WO2022071422A1 - センサー、物品、センサーの製造方法、および導電体 - Google Patents
センサー、物品、センサーの製造方法、および導電体 Download PDFInfo
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- WO2022071422A1 WO2022071422A1 PCT/JP2021/035938 JP2021035938W WO2022071422A1 WO 2022071422 A1 WO2022071422 A1 WO 2022071422A1 JP 2021035938 W JP2021035938 W JP 2021035938W WO 2022071422 A1 WO2022071422 A1 WO 2022071422A1
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- conductive
- less
- sensor
- wiring portion
- resin
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Classifications
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- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
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- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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- G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
Definitions
- the present invention relates to a sensor, an article, a method for manufacturing a sensor, and a conductor.
- image display devices such as smartphones and tablet terminals may be equipped with a touch sensor that can directly input information by touching the image display surface with a finger or the like.
- a sensor such as a touch sensor usually has a conductive portion patterned in a predetermined shape on a base material.
- Indium tin oxide (ITO) is mainly used as the conductive material of the conductive portion.
- ITO Indium tin oxide
- metal nanowires having a fiber diameter of nano size as a conductive material constituting the conductive portion instead of ITO.
- a bridge type sensor is known as a sensor.
- the bridge type sensor has a base material, a first conductive portion formed on one surface side of the base material and extending in the X direction, for example, and a second conductive portion separated from the first conductive portion and extending in the Y direction, for example. It is equipped with a part.
- the first conductive portion has a first electrode portion and a wiring portion, and the second conductive portion straddles the second electrode portion and the wiring portion of the first conductive portion and separates the second conductive portion from the first conductive portion. It has a bridge wiring portion for making it (see, for example, Patent Document 1).
- the second electrode portion is composed of conductive nanowires and the bridge wiring portion is composed of an oxide-based material such as ITO
- the refractive index of the surface of the bridge wiring portion is high because the oxide-based material is densely present. Will be higher. Therefore, the bridge wiring portion can be easily visually recognized from the difference in the refractive index between the electrode portion and the bridge wiring portion.
- metal nanowire patterns containing metal nanowires on the three-dimensional surface of three-dimensional objects having various shapes. Due to the influence of the aspect ratio, the metal nanowires could not be coated uniformly, and it was difficult to obtain the performance according to the purpose, so it was not possible to cope with the three-dimensional surface.
- the present invention has been made to solve the above problems. That is, to provide a sensor having good flexibility and capable of realizing invisibility of a bridge wiring part by a new invisibility technology different from the conventional one, an article equipped with this sensor, and a method for manufacturing such a sensor.
- Another object of the present invention is to provide a conductor having a conductive fiber pattern that can be applied to a three-dimensional surface having various shapes.
- the present invention includes the following inventions.
- a base material a first conductive portion provided on the first surface side of the base material, and a second conductive portion provided on the first surface side of the base material and separated from the first conductive portion.
- a sensor including a portion, wherein the first conductive portion has a plurality of first electrode portions arranged in the first direction and a wiring portion for electrically connecting the adjacent first electrode portions to each other. Then, the second conductive portion electrically connects the plurality of second electrode portions arranged in the second direction intersecting the first direction and the second electrode portions that straddle the wiring portion and are adjacent to each other.
- a sensor having a bridge wiring portion to be connected, wherein the bridge wiring portion includes a resin portion and conductive fibers arranged in the resin portion.
- a base material a first conductive portion provided on the first surface side of the base material, and a second conductive portion provided on the first surface side of the base material and separated from the first conductive portion.
- a sensor including a portion, wherein the first conductive portion has a plurality of first electrode portions arranged in the first direction and a wiring portion for electrically connecting the adjacent first electrode portions to each other. Then, the second conductive portion electrically connects the plurality of second electrode portions arranged in the second direction intersecting the first direction and the second electrode portions that straddle the wiring portion and are adjacent to each other.
- the second electrode portion has a bridge wiring portion to be connected, the second electrode portion contains a conductive material, and the bridge wiring portion is arranged in the resin portion and the resin portion, and is included in the second electrode portion.
- a sensor that includes a conductive material and the same type of conductive material.
- a first conductive portion having a plurality of first electrode portions arranged in the first direction and a wiring portion for electrically connecting the adjacent first electrode portions on the first surface side of the base material.
- the step of forming an electrically insulating layer so as to cover the first conductive fiber arranged in the region where the wiring portion should be formed, and the second step on the electrically insulating layer straddling the wiring portion and adjacent to each other.
- the step of arranging the first conductive fiber is a step of forming a conductive layer containing the resin portion and the first conductive fiber on the first surface side of the base material, and a step of forming the conductive layer in the conductive layer.
- a conductive portion including a three-dimensional object having a three-dimensional surface and a first conductive fiber pattern provided on the three-dimensional surface, which is composed of a plurality of conductive fibers and which follows the shape of the three-dimensional surface. body.
- the three-dimensional object electrically connects the substrate, a plurality of first electrode portions provided on the first surface side of the substrate and arranged in the first direction, and the adjacent first electrode portions.
- a first conductive portion having a wiring portion connected to the substrate, and a second conductive portion provided on the first surface side of the base material, separated from the first conductive portion, and arranged in a second direction intersecting with the first direction.
- a second conductive fiber pattern composed of a plurality of conductive fibers and an electrically insulating layer provided on the wiring portion are provided, and the three-dimensional surface is the surface of the electrically insulating layer and the second conductive fiber pattern.
- the first conductive fiber pattern straddles the wiring portion, and the second conductive fiber patterns adjacent to each other are electrically connected to each other so that the second conductive fiber patterns adjacent to each other are electrically connected to each other.
- a sensor comprising the conductor according to the above [15] or [16].
- a method for manufacturing such a sensor can be provided.
- FIG. 1 is a schematic configuration diagram of a sensor (conductor) according to an embodiment.
- FIG. 2 is a cross-sectional view taken along the line I-I of the sensor shown in FIG.
- FIG. 3 is a cross-sectional view taken along line II-II of the sensor shown in FIG.
- FIG. 4 is a plan view of the bridge wiring portion of the sensor shown in FIG.
- FIG. 5 is a plan view of the samples S1 and S2 when measuring the electric resistance value.
- FIG. 6 is an enlarged view of a part of the sample S1 of FIG.
- FIG. 7 is an enlarged view of a part of the sample S2 of FIG. 8 (A) to 8 (C) are views schematically showing the state of the folding test.
- FIG. 1 is a schematic configuration diagram of a sensor (conductor) according to an embodiment.
- FIG. 2 is a cross-sectional view taken along the line I-I of the sensor shown in FIG.
- FIG. 3 is a cross-sectional view
- FIG. 9 is a plan view of the sample after the folding test.
- FIG. 10 is a schematic configuration diagram of another sensor according to the embodiment.
- FIG. 11 is a cross-sectional view taken along line III-III of the sensor shown in FIG.
- FIG. 12 is a cross-sectional view taken along the line IV-IV of the sensor shown in FIG.
- FIG. 13 is a schematic configuration diagram of another sensor according to the embodiment.
- FIG. 14 is a cross-sectional view taken along the line VV of the sensor shown in FIG. 15 (A) and 15 (B) are diagrams schematically showing the manufacturing process of the sensor according to the embodiment.
- 16 (A) and 16 (B) are diagrams schematically showing the manufacturing process of the sensor according to the embodiment.
- FIG. 15 (A) and 15 (B) are diagrams schematically showing the manufacturing process of the sensor according to the embodiment.
- FIG. 17 is a diagram schematically showing a manufacturing process of the sensor according to the embodiment.
- 18 (A) and 18 (B) are diagrams schematically showing a manufacturing process of another sensor according to the embodiment.
- 19 (A) and 19 (B) are diagrams schematically showing a manufacturing process of another sensor according to the embodiment.
- FIG. 20 is a schematic configuration diagram of an image display device according to an embodiment.
- FIG. 21 is a cross-sectional view of another conductor according to the embodiment.
- FIG. 22 is a schematic configuration diagram of the biosensor according to the embodiment.
- FIG. 1 is a schematic configuration diagram of a sensor (conductor) according to the present embodiment
- FIG. 2 is a cross-sectional view taken along the line I-I of the sensor shown in FIG. 1
- FIG. 3 is shown in FIG. It is sectional drawing in line II-II of the sensor.
- FIG. 4 is a plan view of the bridge wiring portion of the sensor shown in FIG. 1
- FIG. 5 is a plan view of the samples S1 and S2 when measuring the electric resistance value. 6 is an enlarged view of a part of the sample S1 of FIG. 5,
- FIG. 7 is an enlarged view of a part of the sample S2 of FIG.
- FIGS. 8 (A) to 8 (C) are folded. It is a figure which showed the state of a test schematically, and FIG. 9 is a plan view of a sample after a folding test.
- 10 and 13 are schematic configuration diagrams of other sensors according to the present embodiment
- FIG. 11 is a cross-sectional view taken along the line III-III of the sensor shown in FIG. 10
- FIG. 12 is shown in FIG.
- FIG. 14 is a cross-sectional view taken along line IV-IV of the sensor shown
- FIG. 20 is a schematic configuration diagram of an image display device according to the present embodiment
- FIG. 21 is a cross-sectional view of another conductor according to the embodiment
- FIG. 22 is a biotechnology according to the embodiment. It is a schematic block diagram of a sensor.
- the sensor 10 shown in FIG. 1 is provided on the base material 11, the first conductive portion 12 provided on the first surface 11A side of the base material 11, and the first surface 11A side of the base material 11.
- the second conductive portion 13 separated from the conductive portion 12, the electrically insulating layer 14 provided between the wiring portion 12B and the bridge wiring portion 13B described later, and the take-out electrically connected to the first electrode portion 12A described later. It is provided with a wiring unit 15.
- the sensor 10 is an example of a conductor described later.
- the sensor 10 includes the electrical insulating layer 14, but the sensor 10 does not have to include the electrical insulating layer 14 as long as the first conductive portion 12 and the second conductive portion 13 are separated from each other. Further, although the sensor 10 includes the take-out wiring portion 15, it does not have to be provided with the take-out wiring portion 15.
- the first conductive portion 12 has a plurality of first electrode portions 12A arranged in the first direction DR1 (see FIG. 1) and a wiring portion 12B for electrically connecting adjacent first electrode portions 12A to each other.
- the second conductive portion 13 straddles the plurality of second electrode portions 13A arranged in the second direction DR2 (see FIG. 1) intersecting the first direction DR1 and the wiring portion 12B, and is adjacent to each other. It has a bridge wiring portion 13B for electrically connecting the above.
- "straddling the wiring portion” in the present specification means that the bridge wiring portion extends from the second electrode portion to the adjacent second electrode portion through above the wiring portion.
- the second direction DR2 is orthogonal to the first direction DR1.
- the haze value (total haze value) of the sensor 10 is preferably 5% or less. When the haze value of the sensor 10 is 5% or less, sufficient optical performance can be obtained.
- the haze value is a haze meter (for example, product name "HM-150", Murakami Color Technology Research Institute) in accordance with JIS K7136: 2000 under an environment with a temperature of 23 ⁇ 5 ° C and a relative humidity of 30% or more and 70% or less. Can be measured using (manufactured by).
- the haze value is a value measured by the entire sensor.
- the first conductive part side is the non-light source side without curls or wrinkles, fingerprints, dust, etc.
- the arithmetic mean value of the value obtained by measuring 3 times or more is used.
- “measuring three or more times” means measuring three or more different points of a sample, rather than measuring the same place three times or more. It is considered that the average value of the haze values in the entire in-plane of the sensor can be obtained by measuring the haze values at three or more different points of the cut out sample.
- the number of measurements it is preferable to measure 5 times, that is, 5 different points, and it is preferable to obtain an average value from the measured values of 3 points excluding the maximum value and the minimum value among them. If the sample cannot be cut out to the above size, for example, the HM-150 has an inlet opening of 20 mm ⁇ for measurement, so a sample having a diameter of 21 mm or more is required. Therefore, a sample having a size of 22 mm ⁇ 22 mm or more may be appropriately cut out. If the size of the sample is small, set the number of measurement points to three by shifting it little by little or changing the angle so that the light source spot does not deviate.
- the haze value of the sensor 10 is more preferably 3% or less, 2% or less, 1.5% or less, 1.2% or less, or 1.1% or less.
- the variation in the obtained haze value is within 30%, preferably within ⁇ 10%, regardless of whether the measurement target is as long as 1 m ⁇ 3000 m or the size of a 5-inch smartphone, which is preferable.
- the haze value is the same as the above even in the entire laminated body in which a plurality of layers are overlapped, such as a touch panel equipped with a sensor.
