (L/S = Conductive film 1 of 200 μm / 200 μm).

(Manufacture of conductive film laminate)

Then, on the transparent substrate with the conductive film obtained, the transparent double-sided adhesive sheet S-1 was bonded in the same manner as in Example 2 to obtain a conductive film laminate (corresponding to a wiring substrate) T-3.

(Evaluation method 2 (life extension effect measurement))

Using the obtained conductive film laminate, the life was measured under the conditions of a humidity of 85%, a temperature of 85 degrees, a pressure of 1.0 atm, and a voltage of 100 V (the device was EHS-221MD manufactured by ESPEC Co., Ltd.). ).

As the evaluation method, the transparent double-sided adhesive sheet S-0 was first produced in the order of the above-described Example 1 without using tocopherol. Then, on the transparent substrate with the conductive film, the release film on one side of one of the transparent double-sided adhesive sheets S-0 is peeled off, and the surface on which one of the adhesive properties is displayed is laminated as a laminate. Further, the release film on the other side of the other side of the transparent double-sided adhesive sheet was further peeled off, and a PET film (film thickness: 50 μm) was bonded to the surface on the other side showing adhesiveness to obtain a comparative conductive film laminate. Using the obtained comparative conductive film laminate, the life measurement was performed under the above conditions, and the time X until the resistance value between the conductive films was increased by 10% was measured.

Next, the life of the conductive film laminate (also equivalent to the wiring substrate) T-3 was measured under the above conditions, and the time Y at which the resistance value between the conductive films was increased by 10% was measured.

The life improvement effect (Y/X) was calculated using the obtained time X and time Y.

The results of the wiring board obtained in Example 4 are shown in Table 1.

<Example 5>

The wiring board T-4 was produced in the same manner as in the first and second embodiments, except that the following compound A-1 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

[Chemistry 16]

<Example 6>

The wiring board T-5 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-2 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Example 7>

The wiring board T-6 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-3 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

[化18]

<Example 8>

The wiring board T-7 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-4 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Example 9>

The wiring board T-8 was produced in the same manner as in the first embodiment and the fifth embodiment except that the amount of silver was changed from 24.2 μg/mm ² to 0.011 μg/mm ² , and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Example 10>

The wiring board T-9 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-5 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

[Chemistry 20]

<Example 11>

The wiring board T-9 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-6 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Example 12>

The wiring board T-10 was produced in the same manner as in the first embodiment and the second embodiment except that the following compound A-7 was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

[化22]

<Comparative Example 1>

A transparent double-sided adhesive sheet S-0 was produced in the same manner as in Example 1 except that tocopherol was not used.

The wiring board R-1 was produced in the same manner as in the first embodiment and the second embodiment except that the transparent double-sided adhesive sheet S-0 was used instead of the transparent double-sided adhesive sheet S-1, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Comparative Example 2>

According to the method of the second embodiment, the thickness of the metal wiring is adjusted so that the amount of silver contained in the unit area of the silver wiring becomes 76.1 μg/mm ^{2 , and} the metal wiring with L/S=200 μm/200 μm is obtained. Insulating substrate C.

The wiring board R-2 was produced in the same manner as in the first embodiment and the second embodiment except that the insulating substrate C with the metal wiring was used instead of the insulating substrate A with the metal wiring, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

<Comparative Example 3>

The wiring board R-3 was produced in the same manner as in the first embodiment and the second embodiment except that the ascorbic acid was used instead of the tocopherol, and the evaluation of the evaluation method 1 was carried out. The results are shown in Table 1.

Further, the term "peeling" means that the sheet loses the ability to cover the wiring during the heating process during the evaluation, and is short-circuited due to moist heat.

Further, Example 4 is the result of evaluation by the above-described evaluation method 2, and other examples and comparative examples are the results of evaluation by the above-described evaluation method 1.

As shown in the above Table 1, in Examples 2 to 12 in which the predetermined compounds were used, the effect of prolonging the life was excellent, and the insulation properties were confirmed to be improved.

In particular, according to the comparison between Example 2, Example 5 to Example 8, and Example 10 to Example 12, Example 5 in which the compound represented by the formula (5) or the compound represented by the formula (6) is used, In Example 6, Example 10, and Example 11, it was confirmed that the effect was more excellent.

On the other hand, Comparative Example 2 in which the amount of silver is large, and the use of the prescribed compound In Comparative Example 3, the insulation characteristics were not confirmed to be greatly improved.

