JP2009245746A - Conductive laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive laminate having less surface resistance compared with the case of only an oxide transparent conductive layer, having high heat resistance as well as high durability to dynamic stress from the outside and high in patterning accuracy. <P>SOLUTION: The conductive laminate has a conductive layer laminated on at least one face of a transparent polymeric film S. The conductive layer has a metal thin film layer M on the surface of a transparent conductive layer E. The transparent conductive layer E is formed of an amorphous oxide containing at least one kind of metal selected from a group consisting of In, Sn, Zn, F, Mo, Cd, Te, Ge and W, and the metal thin film layer M includes a layer M-1 containing at least one kind of metal selected from a group consisting of Al, Ti and Nd. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive laminate, and more particularly to a conductive laminate useful as an electrode substrate from which a flat panel display with high performance and high mounting reliability can be obtained.

  In recent years, in the field of flat panel displays such as liquid crystal display elements, investigations using a transparent polymer substrate in place of a conventional glass substrate are progressing due to demands for improvement in breakage resistance, weight reduction, and thickness reduction. A transparent conductive layer mainly composed of indium oxide, tin oxide, zinc oxide or the like is formed on the transparent polymer substrate by a vacuum film forming method, and is applied to the display as a transparent conductive laminate.

  Here, when forming a transparent conductive laminated body using a glass substrate, indium tin oxide (ITO) is normally used as a transparent conductive layer. And in order to crystallize an ITO thin film and to reduce surface resistance, it is necessary to make the temperature of the glass substrate at the time of ITO film-forming into the high temperature of 150 to 400 degreeC.

  On the other hand, when forming a transparent conductive laminate using a polymer substrate, since the heat resistance is lower than that of a glass substrate, the substrate temperature when forming an ITO thin film is, for example, 100 ° C. or less. It had to be relatively low temperature. Therefore, the ITO film formed on the polymer substrate is usually amorphous, and there is a problem that the surface resistance is higher than that of ITO formed on the glass substrate. .

  Also, when using a polymer film laminated with an oxide transparent conductive layer such as ITO as an electrode for flat panel displays such as liquid crystal display elements, especially flexible displays, it is generated by external mechanical or thermal stress. There has been a problem that quality degradation such as disconnection of wiring, display unevenness, and low durability is likely to be caused by minute cracks or film peeling.

  Here, the use of aluminum or an aluminum alloy is widely known for the purpose of reducing the resistance of the wiring. Furthermore, in order to solve the problem of hillock generation of aluminum or aluminum alloy, it is also known to form a laminate having a metal thin film having a two-layer structure by covering the surfaces of aluminum and aluminum alloy with a refractory metal.

For example, Patent Document 1 discloses a display device in which an aluminum alloy is covered with a metal selected from the group consisting of Cr, Mo, W, Ti, Zr, Hf, V, Nb, and Ta or an alloy thereof as the second layer. An array substrate is described. In Patent Document 1, by forming a metal thin film having such a two-layer structure, it is possible not only to prevent aluminum alloy hillocks but also to prevent corrosion of the aluminum alloy film during pixel electrode dry etching. .
However, in Patent Document 1, since the metal thin film itself is used as an electrode, there remains a problem that disconnection and short circuit are likely to occur due to migration.

  Then, the method of preventing a disconnection and a short circuit by repeatedly laminating | stacking a transparent thin film and a metal thin film is proposed (refer patent document 2). In Patent Document 2, since the metal thin film is thin enough to obtain transparency, the obtained laminate can be used as a transparent electrode. However, since the thickness of the metal thin film is too thin, there has been no significant improvement with respect to lowering the resistance, and there has been a problem of productivity in that it must be repeatedly laminated.

In addition, in the EL display element, there is a problem that the light emission luminance is reduced from an early stage when the light emitter and the transparent conductive layer are in direct contact. On the other hand, it has been proposed to prevent a decrease in light emission luminance by laminating a metal film on a transparent conductive layer (see Patent Documents 3 and 4).
However, in the laminates described in Patent Documents 3 and 4, it is difficult to precisely process a wiring pattern. Therefore, there is a high risk of disconnection due to migration, and a highly reliable conductive laminate is obtained. It was still difficult.

