WO2016018052A1 - Stratifié conducteur et son procédé de fabrication - Google Patents

Stratifié conducteur et son procédé de fabrication Download PDF

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Publication number
WO2016018052A1
WO2016018052A1 PCT/KR2015/007889 KR2015007889W WO2016018052A1 WO 2016018052 A1 WO2016018052 A1 WO 2016018052A1 KR 2015007889 W KR2015007889 W KR 2015007889W WO 2016018052 A1 WO2016018052 A1 WO 2016018052A1
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Prior art keywords
laminate
transparent conductive
conductive layer
substrate
temperature
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PCT/KR2015/007889
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English (en)
Korean (ko)
Inventor
윤정환
김용찬
송두훈
장성호
임진형
박진우
김기환
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주식회사 엘지화학
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Publication of WO2016018052A1 publication Critical patent/WO2016018052A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present specification relates to a conductive laminate and a method of manufacturing the same. More specifically, the present disclosure relates to a conductive laminate including both a transparent conductive layer and a metal layer, and a method of manufacturing the same.
  • ITO transparent electrodes are mainly used.
  • an ITO transparent electrode is used for the screen portion of the touch sensor, and a metal having a relatively low resistance is used for the wiring portion.
  • a metal having a relatively low resistance is used for the wiring portion.
  • Narrow bezels can be used to increase the size of touch screens in limited mobile device sizes, and the width of metal wiring is gradually decreasing as the number of channels increases depending on the resolution of the screen.
  • the present inventors have found a method of crystallizing a transparent conductive layer after forming a metal layer on an amorphous transparent conductive layer in manufacturing a laminate including a transparent conductive layer and a metal layer.
  • Preparing a laminate comprising a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer;
  • Providing a method of manufacturing a metal layer and a crystallized transparent conductive layer-containing laminate comprising the step of increasing the temperature of the far-infrared heater by a temperature corresponding to the difference (T1-T2) of the temperature between the substrate side and the metal layer side. do.
  • It provides a method of manufacturing a metal pattern and a transparent conductive layer-containing laminate comprising the step of patterning a metal layer of the laminate.
  • Preparing a laminate comprising a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer;
  • a method for setting temperature conditions when crystallizing a transparent conductive layer of a metal layer and a transparent conductive layer-containing laminate by a far-infrared heater comprising calculating a temperature corresponding to a difference (T1-T2) of the temperature between the substrate side and the metal layer side.
  • Heat-treating a laminate including a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer using a far-infrared heater or a box oven, wherein the heat treatment temperature is set. It provides a method for producing a metal layer and a crystallized transparent conductive layer-containing laminate comprising the step of setting using a transparent conductive layer crystallization temperature.
  • Another embodiment of the present specification provides a laminate including a substrate, an amorphous transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer.
  • the adhesive layer is provided on the opposite side of the surface provided with the transparent conductive layer of the substrate and the opposite surface of the metal layer provided with the transparent conductive layer, respectively.
  • the adhesive layer is provided on the opposite side of the surface provided with the transparent conductive layer of the substrate and the opposite side of the surface provided with the transparent conductive layer of the metal layer, A temperature measuring device attached to each of the pressure-sensitive adhesive layer on the substrate and the pressure-sensitive adhesive layer on the metal layer is provided.
  • a sample stage provided to receive a crystallization sample provided in a region where far infrared rays generated from the infrared lamp reach;
  • It provides a far-infrared heater including a temperature controller that adjusts the temperature to increase the temperature by the temperature difference between the top and bottom of the crystallized sample.
  • Another embodiment of the present specification is prepared by the method according to the embodiments described above, and provided with a substrate, a crystallized transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer. It provides a laminate.
  • Another embodiment of the present specification is prepared by the method according to the above-described embodiments, and provided with a substrate, a crystallized transparent conductive layer provided on the substrate, and a metal pattern provided on the transparent conductive layer. To provide a laminate.
  • An amorphous transparent conductive layer provided on the substrate,
  • a metal layer provided on the transparent conductive layer
  • a conductive laminate precursor comprising an infrared absorbing protective film.
  • Preparing a laminate comprising a substrate, an amorphous transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer;
  • It provides a method for producing a conductive laminate precursor comprising a.
  • Another embodiment of the present specification provides a method of manufacturing a conductive laminate including the step of crystallizing the amorphous transparent conductive layer by irradiating infrared rays on at least one surface of the conductive laminate precursor.
  • a crystalline transparent conductive layer provided on the substrate,
  • a metal layer provided on the transparent conductive layer
  • a conductive laminate comprising an infrared absorbing protective film.
  • the transparent conductive layer such as the ITO layer can be efficiently crystallized.
  • the infrared rays irradiated from the infrared lamp by the protective film is absorbed directly or indirectly by the infrared rays reflected from the metal layer, the temperature increase effect is exhibited, and therefore, even when the metal layer is present, the crystallization temperature is determined by the infrared reflection characteristic of the metal layer. Can be prevented from being reduced.
  • the metal layer can be formed on the amorphous layer before the crystallization of the transparent conductive layer such as the ITO layer, the process can be simplified since the amorphous transparent conductive layer and the metal layer can be laminated through the roll-to-roll process. .
