JP5638561B2 - Conductive polymer resin film - Google Patents

Description

  The present invention relates to a conductive polymer resin film. Specifically, PEDOT (Poly (3,4-Ethylene Di Oxy Thiophene)) and PSS (Poly (4-Styrene Sulphonic acid) are used as the conductive polymer. It is related with the conductive polymer resin film which made it easy to make circuit pattern invisible.

  The demand for transparent conductive polymer resin films that are transparent and have excellent conductivity as electrodes in liquid crystal display devices and touch panel applications that have been spreading explosively recently has increased dramatically.

  On the other hand, conventionally, for example, a transparent conductive layer is directly laminated on the surface of a base material to which conductivity is desired, or a transparent conductive layer is laminated on the surface of a transparent plastic film. A conductive polymer resin film has been pasted.

  As a conductive material used for this transparent conductive polymer resin film, ITO (indium tin oxide) is currently widely used. In a conductive polymer resin film in which ITO is laminated and this is used as a circuit, In some cases, a color difference is produced between the ITO laminated portion and the ITO non-laminated portion.

  This is because the transmitted light of ITO exhibits a yellowish color. That is, at the same time that the ITO layered portion looks yellow due to transmitted light, the ITO non-laminated portion is a transparent polymer resin polymer resin film portion on which ITO is not laminated, so it naturally does not exhibit a yellow color, that is, the ITO circuit When the transparent conductive polymer resin film as a whole is observed as a whole because the part looks yellow, the impression that it is uniformly transparent at a glance is thin, that is, the circuit may look like a mottled pattern, It was not necessarily a suitable state.

  In order to solve this problem, Patent Documents 1 and 2 propose inventions in which an insulating color difference adjusting layer is provided on the surface of a base film so that the patterning is raised and cannot be seen.

JP 2010-182528 A JP 2011-077682 A

  In the method described in Patent Document 1, by providing an insulating color difference adjusting layer on the surface of the base film, this adjusts the refractive index of the conductive layer and the lower layer, and exhibits the effect of lowering the reflectance, The idea is that the patterning is raised and cannot be seen.

  However, with this method, after calculating the refractive index due to the conductive layer used and the refractive index due to the surface of the base film without the conductive layer, the most suitable material is selected to adjust them. Is required to be laminated as an insulation color difference adjustment layer, and moreover, it is necessary to consider whether the selected material can be laminated as desired on the surface of the base film, which requires a complicated work. was there.

  Therefore, the present invention has been made in view of such problems, and the purpose of the present invention is to devise a device that does not appear to reveal the portion where the conductive layer exists without requiring complicated calculation or preparation. Another object of the present invention is to provide a conductive polymer resin film.

In order to solve the above problems, the invention according to claim 1 of the present invention is a conductive polymer resin film obtained by laminating a patterned transparent conductive layer on the surface of a base film, wherein the base material before laminating the transparent conductive layer on the film surface, advance Ri name by laminating a blue undercoat layer, the transparent conductive layer is PEDOT (Poly (3,4-Ethylene Di Oxy thiophene)) and PSS (Poly (4 -Styrene Sulfonic acid) .

  The invention according to claim 2 of the present invention is the conductive polymer resin film according to claim 1, wherein the transparent conductive layer is not laminated on the surface of the blue undercoat layer. The b value in the exposed part is -2.0 or more and 0.0 or less.

The invention according to claim 3 of the present invention is the conductive polymer resin film according to claim 1 or 2, wherein the transparent conductive layer is not laminated on the surface of the blue undercoat layer. The sheet resistance value in the exposed portion of the undercoat layer is 10 × 10 ¹³ Ω / □ or more.

  According to a fourth aspect of the present invention, in the conductive polymer resin film according to any one of the first to third aspects, the blue undercoat layer has an azo type, a quinone type, or a triarylmethane type. And any one or a plurality of dyes of cyanine, phthalocyanine, or indigo.

  If it is the conductive polymer resin film concerning this invention, since the undercoat layer which exhibits blue is previously laminated | stacked on the base-material surface, it laminates | stacks as the circuit which patterned the conductive layer by the PEDOT / PSS mixed material on the surface. Even so, it is possible to easily suppress the phenomenon that the circuit portion is raised and seen.