<<2th embodiment>>

(Synthesis Example 1: Production of Transparent Double-sided Adhesive Sheet S-1)

Preparation of an acrylic copolymer: 50 parts by mass of 2-ethylhexyl acrylate and 25 parts by mass of isodecyl acrylate in a reaction vessel having a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet; 15 parts by mass of 2-hydroxyethyl acrylate and 2 parts by mass of acrylic acid were dissolved in 100 parts by mass of ethyl acetate, and the mixture was purged with nitrogen, followed by heating to an internal temperature of 70 °C.

To the reaction mixture, a solution in which 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) and 10 parts of ethyl acetate were dissolved in advance was gradually added dropwise, and the mixture was stirred for 3 hours. Thereafter, the mixture was further heated to an internal temperature of 80 ° C, and a solution of 0.1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) and 10 parts of ethyl acetate dissolved in advance was gradually added dropwise. After stirring for 3 hours, an acrylic copolymer (P-1) having a mass average molecular weight of 400,000 was obtained.

Then, the acrylic copolymer (P-1) and 0.7 parts by weight of an isocyanate-based crosslinking agent (CORONATE L-45 manufactured by Japan Polyurethane Co., Ltd., solid content: 45%) were added and stirred for 5 minutes. A solution in which DL-α-tocopherol (redox potential: 0.56 V) was dissolved in an ethyl acetate/toluene mixed solvent (ethyl acetate/toluene=1/1) was added thereto, and stirred for 5 minutes to obtain a relative The DL-α-tocopherol was 0.5 parts by mass of the adhesive composition in terms of 100 parts by mass of the acrylic copolymer solid content.

The adhesive composition was applied to a PET having a thickness of 50 μm which was peeled off by one side of the ketone compound by a thickness of 50 μm after drying. The film was dried at 75 ° C for 5 minutes. The obtained adhesive sheet was bonded to a PET film having a thickness of 38 μm which was subjected to a release treatment on one side by an oxime compound. Thereafter, aging was carried out at 23 ° C for 5 days to obtain a transparent double-sided adhesive sheet (adhesive sheet without substrate) S-1 having a thickness of 50 μm.

(Synthesis Example 2: Production of Transparent Double-sided Adhesive Sheet S-2)

The amount of the use of the 2-hydroxyethyl acrylate was changed from 15 parts by mass to 20 parts by mass, and the amount of the acrylic acid used was changed from 2 parts by mass to 0 parts by mass, and otherwise transparent in the same manner as in Synthesis Example 1. Double-sided adhesive sheet S-2.

(Synthesis Example 3: Production of Transparent Double-sided Adhesive Sheet S-3)

The amount of the use of the 2-hydroxyethyl acrylate was changed from 15 parts by mass to 25 parts by mass, and the amount of the acrylic acid used was changed from 2 parts by mass to 0 parts by mass, and otherwise transparent in the same manner as in Synthesis Example 1. Double-sided adhesive sheet S-3.

(Synthesis Example 4: Production of Transparent Double-sided Adhesive Sheet S-4)

The amount of use of the 2-hydroxyethyl acrylate was changed from 15 parts by mass to 30 parts by mass, and the amount of the acrylic acid used was changed from 2 parts by mass to 0 parts by mass, and otherwise transparent in the same manner as in Synthesis Example 1. Double-sided adhesive sheet S-4.

(Synthesis Example 5: Production of Transparent Double-sided Adhesive Sheet S-5)

The amount of 2-hydroxyethyl acrylate used was changed from 15 parts by mass to 25 parts by mass, and 25 parts by mass of methyl acrylate and 25 parts by mass of butyl acrylate were added as a monomer to carry out polymerization of the acrylic copolymer. The transparent double-sided adhesive sheet S-5 was produced in the same manner as in Synthesis Example 1 except for the above.

(Synthesis Example 6: Production of Transparent Double-sided Adhesive Sheet S-6)

A transparent double-sided adhesive sheet S-7 was produced in the same manner as in Synthesis Example 5 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 7: Production of Transparent Double-sided Adhesive Sheet S-7)

A transparent double-sided adhesive sheet S-7 was produced in the same manner as in Synthesis Example 5 except that the DL-α-tocopherol was changed to the compound C (the redox potential was 1.17 V).