JP 11-258633 A JP 2006-120916 A JP 08-192493 A Japanese Patent Laid-Open No. 09-011390

  The present invention has been made against the background of the above-described prior art, and has a lower surface resistance than the case of using only an oxide transparent conductive layer and has high durability against external mechanical stress. Another object of the present invention is to provide a conductive laminate having high heat resistance and high patterning accuracy.

  This inventor repeated earnest research in order to solve said subject. As a result, the inventors have found that the above problem can be solved by laminating a specific metal thin film layer on a specific transparent conductive layer, and have completed the present invention.

  That is, the present invention is a conductive laminate in which a conductive layer is laminated on at least one surface of the transparent polymer film (S), and the conductive layer is a metal thin film layer (E) on the surface of the transparent conductive layer (E). M), and the transparent conductive layer (E) contains at least one metal selected from the group consisting of In, Sn, Zn, F, Mo, Cd, Te, Ge, and W. A crystalline oxide, and the metal thin film layer (M) includes a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd. A conductive laminate having a resistance of 20Ω / □ or less.

  The conductive laminate of the present invention has low surface resistance, high durability against external stress, and high patterning accuracy. For this reason, while being excellent in an electrical property, it becomes a conductive laminated body which reduced the risk of disconnection, and ensured high performance and high mounting reliability. Therefore, the transparent conductive laminate of the present invention is a very useful laminate as a transparent conductive substrate for flat panel displays such as electronic paper.

  Further, the metal thin film layer is a laminate of a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd and a layer (M-2) containing Mo. Therefore, high wet heat environment reliability can be obtained.

  In addition, the film thickness of the layer (M-2) containing Mo is 15 with respect to the film thickness of the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd. By setting it to -80%, the generation of cracks in the layer containing Mo (M-2) can be prevented, and a conductive laminate having a higher level of environmental reliability can be obtained.

  Furthermore, in the patterning of the conductive layer, the area of the pattern of the metal thin film layer (M) is set to be half or less of the area of the pattern of the transparent conductive layer (E), thereby obtaining a transparent conductive laminate that ensures transparency. be able to.

Hereinafter, the present invention will be described in detail.
<Conductive laminate>
The conductive laminate of the present invention is a conductive laminate in which a conductive layer is laminated on at least one surface of the transparent polymer film (S), and the conductive layer is a metal on the surface of the transparent conductive layer (E). It has a thin film layer (M). The transparent polymer film (S) and the transparent conductive layer (E) may be adjacent to each other, or other layers may be interposed between these layers.
Hereinafter, each layer which comprises the electroconductive laminated body of this invention is demonstrated.

<Transparent polymer film (S)>
(material)
The material for forming the transparent polymer film (S) is not particularly limited as long as the polymer has good transparency and heat resistance.

  When the conductive laminate of the present invention is used as a transparent electrode substrate for a liquid crystal display panel, the transparent polymer film (S) has a refractive index difference Δn of birefringence at a wavelength of 590 nm and a film thickness d. A retardation value represented by a product Δn · d is 30 nm or less, and a film having optical isotropy with a variation in slow axis within ± 30 degrees, more preferably a retardation value is 20 nm or less, and It is preferable that the film has a high optical isotropy with a slow axis variation of within ± 15 degrees.

  In order to ensure sufficient heat resistance during use, the transparent polymer film (S) is preferably formed of a material mainly composed of an amorphous polymer having a glass transition temperature of 140 ° C. or higher. .

  Examples of the polymer that forms such a transparent polymer film (S) include polycarbonate resins, polyester resins, polyarylate resins, polysulfone resins such as polysulfone, polyethersulfone, and polyallylsulfone, and polyolefin-based resins. Examples thereof include resins, acetate resins such as cellulose triacetate, polyacrylate resins, and various thermosetting resins.