- the total light transmittance of the sensor 10 is preferably 80% or more. When the total light transmittance of the sensor 10 is 80% or more, sufficient optical performance can be obtained.
- the total light transmittance is a haze meter (for example, product name "HM-150", Murakami) in accordance with JIS K7361-1: 1997 under an environment where the temperature is 23 ⁇ 5 ° C and the relative humidity is 30% or more and 70% or less. It can be measured using (manufactured by Color Technology Laboratory).
- the total light transmittance of the sensor 10 is more preferably 85% or more, 88% or more, or 89% or more.
- the total light transmittance is measured at five points and is the average value of the total light transmittances at three points excluding the maximum and minimum values among the measured total light transmittances at the five points.
- the first sensor 10 before and after the folding test is the first.
- the electric resistance value ratio described later in the conductive portion 12 and the electric resistance value ratio in the second conductive portion 13 are 3 or less, respectively.
- the electric resistance value in the conductive part of the sensor after the folding test is higher than the electric resistance value in the conductive part of the sensor before the folding test. Will also rise. Therefore, it is possible to determine whether or not the sensor is cracked or the like by obtaining the electric resistance value ratio in the conductive portion of the sensor before and after the folding test.
- the folding test may be performed so that the sensor 10 is folded so that the first conductive portion 12 and the second conductive portion 13 are on the inside, and the first conductive portion 12 and the second conductive portion 13 are on the outside. In either case, the electrical resistance ratios of the first conductive portion 12 and the second conductive portion 13 of the sensor 10 before and after the folding test are 3 or less, respectively. It is preferable to have.
- the electric resistance ratio of the first conductive portion 12 and the second conductive portion 13 of the sensor 10 before and after the folding test is more preferably 3 or less, respectively.
- the number of foldings is 200,000, 300,000, 500,000 or 1,000,000.
- the electric resistance ratios of the first conductive portion 12 and the second conductive portion 13 before and after the folding test are 3 or less, respectively, and in the folding test in which the number of times of folding is 100,000 times, the first before and after the folding test.
- the reason why the number of times of folding in the above-mentioned folding test is evaluated at least 100,000 times is as follows. For example, assuming that the sensor is incorporated into a foldable smartphone, the frequency of folding (opening and closing frequency) becomes extremely high. Therefore, in the evaluation in which the number of times of folding in the folding test is, for example, 10,000 or 50,000, there is a possibility that the evaluation at a practical level cannot be performed.
- the evaluation that the number of times of folding in the folding test is 10,000 times can only confirm the level that cannot be used as a product, and the one that can be used but is insufficient is also good and cannot be evaluated. Therefore, in order to evaluate whether or not it is at a practical level, it is necessary to evaluate the number of times of folding in the folding test at least 100,000 times.
- the first conductive portion 12 and the second conductive portion 12 of the sensor 10 before and after the folding test are more preferable that the electric resistance value ratio of each of the conductive portions 13 is 1.5 or less.
- the distance ⁇ between the facing sides of the sensor 10 is 3 mm, but from the viewpoint of reducing the thickness of the image display device, the distance ⁇ between the facing sides of the sensor 10 is in a narrower range.
- the electric resistance value ratio of the first conductive portion 12 and the second conductive portion 13 before and after the folding test. is more preferably 3 or less, respectively. Even if the number of times of folding is the same, the narrower the interval ⁇ is, the more difficult it is to make the electric resistance value ratio of the conductive portion before and after the folding test 3 or less. Therefore, the interval ⁇ is 2 mm or 1 mm.
- the electrical resistance ratios of the first conductive portion 12 and the second conductive portion 13 before and after the folding test are 3 or less, respectively, and the first conductive portion 12 and the second conductive portion before and after the folding test having the above-mentioned interval ⁇ of 3 mm. There is a remarkable technical difference from the fact that the electrical resistance value ratios of 13 are 3 or less.
- a predetermined size for example, 125 mm in length ⁇ 50 mm in width
- a predetermined size for example, 125 mm in length ⁇ 50 mm in width
- samples S1 and S2 are cut out (see FIG. 5).
- the sample S1 is cut out from the sensor 10 so that the longitudinal direction of the sample S1 is the direction in which the first conductive portion 12 extends (conduction direction), and the sample S2 has the second conductivity in the longitudinal direction of the sample S2.
- the portion 13 is cut out from the sensor 10 so as to extend in the extending direction (conduction direction).
- the sample may be a size that can be evaluated later as described later after the folding test.
- the sample may be cut out into a rectangular shape having a size of 80 mm ⁇ 25 mm. May be good.
- the electric resistance value of the first conductive portion 12 is measured in the sample S1 before the folding test, and the second conductive portion is measured in the sample S2 before the folding test.
- the electric resistance value of 13 is measured. Specifically, as shown in FIG.
- the measurement distance of the electric resistance value fluctuates on both ends of the samples S1 and S2 in the longitudinal direction (for example, each portion of 10 mm in length ⁇ 50 mm in width).
- a silver paste product name "DW-520H-14", manufactured by Toyobo Co., Ltd.
- the cured silver paste 21 is provided on both ends of the samples S1 and S2. ..
- the sample S1 the cured silver paste 21 is irradiated with a laser beam to remove a part of the silver paste 21 so that the first conductive portion 12 does not electrically conduct with the second conductive portion 13, and the sample is sampled.
- the cured silver paste 21 is irradiated with a laser beam to remove a part of the silver paste 21 so that the second conductive portion 13 does not electrically conduct with the first conductive portion 12 (FIGS. 6 and 6). 7).
- the portion indicated by reference numeral 21A in FIGS. 6 and 7 is a portion from which the silver paste 21 has been removed. In that state, the electric resistance value of each sample is measured using a tester (product name "Digital M ⁇ Hister 3454-11", manufactured by Hioki Electric Co., Ltd.).
- the distance between the silver pastes 21 (the distance of the portion where the silver paste 21 is not provided) is the measurement distance of the electric resistance value in the samples S1 and S2 (for example, 100 mm), and the measurement distance is the measurement distance of the samples S1 and S2. It is constant between S2.
- the probe terminals of the tester are brought into contact with each of the portions of the cured silver paste 21 provided at both ends in contact with the first conductive portion 12.
- the probe terminals of the tester are brought into contact with the portions of the cured silver paste 21 provided at both ends in contact with the second conductive portion 13.
- the measurement of the electric resistance value shall be performed in an environment where the temperature is 23 ⁇ 5 ° C.
- the relative humidity is 30% or more and 70% or less.
- the electric resistance value of the first conductive portion 12 was measured
- the electric resistance value of the second conductive portion 13 was measured, and then with respect to the samples S1 and S2. , Perform folding tests respectively.
- the folding test is conducted as follows. As shown in FIG. 8A, in the folding test, first, the side portion S1a of the selected sample S1 and the side portion S1b facing the side portion S1a are arranged in parallel with each other in a folding durability tester (for example,). , Product name "U-shaped expansion and contraction tester DLDMLH-FS", manufactured by Yuasa System Equipment Co., Ltd., IEC62715-6-1).
- the fixing by the fixing portion 22 is performed by holding the portion of the sample S1 having a length of about 10 mm on one side in the longitudinal direction of the sample S1.
- the measurement can be performed by attaching the sample S1 to the fixing portion 22 with a tape. (That is, the minimum sample is 60 mm ⁇ 25 mm) Further, as shown in FIG. 8A, the fixed portion 22 can be slidably moved in the horizontal direction. It should be noted that the above device is preferable because it is possible to evaluate the durability against a bending load without generating tension or friction on the sample, unlike the conventional method of winding a sample around a rod.
- the central portion S1c of the sample S1 is deformed so as to be folded, and further, as shown in FIG. 8C.
- the fixed portion 22 is moved in the opposite direction to sample. Eliminate the deformation of S1.
- the sample S1 can be folded 180 ° at the central portion S1c. Further, by preventing the bent portion S1d of the sample S1 from protruding from the lower end of the fixed portion 22, the folding test is performed under the following conditions, and the interval when the fixed portion 22 is closest to the fixed portion 22 is controlled to 3 mm.
- the distance ⁇ between the two opposing sides S1a and S1b of the sample S1 can be set to 3 mm. In this case, the outer diameter of the bent portion S1d is regarded as 3 mm.
- the electric resistance value of the first conductive portion 12 is measured in the same manner as the sample S1 before the folding test. Then, the ratio of the electric resistance value of the sample S1 after the folding test to the electric resistance value of the sample S1 before the folding test (the electric resistance value of the sample S1 after the folding test / the electric resistance value of the sample S1 before the folding test) is obtained. ..
- the electric resistance value ratio is 5 times, that is, the electric resistance value ratios of 3 different electric resistance value ratios excluding the maximum value and the minimum value among the measured 5 electric resistance value ratios. Use the arithmetic average value.
- the ratio of the electric resistance value of the sample S2 after the folding test to the electric resistance value of the sample S2 before the folding test (the electric resistance value of the sample S2 after the folding test / the sample S2 before the folding test). Electrical resistance value) is calculated.
- the bent part has a bending habit and micro. Cracks may occur, resulting in poor appearance, specifically, white turbidity and delamination (poor adhesion) starting from microcracks. It is considered that one of the causes of the cloudiness phenomenon is that the crystal state of the organic compound, which is the material of any layer of the sensor, changes. When poor adhesion occurs locally, changes in temperature and humidity may cause moisture to accumulate in the delamination portion or air to enter the delamination portion, which may increase cloudiness.
- microcracks hardly occur in the case of only the base material or only the laminated body in which some functional layer is provided on the base material. That is, the starting point of its occurrence is unknown, but it is presumed that the conductive portion containing conductive fibers is a factor.
- displays are not just flat surfaces, but are foldable, curved, and various three-dimensional designs are increasing. Therefore, suppression of bending habits and microcracks in the bent portion is extremely important for use as an image display device. Therefore, it is preferable that the sensor 10 has excellent flexibility.
- excellent flexibility means that, before and after the folding test, not only the electrical resistance value ratio of the conductive portion is 3 or less, but also folding habits and microcracks are not confirmed.
- the above-mentioned folding habits shall be observed visually, but when observing the folding habits, the bent portion is evenly observed by transmitted light and reflected light in a bright room (800 lux to 2000 lux) with white lighting. In both cases, both the inner part and the outer part of the bent part when folded shall be observed.
- the observation of the bending habit shall be performed in an environment where the temperature is 23 ⁇ 5 ° C. and the relative humidity is 30% or more and 70% or less.
- microcracks shall be observed with a digital microscope (digital microscope).
- the digital microscope include VHX-5000 manufactured by KEYENCE CORPORATION.
- ring illumination is selected as the illumination for the digital microscope, and observation is made in the dark field and reflected light. Specifically, first, the sample after the folding test is slowly spread, and the sample is fixed to the stage of the microscope with tape. At this time, if the crease is strong, the area to be observed should be as flat as possible. However, the planned observation area (bent part) near the center of the sample should not be touched by hand and no force should be applied. Then, it is assumed that both the inner part and the outer part when folded are observed.
- the observation of the microcracks shall be performed in an environment where the temperature is 23 ⁇ 5 ° C. and the relative humidity is 30% or more and 70% or less.
- FIG. 9 shows.
- a mark A1 indicating the bent portion is attached to both ends S1d 1 located in the direction orthogonal to the folding direction FD in the bent portion S1d with an oil-based pen or the like.
- the bent portion S1d at both ends S1d 1 with the sample removed from the durability tester after the folding test.
- the line A2 (dotted line in FIG.
- connecting the marks A1 may be drawn with an oil-based pen or the like. Then, in observing the bending habit, the entire bent portion S1d, which is a region formed by the mark A1 of both ends S1d1 of the bent portion S1d and the line A2 connecting the marks A1 to each other, is visually observed. When observing microcracks, the position of the microscope is adjusted so that the center of the microscope visual field range (the range surrounded by the alternate long and short dash line in FIG. 9) is the center of the bent portion S1d. Be careful not to mark the mark with an oil-based pen in the area required for actual measurement.
- the adhesion between the base material and the resin layer may decrease. Therefore, when the interface between the base material 11 and the resin layer 17, which will be described later, is observed with a digital microscope in the bent portion of the sensor after the folding test, the sensor peels off near the interface between the base material 11 and the resin layer 17. It is preferable that such things are not observed. Examples of the digital microscope include VHX-5000 manufactured by KEYENCE CORPORATION.
- the other film is peeled off together with the adhesive layer or adhesive layer, then the haze value or total light transmittance is measured, and the sensor is folded.
- the test shall be conducted.