(Synthesis Example 8: manufacture of transparent double-sided adhesive sheet S-8)

A transparent double-sided adhesive sheet S-8 was produced in the same manner as in Synthesis Example 1, except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 9: manufacture of transparent double-sided adhesive sheet S-9)

A transparent double-sided adhesive sheet S-9 was produced in the same manner as in Synthesis Example 2 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 10: Production of Transparent Double-sided Adhesive Sheet S-10)

30 parts by mass of methyl acrylate, 70 parts by mass of butyl acrylate, 8 parts by mass of 2-hydroxyethyl acrylate, 2 parts by mass of acrylic acid, 50 parts by mass of 2-ethylhexyl acrylate, and 25 parts by mass of isodecyl acrylate. A transparent double-sided adhesive sheet S-10 was produced in the same manner as in Synthesis Example 1 except that the acrylic copolymer was polymerized with 15 parts by mass of 2-hydroxyethyl acrylate and 2 parts by mass of acrylic acid. .

(Synthesis Example 11: Production of transparent double-sided adhesive sheet S-11)

A transparent double-sided adhesive sheet S-11 was produced in the same manner as in Synthesis Example 10 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 12: Production of transparent double-sided adhesive sheet S-12)

A transparent double-sided adhesive sheet S-12 was produced in the same manner as in Synthesis Example 10 except that the DL-α-tocopherol was changed to the compound C (the redox potential was 1.17 V).

(Synthesis Example 13: Production of Transparent Double-sided Adhesive Sheet S-13)

75 parts by mass of butyl acrylate and 25 parts by mass of 2-hydroxyethyl acrylate are used instead of 50 parts by mass of 2-ethylhexyl acrylate, 25 parts by mass of isodecyl acrylate, and 15 parts by mass of 2-hydroxyethyl acrylate. And the polymerization of the acrylic copolymer was carried out in an amount of 2 parts by mass of the acrylic acid, and the same procedure as in Synthesis Example 1 was carried out. Bright double-sided adhesive sheet S-13.

(Synthesis Example 14: Production of Transparent Double-sided Adhesive Sheet S-14)

A transparent double-sided adhesive sheet S-14 was produced in the same manner as in Synthesis Example 13 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 15: Production of Transparent Double-sided Adhesive Sheet S-15)

A transparent double-sided adhesive sheet S-15 was produced in the same manner as in Synthesis Example 13 except that the DL-α-tocopherol was changed to the compound C (the redox potential was 1.17 V).

(Synthesis Example 16: Production of Transparent Double-sided Adhesive Sheet S-16)

75 parts by mass of butyl acrylate, 15 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of 2-hydroxyethyl acrylate, and 1.5 parts by mass of acrylic acid instead of 50 parts by mass of 2-ethylhexyl acrylate, acrylic acid A transparent double-sided film was produced in the same manner as in Synthesis Example 1 except that 25 parts by mass of oxime ester, 15 parts by mass of 2-hydroxyethyl acrylate, and 2 parts by mass of acrylic acid were used to polymerize the acrylic copolymer. Adhesive sheet S-16.

(Synthesis Example 17: Production of Transparent Double-sided Adhesive Sheet S-17)

A transparent double-sided adhesive sheet S-17 was produced in the same manner as in Synthesis Example 16 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 18: Production of transparent double-sided adhesive sheet S-18)

50 parts by mass of 2-ethylhexyl acrylate and isophthalic acid in the reaction vessel 25 parts by mass of ester, 15 parts by mass of 2-hydroxyethyl acrylate, 2 parts by mass of acrylic acid, and Irgacure 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a polymerization initiator The mixture was mixed, and after nitrogen substitution, the ultraviolet rays were irradiated by a low-pressure mercury lamp for 7 minutes to obtain a viscosity of 2000 mPa. Adhesive composition around s. Thereafter, a solution in which DL-α-tocopherol (redox potential: 0.56 V) was dissolved in an ethyl acetate/toluene mixed solvent (ethyl acetate/toluene=1/1) was added to the adhesive composition. In this case, DL-α-tocopherol is added in an amount of 0.5 part by mass based on 100 parts by mass of the adhesive solid content.

The obtained adhesive composition was applied onto a PET film having a thickness of 50 μm so as to have a thickness of 50 μm after drying, and the solvent was dried. The obtained adhesive sheet was bonded to a PET film having a thickness of 38 μm which was subjected to a release treatment on one side by an oxime compound, and a low-pressure mercury lamp was irradiated from both sides for 5 minutes to obtain a transparent double-sided adhesive sheet S-18.