  • Figure 1 shows a schematic diagram of the ITO crystallization process according to the prior art.
  • FIG. 2 shows a schematic diagram of the ITO crystallization process according to one embodiment of the present specification.
  • FIG 3 and 4 illustrate a far infrared heater internal structure for ITO crystallization according to the embodiments of the present disclosure.
  • 5 and 6 illustrate the structure of a laminate according to embodiments of the present disclosure.
  • FIG. 7 and 8 show schematic diagrams of the traveling direction of the infrared rays according to the infrared irradiation direction.
  • 9-11 show exemplary materials of the metal layer of the laminate and temperatures of the top and bottom of the laminate along the direction of infrared irradiation.
  • FIG 13 illustrates the degree of crystallization of ITO after crystallization according to one embodiment of the present specification.
  • FIG. 14 is a graph showing a decrease in reflectance of a metal layer after crystallization according to one embodiment of the present specification.
  • FIG. 15 shows a schematic diagram of an ITO crystallization process according to one embodiment of the present specification.
  • 16 and 17 illustrate structures of the precursor and the conductive laminate of the conductive laminate according to the exemplary embodiments of the present disclosure, respectively.
  • Figure 18 is a schematic diagram showing the energy behavior by the infrared source to reach the ITO layer with or without the protective film.
  • FIG. 21 and 22 are graphs showing experimental results shown in Table 4.
  • Figure 23 shows the infrared absorption spectrum of the metal and the polymer.
  • An exemplary embodiment of the present specification provides a method of manufacturing a metal layer and a crystallized transparent conductive layer-containing laminate, the laminate including a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer.
  • the step of crystallizing the transparent conductive layer comprises the steps of measuring the temperature T1 of the substrate side of the laminate; Measuring the temperature T2 on the metal layer side of the laminate; And raising the temperature of the far-infrared heater by a temperature corresponding to the difference (T1-T2) of the temperature between the substrate side and the metal layer side.
  • Far Infrared (FIR) heaters generally control the atmosphere temperature inside the heater using the far infrared rays generated by the source of the infrared (IR) lamp.
  • IR infrared
  • the air heated by the internal blower (blower) is circulated, and the temperature is controlled in this manner. Therefore, the elements constituting this temperature can be largely divided into the ambient temperature warmed by the internal infrared rays and the infrared rays emitted.
  • a plastic substrate such as PET or a laminate structure of ITO and plastic substrate is used as the substrate of the conductive laminate, and these are materials in which infrared reflection is not easily generated, but when the metal is deposited, the metal has a relatively high reflectance to infrared rays. Since there is little infrared absorption in a long wavelength region, it has been thought that there exists a possibility that the heat processing function by infrared reflection may fall.
  • the transparent conductive layer is crystallized by heat-treating the laminate in which the base material, the transparent conductive layer, and the metal layer are sequentially stacked, due to the infrared reflection and low absorption characteristics of the metal, the side with the metal layer and the base material are provided. The temperature is different on the side, and thus there is a difficulty in setting the heat treatment temperature.
  • the inventors have found that the proportion of the internal atmosphere temperature is relatively large and the proportion of infrared radiation is relatively small among the elements constituting the temperature in the far-infrared heater, and by compensating for the influence of infrared rays on the temperature, The present invention has been reached that the transparent conductive layer can be crystallized efficiently in a state in which a metal layer is laminated on the transparent conductive layer.
  • FIG. 2 shows a process schematic diagram according to the embodiment.
  • ITO crystallization is performed before forming a metal layer on ITO
  • the method according to the exemplary embodiment of the present disclosure according to FIG. 2 performs ITO crystallization after forming a metal layer on ITO.
  • ITO may be replaced with a transparent conductive material requiring crystallization.
  • the embodiments described herein measure the temperature T1 on the substrate side of the laminate during crystallization of the transparent conductive layer, in order to compensate for the effect of infrared light reflected or not absorbed by the presence of the metal layer on the temperature as described above. Doing; Measuring the temperature T2 on the metal layer side of the laminate; And raising the temperature of the far-infrared heater by a temperature corresponding to the difference (T1-T2) of the temperature between the substrate side and the metal layer side.
  • the substrate is not particularly limited, and materials known in the art may be used.
  • materials known in the art may be used.
  • glass, a plastic substrate, a plastic film, or the like may be used, but is not limited thereto.
  • the transparent conductive layer before crystallization by heat treatment is amorphous.
  • the transparent conductive layer can be adjusted according to the conditions or composition during the manufacturing process, the resistance before the heat treatment, that is, the amorphous state and the crystallized state after the heat treatment, that is, the resistance of the crystalline state.
  • the resistance of the pre-crystallization state and the post-crystallization state is controlled by the fraction of oxygen inflow during the ITO deposition and the tin (Sn) content of the ITO target using, for example, a sputter.
  • the terms "amorphous" and "crystalline” can be identified by their resistance. Those skilled in the art can ascertain the resistance of the amorphous state and the resistance of the crystalline state depending on the material.
  • a transparent conductive oxide layer may be used as the transparent conductive layer.