- the peeling of the other film can be performed, for example, as follows. First, heat the laminate with the other film attached to the sensor via the adhesive layer or the adhesive layer with a dryer, insert the cutting edge of the cutter into the part that seems to be the interface between the sensor and the other film, and slowly peel it off. go. By repeating such heating and peeling, the adhesive layer, the adhesive layer and other films can be peeled off. Even if such a peeling step is performed, it does not have a great influence on the measurement of the haze value or the like and the folding test.
- the size of the sensor 10 is large (for example, if it is long such as a roll), sample the sample from an arbitrary position to A4 size (210 mm x 297 mm) or A5 size (148 mm x 210 mm). After cutting out, the sample shall be cut out to the size of each measurement item. Further, when the sensor 10 is in a roll shape, the quality is stable, not in an ineffective region including both ends extending along the longitudinal direction of the roll while paying out a predetermined length from the roll of the sensor 10.
- the above device when measuring the haze value and total light transmittance of the sensor 10 or when performing a folding test on the sensor 10, the above device is used for measurement, but even if the device is not the above device, the same degree as that of a successor model or the like. It may be measured by the device of.
- the thickness of the sensor 10 is not particularly limited, but can be 500 ⁇ m or less.
- the thickness of the sensor 10 is 5 ⁇ m or more and 500 ⁇ m or less, 5 ⁇ m or more and 250 ⁇ m or less, 5 ⁇ m or more and 100 ⁇ m or less, 10 ⁇ m or more and 500 ⁇ m or less, 10 ⁇ m or more and 250 ⁇ m or less, 10 ⁇ m or more and 100 ⁇ m or less, 20 ⁇ m or more from the viewpoint of handleability and thinning. It is more preferably 500 ⁇ m or less, 20 ⁇ m or more and 250 ⁇ m or less, or 20 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the sensor 10 is 5 ⁇ m or more and 78 ⁇ m or less, 10 ⁇ m or more and 78 ⁇ m or less, 20 ⁇ m or more and 78 ⁇ m or less, especially 5 ⁇ m or more and 45 ⁇ m or less, 10 ⁇ m or more and 45 ⁇ m or less, or 20 ⁇ m or more and 45 ⁇ m or less. It is more preferable to have. Therefore, when flexibility is more important, the thickness of the sensor 10 is preferably 5 ⁇ m or more and 78 ⁇ m or less, more preferably 5 ⁇ m or more and 28 ⁇ m or less, and 5 ⁇ m or more and 20 ⁇ m or less.
- the thickness of the sensor 10 is randomly measured at 10 points from a cross-sectional photograph of the sensor taken using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), or a scanning electron microscope (SEM). , The average value of the thicknesses of 8 points excluding the maximum value and the minimum value among the measured thicknesses of 10 points. Sensors generally have uneven thickness. In the present embodiment, since the sensor is used for optics, the thickness unevenness is preferably ⁇ 2 ⁇ m or less, and more preferably ⁇ 1 ⁇ m or less.
- the thickness of the sensor When measuring the thickness of the sensor using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), it can be measured by the same method as the method for measuring the thickness of the first conductive portion 12. However, the magnification when taking a cross-sectional photograph of the sensor is 100 to 20,000 times.
- the cross section of the sensor When measuring the thickness of the sensor using a scanning electron microscope (SEM), the cross section of the sensor may be obtained by using an ultramicrotome (product name “Ultramicrotome EMUC7”, manufactured by Leica Microsystems) or the like.
- the sample for measurement by TEM or STEM is set to a delivery thickness of 100 nm by using the above-mentioned ultramicrotome, and an ultrathin section is prepared.
- the prepared ultrathin section is collected by a mesh with a collodion membrane (150) and used as a sample.
- a pretreatment for easy cutting such as embedding a sample in resin may be performed.
- the use of the sensor of the present invention is not particularly limited, and the sensor of the present invention can be used for various articles.
- the sensor of the present invention may be used, for example, in optical applications or touch panel applications.
- the sensor of the present invention is used for image display devices (including smartphones, tablet terminals, wearable terminals, personal computers, televisions, digital signage, public information displays (PIDs), in-vehicle displays, etc.) and in-vehicle (train and vehicle construction). Suitable for applications (including all types of vehicles, such as digital signage).
- the senor When the sensor is used as a sensor for in-vehicle use, for example, a sensor arranged in a part touched by a person such as a steering wheel or a seat can be mentioned.
- the sensor is also preferable for applications that require flexibility such as foldable and rollable. Further, it may be used for electric appliances and windows used in houses and cars (including all cars such as trains and vehicle construction machines).
- the sensor of the present invention can be suitably used in a portion where transparency is important. Further, the sensor of the present invention can be suitably used not only for technical viewpoints such as transparency, but also for electric appliances that require design and design.
- sensors other than image display devices include, for example, biosensors, defrosters, antennas, solar cells, audio systems, speakers, electric fans, electronic blackboards, carrier films for semiconductors, and the like.
- the shape of the sensor when used is appropriately designed according to the intended use, and is not particularly limited, but may be, for example, a curved surface.
- the sensor 10 may be cut to a desired size, but may be in a roll shape. If the sensor is in the form of a roll, it may be cut to a desired size at this stage.
- the size of the sensor is not particularly limited and is appropriately determined according to the size of the display surface of the image display device. Specifically, the size of the sensor may be, for example, 5 inches or more and 500 inches or less. As used herein, "inch” means the length of the diagonal line when the sensor is square, the diameter when it is circular, and the minor axis when it is elliptical. It shall mean the average value of the sum of the major axis.
- the aspect ratio of the sensor when obtaining the inch is not particularly limited as long as there is no problem as the display screen of the image display device.
- vertical: horizontal 1: 1, 4: 3, 16:10, 16: 9, 2: 1 and the like can be mentioned.
- the aspect ratio is not limited to this, especially in in-vehicle applications and digital signage, which are rich in design.
- the size of the sensor 10 is large, cut it out from an arbitrary position to a size that is easy to handle, such as A4 size (210 mm x 297 mm) or A5 size (148 mm x 210 mm), and then adjust it to the size of each measurement item. It shall be cut out.
- the quality is not an ineffective region including both ends extending along the longitudinal direction of the roll while paying out a predetermined length from the roll of the sensor 10. It shall be cut out to the desired size from the effective area near the stable center.
- the base material 11 is not particularly limited, but is preferably light-transmitting depending on the intended use.
- the base material has light transmission.
- the term "light transmissive” means the property of transmitting light. Further, “light transmission” does not necessarily have to be transparent, and may be translucent.
- Examples of the constituent material of the light-transmitting base material 11 include a base material containing a light-transmitting resin.
- a resin is not particularly limited as long as it has light transmittance, but for example, a polyolefin resin, a polycarbonate resin, a polyacrylate resin, a polyester resin, an aromatic polyether ketone resin, and a polyether sulfone.
- Examples thereof include a based resin, a polyimide resin, a polyamide resin, a polyamide imide resin, or a mixture of two or more of these resins.
- the base material touches the coating device when coating the first conductive portion or the like, it is easily scratched, but the base material made of polyester resin is hard to be scratched even if it touches the coating device, so the haze value is high.
- the polyester-based resin is preferable because it can suppress the rise and is superior in heat resistance, barrier property, and water resistance to the base material made of a light-transmitting resin other than the polyester-based resin.
- the resin constituting the base material has good flexibility, and therefore, a polyimide-based resin, a polyamide-imide-based resin, a polyamide-based resin, a polyester-based resin, or these. It is preferable to use a mixture. Further, among these, not only has excellent flexibility, but also has excellent hardness and transparency, and also has excellent heat resistance, and by firing, further excellent hardness and transparency are imparted. From the viewpoint that it can also be used, a polyimide resin, a polyamide resin, or a mixture thereof is preferable.
- polystyrene-based resin examples include resins containing at least one of polyethylene, polypropylene, cycloolefin polymer-based resin, and the like as constituents.
- cycloolefin polymer-based resin examples include those having a norbornene skeleton.
- polycarbonate resin examples include aromatic polycarbonate resins based on bisphenols (bisphenol A and the like), aliphatic polycarbonate resins such as diethylene glycol bisallyl carbonate and the like.
- polyacrylate-based resin examples include a poly (meth) methyl acrylate base material, a poly (meth) ethyl acrylate base material, a (meth) methyl acrylate- (meth) butyl acrylate copolymer, and the like.
- polyester-based resin examples include resins containing at least one of polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) as constituents.
- PET is preferable from the following viewpoints.
- aromatic polyetherketone-based resin examples include polyetheretherketone (PEEK) and the like.
- the polyimide-based resin may contain a polyamide structure as a part thereof.
- the polyamide structure that may be contained include a polyamide-imide structure containing a tricarboxylic acid residue such as trimellitic acid anhydride and a polyamide structure containing a dicarboxylic acid residue such as terephthalic acid.
- Polyamide-based resin is a concept including not only aliphatic polyamide but also aromatic polyamide (aramid).
- examples of the polyimide-based resin include compounds having structures represented by the following chemical formulas (1) and (2). In the following chemical formula, n is a repeating unit and represents an integer of 2 or more. Among the compounds represented by the following chemical formulas (1) and (2), the compound represented by the chemical formula (1) is preferable because it has a low phase difference and high transparency.
- the thickness of the base material 11 is not particularly limited, but can be 500 ⁇ m or less, and the thickness of the base material 11 is 3 ⁇ m or more and 500 ⁇ m or less and 3 ⁇ m or more and 250 ⁇ m or less from the viewpoint of handleability and thinning.
- the thickness of the base material 11 is 3 ⁇ m or more and 35 ⁇ m or less, 5 ⁇ m or more and 35 ⁇ m or less, 10 ⁇ m or more and 35 ⁇ m or less, or 20 ⁇ m or more and 35 ⁇ m or less, particularly 3 ⁇ m or more and 18 ⁇ m or less, 5 ⁇ m or more and 18 ⁇ m. It is more preferably 10 ⁇ m or more and 18 ⁇ m or less.
- the thickness of the base material was randomly measured at 10 points from a cross-sectional photograph of the base material taken using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), or a scanning electron microscope (SEM).
- the base material generally has uneven thickness.
- the thickness unevenness is preferably ⁇ 2 ⁇ m or less, more preferably ⁇ 1 ⁇ m or less.
- the thickness of the base material When measuring the thickness of the base material using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), it can be measured by the same method as the method for measuring the thickness of the first conductive portion 12. However, the magnification when taking a cross-sectional photograph of the base material 11 is 100 to 20,000 times.
- the cross section of the base material When measuring the thickness of the base material using a scanning electron microscope (SEM), the cross section of the base material may be obtained by using an ultramicrotome (product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems) or the like. ..
- the TEM and STEM samples are set to a delivery thickness of 100 nm using the above-mentioned ultramicrotome, and ultrathin sections are prepared.
- the prepared ultrathin section is collected by a mesh with a collodion membrane (150) and used as a sample for TEM or STEM.
- a pretreatment for easy cutting such as embedding a sample in resin may be performed.
- Conductive fibers themselves such as silver nanowires are suitable for flexibility, for example, but if the base material for laminating the conductive parts containing the conductive fibers or the resin layer is thick, the base material at the bent part at the time of folding is used. Or the resin layer may be cracked, and the crack may cause the conductive fibers to break, and the base material or the resin layer at the bent portion may be bent or microcracked. In addition to not being able to obtain the desired resistance value due to the above-mentioned disconnection, there is a risk that appearance defects, specifically, white turbidity and poor adhesion due to cracks may occur.
- the thickness of the base material and the resin layer is controlled and the adhesion between the layers (adhesion due to chemical bonds affected by the material and physical adhesion that does not cause cracks) is improved. It will be important.
- the base material 11 contains a polyester-based resin or a polyimide-based resin, the resistance to cracking changes depending on the thickness, so it is important to control the thickness of the base material.
- the thickness of the base material 11 is preferably 45 ⁇ m or less.
- the thickness of the base material 11 is preferably 5 ⁇ m or more and 45 ⁇ m or less, 5 ⁇ m or more and 35 ⁇ m or less, or 5 ⁇ m or more and 29 ⁇ m or less, particularly 5 ⁇ m or more and 18 ⁇ m or less, from the viewpoint of handleability and the like.
- the base material 11 contains, for example, a polyimide resin, a polyamide-based resin, a polyamide-imide-based resin, or a mixture thereof
- the base material 11 is based on the viewpoint of suppressing cracking of the base material 11 during folding, optical properties, and mechanical properties.
- the thickness of the material 11 should be as thin as possible, specifically, it is preferably 75 ⁇ m or less.
- the thickness of the base material 11 is 5 ⁇ m or more and 70 ⁇ m or less, 5 ⁇ m or more and 50 ⁇ m or less, 5 ⁇ m or more and 35 ⁇ m or less, 5 ⁇ m or more and 29 ⁇ m or less, and particularly 5 ⁇ m or more and 20 ⁇ m or less, or 5 ⁇ m or more and 18 ⁇ m or less, from the viewpoint of handleability and the like. Is preferable.
