JP2017138556A - Conductive base material, color filter with wiring, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive base material having low-resistive conductivity and good adhesiveness between a conductive part and a substrate part.SOLUTION: A conductive base material 100 includes a substrate part 10 and a conductive alloy film 3 deposited on at least one surface of the substrate part 10. The conductive alloy film 3 comprises copper, nickel, and a metal element having a specified diffusion coefficient and an oxide formation enthalpy when the metal element included in a copper film is heated at 673K. When content percentages of the copper, the nickel, and the metal element are represented by α, β, and γ, respectively, α is 95.4 at% or more and 99.2 at% or less, β is 0.6 at% or more and 2.2 at% or less, and γ is 0.2 at% or more and 2.4 at% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive substrate, a color filter with a conductive wiring, and a liquid crystal display.

Conventionally, a touch panel type liquid crystal display having a capacitive touch panel is known.
For example, the display device described in Patent Document 1 is manufactured by manufacturing touch panel electrodes and color filters on separate substrates and bonding them together. In such technology, interference stripes are generated by slightly shifting the stripes of the touch panel wiring and the color filter, and the distance between the touch panel surface and the color filter surface increases, so that the parallax is viewed from an oblique direction. There is a problem in terms of display performance, such as In order to solve this problem, for example, Patent Documents 2 and 3 propose techniques for forming touch panel electrodes and color filters on the front and back of the same glass substrate.

As a technique for forming the touch panel electrode and the color filter on the front and back of the same glass substrate, an in-cell type and an on-cell type are known. The in-cell type incorporates a touch panel function in an LCD cell including a TFT (Thin Film Transistor). The on-cell type incorporates a touch panel function between a glass substrate provided with a polarizing plate and a color filter.
ITO (indium tin oxide) is often used for the electrode wiring for touch sensing of the conventional on-cell type and in-cell type touch panel (see, for example, Patent Document 4).
On the other hand, it has also been proposed to use metal wiring as the electrode wiring for touch sensing (Patent Document 5).

JP 2007-178758 A JP 2008-9750 A JP 2010-072584 A JP 2013-117816 A Japanese Patent No. 5632721

However, the above-described conventional electrode wiring for touch sensing and the conductive substrate including the electrode wiring for touch sensing have the following problems.
For example, since the in-cell wiring technology incorporates a touch sensor function inside the pixel on the TFT substrate, there is a concern that the manufacturing yield may be reduced. Furthermore, since the area that can be used for display is reduced by incorporating the touch sensor in the pixel, there is a problem that the image quality is lowered.
For example, when the wiring is formed of ITO as in Patent Document 4, since ITO has a higher specific resistance than the metal wiring, there is a problem that the response speed is lower than that of the metal wiring and low voltage driving becomes difficult. .
As described in Patent Document 5, it is also conceivable to use copper or a copper alloy for the electrode wiring for touch sensing. However, in recent years, the use of touch panels has been expanding, and in many cases, coatings of organic resins having various characteristics are made on a transparent base material serving as a substrate. For this reason, touch sensing electrode wiring is increasingly required to be formed on an organic resin.
However, the metal wiring has a problem of poor adhesion to the organic resin.

The present invention has been made in view of the above problems, and has a low-resistance conductivity, a conductive base material having good adhesion between the conductive portion and the substrate portion, and a color filter with wiring The purpose is to provide.
An object of the present invention is to provide a liquid crystal display capable of improving the responsiveness of touch sensing and the reliability of touch sensing wiring.

In order to solve the above-described problem, the conductive base material according to the first aspect of the present invention includes a substrate part and a laminated film laminated on at least one surface of the substrate part, and the laminated film comprises: The diffusion coefficient when heated to 673K in the state of being contained in copper film with copper, nickel is 5.0 × 10 ⁻²⁰ cm ² / s or more and 5.0 × 10 ⁻¹⁹ cm ² / s or less. And an oxide formation enthalpy at 293K is −2500 kJ / mol or more and −900 kJ / mol or less, and the contents of the copper, the nickel, and the metal element are respectively α, β, In terms of γ, α is 95.4 at% or more and 99.2 at% or less, β is 0.6 at% or more and 2.2 at% or less, and γ is 0.2 at% or more and 2.4 at% or less. Are laminated on the surface.

  In the conductive base material, a specific resistance of the conductive alloy film may be 2.0 μΩ · cm to 15.0 μΩ · cm.

  In the conductive substrate, the metal element may be one or more elements selected from aluminum, silicon, and titanium.

  In the conductive substrate, the laminated film may be formed by laminating a copper alloy film or a copper film having a specific resistance lower than that of the conductive alloy film on the conductive alloy film.

  In the said electroconductive base material, the protective film which has heat resistance may be laminated | stacked on the said copper alloy film or the said copper film.

  In the conductive substrate, the specific resistance of the laminated film may be not less than 2.0 μΩ · cm and not more than 10.0 μΩ · cm.

  In the conductive substrate, the surface on which the laminated film is laminated may be formed of glass.

  In the conductive substrate, the surface on which the laminated film is laminated may be formed of a resin.

  In the conductive substrate, the resin may include carbon particles.

  In the conductive substrate, the resin may be a resin film constituting a black matrix of a color filter.

  In the conductive substrate, the laminated film may include a wiring in which at least the conductive alloy film is patterned.

The color filter with wiring of the 2nd aspect of this invention is equipped with the said electroconductive base material and the colored layer for color filters arrange | positioned at the said electroconductive base material.

  A liquid crystal display according to a third aspect of the present invention includes a liquid crystal, a TFT substrate that drives the liquid crystal, and the conductive base material, and an electrode of a capacitive touch panel is the wiring in the conductive base material. Is formed by.

  A liquid crystal display according to a fourth aspect of the present invention includes a liquid crystal, a TFT substrate that drives the liquid crystal, and the color filter with wiring, and an electrode of a capacitive touch panel has the wiring in the color filter with wiring. Is formed by.

  The liquid crystal display may further include a counter electrode of a capacitive touch panel disposed to face the electrode.