(Synthesis Example 19: Production of Transparent Double-sided Adhesive Sheet S-19)

A transparent double-sided adhesive sheet S-19 was produced in the same manner as in Synthesis Example 18 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 20: Production of Transparent Double-sided Adhesive Sheet S-20)

A transparent double-sided adhesive sheet S-20 was produced in the same manner as in Synthesis Example 18 except that the DL-α-tocopherol was changed to the compound C (the redox potential was 1.17 V).

(Synthesis Example 21: Production of Transparent Double-sided Adhesive Sheet S-21)

After 56 parts by mass of butyl acrylate, 13 parts by mass of cyclohexyl acrylate, 23 parts by mass of 4-hydroxybutyl acrylate, 8 parts by mass of 2-hydroxyethyl acrylate, and Irgacure 651 (0.05 parts by mass) were placed in the reaction container, The ultraviolet rays were irradiated while stirring under a nitrogen atmosphere.

After adding 0.1 parts by mass and 0.5 part by mass of CORONATE L55E and DL-α-tocopherol, respectively, to 100 parts by mass of the adhesive solid component, the mixture was stirred to obtain an adhesive composition.

The above-mentioned adhesive composition was applied onto a PET film having a thickness of 50 μm so as to have a thickness of 50 μm after drying, and the solvent was dried. The obtained adhesive sheet was bonded to a PET film having a thickness of 38 μm which was subjected to a release treatment on one side by an anthrone compound, and a low-pressure mercury lamp was irradiated from both sides for 5 minutes to obtain a transparent double-sided adhesive sheet S-21.

(Synthesis Example 22: Production of transparent double-sided adhesive sheet S-22)

A transparent double-sided adhesive sheet S-22 was produced in the same manner as in Synthesis Example 21 except that the DL-α-tocopherol was changed to the compound B (the redox potential was 1.09 V).

(Synthesis Example 23: Production of Transparent Double-sided Adhesive Sheet S-23)

A transparent double-sided adhesive sheet S-23 was produced in the same manner as in Synthesis Example 21 except that the DL-α-tocopherol was changed to the compound C (the redox potential was 1.17 V).

(Synthesis Example 24: Production of Transparent Double-sided Adhesive Sheet S-24)

A transparent double-sided adhesive sheet S-24 was produced in the same manner as in Synthesis Example 6, except that the content of the compound B was changed to 0.1 part by mass.

(Synthesis Example 25: Production of Transparent Double-sided Adhesive Sheet S-25)

A transparent double-sided adhesive sheet S-25 was produced in the same manner as in Synthesis Example 6, except that the content of the compound B was changed to 1.0 part by mass.

(Synthesis Example 26: Production of transparent double-sided adhesive sheet S-26)

A transparent double-sided adhesive sheet S-26 was produced in the same manner as in Synthesis Example 1 except that DL-α-tocopherol was not used.

(Synthesis Example 27: Production of transparent double-sided adhesive sheet S-27)

A transparent double-sided adhesive sheet S-27 was produced in the same manner as in Synthesis Example 2 except that DL-α-tocopherol was not used.

(Synthesis Example 28: Production of Transparent Double-sided Adhesive Sheet S-28)

A transparent double-sided adhesive sheet S-28 was produced in the same manner as in Synthesis Example 3 except that DL-α-tocopherol was not used.

(Synthesis Example 29: Production of transparent double-sided adhesive sheet S-29)

A transparent double-sided adhesive sheet S-29 was produced in the same manner as in Synthesis Example 4 except that DL-α-tocopherol was not used.

(Synthesis Example 30: Production of Transparent Double-sided Adhesive Sheet S-30)

A transparent double-sided adhesive sheet S-30 was produced in the same manner as in Synthesis Example 5 except that DL-α-tocopherol was not used.

(Synthesis Example 31: Production of Transparent Double-sided Adhesive Sheet S-31)

A transparent double-sided adhesive sheet S-31 was produced in the same manner as in Synthesis Example 1, except that the compound D (redox potential was 0.17 V) was used instead of DL-α-tocopherol.

[化25]

(Synthesis Example 32: Production of transparent double-sided adhesive sheet S-32)

A transparent double-sided adhesive sheet S-32 was produced in the same manner as in Synthesis Example 1, except that the compound E (redox potential was 1.39 V) was used instead of DL-α-tocopherol.

(Synthesis Example 33: Production of Transparent Double-sided Adhesive Sheet S-33)

A transparent double-sided adhesive sheet S-33 was produced in the same manner as in Synthesis Example 10 except that DL-α-tocopherol was not used.

(Synthesis Example 34: Production of Transparent Double-sided Adhesive Sheet S-34)

A transparent double-sided adhesive sheet S-34 was produced in the same manner as in Synthesis Example 13 except that DL-α-tocopherol was not used.