- each of the above-mentioned substrates is 5 ⁇ m or more and 35 ⁇ m or less, particularly when it is 5 ⁇ m or more and 20 ⁇ m or less or 5 ⁇ m or more and 18 ⁇ m or less, it is preferable to attach a protective film at the time of manufacture because the processing suitability is improved.
- the surface of the base material 11 may be subjected to physical treatment such as corona discharge treatment and oxidation treatment in order to improve the adhesiveness. Further, the base material 11 is on at least one surface side to improve the adhesiveness with the other layer, to prevent sticking at the time of winding, and / or to repel the coating liquid forming the other layer. It may have an underlayer for suppressing the above. However, when a conductive portion is formed on the surface of the base layer using a conductive fiber dispersion liquid containing conductive fibers and a dispersion medium, the dispersion medium permeates the base layer, although the degree varies depending on the type of the dispersion system.
- the base layer is not provided on the conductive portion side of the base material, and the conductive portion is directly provided on the base material. Is preferable.
- the base layer existing on at least one surface side of the base material and in contact with the base material shall form a part of the base material.
- the base layer is a layer having a function of improving adhesion with other layers, a function of preventing sticking at the time of winding, and / or a function of suppressing repelling of the coating liquid forming the other layer.
- Whether or not the base material has a base layer is 1000 to 500,000 times (1000 to 500,000 times) using a scanning electron microscope (SEM), a scanning transmission electron microscope (STEM), or a transmission electron microscope (TEM). It can be confirmed by observing the cross section around the interface between the base material 11 and the first conductive portion 12 and around the interface between the base material 11 and the resin layer 17 at (preferably 25,000 to 50,000 times). Since the base layer may contain particles such as a lubricant to prevent sticking during winding, the particles are present between the base material and the first conductive portion and the second electrode portion. Therefore, it can be determined that this layer is the base layer.
- the film thickness of the base layer is preferably 10 nm or more and 1 ⁇ m or less. If the film thickness of the base layer is 10 nm or more, the function as the base layer is fully exhibited, and if the film thickness of the base layer is 1 ⁇ m or less, there is no possibility of optical influence.
- the thickness of the base layer is 1000 to 500,000 times (preferably 25,000 times to) using a scanning electron microscope (SEM), a scanning transmission electron microscope (STEM), or a transmission electron microscope (TEM). The thickness of 10 points was randomly measured from the cross-sectional photograph of the base layer taken at 50,000 times), and the arithmetic average value of the thickness of 8 points excluding the maximum and minimum values among the measured thicknesses of 10 points. do.
- the film thickness of the underlayer is more preferably 10 nm or more and 150 nm or less, 30 nm or more and 1 ⁇ m or less, or 30 nm or more and 150 nm or less.
- the film thickness of the base layer can also be measured by the same method as the film thickness of the first conductive portion 12.
- SEM scanning electron microscope
- TEM TEM
- STEM it is preferable to prepare a sample using an ultramicrotome as described above.
- the base layer contains, for example, an anchor agent and a primer agent.
- the anchor agent and primer agent include polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, and ethylene.
- the base layer may contain particles such as a lubricant to prevent sticking during winding.
- the particles include silica particles and the like.
- the first conductive portion 12 is a portion that is electrically conductive.
- the surface resistance value of the first conductive portion 12 shall be obtained as follows. First, sample S1 for performing a folding test is prepared. After obtaining the sample S1, in an environment of a temperature of 23 ⁇ 5 ° C.
- a tester product name “Digital M ⁇ Hister 3454-11”, manufactured by Hioki Electric Co., Ltd. was applied to the cured silver paste 21.
- the resistance value is measured by contacting the probe terminals.
- the Digital M ⁇ Hister 3454-11 has two probe terminals (a red probe terminal and a black probe terminal, both of which are pin-shaped)
- the red probe terminal is used in one of the cured silver pastes 21.
- the resistance value is measured by contacting the portion in contact with the first conductive portion 12 and contacting the black probe terminal with the portion of the other cured silver paste 21 in contact with the first conductive portion 12.
- the surface resistance value of the first conductive portion 12 is obtained from the following mathematical formula (1).
- Rs R ⁇ (C W ⁇ C N / C L )... (1)
- Rs is the surface resistance value ( ⁇ / ⁇ )
- R is the measured resistance value ( ⁇ )
- C W is the line width ( ⁇ m) of one first conductive portion.
- CN is the number of first conductive portions
- CL is the line length ( ⁇ m) of the first conductive portions.
- the surface resistance value of the first conductive portion 12 is preferably 3 ⁇ / ⁇ or more and 1000 ⁇ / ⁇ or less.
- the surface resistance value of the first conductive portion 12 is 3 ⁇ / ⁇ or more, the optical performance is sufficient, and when the surface resistance value of the first conductive portion 12 is 1000 ⁇ / ⁇ or less, it is particularly used for a touch panel. Problems such as slow response speed can be suppressed.
- the surface resistance value of the first conductive portion 12 is 3 ⁇ / ⁇ or more and 100 ⁇ / ⁇ or less, 3 ⁇ / ⁇ or more and 70 ⁇ / ⁇ or less, 3 ⁇ / ⁇ or more and 60 ⁇ / ⁇ or less, 3 ⁇ / ⁇ or more and 50 ⁇ / ⁇ or less, 5 ⁇ / ⁇ .
- the linear resistance value of the first conductive portion 12 is preferably 15000 ⁇ or less.
- the line resistance value of the first conductive portion 12 is 20 ⁇ or more and 15000 ⁇ or less, 20 ⁇ or more and 12000 ⁇ or less, 20 ⁇ or more and 8000 ⁇ or less, 20 ⁇ or more and 1000 ⁇ or less, 100 ⁇ or more and 15000 ⁇ or less, 100 ⁇ or more and 12000 ⁇ or less, 100 ⁇ or more and 8000 ⁇ or less, 100 ⁇ or more and 1000 ⁇ or less.
- 200 ⁇ or more and 15000 ⁇ or less, 200 ⁇ or more and 12000 ⁇ or less, 200 ⁇ or more and 8000 ⁇ or less, or 200 ⁇ or more and 1000 ⁇ or less are more preferable.
- the thickness T1 (see FIG. 2) of the first conductive portion 12 is preferably 160 nm or more and 1.8 ⁇ m or less.
- the thickness of the first conductive portion 12 is 160 nm or more and 1.6 ⁇ m or less, 160 nm or more and 1.5 ⁇ m or less, 160 nm or more and 1.2 ⁇ m or less, 180 nm or more and 1.8 ⁇ m or less, 180 nm or more from the viewpoint of reliably covering the conductive fiber 18A.
- the thickness of the first conductive portion 12 means the maximum thickness from the first surface 11A of the base material 11 to the surface of the first conductive portion 12.
- the thickness of the first conductive portion 12 is random from a cross-sectional photograph of the first conductive portion 12 taken using a scanning transmission electron microscope (STEM), a transmission electron microscope (TEM), or a scanning electron microscope (SEM).
- STEM scanning transmission electron microscope
- TEM transmission electron microscope
- SEM scanning electron microscope
- a sample for cross-section observation is prepared from the sensor by the same method as described above. If continuity is not obtained in this sample, it may be difficult to see the observation image by STEM, so it is preferable to sputter Pt-Pd for about 20 seconds.
- the spatter time can be adjusted as appropriate, but care must be taken because 10 seconds is less and 100 seconds is too much, so that the sputtered metal becomes a particulate foreign matter image.
- STEM scanning transmission electron microscope
- STEM observation is performed with the detector (selection signal) set to "TE", the acceleration voltage set to "30 kV", and the emission set to "10 ⁇ A".
- magnification adjust the focus and adjust the contrast and brightness appropriately at 5000 to 200,000 times while observing whether each layer can be distinguished.
- the preferred magnification is 10,000 to 100,000 times, the more preferable magnification is 10,000 to 50,000 times, and the most preferable magnification is 25,000 to 50,000 times.
- the beam monitor aperture was set to 3
- the objective lens aperture was set to 3
- the interfacial contrast between the conductive part and other layers should be as clear as possible when observing the cross section. It is important to be able to observe. If this interface is difficult to see due to insufficient contrast, pretreatment generally used in electron microscope observation such as forming a metal layer such as Pt-Pd, Pt or Au by a sputtering method on the surface of the conductive portion is performed. You may go. Further, if a dyeing treatment such as osmium tetroxide, ruthenium tetroxide, or phosphotungstic acid is performed, the interface between the organic layers becomes easy to see, so that the dyeing treatment may be performed.
- a dyeing treatment such as osmium tetroxide, ruthenium tetroxide, or phosphotungstic acid
- the contrast at the interface may be difficult to understand when the magnification is high.
- observe the low magnification at the same time For example, observe at two magnifications, high and low, such as 25,000 times and 50,000 times, and 50,000 times and 100,000 times, obtain the above-mentioned arithmetic mean value at both magnifications, and further calculate the average value of the conductive part. The value of the line thickness.
- the first conductive portion 12 functions as an electrode in the X direction in, for example, a projection type capacitance type touch panel.
- the first conductive portion 12 is provided in a rectangular active area which is a region where a touch position can be detected.
- the first conductive portion 12 has a plurality of first electrode portions 12A and a wiring portion 12B as described above.
- the shape of the first electrode portion 12A is not particularly limited, and may be, for example, a quadrangular shape, a diamond shape, or the like. Since the width W1 (electrode width) of the first electrode portion 12A needs to be the contact area (about 10 mm ⁇ ) or less of the finger, it is preferably 10 mm or less.
- the width W1 of the first electrode portion 12A is 0.35 mm or more and 10 mm or less, 0.35 mm or more and 9 mm or less, 0.35 mm or more and 8.5 mm or less, 0.35 mm or more and 8 mm or less, 0.5 mm or more and 10 mm or less, 0.5 mm.
- the first electrode portion 12A includes a resin portion 17A and a plurality of conductive fibers 18A (first conductive fibers) arranged in the resin portion 17A.
- conductive fibers as used herein means conductive fibers and having a length sufficiently longer than a thickness (for example, a diameter), specifically, a length of 5 times or more the thickness (for example, a diameter). It means that the aspect ratio (length / thickness) is 5 or more).
- the resin portion 17A and the resin portion 17B described later are a part of the resin layer 17 shown in FIG. Since the first electrode portion 12A is formed in a desired shape, the first electrode portion 12A is composed of a plurality of conductive fibers 18A, and the conductive fiber pattern 12A1 formed in a desired shape (see FIG. 2). Includes.
- the resin portion 17A covers the conductive fibers 18A.
- the conductive fibers 18A are prevented from being detached from the first electrode portion 12A and the second electrode portion 13A, and the durability of the first electrode portion 12A and the second electrode portion 13A is prevented. It is possible to improve the property and scratch resistance.
- the thickness of the resin portion 17A is the same as the thickness of the first conductive portion 12, the description thereof will be omitted here.
- the resin portion 17A is not particularly limited, but if the sensor is for optical use, it is preferably a resin having light transmission.
- Examples of the resin portion 17A include those containing a polymer (cured product, crosslinked product) of a polymerizable compound.
- the resin portion 17A may contain a solvent-drying resin in addition to the polymer of the polymerizable compound.
- Examples of the polymerizable compound include an ionizing radiation polymerizable compound and / or a thermally polymerizable compound. Among these, an ionizing radiation polymerizable compound is preferable as the polymerizable compound because the curing rate is high and the design is easy.
- the ionizing radiation polymerizable compound has at least one ionizing radiation polymerizable functional group in one molecule.
- the "ionizing radiation polymerizable functional group” in the present specification is a functional group capable of polymerizing by ionizing radiation irradiation.
- Examples of the ionizing radiation polymerizable functional group include ethylenically unsaturated groups such as (meth) acryloyl group, vinyl group and allylic group.
- the "(meth) acryloyl group” means to include both "acryloyl group” and "methacryloyl group”.
- examples of the ionizing radiation emitted when polymerizing the ionizing radiation polymerizable compound include visible light, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- the ionizing radiation polymerizable compound examples include an ionizing radiation polymerizable monomer, an ionizing radiation polymerizable oligomer, and an ionizing radiation polymerizable prepolymer, which can be appropriately adjusted and used.
- the ionizing radiation polymerizable compound a combination of an ionizing radiation polymerizable monomer and an ionizing radiation polymerizable oligomer or an ionizing radiation polymerizable prepolymer is preferable.
- Examples of the ionizing radiation polymerizable monomer include a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth) acrylate.
- a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth) acrylate.