According to the conductive base material and the color filter with wiring of the present invention, copper, nickel, and a metal element in which a diffusion coefficient and an oxide formation enthalpy are defined when heated to 673 K in a state of being contained in a copper film. And a conductive alloy film laminated on the surface of the substrate portion including only a predetermined composition range, the conductive portion including the conductive alloy film has low resistance conductivity, the conductive portion and the substrate portion, There is an effect that the adhesion of is improved.
According to the liquid crystal display of the present invention, since the conductive base material of the present invention in which the wiring is formed by the conductive alloy film is provided, the responsiveness of touch sensing and the reliability of the wiring for touch sensing can be improved. There is an effect.

It is sectional drawing which shows typically the structural example of the electroconductive base material of the 1st Embodiment of this invention. It is typical sectional drawing which shows the structural example of the color filter with wiring and the electroconductive base material of the 2nd Embodiment of this invention. It is typical sectional drawing which shows the structural example of the color filter with wiring and the electroconductive base material of the modification (1st modification) of the 2nd Embodiment of this invention. It is sectional drawing which shows typically the structural example of the liquid crystal display of the 3rd Embodiment of this invention. It is sectional drawing which shows typically the structural example of the liquid crystal display of the 4th Embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. In all the drawings, even if the embodiments are different, the same or corresponding members are denoted by the same reference numerals, and common description is omitted.

[First Embodiment]
The electroconductive base material of the 1st Embodiment of this invention is demonstrated.
FIG. 1 is a cross-sectional view schematically showing a configuration example of a conductive substrate according to the first embodiment of the present invention.
Since FIG. 1 is a schematic diagram, the shape of each part is simplified and the dimensions are exaggerated (the same applies to the following drawings).

  As shown in FIG. 1, the conductive base material 100 of this embodiment includes a substrate unit 10 and a conductive alloy film 3 (laminated film).

  The substrate unit 10 includes a transparent substrate 1 and a resin film 2 formed on the first surface 1 a that is one surface of the transparent substrate 1.

As the transparent substrate 1, a substrate having optical transparency corresponding to the use of the conductive base material 100 is used. For example, when the conductive substrate 100 is disposed in a light transmission part of the display, the transmittance of the transparent substrate 1 may be 80% or more with respect to visible light. The transmittance of the transparent substrate 1 is more preferably 95% or more with respect to visible light.
The thickness of the transparent substrate 1 may be appropriately set according to the required strength in the use of the conductive base material 100.
As the material of the transparent substrate 1, for example, an inorganic transparent material such as glass, or a transparent resin material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and cyclic olefin copolymer can be used.
The transparent substrate 1 may be formed of one kind of material, or may be formed by combining two or more kinds of materials selected from the inorganic transparent material and the transparent resin material exemplified above.
In particular, in a manufacturing process of the conductive substrate 100 or an application heated when the conductive substrate 100 is used, it is more preferable that a glass substrate having higher heat resistance than the transparent resin material is used as the transparent substrate 1.
In the present embodiment, as an example, the case where the transparent substrate 1 is a glass substrate will be described.

The resin film 2 is used for adding an appropriate function to the first surface 1 a of the transparent substrate 1.
In the present embodiment, as an example, a case where the resin film 2 is a shielding layer that prevents a conductive alloy film 3 described later from being seen from the second surface 1b on the opposite side of the first surface 1a will be described.
In order to cover the conductive alloy film 3 so that it cannot be seen, a colored resin having good adhesion to the transparent substrate 1 is used for the resin film 2.
For example, the resin film 2 may be formed of an acrylic resin in which a black pigment is dispersed. As an example of the black pigment, for example, carbon particles may be used. When the conductive substrate 100 is used for a display, the resin film 2 may constitute a black matrix.
The resin film 2 may cover the entire surface of the first surface 1a, but in the present embodiment, the resin film 2 is formed only in a range where a conductive alloy film 3 described later is formed.

The pattern of the resin film 2 can be an appropriate pattern according to the required pattern of the conductive alloy film 3.
In the present embodiment, as an example, the resin film 2 is patterned in a lattice shape with an appropriate space in the illustrated horizontal direction and an appropriate space in the depth direction of the drawing.
The surface 2 a of the resin film 2 constitutes one surface of the substrate unit 10 together with the first surface 1 a of the transparent substrate 1 excluding the resin film 2.
Since FIG. 1 shows an enlarged part of the cross section, only four columns of the resin film 2 are shown, but the pattern of the resin film 2 is not limited to only four columns.

The conductive alloy film 3 is a laminated film laminated on the surface 2 a of the resin film 2 of the substrate unit 10. The conductive alloy film 3 is provided for imparting conductivity to the conductive substrate 100.
The planar view shape of the conductive alloy film 3 can be set to an appropriate shape according to the use of the conductive substrate 100. The conductive alloy film 3 in the present embodiment is, for example, a stripe shape extending in the depth direction of the drawing with a space similar to that of the resin film 2 in the illustrated horizontal direction so that it can be used as an electrode of a capacitive touch panel. It is patterned.

Since the conductive alloy film 3 is laminated on the surface 2a of the resin film 2, the conductive alloy film 3 is formed of a material having a composition that provides good adhesion to the resin material of the resin film 2.
The conductive alloy film 3 is made of an alloy containing copper (Cu) as a main component and nickel (Ni) and the metal element A.
The metal element A has a diffusion coefficient of 5.0 × 10 ⁻²⁰ cm ² / s or more and 5.0 × 10 ⁻¹⁹ cm ² / s or less when heated to 673 K in a state of being contained in the copper film. Yes, and the oxide formation enthalpy at 293K is not particularly limited as long as it is −2500 kJ / mol or more and −900 kJ / mol or less. Here, the “metal element” means a metal element in a broad sense including a so-called “metalloid”.
Hereinafter, for the sake of simplicity, in the present specification, even if it is simply described as “diffusion coefficient”, it means a value when heated to 673 K in a state of being contained in a copper film unless otherwise specified. Similarly, “oxide formation enthalpy” means a value at 293K.
The metal element A contained in the conductive alloy film 3 may be one kind or two or more kinds of metal elements that satisfy the above conditions.