  Among these, from the viewpoint of relatively little transparency, heat resistance, and optical anisotropy, it is preferable to use a material mainly composed of a polycarbonate resin. Here, “having a polycarbonate-based resin as a main component” means that the other resin compatible with the polycarbonate-based resin is 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, More preferably, it means containing 10% by mass or less, and particularly preferably means comprising 100% by mass of polycarbonate resin. When a polycarbonate resin is used as a material, it is particularly preferable to form a film by a casting method because of excellent surface flatness and optical isotropy.

  As the polycarbonate resin, known bisphenol components can be used. For example, a polycarbonate resin in which the bisphenol component is bisphenol A, or a polycarbonate resin in which the bisphenol component is bisphenol A and the following formula (I) is used. It is preferable. In the case where the bisphenol component is a polycarbonate resin composed of bisphenol A and the following formula (I), it may be a copolymer, a mixture of homopolymers, or a mixture of copolymers, Moreover, as a compound of Formula (I), not only one type but 2 or more types may be used.

Here, R ¹ , R ² , R ³ , and R ⁴ may be the same or different and are selected from a hydrogen atom or a methyl group, and X is a cycloalkylene group having 5 to 10 carbon atoms, It is a group selected from the group consisting of an aralkylene group having 7 to 15 carbon atoms and a haloalkylene group having 1 to 5 carbon atoms.

As specific examples of X, in the case of a cycloalkylene group, for example, 1,1-cyclopentylene, 1,1-cyclohexylene, 1,1- (3,3,5-trimethyl) cyclohexylene, norbornane- 2,2-diyl, tricyclo [5.2.1.0 ^2,6 ] decane-8,8'-diyl and the like can be mentioned, and 1,1-cyclohexylene is particularly preferred because of the availability of raw materials. Or 1,1- (3,3,5-trimethyl) cyclohexylene.

  In the case of an aralkylene group, for example, phenylmethylene, diphenylmethylene, 1,1- (1-phenyl) ethylene, 9,9-fluorenylene and the like can be mentioned. In the case of a haloalkylene group, 2,2-hexafluoropropylene, 2,2- (1,1,3,3-tetrafluoro-1,3-dicyclo) propylene and the like can be mentioned.

  When the conductive laminate of the present invention is used as a display substrate that does not require optical isotropy, a polyester resin is preferably used as the material for the transparent polymer film (S).

  Here, the “polyester” means a polymer having an ester bond as a main bond chain, and preferred polyesters include, for example, ethylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, ethylene-α. , Β-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate, and the like. In this invention, it is preferable to use the polyester-type resin which has at least 1 sort (s) chosen from these as a main structural component.

  These constituent components may be used alone or in combination of two or more. However, when quality, economy, etc. are comprehensively determined, a polyester resin having ethylene terephthalate as a main constituent is used. It is particularly preferred. In applications where heat acts on the substrate, it is preferable to use a polyester-based resin containing polyethylene-2,6-naphthalate, which is excellent in heat resistance and rigidity, as a main constituent component.

  Moreover, as polyester which forms a transparent polymer film (S), the other dicarboxylic acid component and diol component may be partially copolymerized, Preferably 20 mol% or less of all the repeating units may be copolymerized. Further, in the polyester, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a pigment, a dye, an organic or inorganic fine particle, an antistatic agent, etc. are added to a transparent polymer film ( S) may be added to such an extent that the characteristics are not deteriorated. However, since the addition of fine particles tends to increase the haze value, in order to prevent deterioration of characteristics, the fine particles to be added have a small particle size, preferably a particle size of about 1/4 or less of the visible light wavelength. It is preferable to use a material that hardly causes light scattering.

  Moreover, when using a polyester resin as a material, it is preferable that the transparent polymer film (S) is biaxially oriented. Since the transparent polymer film (S) made of a biaxially oriented polyester resin is excellent in mechanical strength, it can be preferably used as a substrate for display. Here, the biaxially oriented polyester film generally refers to an unstretched polyester sheet or film that is stretched about 2 to 6 times in the longitudinal direction and the width direction, and then heat-treated and crystallized. .