  Embodiments of the present invention will be described below. Note that the embodiment shown here is merely an example, and is not necessarily limited to this embodiment.

(Embodiment 1)
A conductive polymer resin film (hereinafter also simply referred to as “conductive film”) according to the present invention will be described as a first embodiment.

  The conductive film according to the present embodiment is a conductive polymer resin film formed by laminating a patterned transparent conductive layer on the surface of a base film, and before laminating the transparent conductive layer on the surface of the base film. In addition, a blue undercoat layer is laminated in advance.

Hereinafter, the description will be made in order.
First, the base film is a resin film that is conventionally used when obtaining a conductive film. For example, a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, a polyethylene naphthalate (PEN) film, A synthetic resin film such as an acrylic film, a polypropylene film, a polystyrene film, a polyamide film, a polyamideimide film, a polyethylene film, and a polyvinyl chloride film, a cellulose-based film, or a composite film thereof can be considered.

  In this embodiment, a PET film is used. In addition, the thickness of the PET film used here may be a thickness as long as it is widely used as a base film of a conventional conductive polymer resin film. Specifically, it may be 25 μm or more and 200 μm or less. In this case, a 188 μm one is used.

A blue undercoat layer is laminated on the surface of the base film.
Suitable materials for use as the blue undercoat layer include, for example, azo, quinone, triarylmethane, cyanine, phthalocyanine, or indigo dyes, or more specifically. May be any one or more of copper phthalocyanine, cobalt aluminate, cobalt stannate, cobalt chrome blue, cobalt aluminum silicon oxide, cobalt zinc silicon oxide, etc. Let us use copper phthalocyanine which is widely used and found in color printing and the like.

  Copper phthalocyanine can be laminated by a vacuum deposition method or a method in which it is contained in a binder resin and applied, but here it is laminated by a very general vacuum deposition method. The thickness may be 1 nm to 10 μm (= 10000 nm), and more preferably 10 nm to 1 μm. In this embodiment, it is assumed that the thickness is 50 nm.

In the present embodiment, it is preferable that the sheet resistance value in an exposed portion of the blue undercoat layer, that is, a portion where a transparent conductive layer described later is not laminated is 10 × 10 ¹³ Ω / □ or more. . If it is less than 10 × 10 ¹³ Ω / □, this means that it is an area of an antistatic level, and if such a member is used for a device such as a touch panel, a malfunction may occur.

  When the blue undercoat layer is laminated, a transparent conductive layer is laminated on the surface. In this embodiment, a PEDOT / PSS mixed material is used as the transparent conductive layer.

  Conventionally, ITO has been widely used as a conductive layer of a conductive film as in this embodiment, but since ITO is a substance related to the so-called rare metal problem, its price is proportional to the increase in demand. In recent years, the use of PEDOT has been attracting attention from the viewpoint that it is soaring or it is rare metal in the first place, that is, its reserves are not so much, and an alternative is necessary when it is depleted.

  In the first place, this PEDOT has the advantage of good conductivity and excellent stability in a doped state. For example, in order to apply and laminate this on the surface of the base film, an aqueous dispersion composed of a PEDOT / PSS mixed material mixed with PSS is used. In this embodiment, “Clevios FET” (solid content 1%) (manufactured by Heraeus Co., Ltd.) was used, and this was laminated with a wire bar.

  In the present embodiment, the thickness of the transparent conductive layer is preferably 1 nm to 10 μm, but more preferably 50 nm to 500 nm in order to achieve both transparency and conductivity. Here, the thickness is set to 150 nm.

  By patterning the conductive layer by PEDOT / PSS laminated in this way, it can finally be used as a conductive film.

  The above procedure in the present embodiment, that is, a specific procedure until patterning is completed will be briefly described again. First, copper phthalocyanine is laminated on the surface of the base film by a vacuum deposition method. Next, a PEDOT / PSS mixed material is laminated on the surface with a wire bar. Next, a photoresist “Clear Image TRP-101” (Toagosei Co., Ltd.) and a developer “Clear Image TRP-D-101” (Toagosei Co., Ltd.) are used on the surface. Are laminated. Then, patterning is performed using a general photolithography method using an etching solution “Clear Image TTE-C-01” (Toagosei Co., Ltd.) and a resist stripping solution “Clear Image TRP-S001” (Toagosei Co., Ltd.). Do. By doing in this way, the conductive polymer resin film concerning this Embodiment is obtained.