Examples of the metal element A include aluminum (Al), silicon (Si), and titanium (Ti).
The diffusion coefficient of aluminum is 6.78 × 10 ⁻²⁰ cm ² / s, the diffusion coefficient of silicon is 3.30 × 10 ⁻¹⁹ cm ² / s, and the diffusion coefficient of titanium is 4.24 × 10 ⁻²⁰ cm. ² / s (see LANDOLT-BORNSTEIN, NEW SERIES GROUP III, VOL. 263, 2, 11, Springer Verlag, Berlin (1990)).

  The oxide formation enthalpy at aluminum temperature 293K is −1678.2 kJ / mol, the oxide formation enthalpy at silicon temperature 293 K is −910.9 kJ / mol, and the oxide formation enthalpy at titanium temperature 293 K is -2457.2 kJ / mol (see sub- smithsmiths Metals Reference Book, Seventh Edition, 8-25, Butterworth-Heinemann (1992)).

The composition of the conductive alloy film 3 satisfies all the following ranges when the contents of copper, nickel, and metal element A in the conductive alloy film 3 are α, β, and γ, respectively.
The range of α is 95.4 at% or more and 99.2 at% or less. The range of β is 0.6 at% or more and 2.2 at% or less. The range of γ is 0.2 at% or more and 2.4 at% or less.

The composition of the conductive alloy film 3 may be a composition that provides a specific resistance lower than that of ITO. The specific resistance of ITO is 986 μΩ · cm.
More preferably, the conductive alloy film 3 has a specific resistance of 2.0 μΩ · cm to 15.0 μΩ · cm. With such a specific resistance, for example, when the conductive alloy film 3 is used as an electrode of a capacitive touch panel, high-speed response is obtained. Furthermore, the voltage applied to the electrode of the capacitive touch panel can be lowered.

In the conductive base material 100 having such a configuration, for example, after the resin film 2 is formed on the transparent substrate 1 and the resin film 2 is patterned, the conductive alloy film 3 is laminated on the surface 2 a of the resin film 2. To be manufactured.
The resin film 2 is formed by applying a raw material resin such as a liquid acrylic resin in which carbon particles are dispersed to the first surface 1a of the transparent substrate 1 and then curing according to the type of the raw material resin. Also good.
As a method for applying the raw material resin, for example, spin coating, spinless coating, dipping, or the like may be used. However, the method of applying the raw material resin is not limited to these methods as long as it can be applied on the transparent substrate 1 with a uniform film thickness.
For the patterning of the resin film 2, for example, a photolithography method may be used.

As a method for forming the conductive alloy film 3, for example, it is uniformly formed on the first surface 1 a of the transparent substrate 1 and the surface 2 a of the resin film 2 by sputtering, and then only on the surface 2 a of the resin film 2. There is a method of patterning so that the conductive alloy film 3 remains. Examples of the patterning method include a photolithography method.
However, the method for forming the conductive alloy film 3 is not limited to the sputtering method as long as a uniform film thickness can be formed on the resin film 2. For example, the conductive alloy film 3 may be formed by a CVD method, a vapor deposition method, a plating method, or the like. Further, the patterning method after the film formation is not limited to the photolithography method as long as the conductive alloy film 3 on the first surface 1a can be removed.

Next, the operation of the conductive substrate 100 will be described.
In the conductive substrate 100, conductivity is obtained by the conductive alloy film 3.
Since the conductive alloy film 3 contains copper as a main component, the specific resistance of the conductive alloy film 3 is significantly lower than that of, for example, ITO.
Since the conductive alloy film 3 is a copper alloy containing nickel, the corrosion resistance is improved compared to metallic copper.
However, a copper film or a copper nickel alloy film has a problem that adhesion to glass or resin is inferior to that of ITO.
Therefore, the present inventors have used a copper nickel alloy as the conductive alloy film 3 to improve the adhesion to glass or resin, and to improve the adhesion to glass or resin. A study was conducted using a ternary alloy added to. As a result of intensive studies, the present inventors have found that the metal element A described above is suitable as a metal element component capable of improving adhesion. The reason why the metal element A is suitable is not necessarily clear, but the following reasons are conceivable.

Metal element A has a diffusion coefficient of 5.0 × 10 ⁻²⁰ cm ² / s or more and 5.0 × 10 ⁻¹⁹ cm ² / s or less when heated to 673 K in a state of being contained in the copper film. In addition, a part of the metal element A in the conductive alloy film 3 containing copper as a main component easily moves to the laminated surface with the resin film 2 in the conductive alloy film 3.
Furthermore, since the enthalpy of oxide formation at 293K is −2500 kJ / mol or more and −900 kJ / mol or less, the metal element A has high chemical affinity with oxygen and high bonding strength. For this reason, it is considered that the metal element A that has moved to the laminated surface easily forms strong bonds with oxygen atoms that are abundantly contained on the surface of the substrate portion 10.
For this reason, when the laminated surface of the conductive alloy film 3 is comprised with the material which contains oxygen atoms abundantly, such as a glass substrate and resin, it is thought that adhesiveness improves especially.
Furthermore, the present inventors have made the composition range of copper, nickel, and metal element A in the range of α, β, and γ in the above range in order to obtain good conductivity after improving the adhesion. The present inventors have found that there is a need to be satisfied, and have reached the present invention.

  As described above, according to the conductive substrate 100 of the present embodiment, the conductive alloy film 3 containing copper, nickel, and the metal element A in a predetermined composition range is laminated on the resin film 2. The conductive portion made of the alloy film 3 has low resistance conductivity, and the adhesion between the conductive portion and the substrate portion is improved.

[Second Embodiment]
Next, the conductive base material of the second embodiment of the present invention and the color filter with wiring including the conductive base material will be described.
FIG. 2 is a schematic cross-sectional view showing a configuration example of a color filter with wiring and a conductive substrate according to the second embodiment of the present invention.