  • the transparent conductive oxides include indium oxide, zinc oxide, indium tin oxide, indium zinc oxide, indium zinc tin oxide, and amorphous transparent conductive polymers, and these may be used alone or in combination of two or more thereof. It doesn't happen.
  • the transparent conductive layer is an indium tin oxide layer.
  • the thickness of the transparent conductive layer may be 15 ⁇ 20nm, but is not limited thereto.
  • the transparent conductive layer may be formed using a deposition process or a printing process using the above-described transparent conductive layer material.
  • the metal layer is not particularly limited as long as it includes a metal having conductivity.
  • the material of the metal layer one or two or more of copper (Cu), aluminum (Al), silver (Ag), neodymium (Nd), molybdenum (Mo), nickel (Ni), and alloys thereof may be used.
  • the present invention is not limited thereto.
  • the metal layer may have a single layer or a laminated structure of two or more layers. For example, a silver (Ag) layer, an Ag-Pd-Cu alloy layer, a Cu-Ni / Cu / Cu-Ni three-layer structure, an aluminum (Al) layer, an Ag / Mo two-layer structure, an APC / Mo two-layer structure, etc.
  • the Ag-Pd-Cu alloy layer an alloy layer including 98 wt% Ag, 1 wt% Pd, and 1 wt% Cu may be used.
  • the Ag-Pd-Cu alloy layer has excellent reliability and adhesion (adhesiveness) such as corrosion resistance, migration resistance, heat resistance, etc., compared to the pure Ag layer.
  • the metal layer may be formed using a method known in the art. For example, it may be formed by a method such as evaporation, sputtering, wet coating, evaporation, electrolytic plating or electroless plating, lamination of metal foil, or the like.
  • the metal layer may be formed by a printing method.
  • an ink or paste containing a metal may be used, and the paste may further include a binder resin, a solvent, a glass frit, and the like, in addition to the metal.
  • the thickness of the metal layer is not particularly limited, the thickness of 0.01 to 30 ⁇ m may exhibit more excellent effects in terms of the conductivity of the metal layer and the economics of the pattern forming process.
  • heat treatment conditions for crystallization in the step of crystallizing the transparent conductive layer may be determined by those skilled in the art according to conditions such as material or thickness of the transparent conductive layer.
  • the infrared irradiation direction of the far infrared heater for heat treatment may be the metal layer side, the substrate side or the protective film side.
  • the infrared irradiation direction is the substrate side or the protective film side, since the infrared energy reflected from the metal layer affects the temperature increase in the heater, there is an advantage in reducing the temperature difference between the top and bottom of the laminate.
  • the absorption of the infrared energy incident on the substrate or the protective film is easier than that when incident on the metal layer side, so the influence of the infrared reflection by the metal layer located on the opposite side of the plane where the infrared ray is incident is not relatively large.
  • FIG. 9 to 10 are formed only on the ITO layer on the PET substrate, or after further forming a metal layer on the ITO layer, when heat-treated at 155 °C 30 minutes in a far infrared heater, the metal layer layer (top, top) or the substrate side (bottom, bottom temperature is shown.
  • FIG. 9 is irradiated with infrared rays from the metal layer side (normal)
  • FIG. 10 is irradiated with infrared rays from the substrate side (reverse). Compared with FIG. 9, it can be seen that the temperature difference between the upper part and the lower part is smaller in FIG. 10.
  • Table 1 below shows the types of metal layers provided on the ITO layer and the temperatures of the upper side (metal layer side) and the lower side (substrate side) according to the infrared irradiation direction. This temperature is also a result of heat treatment at 155 ° C. for 30 minutes in a far infrared heater.
  • the temperature difference between the upper and lower portions of the laminate differs depending on the ultraviolet irradiation direction and the type of the metal layer.
  • the temperature deviation between the upper and lower portions is different from 3 ° C to 32 ° C.
  • crystallization of a transparent conductive layer such as ITO may be efficiently performed by performing the above-described process of compensating for the temperature deviation.
  • the heat treatment temperature of the transparent conductive layer may be carried out at a temperature of 100 ⁇ 180 °C, it may be adjusted as necessary.
  • the heat treatment temperature may be a temperature of 120 ⁇ 160 °C.
  • the crystallization of the transparent conductive layer may be performed from the amorphous state before the crystallization until the resistance of the crystalline state after the crystallization is realized, it can be confirmed that the crystallization was made when the expected resistance is implemented.
  • the ITO layer may be deposited by setting the ITO layer formation conditions such that the ITO layer deposited on the substrate on the film is subjected to heat treatment at 150 ° C. for about 30 minutes to achieve crystallization.
  • the timing of performing the step of measuring the temperature T1 of the substrate side and the temperature T2 of the metal layer side of the laminate and compensating these temperature differences may be determined as necessary.
  • the step of measuring the temperature T1 of the substrate side and the temperature T2 of the metal layer side of the laminate is performed when there is no change between the temperature T1 of the substrate side and the temperature T2 of the metal layer side.
  • the temperature measurement may be measured immediately after the laminate is put in the heater and measured until there is no change in each of the temperature T1 on the substrate side and the temperature T2 on the metal layer side. Measured after 10 minutes have elapsed, the temperatures can be measured until there is no change in each.