- a polyfunctional oligomer having two or more functional groups is preferable, and a polyfunctional oligomer having three or more (trifunctional) ionizing radiation polymerizable functional groups is preferable.
- the polyfunctional oligomer include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and isocyanurate. Examples thereof include (meth) acrylate and epoxy (meth) acrylate.
- the ionizing radiation polymerizable prepolymer has a weight average molecular weight of 10,000 or more, and the weight average molecular weight is preferably 10,000 or more and 80,000 or less, and more preferably 10,000 or more and 40,000 or less.
- the weight average molecular weight exceeds 80,000, the viscosity is high, so that the coating suitability is lowered, and the appearance of the obtained light-transmitting resin may be deteriorated.
- the polyfunctional prepolymer include urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, epoxy (meth) acrylate and the like.
- thermopolymerizable compound has at least one thermopolymerizable functional group in one molecule.
- the "thermopolymerizable functional group” is a functional group capable of polymerizing with each other or with another functional group by heating.
- examples of the thermopolymerizable functional group include a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, a cyclic ether group, and a mercapto group.
- thermopolymerizable compound is not particularly limited, and examples thereof include an epoxy compound, a polyol compound, an isocyanate compound, a melamine compound, a urea compound, and a phenol compound.
- the solvent-drying resin is a resin such as a thermoplastic resin that forms a film simply by drying the solvent added to adjust the solid content at the time of coating. When the solvent-drying resin is added, it is possible to effectively prevent film defects on the coated surface of the coating liquid when the electrically insulating layer 14 is formed.
- the solvent-drying resin is not particularly limited, and in general, a thermoplastic resin can be used.
- thermoplastic resin examples include styrene resin, (meth) acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic olefin resin, polycarbonate resin, polyester resin, and polyamide resin. , Cellulose derivatives, silicone resins and rubbers or elastomers.
- the thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds).
- an organic solvent particularly a common solvent capable of dissolving a plurality of polymers and curable compounds.
- styrene-based resin from the viewpoint of transparency and weather resistance, styrene-based resin, (meth) acrylic-based resin, alicyclic olefin-based resin, polyester-based resin, cellulose derivative (cellulose ester, etc.) and the like are preferable.
- the resin portion 17A can be formed by using a curable resin composition containing a polymerizable compound or the like.
- the resin composition contains the above-mentioned polymerizable compound and the like, but in addition, a solvent and a polymerization initiator may be added, if necessary.
- the resin composition contains conventionally known dispersants, surfactants, silane coupling agents, and thickening agents, depending on the purpose of increasing the hardness of the resin, suppressing curing shrinkage, controlling the refractive index, and the like.
- Agents, color inhibitors, colorants (pigments, dyes), defoamers, flame retardants, UV absorbers, adhesion enhancers, polymerization inhibitors, antioxidants, surface modifiers, slippery agents, etc. are added. May be good.
- solvent examples include alcohols (methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, etc.), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone, etc.).
- alcohols methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, etc.
- ketones acetone, methyl ethyl ketone (MEK), cyclohexanone, etc.
- Methylisobutylketone diacetone alcohol, cycloheptanone, diethylketone, etc.
- ethers (1,4-dioxane, dioxolane, diisopropyletherdioxane, tetrahydrofuran, etc.
- aliphatic hydrocarbons hexane, etc.
- alicyclic Hydrocarbons cyclohexane, etc.
- aromatic hydrocarbons toluene, xylene, etc.
- carbon halides diichloromethane, dichloroethane, etc.
- esters methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, lactic acid) Ethyl, etc.
- cellosolves methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.
- cellosolve acetates sulfox
- a polymerization initiator is a component that is decomposed by light or heat to generate radicals or ionic species to initiate or proceed with the polymerization (crosslinking) of a polymerizable compound.
- the polymerization initiator used in the resin composition is a photopolymerization initiator (for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator) or a thermal polymerization initiator (for example, a thermal radical polymerization initiator, Thermal cation polymerization initiators, thermal anionic polymerization initiators), or mixtures thereof.
- oxime ester compound examples include IRGACURE (registered trademark) OXE01, IRGACURE (registered trademark) OXE02, and IRGACURE (registered trademark) OXE03 (all manufactured by BASF Japan Ltd.).
- a plurality of conductive fibers 18A are present in the resin portion 17A. Since the first electrode portion 12A is electrically conductive, the conductive fibers 18A are in contact with each other in the thickness direction of the first electrode portion 12A.
- the conductive fibers 18A come into contact with each other to form a network structure (mesh structure) in the plane direction (two-dimensional direction) of the first electrode portion 12A.
- a network structure (mesh structure) in the plane direction (two-dimensional direction) of the first electrode portion 12A.
- the thickness of the conductive fiber 18A is preferably 300 nm or less. As long as the low line resistance value can be maintained, it is preferable that the thickness of the first conductive portion is as thin as possible from the viewpoint of optical characteristics and thinning.
- the thickness of the conductive fiber 18A is 10 nm or more and 200 nm or less, 10 nm or more and 145 nm or less, 10 nm or more and 140 nm or less, 10 nm or more and 120 nm or less, 10 nm or more, respectively, from the viewpoint of reducing the thickness and obtaining good optical characteristics such as low haze value. It is more preferably 110 nm or less, 10 nm or more and 80 nm or less, or 10 nm or more and 50 nm or less. When the thickness of the conductive fiber 18A is 10 nm or more, stable electrical conduction can be obtained.
- the lower limit of the film of the conductive fibers 18A is 20 nm or more and 200 nm or less, and 20 nm or more and 145 nm or less.
- the thickness of the conductive fiber 18A is preferably thin, for example, 10 nm or more and 200 nm or less, 10 nm or more and 145 nm or less, 10 nm or more and 120 nm or less.
- the average fiber diameter of the conductive fiber 18A is preferably 30 nm or less.
- the average fiber diameter of the conductive fiber 18A is 30 nm or less, the increase in the haze value of the sensor 10 can be suppressed, and the light transmission performance becomes sufficient.
- the average fiber diameter of the conductive fiber 18A is 5 nm or more and 28 nm or less, 5 nm or more and 25 nm or less, 5 nm or more and 20 nm or less, 7 nm or more and 28 nm or less, 7 nm or more and 25 nm or less, 7 nm or more and 20 nm or less from the viewpoint of conductivity of the first electrode portion 12A. It is more preferably 10 nm or more and 28 nm or less, 10 nm or more and 25 nm or less, or 10 nm or more and 20 nm or less. Among these, in order to control the balance between the resistance value and the haze value in a preferable range, the more preferable range of the fiber diameter of the conductive fiber 18A is 7 nm or more and 25 nm or less.
- a sample is cut out from the sensor to a size of 1 mm ⁇ 10 mm so as to include the first electrode portion, put into a silicone-based embedding plate, an epoxy-based resin is poured, and the entire sample is embedded with the resin. Then, the embedded resin is left at 25 ° C. for 12 hours or more to be cured. Then, using an ultramicrotome (product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.), the delivery thickness is set to 100 nm, and an ultrathin section is prepared. The prepared ultrathin section is collected by a mesh with a collodion membrane (150) and used as a sample for STEM.
- an ultramicrotome product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.
- a cross-sectional photograph of a sample for STEM is taken.
- the detector selection signal
- the acceleration voltage is set to 30 kV
- the emission is set to "10 ⁇ A”.
- the magnification adjust the focus and adjust the contrast and brightness appropriately at 5000 to 200,000 times while observing whether each layer can be distinguished.
- the preferred magnification is 10,000 to 50,000 times, more preferably 25,000 to 40,000 times. If the magnification is increased too much, the pixels at the interface become rough and difficult to understand. Therefore, it is better not to increase the magnification too much in the fiber diameter measurement.
- the beam monitor aperture was set to 3
- the objective lens aperture was set to 3
- the first electrode portion 12A is formed by using the conductive fiber dispersion liquid containing the conductive fiber 18A, and the average fiber diameter of the conductive fiber 18A is measured by using the conductive fiber dispersion liquid. Is also possible.
- the preferred range of the average fiber diameter of the conductive fiber 18A is the case of measuring the average fiber diameter of the conductive fiber 18A using the sensor 10. This is the same as the preferred range of the average fiber diameter of the conductive fiber 18A.
- TEM transmission electron microscope
- the conductive fiber dispersion liquid is diluted with water or alcohol according to the dispersion medium so that the concentration of the conductive fibers is 0.05% by mass or less, or the solid content is 0.2% by mass or less. Is preferable.
- one drop of this diluted conductive fiber dispersion is dropped on a grid mesh with a carbon support film for TEM or STEM observation, dried at room temperature, and observed under the above conditions to obtain observation image data. Based on this, the arithmetic mean value is calculated.
- the grid mesh with carbon support film Cu grid model number "# 10-1012 elastic carbon ELS-C10 STEM Cu100P grid specification" is preferable, and it is high because it is strong against electron beam irradiation and has better electron beam transmittance than plastic support film. Those suitable for magnification and resistant to organic solvents are preferable.
- the fiber diameter can be obtained by actually measuring it based on a photograph, or may be calculated by binarizing it based on image data. In the case of actual measurement, a photograph may be printed and enlarged as appropriate. At that time, the conductive fibers are reflected in a darker density than the other components. The measurement point is measured with the outside of the contour as the starting point and the ending point.
- the concentration of conductive fibers shall be determined by the ratio of the mass of conductive fibers to the total mass of the conductive fiber dispersion, and the solid content shall be a component other than the dispersion medium (conductivity) with respect to the total mass of the conductive fiber dispersion. It shall be determined by the mass ratio of textiles, resin components, and other additives).
- the fiber diameter obtained by using the conductive fiber dispersion liquid and the fiber diameter obtained by actual measurement based on the photograph are almost the same value.
- the average fiber length of the conductive fiber 18A can be measured using the conductive fiber dispersion liquid.
- the average fiber length of the conductive fiber 18A is preferably 15 ⁇ m or more and 20 ⁇ m or less in order to suppress the cloudiness. If the average fiber length of the conductive fiber 18A is 15 ⁇ m or more, the first electrode portion having sufficient conductive performance can be formed, and there is a possibility that the effect of white turbidity due to aggregation, the haze value may increase, and the light transmission performance may decrease. Nor. Further, if the average fiber length of the conductive fiber 18A is 20 ⁇ m or less, the coating can be performed without clogging the filter.
- the average fiber length of the conductive fiber 18A is 5 ⁇ m or more and 40 ⁇ m or less, 5 ⁇ m or more and 35 ⁇ m or less, 5 ⁇ m or more and 30 ⁇ m or less, 5 ⁇ m or more and 20 ⁇ m or less, 7 ⁇ m or more and 40 ⁇ m or less, 7 ⁇ m or more and 35 ⁇ m or less, 7 ⁇ m or more and 30 ⁇ m or less, 7 ⁇ m or more and 20 ⁇ m.
- it may be 10 ⁇ m or more and 40 ⁇ m or less, 10 ⁇ m or more and 35 ⁇ m or less, 10 ⁇ m or more and 30 ⁇ m or less, 10 ⁇ m or more and 20 ⁇ m or less, 15 ⁇ m or more and 40 ⁇ m or less, 15 ⁇ m or more and 35 ⁇ m or less, or 15 ⁇ m or more and 30 ⁇ m or less.
- a measurement sample prepared by the following method is used. First, the conductive fiber dispersion liquid was applied to the untreated surface of a B5 size polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m so that the amount of the conductive fibers applied was 10 mg / m 2 , and the dispersion medium was dried. Conductive fibers are placed on the surface of the PET film to fabricate the sensor. Cut out from the center of this sensor to a size of 10 mm x 10 mm.
- PET polyethylene terephthalate
- this cut-out sensor is used on an SEM sample table having a 45 ° inclination (model number "728-45", manufactured by Nissin EM, inclined sample table 45 °, ⁇ 15 mm ⁇ 10 mm, made of M4 aluminum) using silver paste. Stick it flat on the surface of the table. Further, Pt-Pd is sputtered for 20 to 30 seconds to obtain continuity. The image may be difficult to see without an appropriate sputter film. In that case, adjust as appropriate.
- the fiber length can be obtained by actually measuring it based on a photograph, or may be calculated by binarizing it based on image data. When actually measuring based on a photograph, the same method as above shall be used. The fiber length obtained by using the conductive fiber dispersion and the fiber length actually measured based on the photograph are almost the same value.
- the conductive fiber 18A is preferably at least one fiber selected from the group consisting of conductive carbon fibers, metal fibers such as metal nanowires, metal-coated organic fibers, metal-coated inorganic fibers, and carbon nanotubes.
- the conductive fiber 18A is not subjected to a blackening treatment for suppressing metallic luster.