As shown in FIG. 2, the color filter with wiring 200 of the present embodiment includes a substrate unit 10 similar to that in the first embodiment, a stacked film 12 stacked on the substrate unit 10, a colored layer 11 </ b> R, 11G and 11B and the insulating protective layer 6 are provided. In the color filter with wiring 200 of the present embodiment, the substrate unit 10 and the laminated film 12 constitute a conductive base material 110.
Hereinafter, a description will be given centering on differences from the first embodiment.

  The laminated film 12 is laminated on the surface 2a. In the laminated film 12, the same conductive alloy film 3, the metal film 4, and the protective film 5 as those in the first embodiment are laminated in this order from the surface 2a side.

The metal film 4 is made of a good conductor. The metal film 4 is laminated on the conductive alloy film 3 in order to reduce the specific resistance as the laminated film 12.
The material of the metal film 4 is not particularly limited as long as the specific resistance as the multilayer film 12 can be reduced as compared with the case where the conductor portion of the multilayer film 12 is only the conductive alloy film 3.
For example, the material of the metal film 4 is a single metal such as copper, silver (Ag), gold (Au), aluminum, nickel, manganese (Mn), or two or more metals selected from these metals. An alloy formed by blending may be used.
For example, a copper alloy film having a specific resistance lower than that of the conductive alloy film 3 is suitable as the metal film 4 because it can reduce the specific resistance of the laminated film 12 and is inexpensive. Furthermore, the copper film is more preferable as the metal film 4 because it has a lower specific resistance than the conductive alloy film 3 and is inexpensive.

The protective film 5 is stacked so as to be in close contact with the metal film 4 and cover the metal film 4.
The protective film 5 is laminated in close contact with the metal film 4 to protect the metal film 4 from one or more kinds of stress among, for example, mechanical / physical stress, chemical stress, and thermal stress.
In the present embodiment, the protective film 5 has a protective function for suppressing oxidation of the metal film 4 at least in the manufacturing process of the color filter with wiring 200. For this reason, the protective film 5 is comprised with the material provided with the heat resistance which endures the baking temperature at the time of baking the colored layers 11R, 11G, and 11B mentioned later. The protective film 5 may be a conductor or an insulator.
In this embodiment, the protective film 5 is made of ITO, which has a high effect of suppressing the oxidation of the metal film 4.

The colored layers 11R, 11G, and 11B function as color filters in the color filter 200 with wiring. The colored layers 11R, 11G, and 11B are resin layers colored in red (R), blue (G), and green (B), respectively. For example, in the present embodiment, the colored layers 11R, 11G, and 11B are made of an acrylic resin in which R, G, and B pigments are dispersed, respectively.
The colored layers 11R, 11G, and 11B are stacked on the first surface 1a in the region sandwiched between the wiring patterns of the resin film 2 and the stacked film 12 in the illustrated horizontal direction. The colored layers 11R, 11G, and 11B are stacked on the first surface 1a in the region sandwiched between the lattice patterns of the resin film 2 in the depth direction of the drawing. The thickness of the colored layers 11R, 11G, and 11B is not particularly limited as long as it exceeds the height from the first surface 1a to the surface 12a of the laminated film 12 on the side opposite to the resin film 2. For example, the thickness of the colored layers 11R, 11G, and 11B may be 0.5 μm or more and 3.0 μm or less.
In FIG. 2, the colored layers 11R, 11G, and 11B are arranged in this order in the horizontal direction in the drawing as appropriate according to the arrangement of the pixels corresponding to the R, G, and B colors in the display to which the wired color filter 200 is attached. Is possible.

The insulating protective layer 6 is formed in a layer shape covering from the lower side in the figure with a transparent material having electrical insulating properties in order to protect at least the colored layers 11R, 11G, and 11B.
In the present embodiment, as an example, the insulating protective layer 6 is made of an organic transparent resin material having photosensitivity. As the organic material used for the insulating protective layer 6 in this embodiment, for example, a UV curable coating composition containing a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives may be used. Good.
As shown in FIG. 2, in this embodiment, the insulating protective layer 6 is formed in a layer shape that covers the colored layers 11 </ b> R, 11 </ b> G, and 11 </ b> B and the protective films 5 of the laminated film 12.
For this reason, in the color filter with wiring 200, the surface opposite to the transparent substrate 1 is formed by the surface 6 a of the insulating protective layer 6. For this reason, the laminated film 12 is sandwiched between the transparent substrate 1 and the insulating protective layer 6 and insulated from the outside.

In order to manufacture the color filter with wiring 200 having such a configuration, first, the conductive alloy film 3 is laminated on the substrate portion 10 in the same manner as in the first embodiment. Thereafter, the metal film 4 and the protective film 5 are laminated on the conductive alloy film 3, and the metal film 4 and the protective film 5 are patterned as necessary.
The method for forming the metal film 4 and the protective film 5 is not particularly limited as long as the metal film 4 and the protective film 5 can be formed with a uniform film thickness on each laminated portion. For example, the method for forming the metal film 4 and the protective film 5 may be selected from the same film forming method as exemplified as the method for forming the conductive alloy film 3 in the first embodiment.
The patterning method of the metal film 4 and the protective film 5 is not particularly limited, and for example, a photolithography method, wet etching, or the like may be used.

After the laminated film 12 is formed, the colored layers 11R, 11G, and 11B are formed.
The colored layers 11R, 11G, and 11B are appropriately formed by, for example, a well-known technique for manufacturing a color filter for a liquid crystal display.
For example, first, the resin material for forming the colored layer is applied onto the first surface 1a and the laminated film 12 by using an appropriate application method such as spin coating, spinless coating, or dipping, so that the kind of the resin material is obtained. It is cured by a suitable curing means. Thereafter, for example, patterning is performed by using a photolithography method or the like to leave only at the arrangement position of the colored layer. By repeating this for each color, the colored layers 11R, 11G, and 11B are formed.