(Film thickness)
The thickness of the transparent polymer film (S) is preferably in the range of 0.01 to 1.0 mm. When the thickness is smaller than 0.01 mm, there is not sufficient rigidity, and it is easily deformed during panel processing and difficult to handle. On the other hand, when the thickness is larger than 1.0 mm, deformation hardly occurs, but it becomes difficult to form a transparent conductive layer and a metal thin film layer by a roll-to-roll method, and productivity of the conductive laminate is lowered.

<Conductive layer>
The conductive layer constituting the conductive laminate of the present invention has a metal thin film layer (M) on the surface of the transparent conductive layer (E). Below, each layer is demonstrated.

[Transparent conductive layer (E)]
(material)
The transparent conductive layer (E) constituting the conductive layer is selected from the group consisting of In, Sn, Zn, F, Mo, Cd, Te, Ge, and W in terms of transparency, conductivity, and mechanical properties. An amorphous oxide containing at least one metal. Among these, a transparent conductive film mainly composed of indium oxide is preferable because it is excellent in transparency and conductivity, and since amorphous properties can be secured even when heat treatment or the like is applied, a composite oxide of indium oxide and zinc oxide is particularly preferable. preferable.

(nature)
The transparent conductive layer (E) needs to be an amorphous layer from the viewpoint of patterning the conductive laminate obtained. If it is an amorphous transparent conductive layer (E), the etching rate is relatively close to a specific metal thin film layer (M) described later, so that the pattern processability is excellent, and as a result, the disconnection due to migration is suppressed, A highly reliable conductive laminate can be obtained.

(Formation method)
The method for forming the transparent conductive layer (E) is not particularly limited, and examples thereof include conventionally known sputtering methods, ion plating methods, and vacuum deposition methods. In addition, it is preferable that the heating temperature at the time of film-forming of a transparent conductive layer (E) shall be below the heat deformation temperature of a polymer film (S).

(Film thickness)
The film thickness of the transparent conductive layer (E) depends on the balance with the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd according to the target surface resistance. Can be set as appropriate. Preferably, when the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd is in the range of 10 to 300 nm, the transparent conductive layer (E) is 10 to 300 nm. More preferably, when the (M-1) layer is in the range of 10 to 150 nm, the transparent conductive layer (E) is in the range of 10 to 100 nm, and more preferably the (M-1) layer. Is in the range of 20 to 80 nm, the transparent conductive layer (E) is in the range of 10 to 50 nm. The transparent conductive layer (E) may be a laminate of a plurality of layers as well as one layer.

(Surface roughness)
The surface roughness of the transparent conductive layer (E) before laminating the metal thin film layer (M) is preferably less than 5 nm in terms of Ra value, more preferably less than 3 nm, and particularly preferably less than 1 nm. preferable. When the surface is excellent in flatness, the characteristic stability of the metal thin film layer laminated on the surface of the transparent conductive layer (E) is improved, and the risk of disconnection can be reduced.

[Metal thin film layer (M)]
The metal thin film layer (M) constituting the conductive layer includes at least a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd. Even if it is only one layer (M-1) including at least one metal selected from the group consisting of Al, Ti, and Nd, a plurality of layers including the (M-1) layer are stacked. It may be a body.

  The layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd may be a layer formed of a pure metal of these metals, or at least one of these metals It may be an alloy containing seeds. Among these, from the viewpoint of hillock resistance, migration resistance, and low resistance, it is preferable to use an Al—Nd alloy or an Al—Ti alloy. Furthermore, since the resistance to microphone is particularly excellent, an Al—Nd alloy is preferably used. It is particularly preferable to use it.

  The configuration of the metal thin film layer (M) includes a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd. Preferably, the (M-1) layer is It is preferable to form a multilayer structure in which another layer is laminated. Providing the metal thin film layer (M) with a desired function by providing a layer different from the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd Can do. When the metal thin film layer (M) has a multilayer structure, it may have a three-layer structure or more, but a two-layer structure is most preferable.