  • the laminate further includes a protective film provided on the opposite side of the surface provided with a transparent conductive layer of the substrate.
  • the step of measuring the temperature T1 of the substrate side is to measure the temperature on the protective film side.
  • the above-described adhesive layer may be provided on the protective film rather than on the substrate.
  • the protective film serves to protect the substrate during the manufacturing process or when using the final product.
  • the material of the protective film those known in the art may be used.
  • the protective film a film made of a polymer material that is easy to absorb infrared rays, etc. as compared to the metal may be used.
  • a PET film may be used as the protective film.
  • the adhesive layer is provided on the opposite side of the surface provided with the transparent conductive layer of the substrate of the laminate and the opposite side of the surface provided with the transparent conductive layer of the metal layer of the laminate.
  • a pressure-sensitive adhesive layer may be used for the purpose of adhering the temperature measuring device to measure the temperature difference between the upper portion provided with the metal layer of the laminate and the lower portion provided with the substrate.
  • the adhesive layer provided on the metal layer and the adhesive layer provided on the substrate are preferably made of the same material.
  • the adhesive layer may be a material that has IR absorption.
  • a polyimide adhesive tape may be used.
  • the IR absorption change when the polyimide adhesive tape is attached to the above-described laminate is shown in FIG. 12.
  • the difference in the IR absorption rates of # 1 and # 5 was smaller than that of the absorption rates of # 2 and # 6, which means that when the IR is irradiated from the metal side of the laminate, the poly provided on the opposite side of the metal The mid tape shows little influence on IR absorption.
  • the difference in IR absorption rates of # 2 and # 4 was larger than that of IR absorptions of # 1 and # 3, which is due to the sum of the absorption rates of each of the polymers constituting the substrate and the polyimide. It shows that the IR absorption rate is increased.
  • polyimide adhesive tape A commercially available thing can be used as said polyimide adhesive tape,
  • a brand name Kapton tape can be used.
  • the polyimide adhesive tape may be used having a thickness of 30-200 micrometers.
  • the polyimide adhesive tape is selected from, for example, an adhesion force to a metal of 0.5 to 12 N / 25mm, elongation 40-70%, breakdown voltage 4-10 Kv, and short-time 150-280 ° C. It may have the above physical properties.
  • the width of the tape can be selected as needed, for example, a tape having a width of 5 to 100 mm can be used.
  • the adhesive layer is provided on the opposite side of the surface provided with the transparent conductive layer of the substrate of the laminate and the opposite side of the surface provided with the transparent conductive layer of the metal layer of the laminate,
  • a temperature measuring device attached to each of the pressure-sensitive adhesive layer on the substrate and the pressure-sensitive adhesive layer on the metal layer is further provided.
  • a thermal couple may be used as the temperature measuring device.
  • the thermal couple may be attached to the laminate by the adhesive layer described above or may sense a temperature.
  • the thermal couple may be in the form of a line, but is not particularly limited as long as it can sense the temperature.
  • the temperature measuring device may further include a temperature data record capable of receiving and recording temperature information detected by the thermal couple by wire or wirelessly. In this case, the temperature data record is not directly attached to the laminate or through an adhesive, and only a thermal couple is attached to the laminate to sense a temperature.
  • the method according to the embodiments described above further comprises the step of moving the stack into a far infrared heater using a conveyor belt to heat-treat the stack in a far infrared heater.
  • the conveyor belt may be provided to continuously move the laminate from the outside of the far infrared heater to the outside through the inside.
  • the conveyor belt is stopped after moving the laminate from the outside to the inside of the far-infrared heater, and is stopped to move the laminate to the outside of the far-infrared heater after the transparent conductive layer crystallization is performed.
  • Figure 3 shows a schematic diagram showing the interior of the far-infrared heater according to an example.
  • a conveyor belt is provided inside the heater according to FIG. 3, and a stage on which the above-mentioned stack is accommodated is provided on the conveyor belt.
  • the stage may be provided as needed, but may not be provided.
  • the conveyor belt may include a stage capable of receiving the stack.
  • the means for moving the stack outside the far infrared heater is not limited to the conveyor belt.
  • the stack may be moved into the heater.
  • the roll may serve as a stage to accommodate the laminate described above. 4 shows an example in which a roll is provided as a means for supporting the laminate in the far infrared heater.
  • Another embodiment of the present specification includes the steps of preparing a metal layer and a crystallized transparent conductive layer-containing laminate by the method for producing a metal layer and a crystallized transparent conductive layer-containing laminate as described above; And patterning a metal layer of the laminate, to provide a method of manufacturing a laminate including a metal pattern and a transparent conductive layer.
  • the method for patterning the metal layer may use a method known in the art, and is not particularly limited.
  • a photoresist method may be used for patterning the metal layer.
  • a photoresist pattern is formed on the metal layer by selective exposure and development, or a resist pattern is formed by a printing method, and the metal layer that is not applied by the resist pattern is selectively etched using the resist pattern as a mask. Method can be used.
  • the line width and line spacing of the metal pattern patterned by the above method can be designed according to the end use.
  • the line width of the pattern may be greater than 0 and 50 ⁇ m or less, but may be greater than 0 and 30 ⁇ m or less, but is not limited thereto.