After the colored layers 11R, 11G, and 11B are formed, the insulating protective layer 6 is formed.
In order to form the insulating protective layer 6, first, a resin material for forming the insulating protective layer 6 is applied so as to cover the colored layers 11 </ b> R, 11 </ b> G, and 11 </ b> B and the surface 12 a of the through-hole portion 12. As a method for applying the resin material, for example, an appropriate application method such as spin coating, spinless coating, or dipping is used. Thereafter, the applied resin material is cured. For example, when the resin material is a UV curable resin, the resin material is cured by irradiation with UV light. Thereby, the insulating protective layer 6 is formed.

The color filter with wiring 200 having such a configuration can constitute a color display by being overlaid on a display unit of an appropriate method. At that time, the laminated film 12 is used as an electrode of a capacitive touch panel, whereby the color display can have a touch sensing function.
In the color filter with wiring 200 according to the present embodiment, colored layers 11R, 11G, and 11B partitioned by the resin film 2 are formed between the laminated films 12. In the present embodiment, since the resin film 2 is black, the resin film 2 has a function of a black matrix in a color display.

  The color filter with wiring 200 of the present embodiment includes a laminated film 12 that is patterned according to the application. The laminated film 12 functions as a wiring because at least the conductive alloy film 3 and the metal film 4 have conductivity.

As described above, according to the color filter with wiring 200 of the present embodiment, the conductive alloy film 3 containing the metal element A is laminated on the resin film 2 as in the case of the conductive substrate 100 of the first embodiment. Is done. For this reason, the conductive part including the conductive alloy film 3 has low resistance conductivity, and the adhesion between the conductive part and the substrate part is improved.
Furthermore, in the present embodiment, the conductive alloy film 3 and the metal film 4 having a specific resistance smaller than that of the conductive alloy film 3 are stacked in the stacked film 12 that is a wiring. For this reason, the specific resistance as the wiring is reduced as compared with the wiring in which the conductive portion is made of only the conductive alloy film 3 as in the conductive base material 100 of the first embodiment.
As a result, the conductivity of the laminated film 12 becomes good. For example, when the laminated film 12 is used as a wiring for touch sensing, responsiveness is improved or driving with a lower voltage is possible.
Furthermore, in this embodiment, since the laminated film 12 is sandwiched between the transparent substrate 1 and the insulating protective layer 6, the conductive alloy film 3 and the metal film 4 of the laminated film 12 are not easily affected by the external environment.

[First Modification]
Next, a color filter with wiring according to a modification (first modification) of the present embodiment will be described.
FIG. 3 is a schematic cross-sectional view showing a configuration example of a color filter with wiring according to a modification (first modification) of the second embodiment of the present invention.

As shown in FIG. 3, the color filter with wiring 300 of the present embodiment is configured by adding a counter electrode 7 to the color filter with wiring 200 of the second embodiment.
Hereinafter, a description will be given focusing on differences from the second embodiment.

The counter electrode 7 constitutes a wiring pattern in which the laminated film 12 is spaced apart in the horizontal direction in the figure and extended in the depth direction of the paper, whereas the counter electrode 7 is a stripe extended in the horizontal direction in the figure and spaced apart in the depth direction of the paper. The wiring pattern is formed.
The counter electrode 7 is formed on the second surface 1 b of the transparent substrate 1. Although not particularly illustrated, an insulating protective film made of a transparent resin material or the like is laminated on the counter electrode 7 and the second surface 1b.

The material of the counter electrode 7 is not particularly limited as long as it is a conductor that can form a capacitance with the laminated film 12.
For example, the counter electrode 7 may be formed of a transparent material such as ITO.
For example, the counter electrode 7 may be formed of an opaque metal film or metal alloy film. When an opaque material is used as the counter electrode 7, the counter electrode 7 is preferably formed in a range that does not overlap with the colored layers 11R, 11G, and 11B in plan view. Further, when an opaque material is used as the counter electrode 7, a resin film of the same material as the resin film 2 may be laminated on the surface of the counter electrode 7 on the side opposite to the transparent substrate 1. Thereby, since the reflected light by the counter electrode 7 is suppressed, the counter electrode 7 does not stand out from the outside.
For example, a laminated film having the same configuration as that of the laminated film 12 may be used as the counter electrode 7. Since the conductive alloy film 3 has good adhesion to a glass material, it can be directly laminated on the surface 2a.

According to the color filter with wiring 300 of this modified example having such a configuration, since the same conductive substrate as that of the second embodiment is provided, the same effects as those of the second embodiment are provided.
Furthermore, according to this modification, by detecting the electrostatic capacitance between the laminated film 12 that is the wiring and the counter electrode 7, the laminated film 12 and the counter electrode 7 are detected by the capacitive touch panel. It can be used as an electrode and a counter electrode. For this reason, the color filter with wiring 300 can be configured to overlap with a display unit of an appropriate method to constitute a color display having a touch sensing function.

[Third Embodiment]
Next, a liquid crystal display according to a third embodiment of the present invention will be described.
FIG. 4 is a cross-sectional view schematically showing a configuration example of a liquid crystal display according to the third embodiment of the present invention.

As shown in FIG. 4, the liquid crystal display 400 of this embodiment includes a TFT substrate 30, a liquid crystal 20, and a color filter with wiring 200 of the second embodiment stacked in this order to form a display unit. . Further, the liquid crystal display 400 includes a touch sensing control unit 40.
Hereinafter, a description will be given focusing on differences from the second embodiment.

The TFT substrate 30 is a drive circuit substrate including TFTs that drive the liquid crystal 20 described later for each sub-pixel.
The liquid crystal 20 is a liquid crystal panel in which pixel electrodes (not shown) are arranged at positions corresponding to the colored layers 11R, 11G, and 11B of the color filter 200 with wiring. Each pixel electrode in the liquid crystal 20 is electrically connected to a drive circuit of the TFT substrate 30.
For example, the liquid crystal 20 has a known configuration in which the liquid crystal is sandwiched between polarizing plates. The liquid crystal driving method in the liquid crystal 20 is not particularly limited.