  When the metal thin film layer (M) has a multilayer structure, the first layer, the second layer, and the third layer are referred to as the first layer, the second layer, and the third layer from the transparent conductive layer (E) to the outermost surface side. The first layer is a layer that conducts electricity as a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd, and the second layer is a layer containing Mo (M- 2) is preferable. Since Mo is a metal having a lower oxidation-reduction potential than Al and a low reactivity with oxygen, water, and the like, the layer containing Mo (M-2) is a layer with high environmental reliability. For this reason, it becomes possible to prevent corrosion of the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd as the first layer, and as a result, the obtained conductivity High reliability can be imparted to the laminate. The layer containing Mo (M-2) may be pure Mo metal or an alloy containing Mo.

  In the case of a three-layer structure, the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd, which is the first layer in the above-described two-layer structure, and a transparent conductive layer One metal thin film layer is newly provided between the layer (E). As a material for a new layer in the case of a three-layer structure, a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd that conducts the first layer is used. It is desirable to use a metal that lowers the contact resistance with the transparent conductive layer (E). In order to prevent the film thickness of the transparent conductive layer (E) from being reduced due to over-etching during patterning, it is effective to use a metal having a lower etching rate than the first layer and the second layer.

(Formation method)
The method for forming the metal thin film layer (M) is not particularly limited, and examples thereof include conventionally known sputtering methods, ion plating methods, and vacuum deposition methods. In addition, it is preferable that the heating temperature at the time of film-forming of a metal thin film layer (M) shall be below the heat deformation temperature of a polymer film (S).

(Film thickness)
The film thickness of the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd depends on the balance with the transparent conductive layer (E) according to the target surface resistance. Set as appropriate. As described above, preferably, when the transparent conductive layer (E) is 10 to 300 nm, the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd is 10 to 10 nm. When the transparent conductive layer (E) is 10 to 100 nm, the (M-1) layer is preferably 10 to 150 nm, and more preferably the transparent conductive layer (E) is in the range of 300 nm. When it is 10 to 50 nm, the (M-1) layer is in the range of 20 to 80 nm.

  In addition, when laminating the layer (M-2) containing Mo, the film thickness of the layer (M-2) containing Mo is made from Al, Ti, And a range of 15 to 80% with respect to the film thickness of the layer (M-1) containing at least one metal selected from the group consisting of Nd. More preferably, it is 40 to 70% of range.

[Patterning]
The conductive laminate of the present invention can ensure transparency due to the difference in line width after patterning between the transparent conductive layer (E) and the metal thin film layer (M). In order to obtain high transparency, it is preferable that the area of the pattern of the metal thin film layer (M) is not more than half of the area of the pattern of the transparent conductive layer (E). It is more preferable to set it to 1/5 or less, and it is especially preferable to set it to 1/5 or less.

  The patterning method is not particularly limited. For example, from the viewpoint of efficiency, a space is formed by simultaneous etching of the transparent conductive layer (E) and the metal thin film layer (M) as the first step, and only the metal thin film layer (M) is etched as the second step. It is desirable. At this time, in the second stage, in order to prevent the film thickness of the transparent conductive layer (E) from being reduced due to over-etching and consequently increase in line resistance, the metal thin film layer (M) to be removed must be transparent. It may be left as thin as possible.

In addition, if the pattern shape of a metal thin film layer (M) is on the pattern of a transparent conductive layer (E), it will not be restricted to a linear shape, Arbitrary shapes can be formed. For example, it is possible to form a pattern of the metal thin film layer (M) having a honeycomb shape or a mesh shape on the pattern of the transparent conductive layer (E). By forming such a pattern, the metal thin film layer ( It is possible to reduce the disconnection risk of E).
By leaving the metal thin film layer (M) without being removed by etching or the like as the lead-out portion of the electrode that is the mounting portion, it is possible to obtain high durability against stress and impact.