(Synthesis Example 35: Production of Transparent Double-sided Adhesive Sheet S-35)

DL-α-tocopherol was not used, and otherwise the same as in Synthesis Example 16 The transparent double-sided adhesive sheet S-35 is manufactured in sequence.

(Synthesis Example 36: Production of Transparent Double-sided Adhesive Sheet S-36)

60 parts by mass of butyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of methyl methacrylate, 50 parts by mass of 2-ethylhexyl acrylate, 25 parts by mass of isodecyl acrylate, and acrylic acid The polymerization of the acrylic copolymer was carried out by using a monomer of 15 parts by mass of 2-hydroxyethyl ester and 2 parts by mass of acrylic acid, and the same procedure as in Synthesis Example 1 was carried out except that DL-α-tocopherol was not used. Transparent double-sided adhesive sheet S-36.

(Synthesis Example 37: Production of Transparent Double-sided Adhesive Sheet S-37)

60 parts by mass of butyl acrylate, 25 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of methyl methacrylate, 50 parts by mass of 2-ethylhexyl acrylate, 25 parts by mass of isodecyl acrylate, and acrylic acid A transparent double-sided adhesive sheet S-37 was produced in the same manner as in Synthesis Example 1 except that the acrylic copolymer was polymerized in an amount of 15 parts by mass of the -2-hydroxyethyl group and 2 parts by mass of the acrylic acid.

(Synthesis Example 38: Production of transparent double-sided adhesive sheet S-38)

A transparent double-sided adhesive sheet S-38 was produced in the same manner as in Synthesis Example 21 except that DL-α-tocopherol was not used.

<Example 1A>

A striped silver wiring pattern of L/S = 40 μm / 40 μm was formed on the PET substrate by a screen printing method using silver paste (LS-450-7HL manufactured by Asahi Chemical Research Institute). Thereafter, heat treatment was performed at 130 ° C for 30 minutes to cure the silver wiring, thereby producing an insulating substrate with metal wiring including silver wiring.

(Manufacture of wiring board)

On the insulating substrate with the metal wiring obtained, the release film on one side of one of the transparent double-sided adhesive sheets S-1 is peeled off, and the surface on which one of the adhesiveness is displayed is laminated as a layer. Further, the release film on the other side of the other side of the transparent double-sided adhesive sheet was peeled off, and a PET film (film thickness: 50 μm) was bonded to the other surface on which adhesiveness was exhibited to obtain a wiring substrate. Thereafter, the obtained wiring substrate was subjected to autoclave treatment at 45 ° C and 0.5 MPa for 20 minutes. Thereby, the wiring substrate T-1 is obtained.

The following life measurement was performed about the obtained wiring board T-1.

(Evaluation method (life extension effect evaluation))

Using the obtained wiring substrate T-1, the life was measured under the conditions of a humidity of 85%, a temperature of 85 degrees, a pressure of 1.0 atm, and a voltage of 15 V (the device was EHS-221MD manufactured by ESPEC Co., Ltd.). ). The time X until the resistance value between the silver wirings was less than 1 × 10 ⁵ Ω was measured and evaluated according to the following criteria. Practically it must be A or B.

"A": Time X is 40 hours or more

"B": Time X is 30 hours or more and less than 40 hours

"C": Time X is less than 30 hours

The results of the wiring board obtained in Example 1A are shown in Table 2.

(Environmental test (whitening evaluation))

The transparent double-sided adhesive sheet S-1~transparent double-sided adhesive sheet S-38 is cut into a predetermined size (length 5 cm × width 4 cm × thickness 50 μm), and peeling off one side of one side is peeled off For the film, the surface of one of the adhesive layers is attached as a laminate to the glass substrate, and the release film on the other side of the transparent double-sided adhesive sheet is further peeled off, and the PET substrate (thickness: 50 μm) is attached. A sample for evaluation was produced.

The sample for evaluation was allowed to stand under the conditions of 65 ° C and 95% RH for 72 hours. Then, when the sample for evaluation was placed under conditions of 23 ° C and 50% RH, the time until the haze of the transparent adhesive layer in the sample for evaluation reached 3% or less was evaluated according to the following criteria. Practically, if it is A or B, it is excellent in whitening resistance.

"A": Time X is less than 6 hours

"B": Time X is 6 hours or more and 12 hours or less

"C": Time X exceeds 12 hours

In addition, the haze was measured using "HR-100 type" manufactured by Murakami Color Technology Research Institute.