The color filter 200 with wiring in the present embodiment is laminated on the liquid crystal 20 so that the colored layers 11R, 11G, and 11B overlap with the sub-pixels of the liquid crystal 20, respectively.
The conductive portion of the laminated film 12 of the color filter with wiring 200 is electrically connected to the touch sensing control unit 40.
The touch sensing control unit 40 performs capacitive touch sensing by detecting a change in capacitance on the transparent substrate 1 using a wiring pattern formed by the laminated film 12.

The liquid crystal display 400 includes the color filter with wiring 200 and the conductive substrate of the second embodiment included in the color filter with wiring 200, and a color liquid crystal display using the laminated film 12 as an electrode of a capacitive touch panel. It has become.
Since the laminated film 12 is a separate substrate from the liquid crystal 20 and the TFT substrate 30, it is possible to increase the area of the subpixel as compared with the case where the touch sensing wiring is formed on the liquid crystal 20 and the TFT substrate 30. And high image quality is possible.
In the conductive substrate of the second embodiment, the conductive portion including the conductive alloy film 3 has low resistance conductivity, and the adhesion between the conductive portion and the substrate portion is good. For this reason, according to the liquid crystal display 400, the responsiveness of touch sensing and the reliability of the wiring for touch sensing are improved.

[Fourth Embodiment]
Next, a liquid crystal display according to a fourth embodiment of the present invention will be described.
FIG. 5 is a cross-sectional view schematically showing a configuration example of a liquid crystal display according to the fourth embodiment of the present invention.

  As shown in FIG. 5, the liquid crystal display 500 according to the present embodiment includes a color filter 300 with wiring in place of the color filter 200 with wiring and the touch sensing control unit 40 of the touch sensing control unit 400 according to the fourth embodiment, A touch sensing control unit 50 is provided. Hereinafter, a description will be given centering on differences from the third embodiment.

The color filter 300 with wiring in the present embodiment is laminated on the liquid crystal 20 so that the colored layers 11R, 11G, and 11B overlap with the sub-pixels of the liquid crystal 20, respectively.
The conductive portion of the laminated film 12 of the color filter with wiring 300 and the counter electrode 7 are electrically connected to the touch sensing control unit 50.
The touch sensing control unit 50 detects capacitance change on the transparent substrate 1 by using the wiring pattern by the laminated film 12 and the wiring pattern by the counter electrode 7, thereby performing capacitive touch sensing. Do.

The liquid crystal display 500 includes the color filter with wiring 300 and the conductive substrate of the second embodiment included in the color filter with wiring 300, and the laminated film 12 and the counter electrode 7 are connected to detection electrodes of a capacitive touch panel and It is a color liquid crystal display used for the counter electrode.
The liquid crystal display 500 has the same configuration as the liquid crystal display 400 in the third embodiment except that the detection electrode and the counter electrode are used for touch sensing, and has the same functions and effects as the liquid crystal display 400. .

In the description of each of the above-described embodiments and modifications, an example in which the resin film 2 and the conductive alloy film 3 in the conductive base material are patterned and the conductive alloy film 3 forms a touch sensing wiring. Explained. However, for example, depending on the use of the conductive base material, the pattern shape of the resin film 2 and the conductive alloy film 3 may be a solid pattern that is not patterned.
Furthermore, even when the resin film 2 and the conductive alloy film 3 are patterned, the patterning shape is not limited to the above-described shape.
For example, the pattern of the resin film 2 is not limited to the lattice shape depending on the use of the conductive substrate, and is not limited to the shape of the black matrix of the liquid crystal display.
For example, the pattern of the conductive alloy film 3 may be patterned into a wiring shape other than the touch sensing wiring depending on the use of the conductive base material. Furthermore, the pattern of the conductive alloy film 3 may be patterned into a shape such as an appropriate electrode other than the wiring and a ground pattern.

In the said 2nd Embodiment, the laminated film 12 of the color filter 200 with wiring demonstrated the example in the case of having the metal film 4 and the protective film 5. FIG.
However, the metal film 4 may be omitted when necessary conductivity is obtained by the conductive alloy film 3.
When the metal film 4 is made of a material that does not need to be protected by the protective film 5, the protective film 5 may be omitted.
When the metal film 4 and the protective film 5 can be deleted, the color filter with wiring 200 may include the configuration of the conductive base material 100 in the first embodiment.

  In the description of the third and fourth embodiments, the liquid crystal displays 400 and 500 are described as examples in which the conductive substrate 110 is provided. However, the liquid crystal displays 400 and 500 may include the conductive substrate 100 in the first embodiment as a conductive substrate, and the metal film 4 or the protective film 5 is deleted from the conductive substrate 110. May be provided.

  Hereinafter, Examples 1-27 of the conductive substrate 100 of the first embodiment and the liquid crystal display 400 of the third embodiment using the same will be described together with Comparative Examples 1-14 of the conductive substrate. .

[Conductive substrate]
About the structure and evaluation result of each electroconductive base material of Examples 1-27 and Comparative Examples 1-14, it shows in following [Table 1] and [Table 2].

[Example 1]
In the conductive substrate 100 of Example 1, alkali-free glass was used as the transparent substrate 1.
As the resin film 2, a black matrix resin in which a black pigment is mixed with an acrylic resin is used. Specifically, a black matrix resin having a photosensitive resist material as a base resin was applied on the first surface 1a by a spin coating method. This coating film was dried on a hot plate at 120 ° C. for 2 minutes.
Thereafter, the coating film was patterned by a photolithography method. Specifically, the coating film was exposed through a photomask having an opening corresponding to the patterning shape. A high pressure mercury lamp was used as the exposure light source, and the exposure energy was 100 mJ / cm ² .
Thereafter, the coating film was subjected to shower cleaning for 30 seconds with a 0.2 mass% aqueous sodium hydrogen carbonate solution. Furthermore, after washing with water, heat treatment was performed at 230 ° C. for 30 minutes in a hot air circulation oven. As a result, the resin film 2 was formed on the first surface 1 a of the transparent substrate 1.