<Radiation curable resin layer>
In the conductive laminate of the present invention, a conductive layer is laminated on at least one surface of the transparent polymer film (S), and the conductive layer is formed from the transparent polymer film (S) side with a transparent conductive layer ( E), and at least one metal thin film layer (M) is sequentially laminated on the surface of the transparent conductive layer (E), but the surface insulation of the base of the transparent conductive layer (E) even in a high temperature and high humidity environment In order to keep the resistance sufficiently high and improve the surface smoothness, at least one component selected from the group consisting of alkali metals, alkaline earth metals and halogens is not substantially contained, and silicon oxide fine particles are contained. The radiation curable resin layer is preferably provided between the transparent polymer film (S) and the transparent conductive layer (E).

<Gas barrier layer>
Furthermore, when the conductive laminate of the present invention is used as an electrode substrate for applications that require high gas barrier properties such as liquid crystal display elements and electronic paper, at least one gas barrier layer is used as a transparent polymer. It is preferable to make it exist in surfaces other than the surface of a transparent conductive layer (E) and a metal thin film layer (M) in the surface of at least one side of a film (S).

  The gas barrier layer can be produced by a known method using a known material. Among these, a metal oxide layer containing silicon oxide as a main component is preferable from the viewpoint of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like.

<Other layers>
As long as the effect of the present invention is not reduced, chemical treatment such as lamination of various undercoat layers for enhancing adhesion between layers, or physical treatment such as corona treatment, plasma treatment, and UV irradiation. You may do it. In addition, when the transparent conductive substrate of the present invention is handled in the form of a film roll, a surface sufficient for imparting slipperiness to the laminate on the surface opposite to the surface on which the metal thin film layer (M) is laminated. You may provide the layer which has a crosslinked structure which has roughness and sufficient durability with respect to the chemical | medical agent used by the process step of various flat panel displays.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further more concretely, this invention is not limited to this Example etc. at all. In Examples and the like, “parts” and “%” are based on mass unless otherwise specified.

<Measurement method>
In Examples and Comparative Examples, the following items were measured and evaluated by the following methods.

(1) Surface resistance The conductive laminate was cut to 4 mm × 8 mm, and the center of the obtained cut piece was manufactured by Mitsubishi Chemical Corporation, using a product name: Loresta MP MCP-T350, with a four-probe method. Measurements were performed. Two cut pieces were prepared, and measurement was performed five times for each of them (n = 10), and the average value was R0.

(2) Heat resistance In a 160 degreeC oven, the cut piece sample of the electroconductive laminated body cut into 4 mm x 8 mm was stored, and the sample was taken out when 90 minutes passed continuously. Waiting for the sample temperature to return to room temperature, the surface resistance was measured using the same apparatus and method as in (1) above. In addition, two cut pieces were produced similarly to (1), and the measurement was performed five times for each (n = 10), and the average value was defined as R1. In the evaluation of heat resistance, the rate of change of the surface resistance value was determined by calculating the ratio (R1 / R0) between R0 and R1 obtained in (1) above.

(3) Bending resistance Doteite was applied to both ends of the conductive laminate so that the conducting part had a width of 10 mm and a length of 100 mm, and heat treatment was performed at 160 ° C. for 1.5 hours. About the sample after a process, the surface resistance between dotites was measured using the two-terminal method, and the obtained result was set to R0 '.
Subsequently, the sample was wound around the 6 mmφ and 2 mmφ rods so that the conductive surface was on the outside, and the sample was allowed to stand for 1 minute while applying a weight of 100 g. The surface resistance of the sample after bending was measured by the same method, and the obtained result was defined as R1 ′.
Further, each of the bent samples was again heat-treated at 160 ° C. for 1.5 hours, and the surface resistance of the sample after the treatment was measured, and the obtained result was defined as R2 ′.
In evaluating the bending resistance, the ratio of R0 ′ to R1 ′ obtained (R1 ′ / R0 ′) and the ratio of R0 ′ to R2 ′ (R2 ′ / R0 ′) were calculated, and the surface resistance was calculated. The rate of change of value was determined.