- Examples of the conductive carbon fiber include vapor phase growth method carbon fiber (VGCF), carbon nanotubes, wire cups, wire walls and the like. One kind or two or more kinds of these conductive carbon fibers can be used.
- VGCF vapor phase growth method carbon fiber
- carbon nanotubes carbon nanotubes
- wire cups wire walls
- wire walls wire walls
- One kind or two or more kinds of these conductive carbon fibers can be used.
- the metal fiber examples include stainless steel, Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, Ti, or a metal composed of an alloy thereof.
- Nanowires are preferable, and among metal nanowires, silver nanowires are preferable from the viewpoints of being able to realize a low resistance value, being difficult to oxidize, and being suitable for wet coating.
- the metal fiber for example, a fiber produced by a wire drawing method or a cutting method in which the metal is stretched thinly and long can be used. One kind or two or more kinds of such metal fibers can be used.
- the silver nanowires can be synthesized by liquid phase reduction of a silver salt (eg, silver nitrate) in the presence of a polyol (eg, ethylene glycol) and poly (vinylpyrrolidone).
- a silver salt eg, silver nitrate
- a polyol eg, ethylene glycol
- poly (vinylpyrrolidone) e.g, poly(vinylpyrrolidone.
- Mass production of uniform size silver nanowires is described, for example, in Xia, Y. et al. et al. , Chem. Mater. (2002), 14, 4736-4745 and Xia, Y. et al. et al. , Nanoletters (2003) 3 (7), 955-960.
- the means for producing metal nanowires is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Further, the specific manufacturing method is not particularly limited, and a known manufacturing method can be used. For example, as a method for producing silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc., JP-A-2006-233252 as a method for producing gold nanowires, JP-A-2002-266007 as a method for producing Cu nanowires, and the like, as a method for producing cobalt nanowires. Japanese Patent Publication No. 2004-149871 and the like can be referred to.
- Examples of the metal-coated synthetic fiber include fibers obtained by coating acrylic fiber with gold, silver, aluminum, nickel, titanium, or the like. As such a metal-coated synthetic fiber, one kind or two or more kinds can be used.
- the wiring portion 12B also extends along the first direction DR1 (see FIG. 1). As shown in FIG. 3, the wiring portion 12B contains the conductive fiber 18A as in the first electrode portion 12A, but when the metal nanowire is used as the conductive fiber 18A, the metal nanowire is broken due to the concentration of static electricity. There is a risk.
- the width W2 (neck width) of the wiring portion 12B is preferably 0.35 mm or more.
- the width W2 of the wiring portion 12B is 0.35 mm or more and 5.0 mm or less, 0.35 mm or more and 4.5 mm or less, 0.35 mm from the viewpoint of further suppressing the disconnection and securing the area of the first electrode portion 12A.
- 4.0 mm or less 0.4 mm or more and 5.0 mm or less, 0.4 mm or more and 4.5 mm or less, 0.4 mm or more and 4.0 mm or less, 0.45 mm or more and 5.0 mm or less, 0.45 mm or more and 4.5 mm or less , 0.45 mm or more and 4.0 mm or less, 0.5 mm or more and 5.0 mm or less, 0.5 mm or more and 4.5 mm or less, or 0.5 mm or more and 4.0 mm or less is preferable.
- the width W2 of the wiring portion 12B is preferably 1/2 or less of the width W1 (electrode width) of the first electrode portion 12A from the viewpoint of securing the area of the first electrode portion 12A.
- the upper limit of the width W2 of the wiring portion 12B is preferably 1/3 or less or 1/4 or less of the width W1 of the first electrode portion 12A from the viewpoint of further securing the area of the first electrode portion 12A.
- the wiring portion 12B includes a constituent material (for example, resin) of the electrically insulating layer 14 and a plurality of conductive fibers 18A arranged in the constituent material of the electrically insulating layer 14. Further, since the wiring portion 12B extends along the first direction DR1, the wiring portion 12B is composed of a plurality of conductive fibers 18A, and the conductive fiber pattern 12B1 extending along the first direction DR1 (FIG. 3). See). Since the constituent materials of the electrically insulating layer 14 will be described in the column of the electrically insulating layer 14, the description thereof will be omitted here. Further, since the conductive fiber 18A has been described in the column of the first electrode portion 12A, the description thereof will be omitted.
- the refractive index of the wiring portion 12B-the refractive index of the electrically insulating layer 14 ⁇ is preferably 0.08 or less. That is, the refractive index of the wiring portion 12B is almost the same as the refractive index of the base material 11 and the refractive index of the electrically insulating layer 14.
- the wiring portion 12B contains the conductive fiber 18A, so that the influence of the conductive fiber 18A is not taken into consideration in the refractive index of the wiring portion 12B, and the refractive index of the wiring portion 12B enters the wiring portion 12B.
- the refractive index of the constituent material of the electrically insulating layer 14 Therefore, the interfacial reflection between the wiring portion 12B and the base material 11 and the interfacial reflection between the wiring portion 12B and the electrical insulating layer 14 can be suppressed, so that the wiring portion 12B can be suppressed from being visually recognized.
- the refractive index difference between the wiring portion 12B and the base material 11 and the refractive index difference between the wiring portion 12B and the electrically insulating layer 14 are 0.07 or less, 0.06 or less, or 0.05 or less, respectively.
- the second conductive portion 13 is a portion that is electrically conductive. Since the surface resistance value, the linear resistance value, and the thickness T2 (see FIG. 3) of the second conductive portion 13 are the same as the surface resistance value, the linear resistance value, and the thickness T1 of the first electrode portion 12A, the description thereof will be omitted. And.
- the second conductive portion 13 functions as an electrode in the Y direction in, for example, a projection type capacitance type touch panel.
- the second conductive portion 13 is provided in a rectangular active area, which is a region where the touch position can be detected.
- the second conductive portion 13 has a plurality of second electrode portions 13A and a bridge wiring portion 13B as described above.
- the shape of the second electrode portion 13A is not particularly limited, and may be, for example, a quadrangular shape, a diamond shape, or the like. Since the width W3 (electrode width) of the second electrode portion 13A needs to be the contact area of the finger (about 10 mm ⁇ ) or less, it is preferably 10 mm or less.
- the width W3 of the second electrode portion 13A is 0.35 mm or more and 10 mm or less, 0.35 mm or more and 9 mm or less, 0.35 mm or more and 8.5 mm or less, 0.35 mm or more and 8 mm or less, 0.5 mm or more and 10 mm or less, 0.5 mm.
- the second electrode portion 13A includes a resin portion 17A and a plurality of conductive fibers 18A arranged in the resin portion 17A as shown in FIG. Further, since the second electrode portion 13A is formed in a predetermined shape, the second electrode portion 13A is composed of a plurality of conductive fibers 18A, and the conductive fiber pattern 13A1 (second) formed in a desired shape. It contains a conductive fiber pattern, see FIG. 3). Since the resin portion 17A and the conductive fiber 18A have been described in the column of the first electrode portion 12A, the description thereof will be omitted.
- the bridge wiring portion 13B also extends along the second direction DR2 (see FIG. 1).
- the bridge wiring portion 13B includes a resin portion 17B and conductive fibers 18B (second conductive fibers) arranged in the resin portion 17B. Since the resin portion 17B is the same as the resin portion 17A and the conductive fiber 18B is the same as the conductive fiber 18A, the description thereof will be omitted. Further, since the bridge wiring portion 13B extends along the second direction DR2, the bridge wiring portion 13B is composed of a plurality of conductive fibers 18B, and the conductive fiber pattern 13B1 extending along the second direction DR2 ( (See FIG. 3).
- the width W4 (neck width) of the bridge wiring portion 13B is preferably 0.35 mm or more for the same reason as described in the column of the wiring portion 12B.
- the width W4 of the bridge wiring portion 13B is 0.35 mm or more and 5.0 mm or less, 0.35 mm or more and 4.5 mm or less, 0.
- it is preferably 0.45 mm or more and 4.0 mm or less, 0.5 mm or more and 5.0 mm or less, 0.5 mm or more and 4.5 mm or less, or 0.5 mm or more and 4.0 mm or less.
- the width W4 of the bridge wiring portion 13B is preferably 1/2 or less of the width W3 (electrode width) of the second electrode portion 13A from the viewpoint of securing the area of the second electrode portion 13A.
- the upper limit of the width W4 of the bridge wiring portion 13B is preferably 1/3 or less or 1/4 or less of the width W3 of the second electrode portion 13A from the viewpoint of further securing the area of the second electrode portion 13A.
- the thickness T3 (see FIG. 3) of the bridge wiring portion 13B is preferably 0.16 ⁇ m or more and 1.8 ⁇ m or less. If the thickness of the bridge wiring portion 13B is 0.16 ⁇ m or more, the reliability can be improved by covering the conductive fiber 18B with the resin 17B, and if it is 1.8 ⁇ m or less, flexibility can be ensured.
- the thickness T3 of the bridge wiring portion 13B is 0.2 ⁇ m or more and 1.6 ⁇ m or less, 0.2 ⁇ m or more and 1.4 ⁇ m or less, 0.2 ⁇ m or more and 1.2 ⁇ m or less, 0.3 ⁇ m or more and 1.6 ⁇ m or less, 0.3 ⁇ m or more 1 It is more preferably 0.4 ⁇ m or less, 0.3 ⁇ m or more and 1.2 ⁇ m or less, 0.5 ⁇ m or more and 1.6 ⁇ m or less, 0.5 ⁇ m or more and 1.4 ⁇ m or less, or 0.5 ⁇ m or more and 1.2 ⁇ m or less.
- the thickness of the bridge wiring portion 13B means the distance from the upper surface 14A1 of the electrical insulating layer 14 to the surface of the resin portion 17B.
- the bridge wiring portion 13B contains the same kind of conductive material as the conductive material contained in the second electrode portion 13A.
- the bridge wiring portion 13B also contains conductive fibers.
- the same kind in this specification means that the kind is the same, and it is not necessary that the length and the diameter are the same.
- the mass concentration of the conductive fiber including the bridge wiring portion 13B and measured in a 1 cm square sample centered on the bridge wiring portion 13B is less than 10 wt%.
- the conductive fibers used for measuring the mass concentration may include the conductive fibers 18B in the bridge wiring portion 13B and the conductive fibers in the portion other than the bridge wiring portion 13B.
- the mass concentration of the conductive fibers can be obtained from the ratio of the mass before and after the removal of the organic matter such as the resin portion 17B contained in the bridge wiring portion 13B by the dry ashing method.
- the bridge wiring portion 13B is substantially composed of the resin portion 17B, so that the refractive index of the bridge wiring portion is substantially the refractive index of the resin portion 17B, and the conductive fiber 18B. Is hard to see.
- the mass concentration of the conductive fibers is 0.2 wt% or more and 40 wt% or less, 0.2 wt% or more and 30 wt% or less, 0 from the viewpoint of ensuring the continuity of the bridge wiring portion 13B and making it difficult for the bridge wiring portion 13B to be visually recognized.
- wt% or more and 20 wt% or less 0.2 wt% or more and 15 wt% or less, 0.5 wt% or more and 40 wt% or less, 0.5 wt% or more and 30 wt% or less, 0.5 wt% or more and 20 wt% or less, 0.5 wt% or more and 15 wt % Or less, 1 wt% or more and 40 wt% or less, 1 wt% or more and 30 wt% or less, 1 wt% or more and 20 wt% or less, or 1 wt% or more and 15 wt% or less.
- the conductive fibers 18B are unevenly distributed on the base material 11 side from the position HL which is half the thickness of the bridge wiring portion 13B (resin portion 17B). Since the conductive fibers 18B are unevenly distributed on the base material 11 side, the number of conductive fibers 18B existing on the surface side of the bridge wiring portion 13B is reduced, so that the surface of the bridge wiring portion 13B becomes substantially the resin portion 17B, whereby the bridge The wiring portion 13B is less likely to be visually recognized. Whether or not the conductive fibers 18B are unevenly distributed on the base material 11 side from the position HL which is half the thickness of the bridge wiring portion 13B can be determined as follows.
- a sample for cross-section observation is prepared from the sensor. Specifically, a sample is cut out from the sensor to a size of 2 mm ⁇ 5 mm so as to include the bridge wiring portion. Then, the cut out sample is placed in a silicone-based embedding plate, an epoxy-based resin is poured into the sample, and the entire sample is embedded with the resin. Then, the embedded resin is left at 65 ° C. for 12 hours or more to be cured. Then, using an ultramicrotome (product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.), the delivery thickness is set to 100 nm, and an ultrathin section is prepared.
- Ultramicrotome product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.