<Example 2A to Example 25A, and Comparative Example 1A to Comparative Example 15A>

As shown in Table 2, the transparent double-sided adhesive sheet S-2 to the transparent double-sided adhesive sheet S-38 was used instead of the transparent double-sided adhesive sheet S-1, and the wiring substrate was produced in the same manner as in the example 1A. Life extension effect measurement and environmental testing. The results are summarized in Table 2.

<Example 26A>

A wiring board was produced in the same manner as in Example 6A except that the L/S was set to 30 μm/30 μm, and the same life measurement as in Example 1A was performed.

In Table 2, the components of the "monomer component of the acrylic copolymer" column The values in the column indicate the parts by mass.

In Table 2, the numerical values in the column of the "Compound" column indicate the parts by mass.

According to the results of Table 2, in Examples 1A to 26A corresponding to the second embodiment of the present invention, excellent results were obtained in the whitening evaluation and the life extension effect evaluation.

On the other hand, in Comparative Examples 1A to 15A in which the compound which does not exhibit the predetermined redox electrons or the transparent adhesive layer did not exhibit the predetermined characteristics, the evaluation of at least one of the whitening evaluation and the life extension effect evaluation was poor.

10‧‧‧Wiring substrate

12‧‧‧Insert substrate

14‧‧‧Metal wiring

16‧‧‧Insulated substrate with metal wiring

18‧‧‧ Silver ion diffusion suppression layer

Claims (25)