  • preparing a laminate comprising a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer; And heat-treating the laminate inside the far-infrared heater, wherein the heat treatment includes: measuring a temperature T1 of the substrate side of the laminate; Measuring the temperature T2 on the metal layer side of the laminate; And calculating a temperature corresponding to the difference between the temperatures of the substrate side and the metal layer (T1-T2), when crystallizing the transparent conductive layer of the metal layer and the transparent conductive layer-containing laminate by a far-infrared heater.
  • a temperature condition may be set at the time of crystallizing the transparent conductive layer based on a temperature corresponding to the difference (T1-T2) between the calculated substrate side and the metal layer side.
  • the temperature increased by the difference in temperature in the temperature in the heat treatment step can be set.
  • the temperature conditions in the actual process can be set more efficiently.
  • the transparent conductive layer crystallization temperature by the method for setting the temperature conditions during the crystallization of the transparent conductive layer of the metal layer and the transparent conductive layer-containing laminate by the above-described far infrared heater; And heat treating a laminate including a substrate, a transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer using a far infrared ray heater or a box oven, wherein the heat treatment temperature is measured. It provides a method for producing a metal layer and a crystallized transparent conductive layer-containing laminate comprising the step of setting using the determined transparent conductive layer crystallization temperature.
  • the temperature compensated by their temperature difference (T1-T2) based on the difference between the upper and lower temperatures of the laminate measured and calculated in setting the crystallization temperature. Can be set as the heat treatment temperature.
  • the temperature measured on the substrate side of the laminate in the step of setting the crystallization temperature may be set as the heat treatment temperature.
  • Another embodiment of the present specification provides a laminate including a substrate, an amorphous transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer.
  • a method of crystallizing the transparent conductive layer is used before forming the metal layer, the laminate having the above structure does not exist. Since the laminate as described above forms a metal layer thereon in a state in which the transparent conductive layer is amorphous, a roll-to-roll process may be used, thereby simplifying the process.
  • 5 illustrates the structure of a laminate according to the embodiment.
  • the protective film may be additionally provided on the surface of the laminate.
  • the protective film may be applied to the contents described in the embodiment of the method described above.
  • the laminate may be provided with a pressure-sensitive adhesive layer on an opposite side of the surface provided with the transparent conductive layer of the substrate and an opposite side of the surface provided with the transparent conductive layer of the metal layer.
  • a temperature measuring device attached to each of the pressure-sensitive adhesive layer on the substrate and the pressure-sensitive adhesive layer on the metal layer may be provided and configured to compensate for the temperature difference thereof.
  • the configuration of the laminate may be applied to the contents described in the embodiments of the method described above.
  • Another exemplary embodiment of the present specification includes an infrared lamp, a sample stage provided to receive a crystallized sample provided in a region where far infrared rays generated from the infrared lamp reach; And it provides a far-infrared heater comprising a temperature controller for adjusting the temperature to increase the temperature by the temperature difference between the top and bottom of the crystallized sample.
  • the crystallization sample may be a laminate including the substrate described above, an amorphous transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer.
  • the far-infrared heater has a temperature controller that adjusts the temperature to increase the temperature by a temperature difference between the upper and lower portions of the crystallized sample, so that in the embodiments of the above-described method, the metal layer is formed on the transparent conductive layer.
  • the conductive layer can be crystallized efficiently.
  • the temperature controller adjusts the temperature of the top and bottom of the crystallization sample, respectively, so that the user can recognize the temperature difference between the top and bottom of the crystallization sample, such as the aforementioned laminate, and control the temperature to compensate for the temperature difference.
  • the far-infrared heater may include a conveyor belt for moving the crystallization sample to a region where far-infrared rays generated from the infrared lamp reach, and the sample stage may be provided on the conveyor belt.
  • 3 and 4 show examples of the internal structure of the far infrared heater.
  • the metal layer and the crystallized transparent conductive layer-containing laminate prepared by the method for producing a substrate, the crystallized transparent conductive layer provided on the substrate, and the transparent conductive layer Provided is a laminate provided with a metal layer provided on the substrate.
  • FIG. 13 illustrates the degree of crystallization of ITO after crystallization according to one embodiment of the present specification. More specifically, FIG. 13 (a) shows the degree of crystallization in the state of precrystallization of ITO as a prior art, and (b) shows the degree of crystallization of the state of post-crystallization of ITO as an exemplary embodiment of the present specification. , (c) shows a case where an amorphous region is included in ITO post-crystallization. That is, in the case of post-crystallization of ITO, there may be an amorphous region depending on the heat treatment conditions, it can be seen that the selection of detailed temperature conditions during the ITO post-crystallization is very important.
  • the step of raising the temperature of the far-infrared heater by the temperature corresponding to the difference (T1-T2) of the temperature between the substrate side and the metal layer side, thereby, the amorphous region There exists a characteristic which can form the ITO layer which does not exist and shows favorable crystallinity.
  • a laminate having a substrate, a crystallized transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer, the reflectivity of the metal layer is not heat-treated
  • a laminate in which the reflectance is reduced compared to the metal layer.