  In addition, logically, a laminate may be considered in addition to the configuration of “base film / blue UC layer / conductive layer”, or a laminate may exist between “blue UC layer and conductive layer”. It is conceivable to further develop the above-described manufacturing method and the like so that a laminate is further laminated on the surface of the conductive layer.

  A manufacturing method etc. are further demonstrated about the electroconductive film concerning this Embodiment comprised by the above member. In addition, the structure of the conductive film in the following description is simply “base film / blue UC layer / conductive layer”.

  First, copper phthalocyanine is laminated as a blue UC layer on the entire surface of a PET film that is a base film. The laminating method may be as described above, and in this case, the layers are laminated by a vacuum deposition method so that the thickness of the layer becomes 50 nm.

  Next, a PEDOT / PSS mixed material is laminated as a conductive layer on the surface of the blue UC layer. As a lamination method at this time, a wire bar method is used, and the thickness thereof is set to 150 nm.

  Here, since the PEDOT / PSS mixed material is a portion that becomes a circuit of the transparent conductive polymer resin film, the PEDOT / PSS mixed material may be patterned in advance so as to become a circuit at the time of lamination, or patterned to become a circuit after lamination. However, here, it is assumed that the circuit is previously patterned at the time of stacking.

  As previously mentioned herein, great care must be taken to use PEDOT / PSS mixed materials.

  More specifically, the PEDOT / PSS mixed material uses PEDOT / PSS colloidal particles, but the following points should be noted.

  That is, when the film thickness of the conductive layer is several μm, a suitable conductive layer is shown, but the visible light transmittance is almost 0%, that is, the film is not transparent. If the thickness is several tens of nm, the transmittance certainly exceeds 90%, so it looks suitable at first glance. However, the conductivity is 1 S / 1 cm, and the conductivity is remarkably lowered. It is necessary to pay attention to this.

  The reason for this is that if the size of the colloidal particles is not uniform, the degree of contact between the particles is reduced, and even if the particle size is uniform, the PSS film covering the surface of the colloidal particles is an insulator. Therefore, it can be considered that the current flow does not improve as it is. Therefore, in order to solve this problem, in the present embodiment, the colloidal particle sizes are aligned by a centrifugal separation method, and then the PSS film on the surface of the colloidal particles is dissolved using ethylene glycol, which is an organic solvent, and then conductive. Laminated as a layer. By doing in this way, it can have high transparency and electroconductivity equivalent to the case of ITO.

The case where the conductive film thus obtained is viewed from a plane will be described.
Assume that the blue UC layer is not laminated. In this case, that is, if a circuit made of a PEDOT / PSS mixed material is directly laminated as a conductive layer on the surface of the PET film, a conductive layer portion and a portion where the conductive layer is not laminated can be visually recognized. That is, it can be seen that the circuit pattern is laminated on the surface of the transparent PET film. This is because, as described above, when the PEDOT / PSS mixed material is irradiated with natural light, the PEDOT / PSS mixed material portion, that is, the conductive layer portion looks slightly blue because the blue color is reflected. However, at the same time, the PET film is colorless and transparent. Therefore, in the case of the conductive film having such a configuration, there is a problem that the circuit portion made of the PEDOT / PSS mixed material is raised and seen.

  However, in the present embodiment, the blue UC layer made of copper phthalocyanine is laminated between the PET film and the conductive layer, so that the laminated portion of the PEDOT / PSS mixed material as described above, that is, the circuit portion is light. There is no such thing as trying to come out blue.

  This means that patterning is made as inconspicuous as possible by placing the same dye layer as the conductive layer under the conductive layer. That is, it is possible to suppress a phenomenon in which almost the same blue-colored portions are adjacent to each other in a plan view, and as a result, the above-described circuit portion appears to be raised.

This phenomenon will be further described.
Here, the color is measured and determined by the so-called Lab method.
The L value, the a value, and the b value in each of the portion where the blue UC layer is exposed, the portion where the transparent conductive layer is laminated on the surface thereof, are measured. Then, these values are applied to the following mathematical formula to obtain ΔE as a color difference.