- the prepared ultrathin section is collected by a mesh with a collodion membrane (150) and used as a sample for STEM. If continuity is not obtained in this sample, it may be difficult to see the observation image by STEM, so it is preferable to sputter Pt-Pd for about 20 seconds.
- the spatter time can be adjusted as appropriate, but care must be taken because 10 seconds is less and 100 seconds is too much, so that the sputtered metal becomes a particulate foreign matter image.
- STEM scanning transmission electron microscope
- the position of half the thickness of the bridge wiring portion is obtained in each cross-sectional photograph. Then, it is determined whether or not the conductive fibers appearing in the cross-sectional photograph are present on the substrate side of the half position. Specifically, first, in the cross-sectional photograph of the bridge wiring portion in the electron microscope, the conductive fibers appear in a darker color (for example, black) than the resin portion, and therefore, in the cross-sectional photograph of the bridge wiring portion, the conductive fibers are conductive. You can see the fibers. On the other hand, when this cross-sectional photograph is enlarged, pixels appear.
- the pixels have the same size and are square-shaped (lattice-shaped), the number of pixels in which conductive fibers located on the substrate side from the above-mentioned half position are displayed in each cross-sectional photograph and the above-mentioned Count the number of pixels displaying conductive fibers located on the surface side of the bridge wiring from half the position, and position them on the substrate side from the above half position with respect to the total number of pixels displaying conductive fibers. Obtain the ratio of the number of pixels in which the conductive fibers to be displayed are displayed.
- the pixel on which the conductive fiber is displayed straddles the above half position, in each pixel, the portion existing on the base material side from the above half position and the bridge wiring from this position.
- the above ratio obtained from this cross-sectional photograph is defined as the abundance ratio of conductive fibers located on the substrate side from the position of half the thickness of the bridge wiring portion, and when this abundance ratio is 55% or more, it is conductive. It is determined that the fibers are unevenly distributed on the substrate side from the position of half the thickness of the bridge wiring portion.
- This abundance ratio shall be the arithmetic mean value of the abundance ratio obtained from each cross-sectional photograph.
- the conductive fibers are uniformly present in the bridge wiring portion, so even if the abundance ratio of the conductive fibers is obtained by using a cross-sectional photograph of a part of the bridge wiring portion. , It is considered to represent the abundance ratio of conductive fibers in the entire bridge wiring portion.
- the abundance ratio of the conductive fibers located on the substrate side from the position of half the thickness of the bridge wiring portion obtained from the cross-sectional photograph is more preferably 70% or more, further preferably 80% or more.
- Whether or not the conductive fibers 18B are unevenly distributed on the base material 11 side from the position HL which is half the thickness of the bridge wiring portion 13B can also be determined as follows. First, a first sample in which a metal layer such as Pt-Pd, Pt or Au is formed on the surface of the bridge wiring portion of the sensor by a sputtering method, and a second sample in which a metal layer is not formed on the surface of the sensor are obtained. prepare. Then, using the first sample, the thickness of the bridge wiring portion 13B is measured by the measurement method described later.
- a metal layer such as Pt-Pd, Pt or Au
- the proportion of the black portion in the area on the substrate side from the position of half the thickness of the bridge wiring portion is larger than the proportion of the black portion in the region on the surface side of the bridge wiring portion from the above half position. It can be determined that the conductive fibers 18B are unevenly distributed on the base material 11 side from the position HL which is half the thickness of the bridge wiring portion 13B.
- the black portion can be extracted by the brightness.
- the area can be measured only by automatic area measurement because the contrast between metal and organic matter is clearly different.
- Area measurement by the above binarization process is performed by the following procedure.
- the image of the cross-sectional photograph is read by the above software and called to the image window of the software.
- the area ROI (processing range) to be image-processed is selected from half the thickness to the bottom and the top, respectively, and binarized to calculate the total area of the conductive fiber portion.
- the processing range is set by selecting the rectangular ROI button to be drawn from the image toolbar and setting the rectangular ROI in the image window.
- the measured value is output in pixel units, but the measured value can be converted to the actual length and output by calibration.
- the STEM image has a scale display, it can be used to perform calibration in the ROI region. Specifically, from the image toolbar, use the line ROI button to draw a line for the length of the STEM image scale, display the calibration dialog, check the set line, and correspond to the STEM image scale. Set the length and unit to be used. In the binarization process, the region of the conductive fiber portion to be measured and the other regions are separated. Specifically, binarization with two thresholds is selected from the binarization processing menu.
- Conductive fibers have a high density and appear black, and the other parts appear white to gray. Therefore, enter the two density (brightness) thresholds as appropriate (for example, 0 and 80) and use the two thresholds for 2 Execute the quantification process. If the conductive fibers in the actual STEM image and the conductive fibers in the binarized image that are displayed in two colors (such as the conductive fibers turning green) do not match due to the threshold value, the threshold value is used. Is changed as appropriate and corrected until it is closest to the STEM image. For example, the difference between the STEM image and the binarized image is appropriately corrected by selecting fill-in-the-blank or deleting from the binarization processing menu.
- the extraction area can be filled or deleted by setting the threshold value of the area. Clicking on the part you want to delete will give you a threshold to delete it.
- the STEM image and the binarized image are modified and matched as much as possible in the items in the binarized processing menu. It is also possible to manually select and delete unnecessary parts of the binarized image by using the eraser tool button. It is also possible to manually paint the window and correct the coloring using the pen tool button.
- the absolute value of the refractive index difference between the bridge wiring portion 13B and the electrically insulating layer 14 is preferably 0.08 or less. That is, the refractive index of the bridge wiring portion 13B is almost the same as the refractive index of the electrically insulating layer 14. This is because the bridge wiring portion 13B contains the conductive fiber 18B, but the influence of the conductive fiber 18B is not considered in the refractive index of the bridge wiring portion 13B, and the refractive index of the bridge wiring portion 13B is the resin portion 17B. This is because it becomes the refractive index of.
- the interfacial reflection between the bridge wiring portion 13B and the electrical insulating layer 14 can be suppressed, it is possible to suppress the visibility of the bridge wiring portion 13B.
- the conductive fiber 18B is visually recognized, it is not a problem of interfacial reflection but the influence of haze due to scattering of the conductive fiber. Therefore, if the fiber diameter of the conductive fiber 18B is reduced, for example, it may be 30 nm or less. It can be resolved.
- the difference in refractive index between the bridge wiring portion 13B and the electrically insulating layer 14 is more preferably 0.07 or less, 0.06 or less, or 0.05 or less.
- the method for measuring the refractive index of the bridge wiring portion 13B is not particularly limited, and it can be measured by the Becke method.
- the Becke method uses a refraction standard solution with a known refractive index, places a piece collected from the bridge wiring on a slide glass, etc., drops the refraction standard solution onto the piece, and separates the piece with the refraction standard solution. Immerse and observe the state by microscopic observation, and the refraction standard solution that makes it impossible to visually observe the emission lines (Becke lines) generated on the surface of the fragment due to the difference in refraction of the surface of the bridge wiring part and the refraction standard solution.
- This is a method in which the refractive index is the refractive index of the bridge wiring portion.
- the fragments are collected from the surface side of the bridge wiring portion 13B.
- the fragment may include the resin portion 17B and the conductive fiber 18B, or may include only the resin portion 17B that does not contain the conductive fiber 18B.
- the observation by the Becke method is performed by visual observation using a microscope, the observation is performed at a low magnification.
- the conductive fiber 18B cannot be visually observed by observation at such a low magnification. Therefore, the fragment may be only the resin portion 17B that does not contain the conductive fiber 18B.
- the refractive index of the bridge wiring portion 13B was measured for each of the five pieces taken out by the Becke method, and the refraction of the three pieces excluding the maximum value and the minimum value among the measured refractive indexes of the five pieces.
- the arithmetic mean value of the rate is taken as the refractive index of the bridge wiring portion 13B.
- the refractive index of the base material 11, the wiring portion 12B, and the electrically insulating layer 14 can also be measured by the same method as that of the bridge wiring portion 13B.
- the refractive index of the bridge wiring portion 13B is not particularly limited, but may be, for example, 1.45 or more and 1.60 or less.
- the conductive fibers 18B in the bridge wiring portion 13B may be randomly arranged, but may be arranged along the second direction DR2 as shown in FIG. Whether the conductive fibers 18B are lined up along the second direction DR2 is determined by, for example, the surface fiber orientation analysis program (V.8.03) (http://www.enomae.com/FiberOri/index.htm). Can be confirmed using.
- This program is Enomae, T., Han, Y.-H. and Isogai, A., "Nondestructive determination of fiber orientation distribution of fiber surface by image analysis", Nordic Pulp and Paper Research Journal 21 (2): 253 259 (2006) and Enomae, T., Han, Y.-H.
- this fiber orientation distribution is approximated to an ellipse, the angle formed by the major axis of the approximate ellipse and the second direction is defined as the orientation angle, and the ratio of the major axis length to the minor axis length of the approximate ellipse (major axis length / minor axis). Length) is calculated as the orientation strength.
- 10 plane photographs of the conductive fibers of the conductive part by SEM were taken at a magnification of 1000 to 6000 times, the fiber orientation distribution was calculated for each of the 10 photographs, and the fiber orientation distributions were averaged. Calculate the average fiber orientation distribution.
- the orientation angle and orientation strength calculated from the average fiber orientation distribution according to the above are used.
- the orientation angle is 0 ° ⁇ 10 ° (however, the calculated orientation angle is a numerical value from 0 ° to 180 °, but 180 ° to 90 ° is ⁇ 0 ° to ⁇ —. If it is within (read as 90 °) and the orientation strength is 1.2 or more, it can be determined that the conductive fibers 18B are lined up in the second direction.
- the orientation angle is more preferably 0 ° ⁇ 5 ° or less, and the orientation strength is more preferably 1.3 or more, 1.5 or more, or 1.7 or more.
- the conductive fibers 18B of the bridge wiring portion 13B are lined up along the second direction DR2, but the first electrode portion 12A and the conductive fibers 18A of the wiring portion 12B are lined up along the first direction DR1.
- the conductive fibers 18A of the second electrode portion 13A may be arranged along the second direction DR2. Further, when the conductive fibers 18B in the bridge wiring portion 13B are randomly arranged, substantially the same resistance value can be obtained even when the resistance values are measured in various directions.
- the electrical insulating layer 14 is provided between the wiring portion 12B and the bridge wiring portion 13B. By providing such an electrically insulating layer 14, it is possible to suppress the contact between the wiring portion 12B and the bridge wiring portion 13B, so that it is possible to prevent the first conductive portion 12 and the second conductive portion 13 from being electrically short-circuited.
- the size of the electrical insulating layer 14 is preferably larger than the size of the wiring portion 12B and the bridge wiring portion 13B. As a result, the contact between the wiring portion 12B and the bridge wiring portion 13B can be reliably suppressed.
- the thickness of the electrical insulating layer 14 is preferably 160 nm or more and 2000 nm or less. If the thickness of the electrical insulating layer 14 is 160 nm or more, the contact between the wiring portion 12B and the bridge wiring portion 13B can be reliably suppressed, and if the thickness of the electrical insulating layer 14 is 2000 nm or less, cracks during bending are suppressed. can do.
- the thickness of the electrical insulating layer 14 is 160 nm or more and 2000 nm or less, 160 nm or more and 1500 nm or less, from the viewpoint of more reliably suppressing the contact between the wiring portion 12B and the bridge wiring portion 13B and suppressing cracks when bent.
- the thickness of the electrically insulating layer 14 is randomly set at 10 points from a cross-sectional photograph of the electrically insulating layer taken by using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), or a scanning electron microscope (SEM). Is measured, and the average value of the thicknesses of 8 points excluding the maximum value and the minimum value among the measured thicknesses of 10 points is used.
- the electrically insulating layer generally has uneven thickness. In the present embodiment, since the electrically insulating layer is used for optics, the thickness unevenness is preferably ⁇ 10% or less on average thickness, and more preferably ⁇ 5% or less on average thickness.
- the thickness of the electrically insulating layer 14 When measuring the thickness of the electrically insulating layer 14 using a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), it can be measured by the same method as the method for measuring the thickness of the first conductive portion 12. However, the magnification when taking a cross-sectional photograph of the electrically insulating layer 14 is 100 to 20,000 times.
- the cross section of the electrically insulating layer 14 can be obtained by using an ultramicrotome (product name “Ultramicrotome EMUC7”, manufactured by Leica Microsystems) or the like. It is good.
- the TEM and STEM samples are set to a delivery thickness of 100 nm using the above-mentioned ultramicrotome, and ultrathin sections are prepared.
- the prepared ultrathin section is collected by a mesh with a collodion membrane (150) and used as a sample for TEM or STEM.
- a pretreatment for easy cutting such as embedding a sample in resin may be performed.