Thereafter, a conductive alloy film 3 was formed on the surface 2 a of the resin film 2. As described in [Table 1] above, the composition of the conductive alloy film 3 was 97.6 at%, 2.2 at%, and 0.2 at% for Cu, Ni, and Al, respectively.
The conductive alloy film 3 was formed by sputtering to a uniform thickness of 160 nm and then patterned by photolithography so as to achieve the above content. However, each content rate is rounded to the first decimal place. For example, a slight change in composition due to mixing of impurities contained in the target metal is ignored (the same applies to other content rates).

[Examples 2 to 27]
In the same manner as in Example 1, conductive substrates 100 of Examples 2 to 27 in which only the composition of the conductive alloy film 3 was different were produced. Each composition was set to the content shown in the above [Table 1] and [Table 2].
Examples 2 to 9 are examples in the case where the metal element A is Al, as in Example 1 above. The conductive alloy films 3 of Examples 2 to 9 were ternary alloys made of Cu, Ni, and Al, and the respective contents were changed.
Examples 10 to 18 are examples where the metal element A is Si. The conductive alloy films 3 of Examples 10 to 18 were ternary alloys made of Cu, Ni, and Si, and the respective contents were changed.
Examples 19 to 27 are examples where the metal element A is Ti. The conductive alloy films 3 of Examples 19 to 27 are ternary alloys composed of Cu, Ni, and Ti, and the respective contents are changed.

[Comparative Examples 1-14]
As shown in [Table 2], Comparative Example 1 is an example in which an ITO film having the same thickness was used in place of the conductive alloy film 3 of Example 1 above.
Comparative Example 2 is an example in which a Cu film having the same thickness was used in place of the conductive alloy film 3 of Example 1 above.
Comparative Example 3 is an example in which a binary alloy film of the same thickness made of Cu and Ni was used instead of the conductive alloy film 3 of Example 1 above.
Comparative Example 4 is an example in which a binary alloy film of the same thickness made of Cu and Al was used in place of the conductive alloy film 3 of Example 1 above.
Comparative Examples 5 to 8 are examples in which the metal element A is Al, as in Examples 1 to 9. However, in Comparative Examples 5 to 8, at least one of the Ni content β and the Al content γ does not satisfy the above-described proper composition range.
Comparative Examples 9 to 11 are examples in which a ternary alloy film of the same thickness made of Cu, Ni, and In (indium) was used instead of the conductive alloy film 3 of Example 1 above.
In has a diffusion coefficient of 1.22 × 10 ⁻¹⁹ cm ² / s, but does not correspond to the metal element A because the oxide formation enthalpy is −618 kJ / mol.
Comparative Examples 12 to 14 are examples in which a ternary alloy film of the same thickness made of Cu, Ni, and Ag (silver) was used instead of the conductive alloy film 3 of Example 1 above.
Ag does not correspond to the metal element A because the diffusion coefficient is 4.2 × 10 ⁻²⁰ cm ² / s and the oxide formation enthalpy is −61 kJ / mol.

These conductive substrates were evaluated for specific resistance and adhesion for the resin film 2.
The specific resistance was converted based on the thickness of the conductive alloy film by measuring the sheet resistance value of the conductive alloy film. A four-probe method was used as a method for measuring the sheet resistance value.
The measured value of the sheet resistance value and the converted value of the specific resistance in each example and each comparative example are as described in [Table 1] and [Table 2].
Evaluation of the adhesion of the conductive alloy film was performed by a cross-cut method. Specifically, the cross cut method was performed based on JIS K5600. In [Table 1], evaluation results in each example and each comparative example are described according to classifications 0 to 5 of JIS K5600.
Class 0 indicates that “the edges of the cut are completely smooth and there is no peeling to any grid eye”. Classifications 1 to 5 indicate that some peeling occurred.

As can be seen from the evaluation results described in [Table 1] and [Table 2], the specific resistances of Examples 1 to 27 are in the range of 3.2 μΩ · cm to 12.8 μΩ · cm. The resistivity of 1 ITO is extremely low compared to the specific resistance of 986 μΩ · cm.
Furthermore, all the adhesion evaluation of Examples 1-7 became classification 0, and it turned out that peeling etc. do not generate | occur | produce.

In the case of Comparative Example 1, the adhesion was good, but the specific resistance was remarkably increased.
In the case of Comparative Examples 2 to 14, the adhesion was not good, such as peeling off.
Comparative Examples 5 to 8 are examples in which the adhesiveness deteriorates because at least one of the Ni content and the metal element A content is not included in the predetermined range. That is, when combined with the adhesion evaluation results of Examples 1 to 27, α is 95.4 at% or more and 99.2 at% or less, β is 0.6 at% or more and 2.2 at% or less, and γ is 0. It can be seen that it is necessary to set the value between 2 at% and 2.4 at%.
Comparative Examples 9 to 14 are examples in which good adhesion cannot be obtained with a ternary alloy in which the conductive alloy film is composed of elements other than the metal element A and Cu and Ni. .

[LCD]
The liquid crystal display was produced by processing the conductive substrates 100 of Examples 1 to 27 as follows.
First, a metal film 4 having a thickness of 300 nm was formed on the conductive alloy film 3 of the conductive substrate 100 using a sputtering method. Further, an ITO film having a thickness of 50 nm was formed as the protective film 5 by the same sputtering method.
Thereafter, the protective film 5, the metal film 4, and the conductive alloy film 3 are formed by a wet etching method using an etching solution in which 0.2 mass% sulfuric acid and 0.2 mass% hydrogen peroxide water are mixed. Patterning was performed.