  • the reflectance is determined according to the material or thickness of the metal layer, and the reflectance of the unheated metal layer may be determined by a person skilled in the art.
  • the metal layer of the laminate according to the above-described embodiment has a reduced reflectance compared to the metal layer that has not been heat treated.
  • the method of measuring the reflectance is not particularly limited, and the method of measuring the reflectance of the metal layer according to the above-described embodiment and the reflectance of the non-heat-treated metal layer are not particularly limited.
  • the metal layer and the crystallized transparent conductive layer-containing laminate are manufactured by the above-described method, the metal layer also undergoes a crystallization process of the transparent conductive layer, so that the heat treatment is performed, thereby blurring the surface of the metal layer during the heat treatment. Can change. This reduces the reflectance of the metal layer as compared with the case where the heat treatment is not performed.
  • the reflectance can be measured for a visible light region, such as a wavelength of 380 to 800 nm, and the reflectance reduction can occur in at least some of the visible light region.
  • Figure 14 shows the decrease in reflectance of the Ag layer with the IR heat treatment temperature. According to FIG. 14, the reflectance decreased after 25 minutes at 135 ° C. and 155 ° C. and after 35 minutes at 165 ° C. and 175 ° C., which coincided with the time point at which the Ag layer surface was changed.
  • an embodiment of the present disclosure is prepared by the method of manufacturing a metal pattern and a crystallized transparent conductive layer-containing laminate described above, the substrate, the crystallized transparent conductive layer provided on the substrate, and the transparent conductive layer Provided is a laminate having a metal pattern provided thereon.
  • the metal pattern and the crystallized transparent conductive layer-containing laminate are manufactured by the above-described method, since the crystallization is performed by heat treatment in the state where the metal is provided on the transparent conductive layer, the transparent conductive layer is not provided with metal. In comparison with the case of crystallization, an amorphous region may be present in the transparent conductive layer.
  • a laminate having a substrate, a crystallized transparent conductive layer provided on the substrate, and a metal pattern provided on the transparent conductive layer, wherein the reflectivity of the metal pattern is heat treated.
  • a laminate in which the reflectance is reduced compared to a metal pattern that is not. The description of the reflectance reduction is as described above.
  • An exemplary embodiment of the present specification is a conductive laminate precursor comprising a substrate, an amorphous transparent conductive layer provided on the substrate, a metal layer provided on the transparent conductive layer, and an infrared absorptive protective film provided on the metal layer.
  • a conductive laminate precursor comprising a substrate, an amorphous transparent conductive layer provided on the substrate, a metal layer provided on the transparent conductive layer, and an infrared absorptive protective film provided on the metal layer.
  • the conductive laminate precursor means that the conductive laminate is formed by crystallization of the amorphous transparent conductive layer.
  • the conductive precursor is a state before the crystallization of the conductive laminate.
  • An infrared absorbing protective film is disposed on a metal layer of a precursor of a conductive laminate including an amorphous transparent conductive layer and a metal layer.
  • FIG. 2 is a process schematic diagram illustrating a crystallization process using the conductive laminate precursor.
  • ITO crystallization is performed before forming a metal layer on ITO
  • the method according to the exemplary embodiment of the present disclosure according to FIG. 2 performs ITO crystallization after forming a metal layer on ITO.
  • ITO may be replaced with a transparent conductive material requiring crystallization.
  • FIG. 2 by stacking an infrared absorbing protective film on the metal layer before crystallization, the infrared rays reflected by the metal layer may be absorbed by the protective film, thereby preventing a decrease in temperature generated from the infrared light.
  • the infrared absorbing protective film is a polymer film.
  • FIG. 23 is an excerpt from Masaaki Saito's data (August 22, 2014) of Heraeus, which illustrates the infrared absorption spectra of metals, ceramics and polymers. The different infrared absorption spectra depending on the material is described by W. Sieber, "Zusammensen effort der von Werk und Baustoflen zUrUckge worfenen Wiirmestrahlung," Z. Tech. Physik 22, 130 (1941). As described above, metals, ceramics, and polymers have different characteristics in infrared absorption, and the above-described effects can be obtained by using a film including a polymer having excellent infrared absorption properties as the protective film.
  • the polymer film may be determined by a person skilled in the art within a range that does not adversely affect the crystallization of the amorphous transparent conductive layer, and may have a thickness of several ⁇ m to several mm, preferably tens of ⁇ m to several hundred ⁇ m. Infrared absorption can occur efficiently within the thickness range. For example, the thickness can be determined within the range of 1 ⁇ m to 10 mm.
  • the material of the infrared absorbing protective film is not particularly limited, but polyesters such as polyethylene terephthalate (PET), polyethylene (PE), cellulose acetate, polyvinylidene chloride, polytetrafluoroethylene, polyimide, polyurethane, Polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylates such as PMMA, polycarbonate (PC), polyamides such as nylon (PA), polypropylene (PP), polystyrene (PS) and the like.
  • PET polyethylene terephthalate
  • PE polyethylene
  • PVA polyvinyl alcohol
  • PA polyacrylates
  • PP polypropylene
  • PS polystyrene
  • the infrared absorption properties of these materials are described in Fortschr. Hochpolym.-Forsch., Bd. 2, S. 51-172 (1960) and the like. Infrared absorption characteristics of the polymers described in the documents are shown in
  • the method of laminating the protective film on the metal layer is not particularly limited.