(4) Environmental reliability When a cut sample of a conductive laminate cut to 4 mm × 8 mm is stored in a constant temperature and humidity oven at a temperature of 60 degrees and a humidity of 90% RH, and 250 hours have passed continuously. A sample was removed. Waiting for the sample temperature to return to room temperature, the surface resistance was measured using the same apparatus and method as in (1) above. In addition, two cut pieces were produced similarly to (1), and the measurement was performed 5 times for each (n = 10), and the average value was R2. In evaluating the environmental reliability, the ratio of the surface resistance value was calculated by calculating the ratio (R2 / R1) of R1 and R2 obtained in (2) above.

(5) Wiring resistance and transparency An electrode was formed by forming a pattern on the transparent conductive layer (E) and the metal thin film layer (M) of the conductive laminate by a general photolithography method. Specifically, two-stage patterning was performed using a mixed acid composed of phosphoric acid, nitric acid, and acetic acid as an etchant. In the first stage, the pattern is cut so that both the metal thin film layer (M) and the transparent conductive layer (E) have a width of 100 μm, and then in the second stage, only the metal thin film layer (M) has a width of 50 μm. Cut the pattern to be.
As for the wiring resistance, the wiring width to be measured was set to 100 μm, and the length of the line 10 mm obtained by the above two-stage patterning was measured.
About transparency, the light transmittance of the parallel light in wavelength 550nm was measured about the electroconductive laminated body after patterning using the spectrophotometer (the product made by HITACHI, model: U-4000).

<Compounds used in Examples and Comparative Examples>
BisA: 2,2-bis (4-hydroxyphenyl) propane BCF: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene IZO: zinc oxide-added indium oxide (addition of 10% zinc)
-ITO: Indium oxide with tin oxide added (5% tin added)
・ Al-Nd: Aluminum-neodymium alloy (added 2% neodymium)
-Mo: Molybdenum-BPEFA: Bisphenoxyethanol full orange acrylate-DCPA: Dicyclopentanyl diacrylate-DPEHA: Dipentaerythritol hexaacrylate-HCPK: 1-hydroxycyclohexyl phenyl ketone

<Example 1>
[Creation of transparent polymer film (S)]
A polycarbonate resin (average molecular weight: 37,000, Tg: 211 ° C.) having a bisphenol component of BisA / BCF = 50/50 (molar ratio) was dissolved in methylene chloride so as to be 20% by mass. The resulting solution is cast on a polyester film having a thickness of 175 μm by a die coating method, then dried in a drying furnace until the residual solvent concentration becomes 13% by mass, and then peeled off from the polyester film to remove the polycarbonate film. Obtained. Residual solvent concentration in the film while keeping the obtained polycarbonate film in a drying oven at a temperature of 180 ° C. with as little difference as possible between the longitudinal and lateral tensions and with the minimum tension capable of holding the film. Was dried to 0.3 mass% to obtain a transparent polymer film (S) having a thickness of 120 μm. The transparent polymer film (S1) thus obtained had a retardation value of 1 nm and a glass transition temperature measured by the DSC method of 211 ° C.

[Formation of radiation curable resin layer (A)]
Into a 2-liter three-necked reaction flask, 1.3 kg of isopropyl alcohol was inserted, and subsequently 280 mL of deionized water and 70 mL of acetic acid were added and stirred, and further 534 g of tetramethoxysilane was added. Stirring was continued at 50 ° C. for 3 hours to prepare colloidal silica (a) dispersed in isopropyl alcohol. The obtained colloidal silica (a) had a solid content of 12%, an average primary particle size of 13 nm, and each of the ion contents of Na, K, Ca and Cl was less than 0.1 ppm.

  By mixing 100 parts of the obtained colloidal silica (a), 60 parts of BPEFA, and 40 parts of DPEHA with a mixed solvent of 180 parts of xylene and 120 parts of cyclohexanone, and further adding 5 parts of HCPK, the inorganic fine particles are stirred. The containing coating composition (ac) was prepared.