A conductive film laminate comprising a transparent substrate, a conductive film containing silver disposed on the transparent substrate, and a transparent double-sided adhesive sheet laminated on the conductive film, The conductive film has a silver content of 50 μg/mm ² or less per unit area, and the transparent double-sided adhesive sheet contains a transparent resin and a compound selected from the group consisting of compounds represented by formulas (1) to (3). At least one compound of the group; In the formula (1), R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom; Z represents a hydrogen atom, a fluorenyl group, or an RzOC(=O) group; and Rz represents an aliphatic hydrocarbon group or The aromatic hydrocarbon group; wherein, the total number of carbon atoms contained in each of R ₁ to R ₅ is 4 or more; and R ₁ to R ₅ may be bonded to each other to form a ring; in the formula (2), R ₆ ~R ₈ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups; wherein, the total number of carbon atoms contained in each of R ₆ to R ₈ is 6 or more; And R ₉ to R ₁₂ each independently represent an alkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, or a group in which these groups are combined; wherein R ₉ to R ₁₂ are contained in each group; The total number of carbon atoms is 6 or more. The conductive film laminate according to claim 1, wherein the compound is selected from the group consisting of compounds represented by formulas (4) to (6); In the formula (4), R ₁ to R ₃ and R ₁₄ to R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom; and Z represents a hydrogen atom, a fluorenyl group, or an RzOC(=O) group; Rz represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group; wherein at least one of R ₁ , R ₂ , R ₁₄ and R ₁₅ has 1 to 40 carbon atoms, and R ₁ , R ₂ , R ₁₄ and R ₁₅ The total number of carbon atoms contained in each group is 4 or more; [Chemical 3] In the formula (5), R ₃₁ to R ₃₈ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; and the total molecular weight of each of R ₃₁ to R ₃₈ is 24 or more; R ₃₉ represents an aliphatic hydrocarbon group which may contain a hetero atom having a carbon number of 1 to 20; R ₃₁ to R ₃₈ may be bonded to each other to form a ring; in the formula (6), R ₄₁ to R ₄₄ Each of the hydrogen atoms, the hydroxyl group, or the hydrocarbon group having a carbon number of 1 to 20 which may include a hetero atom; and the total molecular weight of each of R ₄₁ to R ₄₄ is 40 or more; and, R ₄₁ to R ₄₄ may be Each of them is bonded to each other to form a ring; L represents a divalent to trivalent hydrocarbon group which may contain a hetero atom, -S-, or a combination of these groups; and n represents an integer of 2 or 3. The conductive film laminate according to claim 1 or 2, wherein the compound is selected from the group consisting of the compound represented by the formula (5) and the formula (6) A group of compounds represented. The conductive film laminate according to claim 1 or 2, wherein a mass ratio (A/C) of the total mass A of the compound to the total mass C of the transparent resin is 0.0001 to 0.1. The conductive film laminate according to claim 1 or 2, wherein the conductive film contains a metal nanowire comprising silver or a silver alloy. The conductive film laminate according to the first or second aspect of the invention, wherein the transparent resin comprises an acrylic adhesive. A touch panel comprising the conductive film laminate according to any one of claims 1 to 6. A wiring board comprising: an insulating substrate; a metal wiring including silver disposed on the insulating substrate; and a silver ion diffusion suppression layer disposed on the metal wiring, wherein silver contained in each unit area of the metal wiring The amount of the silver ion diffusion-suppressing layer is at least one compound selected from the group consisting of compounds represented by the formulas (1) to (3), and the amount is 50 μg/mm ² or less; ] In the formula (1), R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom; Z represents a hydrogen atom, a fluorenyl group, or an RzOC(=O) group; and Rz represents an aliphatic hydrocarbon group or The aromatic hydrocarbon group; wherein, the total number of carbon atoms contained in each of R ₁ to R ₅ is 4 or more; and R ₁ to R ₅ may be bonded to each other to form a ring; in the formula (2), R ₆ ~R ₈ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups; wherein, the total number of carbon atoms contained in each of R ₆ to R ₈ is 6 or more; And R ₉ to R ₁₂ each independently represent an alkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, or a group in which these groups are combined; wherein R ₉ to R ₁₂ are contained in each group; The total number of carbon atoms is 6 or more. The wiring substrate according to claim 8, wherein the compound is selected from the group consisting of compounds represented by formulas (4) to (6); [Chemical 5] In the formula (4), R ₁ to R ₃ and R ₁₄ to R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have a hetero atom; and Z represents a hydrogen atom, a fluorenyl group, or an RzOC(=O) group; Rz represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group; wherein at least one of R ₁ , R ₂ , R ₁₄ and R ₁₅ has 1 to 40 carbon atoms, and R ₁ , R ₂ , R ₁₄ and R ₁₅ The total number of carbon atoms contained in each group is 4 or more In the formula (5), R ₃₁ to R ₃₈ each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; and the total molecular weight of each of R ₃₁ to R ₃₈ is 24 or more; R ₃₉ represents a divalent aliphatic hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; R ₃₁ to R ₃₈ may be bonded to each other to form a ring; in the formula (6), R ₄₁ to R ₄₄ respectively The hydrogen atom, the hydroxyl group, or the hydrocarbon group having a carbon number of 1 to 20 which may include a hetero atom; and the total molecular weight of each of R ₄₁ to R ₄₄ is 40 or more; and R ₄₁ to R ₄₄ may be respectively Bonded to each other to form a ring; L represents a divalent to trivalent hydrocarbon group which may contain a hetero atom, -S-, or a combination of these groups; n represents an integer of 2 or 3. The wiring board according to Item 8 or 9, wherein the compound is selected from the group consisting of the compound represented by the formula (5) and the compound represented by the formula (6). . The wiring board according to Item 8 or 9, wherein the mass ratio (A/B) of the total mass A of the compound to the total mass B of the insulating resin is 0.0001 to 0.1. An electronic device comprising the wiring substrate according to any one of claims 8 to 11. A transparent double-sided adhesive