  • the protective film may be laminated on the metal layer, or may be dried or cured after coating the protective film composition on the metal layer.
  • the lamination may be carried out using a conventional laminator, for example, a device capable of performing lamination by applying pressure and temperature to a roller existing on the upper and lower parts, if necessary.
  • the protective film and the metal layer may directly contact each other, and the adhesive layer does not necessarily need to be present.
  • an additional rear film may be provided on an opposite side of the surface of the laminate precursor that contacts the transparent conductive layer.
  • the back film may serve to protect the substrate during the manufacturing process or during use of the final product.
  • the material of the back film those known in the art may be used.
  • the back film a film made of a polymer material which is easy to absorb infrared rays and the like compared to the metal may be used.
  • a PET film may be used as the back film.
  • Another embodiment of the present specification comprises the steps of preparing a laminate comprising a substrate, an amorphous transparent conductive layer provided on the substrate, and a metal layer provided on the transparent conductive layer; And it provides a method for producing a conductive laminate precursor comprising the step of laminating an infrared absorbing protective film on the laminate.
  • the material of each layer is as described above.
  • Laminating the infrared absorbing protective film may be performed in the manner described above.
  • Another embodiment of the present specification provides a method for manufacturing a conductive laminate including the step of crystallizing the amorphous transparent conductive layer by irradiating at least one surface of the conductive laminate precursor according to the above-described embodiment.
  • heat treatment conditions for crystallization in the step of crystallizing the transparent conductive layer may be determined by those skilled in the art according to conditions such as material or thickness of the transparent conductive layer.
  • the infrared irradiation direction of the far infrared heater for heat treatment may be the protective film side or the substrate side on the metal layer.
  • the heat treatment temperature of the transparent conductive layer may be carried out at a temperature of 100 ⁇ 180 °C, it may be adjusted as necessary.
  • the heat treatment temperature may be a temperature of 120 ⁇ 160 °C.
  • the crystallization of the transparent conductive layer may be performed from the amorphous state before the crystallization until the resistance of the crystalline state after the crystallization is realized, it can be confirmed that the crystallization was made when the expected resistance is implemented.
  • the ITO layer may be deposited by setting the ITO layer formation conditions such that the ITO layer deposited on the substrate on the film is subjected to heat treatment at 150 ° C. for about 30 minutes to achieve crystallization.
  • FIG. 18 shows the energy behavior by the infrared source with or without the protective film.
  • FIG. 18 shows only the energy behavior by the infrared source reaching the ITO layer, and the actual upper and lower temperature measurement results may be affected by the ambient temperature control (hot air).
  • an infrared lamp irradiates infrared rays from the metal layer side (Normal direction) or the substrate side (Reverse direction) of the conductive laminate precursor.
  • the protective film when infrared rays are directly irradiated onto the metal layer, most of the infrared rays are reflected, thereby reducing the heat rise due to less heat derived from the infrared rays.
  • the infrared rays are partially absorbed by the substrate or the back film when present, depending on the material of the substrate.
  • the infrared absorbing protective film when the infrared ray is irradiated on the metal layer side, that is, the infrared absorbing protective film side, the infrared absorbing protective film directly absorbs the infrared rays obtained from the protective film. In addition, by indirectly absorbing the infrared rays reflected from the metal layer, it is possible to prevent a decrease in temperature rise due to the infrared reflection on the metal layer side.
  • Table 3 below shows the results of experimenting with the temperature difference between both sides of the laminate with or without the protective film.
  • the irradiation in the reverse direction may affect the relatively increase the temperature, it can be seen that the effect of the presence of the protective film in both the irradiation in the forward direction or in the reverse direction can be seen.
  • a tendency of temperature rise according to the irradiation direction as described above may vary.
  • an intermediate layer may be further provided between the transparent conductive layer and the metal layer.
  • an adhesion promoting layer may be included as an intermediate layer, and an Mo layer may be used as the adhesion promoting layer.
  • the thickness of the intermediate layer can be determined as necessary.
  • Table 4 shows the results of experiments on the temperature difference at both sides of the laminate according to the presence or absence of a protective film when the Mo layer is provided as an intermediate layer.
  • Experimental conditions and layer configuration except for the Mo layer are the same as in Table 3.
  • Table 5 shows the results of experimenting with the degree of crystallization of the transparent conductive layer of the laminate with or without the protective film. The crystallization was maintained at 155 ° C. for 30 minutes by infrared irradiation. At this time, the kind of base material is as showing in Table 3.
  • the method may further include moving the laminate precursor into the far infrared heater by using the conveyor belt to heat-treat the laminate precursor inside the far infrared heater.
  • the conveyor belt may be provided to continuously move the laminate precursor from the outside of the far infrared heater to the outside through the inside.
  • the conveyor belt is stopped after moving the laminate precursor from the outside of the far infrared heater to the inside, and after the transparent conductive layer crystallization is performed, to move the laminate outside the far infrared heater. It may be provided.