Thereafter, colored layers 11R, 11G, and 11B were sequentially formed with a thickness of 2.5 μm on the first surface 1a between the laminated films 12.
Each colored layer was formed by applying an acrylic resin resist colored in each color by spin coating and then patterning by photolithography. The applied acrylic resin resist was exposed at a light amount of 100 mJ / cm ² by a high-pressure mercury lamp through a mask corresponding to the arrangement of each color, and the exposed portion was cured. Thereafter, development was performed by applying a shower of 0.2 mass% sodium bicarbonate aqueous solution for 30 seconds. Thereby, the acrylic resin resist of the location which is not exposed was removed.
Then, in order to form the insulating protective layer 6, the coating liquid which consists of overcoat agent V-259PA (brand name; Nippon Steel & Sumikin Chemical Co., Ltd.) was apply | coated by the spin coat method. Then, the coating film was dried by drying at 100 degreeC for 5 minute (s) with a hotplate. After the coating film was dried, the coating film was exposed with a light amount of 100 mJ / cm ² using a high-pressure mercury lamp. Thereby, the coating film hardened | cured and the insulating protective layer 6 was formed.

With the above, the color filter 200 with wiring of the second embodiment was formed by the conductive base material 100 of Examples 1-27.
Thereafter, the facing surfaces of the color filter with wiring 200 and the TFT substrate 30 were bonded together with a sealing material with the liquid crystal 20 interposed therebetween. Thereby, the liquid crystal display 400 of the said 3rd Embodiment was manufactured.

In these liquid crystal displays 400, a control IC including the function of the touch sensing control unit 40 is connected to the laminated film 12, and operation confirmation between the touch sensing operation and the liquid crystal driving operation is performed.
In the liquid crystal display 400 corresponding to any of the examples, the touch sensing operation and the liquid crystal driving operation were good.

As mentioned above, although preferable embodiment of this invention was described with each Example, this invention is not limited to this embodiment and each Example. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention.
Further, the present invention is not limited by the above description, and is limited only by the appended claims.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 1a 1st surface 1b 2nd surface 2 Resin film 3 Conductive alloy film 4 Metal film 5 Protective film 6 Insulating protective layer 7 Counter electrode 10 Substrate part 11R, 11G, 11B Colored layer 12 Laminated film 20 Liquid crystal 30 TFT substrate 40, 50 Touch sensing control unit 100, 110 Conductive substrate 200, 300 Color filter with wiring 400, 500 Liquid crystal display

The colored layers 11R, 11G, and 11B function as color filters in the color filter 200 with wiring. The colored layers 11R, 11G, and 11B are resin layers colored in red (R), blue (G), and green (B), respectively. For example, in the present embodiment, the colored layers 11R, 11G, and 11B are made of an acrylic resin in which R, G, and B pigments are dispersed, respectively.
The colored layers 11R, 11G, and 11B are stacked on the first surface 1a in the region sandwiched between the wiring patterns of the resin film 2 and the stacked film 12 in the illustrated horizontal direction. The colored layers 11R, 11G, and 11B are stacked on the first surface 1a in the region sandwiched between the lattice patterns of the resin film 2 in the depth direction of the drawing. The thickness of the colored layers 11R, 11G, and 11B is not particularly limited as long as it exceeds the height from the first surface 1a to the surface 12a of the laminated film 12 on the side opposite to the resin film 2. For example, the thickness of the colored layers 11R, 11G, and 11B may be 0.5 μm or more and 3.0 μm or less.
Wearing color layer 11R, 11G, 11 sequence of B may be R, G, suitable sequences corresponding to the arrangement of pixels corresponding to each color of B is in the display of attaching the wiring with a color filter 200.

Claims (15)

A substrate section;
A laminated film laminated on at least one surface of the substrate part;
With
The laminated film is
The diffusion coefficient when heated to 673K in a state of being contained in copper, nickel and a copper film is 5.0 × 10 ⁻²⁰ cm ² / s or more and 5.0 × 10 ⁻¹⁹ cm ² / s or less. And an oxide formation enthalpy at 293K is −2500 kJ / mol or more and −900 kJ / mol or less, and
Representing each content of copper, nickel, and metal element by α, β, γ,
α is 95.4 at% or more and 99.2 at% or less,
β is 0.6 at% or more and 2.2 at% or less,
γ is 0.2 at% or more and 2.4 at% or less,
A conductive substrate having a conductive alloy film laminated on the surface. The specific resistance of the conductive alloy film is
The conductive substrate according to claim 1, which is 2.0 μΩ · cm or more and 15.0 μΩ · cm or less. The metal element is
One or more elements selected from aluminum, silicon, and titanium,
The electroconductive base material of Claim 1 or 2. The laminated film is
The conductive base material according to claim 1, wherein a copper alloy film or a copper film having a specific resistance lower than that of the conductive alloy film is laminated on the conductive alloy film.   The conductive base material according to claim 4, wherein a protective film having heat resistance is laminated on the copper alloy film or the copper film. The specific resistance of the laminated film is
The conductive substrate according to any one of claims 1 to 5, which is 2.0 µΩ · cm or more and 10.0 µΩ · cm or less. The surface on which the laminated film is laminated,
The electroconductive base material of any one of Claims 1-6 currently formed with glass. The surface on which the laminated film is laminated,
The electroconductive base material of any one of Claims 1-6 currently formed with resin. The resin is
The electroconductive base material of Claim 8 containing a carbon particle. The resin is
The electroconductive base material of Claim 8 or 9 which is a resin film which comprises the black matrix of a color filter. The laminated film is
The conductive base material according to claim 1, comprising at least a wiring in which the conductive alloy film is patterned. The conductive substrate according to claim 11;
A colored layer for a color filter disposed on the conductive substrate;
A color filter with wiring. Liquid crystal,
A TFT substrate for driving the liquid crystal;
The conductive substrate according to claim 11;
With
The electrode of the capacitive touch panel is formed by the wiring in the conductive base material,
LCD display. Liquid crystal,
A TFT substrate for driving the liquid crystal;
A color filter with wiring according to claim 12,
With
The electrode of the capacitive touch panel is formed by the wiring in the color filter with wiring,
LCD display. Further comprising a counter electrode of a capacitive touch panel disposed to face the electrode;
The liquid crystal display according to claim 13 or 14.

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