The obtained coating composition (ac) was coated on one side of the transparent polymer film (S) obtained above, heated at 60 ° C. for 1 minute, and then used a 120 mW / cm ² high-pressure mercury lamp. Then, the radiation curable resin layer (A) containing inorganic oxide fine particles having a thickness of 2 μm was formed by irradiating ultraviolet rays under conditions of an integrated light quantity of 450 mJ / cm ² to cure the coating film.

[Formation of transparent conductive layer (E)]
A transparent conductive film was obtained by providing a transparent conductive layer (E) composed of an IZO film having a thickness of 25 nm by a magnetron sputtering method on the surface on which the radiation curable resin layer (A) was formed.

[Formation of metal thin film layer (M-1) layer and (M-2) layer]
On the transparent conductive layer (E), an Al—Nd layer having a thickness of 30 nm was formed as the (M-1) layer by magnetron sputtering. On the formed Al—Nd layer, an Mo layer having a thickness of 20 nm was formed as the (M-2) layer by magnetron sputtering to obtain a conductive laminate.

[Measurement evaluation]
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1.

<Example 2>
Example 1 except that the metal thin film layer (M-1) was changed to a 20 nm thick Al—Nd film, and the (M-2) layer was changed to a 10 nm thick Mo film. A conductive laminate was obtained in the same manner as above.
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1.

<Example 3>
A conductive laminate was obtained in the same manner as in Example 1 except that the metal thin film layer (M-2) layer was not laminated.
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1.

<Comparative Example 1>
A conductive laminate was obtained in the same manner as in Example 1 except that the transparent conductive layer (E) was changed to a crystalline ITO film.
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1. Since the etching rates of the metal layer and the ITO film are greatly different, a pattern for measuring the wiring resistance cannot be formed, and as a result, the wiring resistance cannot be measured.

<Comparative Example 2>
A conductive laminate was obtained in the same manner as in Example 3 except that the metal thin film layer (M-1) was a Cu film having a thickness of 30 nm.
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1. When a pattern for measuring wiring resistance was formed, disconnection due to migration occurred.

<Comparative Example 3>
A conductive laminate was obtained in the same manner as in Example 1 except that the metal thin film layer (M-1) layer was not laminated.
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1. Note that cracks occurred during heat treatment due to the difference in linear expansion coefficient, and it was impossible to obtain surface resistance values for heat resistance, flex resistance, and environmental reliability evaluation.

<Comparative example 4>
A conductive laminate was obtained in the same manner as in Example 1 except that the metal thin film layer (M) was not laminated and the film outermost surface remained the IZO film of the transparent conductive layer (E).
Various measurement evaluation was performed about the obtained electroconductive laminated body. The results are shown in Table 1.

  The conductive laminate of the present invention is a laminate having a low surface resistance, high durability against external mechanical stress, heat resistance, and high patterning accuracy. For this reason, liquid crystal display elements, electroluminescence (EL) display elements, or various display bodies using electrophoretic, thermal rewritable, PDLC, chiral nematic liquid crystal, electrochromic, twist ball, toner display, etc. It can be preferably used.

Claims (4)

A conductive laminate in which a conductive layer is laminated on at least one surface of the transparent polymer film (S),
The conductive layer has a metal thin film layer (M) on the surface of the transparent conductive layer (E),
The transparent conductive layer (E) is an amorphous oxide containing at least one metal selected from the group consisting of In, Sn, Zn, F, Mo, Cd, Te, Ge, and W,
The metal thin film layer (M) includes a layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd,
A conductive laminate having a surface resistance of 20Ω / □ or less.   A layer (M-2) containing Mo is formed on the layer (M-1) containing at least one metal selected from the group consisting of the Al, Ti, and Nd. The conductive laminate according to claim 1, which is laminated. The film thickness of the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd is 10 to 300 nm,
The film thickness of the layer containing Mo (M-2) is 15 with respect to the film thickness of the layer (M-1) containing at least one metal selected from the group consisting of Al, Ti, and Nd. The conductive laminate according to claim 1 or 2, which is -80%.   The said conductive layer is patterned, In the said patterning, the area of the pattern of the said metal thin film layer (M) is below half of the area of the pattern of a transparent conductive layer (E). Conductive laminate.