  • Figure 3 shows a schematic diagram showing the interior of the far-infrared heater according to an example.
  • a conveyor belt is provided inside the heater according to FIG. 3, and a stage on which the above-mentioned stack is accommodated is provided on the conveyor belt.
  • the stage may be provided as needed, but may not be provided.
  • the conveyor belt may include a stage capable of receiving the laminate precursor or the laminate.
  • the means for moving the stack outside the far infrared heater is not limited to the conveyor belt.
  • the stack precursor may be moved into the heater.
  • the roll may serve as a stage to receive the laminate precursor described above. 4 illustrates an example in which a roll is provided as a means for supporting the laminate precursor in a far infrared heater.
  • the method of manufacturing the conductive laminate further includes removing the infrared absorbing protective film.
  • the method of manufacturing the conductive laminate includes removing the infrared absorbing protective film; And patterning the metal layer.
  • the method for patterning the metal layer may use a method known in the art, and is not particularly limited.
  • a photoresist method may be used for patterning the metal layer.
  • a photoresist pattern is formed on the metal layer by selective exposure and development, or a resist pattern is formed by a printing method, and the metal layer that is not applied by the resist pattern is selectively etched using the resist pattern as a mask. Method can be used.
  • the line width and line spacing of the metal pattern patterned by the above method can be designed according to the end use.
  • the line width of the pattern may be greater than 0 and 50 ⁇ m or less, but may be greater than 0 and 30 ⁇ m or less, but is not limited thereto.
  • a conductive laminate including a substrate, a crystalline transparent conductive layer provided on the substrate, a metal layer provided on the transparent conductive layer, and an infrared absorbing protective film provided on the metal layer. Provide a sieve.
  • a conductive laminate can be produced by the method described above. An example of the structure of the conductive laminate is illustrated in FIG. 17.
  • an additional rear film may be provided on the opposite side of the surface of the conductive laminate contacting the transparent conductive layer.
  • the description of the back film may be applied to the content described in the aforementioned conductive laminate precursor.
  • the conductive laminate as described above may be used as a component of a device requiring conductivity as it is, or after the protective film is peeled off, or after the metal layer is patterned as described above. For example, it can be used as an electrode of an electronic device.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Abstract

La présente invention se rapporte à un stratifié conducteur et à son procédé de fabrication, le procédé comprenant une étape consistant à traiter thermiquement, dans un dispositif de chauffage infrarouge lointain, le stratifié comprenant une couche conductrice transparente agencée sur un substrat et une couche métallique agencée sur la couche conductrice transparente de sorte à cristalliser la couche conductrice transparente d'un stratifié, l'étape consistant à cristalliser la couche conductrice transparente comprenant les étapes consistant à : mesurer une température (T1) côté substrat du stratifié ; mesurer une température (T2) côté couche métallique du stratifié ; et augmenter la température du dispositif de chauffage infrarouge lointain jusqu'à une température correspondant à une différence (T1 - T2) entre les températures du côté substrat et du côté couche métallique.
PCT/KR2015/007889 2014-07-29 2015-07-28 Stratifié conducteur et son procédé de fabrication WO2016018052A1 (fr)

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KR20140126749 2014-09-23
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109136845A (zh) * 2018-07-11 2019-01-04 中国航发北京航空材料研究院 一种曲面玻璃上透明导电薄膜的梯度晶化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003057116A (ja) * 2001-08-14 2003-02-26 Canon Inc 温度検出方法
WO2012067444A2 (fr) * 2010-11-17 2012-05-24 주식회사 엘지화학 Film conducteur doté d'un film d'oxyde et son procédé de production
JP2012199215A (ja) * 2010-07-06 2012-10-18 Nitto Denko Corp 透明導電性フィルムおよびその製造方法
US20120273344A1 (en) * 2007-10-22 2012-11-01 Nitto Denko Corporation Method for production of transparent conductive film and touch panel therewith
KR101260925B1 (ko) * 2010-07-05 2013-05-06 에코페라 주식회사 챔버형 기판 코팅장치 및 기판 코팅방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101173212B1 (ko) 2008-12-18 2012-08-13 한국전자통신연구원 터치 패널 필름 및 그의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003057116A (ja) * 2001-08-14 2003-02-26 Canon Inc 温度検出方法
US20120273344A1 (en) * 2007-10-22 2012-11-01 Nitto Denko Corporation Method for production of transparent conductive film and touch panel therewith
KR101260925B1 (ko) * 2010-07-05 2013-05-06 에코페라 주식회사 챔버형 기판 코팅장치 및 기판 코팅방법
JP2012199215A (ja) * 2010-07-06 2012-10-18 Nitto Denko Corp 透明導電性フィルムおよびその製造方法
WO2012067444A2 (fr) * 2010-11-17 2012-05-24 주식회사 엘지화학 Film conducteur doté d'un film d'oxyde et son procédé de production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109136845A (zh) * 2018-07-11 2019-01-04 中国航发北京航空材料研究院 一种曲面玻璃上透明导电薄膜的梯度晶化方法
CN109136845B (zh) * 2018-07-11 2020-10-20 中国航发北京航空材料研究院 一种曲面玻璃上透明导电薄膜的梯度晶化方法

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