sheet comprising a transparent resin and at least one compound selected from the group consisting of compounds represented by formula (1), formula (2) and formula (3), [Chem. 7] In the formula (1), R ₁ to R ₅ each independently represent a hydrogen atom, a hydroxyl group, a hydrocarbon group which may have a hetero atom; Z represents a hydrogen atom, a fluorenyl group, or an RzOC(=O) group; and Rz represents an aliphatic hydrocarbon group or aroma. a hydrocarbon group; wherein, the total number of carbon atoms contained in each of R ₁ to R ₅ is 4 or more; and R ₁ to R ₅ may be bonded to each other to form a ring; in the formula (2), R ₆ ~ R ₈ each independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of these groups; wherein the total number of carbon atoms contained in each of R ₆ to R ₈ is 6 or more; Wherein R ₉ to R ₁₂ each independently represent an alkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, or a group in which these groups are combined; wherein R ₉ to R ₁₂ are contained in each group; The total number of carbon atoms is 6 or more. A wiring board comprising: an insulating substrate; a plurality of metal wires including silver disposed on the insulating substrate; and a transparent adhesive layer disposed on the metal wiring in direct contact with the metal wiring, wherein adjacent The minimum distance between the metal wirings is less than 50 μm. The transparent adhesive layer contains a compound having an oxidation-reduction potential of 0.40 V to 1.30 V, and an adhesive layer which is a transparent adhesive layer having a time X of 12 hours or less in the following environmental test, and the environmental test is The transparent adhesive layer is disposed on the substrate, and a PET substrate is further disposed on the transparent adhesive layer to prepare a sample for evaluation, and the sample for evaluation is allowed to stand under conditions of 65° C. and 95% RH for 72 hours, and thereafter The sample for evaluation was placed in an environment of 23 ° C and 50% RH, and the time X of the haze of the transparent adhesive layer was determined to be 3%, wherein the length of the transparent adhesive layer was × cm × thickness × 5 cm × 4 cm × 50 μm, the thickness of the PET substrate was 50 μm. The wiring substrate according to claim 14, wherein the compound contains a phenol compound. The wiring board according to Item 14 or 15, wherein the compound contains a phenol compound having an oxidation-reduction potential of 0.50 V to 1.20 V. The wiring board according to Item 14 or 15, wherein the compound contains at least one selected from the group consisting of compounds represented by Formulas (1A) to (3A). Formula (1A) Formula (2A) In the formula (3A), R _11a to R _15a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; form a ring and, R _11a ~ R _15a may each be bonded to each other;; _11a ~ total molecular weight of each group of R _15a of 21 or more in the formula _{(2A), R 16a ~ R} 23a each independently represent a hydrogen atom, a hydroxyl group Or a hydrocarbon group having a carbon number of 1 to 20 which may be a hetero atom; and the total molecular weight of each of R _16a to R _23a is 24 or more; and R _16a to R _23a may be bonded to each other to form a ring; R _24a represents a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; in the formula (3A), R _25a to R _28a each independently represent a hydrogen atom, a hydroxyl group, or a carbon atom which may contain a hetero atom a hydrocarbon group of 1 to 20; further, a total of molecular weights of each of R _25a to R _28a is 40 or more; and R _25a to R _28a may each bond to each other to form a ring; L represents a divalent or divalent atom or a trivalent hydrocarbon group, -S-, or a combination of these groups; m represents an integer of 2 or 3. The wiring board according to Item 14 or 15, wherein the time X is less than 6 hours. The wiring board according to Item 14 or 15, wherein the minimum distance between the adjacent metal wirings is less than 40 μm. A transparent adhesive sheet comprising at least a transparent adhesive layer comprising a compound having an oxidation-reduction potential of 0.40 V to 1.30 V and an adhesive, the transparent adhesive layer being 12 hours in the following environmental test. Take In the environmental test, the transparent adhesive layer is placed on a substrate, and a PET substrate is further disposed on the transparent adhesive layer to prepare a sample for evaluation, and the sample for evaluation is at 65 ° C, 95% RH. After being allowed to stand for 72 hours, the evaluation sample was placed in an environment of 23 ° C and 50% RH, and the time at which the haze of the transparent adhesive layer reached 3% was measured, wherein the length of the transparent adhesive layer was × The width × thickness is 5 cm × 4 cm × 50 μm, and the thickness of the PET substrate is 50 μm. The transparent adhesive sheet of claim 20, wherein the compound comprises a phenol compound. The transparent adhesive sheet according to claim 20, wherein the compound comprises a phenol compound having an oxidation-reduction potential of 0.50 V to 1.20 V. The transparent adhesive sheet according to claim 20, wherein the compound comprises at least one selected from the group consisting of compounds represented by formulas (1A) to (3A). In the formula (1A), R _11a to R _15a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; and the total molecular weight of each of R _11a to R _15a is 21 or more; further, R _11a to R _15a may be bonded to each other to form a ring; in the formula (2A), R _16a to R _23a each independently represent a hydrogen atom, a hydroxyl group, or a carbon atom which may contain a hetero atom is 1~ Further, the hydrocarbon group of each of R _16a to R _{23a has a} molecular weight of 24 or more; and R _16a to R _23a may be bonded to each other to form a ring; R _24a represents a hydrogen atom or may contain a hetero atom; a hydrocarbon group having 1 to 20 carbon atoms; in the formula (3A), R _25a to R _28a each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having a carbon number of 1 to 20 which may contain a hetero atom; and R _25a to R The total molecular weight of each group of _28a is 40 or more; further, R _25a to R _28a may be bonded to each other to form a ring; L represents a divalent or trivalent hydrocarbon group which may have a hetero atom, -S-, or these groups A combination of bases; m represents an integer of 2 or 3. The transparent adhesive sheet of claim 20 or 21, wherein the time X is less than 6 hours. A touch panel comprising the wiring substrate according to any one of claims 14 to 19.