  Here, the b value is a value related to so-called yellow and blue, and when it is “plus (+)”, “yellowness” becomes strong, and when it is “minus (−)”, “blueness” becomes strong. Become. Further, if ΔE is in the range of −2.0 to 2.0, it is said that the color is not so much perceived by human eyes, that is, it can be said that a transparent feeling is felt.

  If described using this b value, it can be said that the b value in the exposed portion of the blue undercoat layer in the present embodiment is preferably -2.0 or more and 0.0 or less. That is, when the b value exceeds 0.0, the blue color disappears, and when the b value becomes −2.0 or less, it is now more than necessary in comparison with the above-described laminated portion of the PEDOT / PSS mixed material. This means that the blue color becomes stronger.

The conductive polymer resin film according to the present embodiment is manufactured by the procedure described above. At this time, “A4100 (thickness 125 μm)” (trade name, manufactured by Toyobo Co., Ltd.) was used as a PET film as a base material. For comparison, a PEDOT layer was directly provided without providing a UC layer on the PET film surface. The Lab value was measured with a spectrophotometer “UV-3100” manufactured by Shimadzu Corporation.
The measurement results are shown below.
In the table, L value, a value, and b value were measured for the laminated states of 1 to 5, respectively. Moreover, (DELTA) E was calculated separately about 3-5. No special measurement or calculation is performed for the blank area. No. 5 was prepared for comparison with ΔE, and conventionally known substrates and ITO were used.

  As can be seen from the above results, it can be seen from “2” that the b value at the place where the PEDOT film is not removed is almost zero. That is, the color is neutral. Moreover, since the b value of “1”, that is, the substrate is 2.1, it can be seen that the substrate is strongly yellowish, but “b” is reduced to 0 by laminating the “3”, that is, the undercoat layer and the PEDOT layer. Therefore, it is conceivable that the color is not disturbed when applied to a touch panel or a display.

  In addition, it is a case where ITO conventionally well-known is laminated | stacked, Comprising: (DELTA) E exceeds 2.0 as seen in "5", unless the optical adjustment layer is laminated | stacked on the lower layer of ITO layer, In these cases, it is known that the circuit portion appears to be raised. However, in the case of the configuration of “4”, ΔE exceeds 2.0 similarly, that is, color eyes are generated. This means that the circuit part is visible.

  However, in the case of “3”, that is, in the case where a blue undercoat layer is interposed, ΔE is less than 2.0, that is, the color is not generated, in other words, the circuit part appears to be raised. It can be seen that is suppressed.

  In the case of the conductive polymer resin film described above, when it is assumed that PEDOT is used, the undercoat layer laminated on the base material surface is a blue undercoat layer using a blue material. Since it is possible to easily suppress the phenomenon that the circuit portion appears to be raised, it is possible to provide a transparent conductive circuit that exhibits a high quality feeling.

Claims (4)

A conductive polymer resin film formed by laminating a patterned transparent conductive layer on the surface of a base film,
Before laminating the transparent conductive layer to the substrate film surface, Ri name previously laminating a blue undercoat layer,
The transparent conductive layer is made of PEDOT (Poly (3,4-Ethylene Di Oxy Thiophene)) and PSS (Poly (4-Styrene Sulphonic acid);
A conductive polymer resin film characterized by In the conductive polymer resin film according to claim 1,
The transparent conductive layer is not laminated on the surface of the blue undercoat layer, the b value in the exposed portion of the blue undercoat layer is −2.0 or more and 0.0 or less,
A conductive polymer resin film characterized by In the conductive polymer resin film according to claim 1 or 2,
The transparent conductive layer is not laminated on the surface of the blue undercoat layer, the sheet resistance value in the exposed portion of the blue undercoat layer is 10 × 10 ¹³ Ω / □ or more,
A conductive polymer resin film characterized by In the conductive polymer resin film according to any one of claims 1 to 3,
The blue undercoat layer is made of an azo, quinone, triarylmethane, cyanine, phthalocyanine, or indigo dye or a plurality of dyes,
A conductive polymer resin film characterized by