- the constituent material of the electrically insulating layer 14 is not particularly limited as long as it is an electrically insulating material having electrical insulation, but if the sensor is for optical use, it is preferably a material having light transmission.
- the constituent material of the electric insulating layer 14 is a resin
- the resin may be the same as the resin described in the column of the first electrode portion 12A, and thus the description thereof will be omitted here.
- the take-out wiring portion 15 is electrically connected to the first electrode portion 12A. Specifically, the take-out wiring portion 15 is electrically connected to the first electrode portion 12A at the end of the plurality of first electrode portions 12A arranged along the first direction DR1. The take-out wiring portion 15 shown in FIG. 1 is formed on the first electrode portion 12A and the base material 11.
- the take-out wiring portion 15 is not particularly limited as long as it is made of a conductive material.
- the take-out wiring portion may be composed of a cured conductive paste.
- the conductive paste is not particularly limited, and examples thereof include silver paste and the like.
- the conductive fibers 18A of the first electrode portion 12A and the second electrode portion 13A are covered with the resin portion 17A, but the first electrode portion 12A and the second electrode are as shown in the sensor 30 shown in FIG.
- the conductive fibers 18A of the portion 13A may be covered with the resin portions 17A and 17C (see FIGS. 11 and 12).
- the thickness of the resin portion 17C is preferably 40 nm or more and 100 nm or less.
- the thickness of the resin portion 17C is 40 nm or more, the peeling of the conductive fiber 18A as described above can be suppressed by winding the laminate in which the resin portion 17C is formed on the conductive fiber 18A. can. Further, the thinner the resin portion 17C, the more the conductive fibers 18A are exposed from the resin portion 17C. Therefore, if the thickness of the resin portion 17C is 100 nm or less, the thickness of the resin portion 17C is thin, so that the portion of the conductive fiber 18A exposed from the resin portion 17C increases, which causes the first conductive portion 12 and the take-out wiring portion. The contact resistance value of 15 can be reduced.
- the sensor 10 does not have an electrically insulating wall portion between the first conductive portion 12 and the second electrode portion 13A, but the first conductive portion 12 and the second electrode portion as in the sensor 40 shown in FIG.
- An electrically insulating wall portion 41 may be provided between the 13A.
- the wall portion 41 has a function of guiding the filling of the first conductive portion 12 and the second electrode portion 13A, and also has a function of suppressing an electrical short circuit between the first conductive portion 12 and the second electrode portion 13A.
- the wall portion 41 is made of an electrically insulating material. Examples of the electrically insulating material include resin. The resin is not particularly limited, and examples thereof include the resin described in the column of the electrically insulating layer.
- the width W5 of the wall portion 41 is preferably 5 ⁇ m or more and 500 ⁇ m or less.
- the width W5 of the wall portion 41 is 5 ⁇ m or more, it is less likely to fall down when filled with the conductive fiber dispersion liquid described later, and an electrical short circuit can be further suppressed.
- the width W of the wall portion 41 is 500 ⁇ m or less, a fine pattern can be arranged.
- the width W of the wall portion 41 is 5 ⁇ m or more and 300 ⁇ m or less, 5 ⁇ m or more and 200 ⁇ m or less, 5 ⁇ m or more and 100 ⁇ m or less, 10 ⁇ m or more and 500 ⁇ m or less, 10 ⁇ m or more and 300 ⁇ m or less, 10 ⁇ m or more and 200 ⁇ m or less, 10 ⁇ m or more and 100 ⁇ m or less, 20 ⁇ m or more and 500 ⁇ m or less, 20 ⁇ m or more.
- the width W5 of the wall portion 41 was measured by randomly measuring the width of 10 points from a cross-sectional photograph of the wall portion 41 taken using a scanning transmission electron microscope (STEM) or a transmission electron microscope (TEM). Of the widths of 10 points, the arithmetic average value of the widths of 8 points excluding the maximum value and the minimum value is used.
- the method of taking a cross-sectional photograph of the wall portion 41 is the same as the method of taking a cross-sectional photograph of the first conductive portion 12.
- the thickness of the wall portion 41 is preferably larger than the thickness of the first conductive portion 12 and the second electrode portion 13A.
- the thickness T of the wall portion 41 is larger than the thickness of the first electrode portion 12A.
- the thickness of the wall portion 41 is the length of the wall portion 41 in the normal direction of the base material 11, and the thickness of the first conductive portion 12 and the second electrode portion 13A is the first conductivity in the normal direction of the base material 11.
- the length is the length of the portion 12 and the second electrode portion 13A.
- the thickness of the wall portion 41 is preferably 0.1 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the wall portion 41 is 0.1 ⁇ m or more, it is possible to prevent the conductive fiber dispersion liquid from overflowing when the conductive fiber dispersion liquid described later is filled.
- the thickness of the wall portion 41 is 50 ⁇ m or less, the foldability can be guaranteed and the followability at the time of bonding can be guaranteed.
- the thickness of the wall portion 41 is 0.1 ⁇ m or more and 40 ⁇ m or less, 0.1 ⁇ m or more and 30 ⁇ m or less, 0.1 ⁇ m or more and 25 ⁇ m or less, 0.2 ⁇ m or more and 100 ⁇ m or less, 0.2 ⁇ m or more and 40 ⁇ m or less, 0.2 ⁇ m or more and 30 ⁇ m or less, 0.
- ⁇ m or more and 25 ⁇ m or less 0.5 ⁇ m or more and 100 ⁇ m or less, 0.5 ⁇ m or more and 40 ⁇ m or less, 0.5 ⁇ m or more and 30 ⁇ m or less, 0.5 ⁇ m or more and 25 ⁇ m or less, 1 ⁇ m or more and 100 ⁇ m or less, 1 ⁇ m or more and 40 ⁇ m or less, 1 ⁇ m or more and 30 ⁇ m or less, or It is preferably 1 ⁇ m or more and 25 ⁇ m or less.
- the thickness of the wall portion 41 was measured by randomly measuring the thickness at 10 points from a cross-sectional photograph of the wall portion 41 taken using a scanning transmission electron microscope (STEM) or a transmission electron microscope (TEM). It is the arithmetic average value of the thickness of 8 points excluding the maximum and minimum values in the thickness of the points.
- the method of taking a cross-sectional photograph of the wall portion 41 is the same as the method of taking a cross-sectional photograph of the first conductive portion 12.
- the absolute value of the refractive index difference between the wall portion 41 and the base material 11 is preferably 0.2 or less.
- the refractive index of the wall portion 41 can be measured by the same method as the refractive index of the first conductive portion 12 and the like.
- the wall portion 41 can be formed by applying a composition for a wall portion containing a polymerizable compound such as an ionizing radiation polymerizable compound to the first surface 11A of the base material 11 and curing it.
- the wall composition can be applied, for example, by flexographic printing, offset printing, gravure printing, screen printing, inkjet method, or dispenser.
- the sensor 10 can be manufactured, for example, as follows. First, as shown in FIG. 15A, the region on the first surface 11A of the base material 11 on which the first conductive portion 12 and the second electrode portion 13A should be formed is made conductive by using a dispenser or an inkjet method. A conductive fiber dispersion liquid containing the fibers 18B and a dispersion medium is applied and dried to dispose the conductive fibers 18A in the region where the first conductive portion 12 and the second electrode portion 13A are to be formed.
- the conductive fiber dispersion liquid may contain a resin component composed of a thermoplastic resin or a polymerizable compound in addition to the conductive fiber 18A and the dispersion medium.
- resin component refers to resin (however, to prevent self-welding of conductive fibers covering the conductive fibers and reaction with substances in the atmosphere, etc., during the synthesis of the conductive fibers.
- the concept includes a component that can be polymerized to become a resin, such as a polymerizable compound.
- the dispersion medium may be either an aqueous dispersion medium or an organic dispersion medium.
- the content of the resin component in the conductive fiber dispersion liquid is too large, the resin component may enter between the conductive fibers and the conduction of the conductive portion may be deteriorated. In particular, when the film thickness of the conductive portion is thin, the continuity of the conductive portion tends to deteriorate.
- the organic dispersion medium is used, the resin content in the conductive fiber dispersion liquid is smaller than when the aqueous dispersion medium is used.
- the organic dispersion medium may contain less than 10% by mass of water.
- the organic dispersion medium is not particularly limited, but is preferably a hydrophilic organic dispersion medium.
- the organic dispersion medium include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, propanol and butanol; acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone.
- Ketones such as diisobutylketone; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran, dioxane and diethyl ether; N, N-dimethylformamide, N-methylpyrrolidone (NMP), N, N-dimethylacetamide And the like; examples thereof include halogenated hydrocarbons such as ethylene chloride and chlorbenzene. Among these, alcohols are preferable from the viewpoint of stability of the conductive fiber dispersion liquid.
- thermoplastic resin examples include acrylic resins; polyester resins such as polyethylene terephthalate; aromatic resins such as polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, and polyamideimide.
- Polyurethane-based resin Epoxy-based resin; Polyethylene-based resin; Acrylonitrile-butadiene-styrene copolymer (ABS); Cellulous-based resin; Polyvinyl chloride-based resin; Polyacetate-based resin; Polynorbornene-based resin; Synthetic rubber; Fluorine-based Examples include resin.
- Examples of the polymerizable compound that may be contained in the conductive fiber dispersion include the same polymerizable compounds as those described in the column of the electrically insulating layer 14, so the description thereof will be omitted here.
- the surface of the conductive fibers 18A After arranging the conductive fibers 18A, the surface of the conductive fibers 18A to be the first electrode portion 12A located at the end of the plurality of first electrode portions 12A along the first direction DR1 by using a dispenser or an inkjet method.
- a conductive paste is applied to a part of the surface to form a coating film.
- the conductive paste is cured by heating at a temperature of 80 ° C. or higher and 150 ° C. or lower for a predetermined time to form the take-out wiring portion 15 shown in FIG. 15 (B).
- the composition for the electric insulating layer is applied to the conductive fibers 18A arranged in the region where the wiring portion 12B should be formed by using a dispenser or an inkjet method, dried, and coated.
- the composition for an electrically insulating layer contains a polymerizable compound and a solvent, but in addition, a polymerization initiator or a reaction inhibitor may be added, if necessary.
- the coating film is irradiated with ionizing radiation such as ultraviolet rays to polymerize (crosslink) the polymerizable compound to cure the coating film, thereby forming the electrically insulating layer 14 shown in FIG. 16 (A).
- the conductive fiber dispersion liquid containing the conductive fibers 18B and the dispersion medium is bridged on the surface of the electrically insulating layer 14 and the surface of the conductive fiber pattern 13A1 by using a dispenser or an inkjet method.
- the wiring portion 13B is applied to the region to be formed, dried, and the conductive fibers 18B shown in FIG. 16B are arranged.
- the viscosity of the conductive fiber dispersion is preferably 0.01 Pa ⁇ s or more and 20 Pa ⁇ s or less. If the viscosity of the conductive fiber dispersion is 0.01 Pa ⁇ s or more, for example, when the conductive fiber dispersion is applied to the three-dimensional surface described later, the conductive fiber dispersion does not easily flow down, and the conductive fiber dispersion is conductive at a desired location. The textile dispersion can be retained.
- the viscosity of the conductive fiber dispersion liquid is 20 Pa ⁇ s or less, clogging of the conductive fiber dispersion liquid can be suppressed when the conductive fiber dispersion liquid is applied using a dispenser or an inkjet method, and the liquid is discharged.
- the viscosity of the conductive fiber dispersion is 0.01 Pa ⁇ s or more and 10 Pa ⁇ s or less, 0.01 Pa ⁇ s or more and 8 Pa ⁇ s or less, 0.01 Pa ⁇ s or more and 5 Pa ⁇ s or less, 0.01 Pa ⁇ s or more and 1 Pa ⁇ s.
- the viscosity of the conductive fiber dispersion can be measured using a vibration viscometer (for example, product name "VM-10A-M", manufactured by Sekonic Corporation). Specifically, the viscosity of the conductive fiber dispersion was measured 10 times in an environment of a temperature of 25 ° C. and a relative humidity of 30% to 70%, and the maximum value and the minimum value were excluded from the measured 10 viscosities. Viscosity is determined by calculating the arithmetic average of the eight viscosities.
- the conductive fiber dispersion liquid is applied using a contact dispenser.
- the conductive fibers 18B of the bridge wiring portion 13B can be arranged in the second direction DR2. Specifically, while moving the discharge portion of the contact type dispenser to the second direction DR2 relative to the base material 11, the conductive fiber dispersion liquid is discharged from the discharge portion along the second direction DR2. Apply the conductive fiber dispersion liquid linearly. As a result, conductive fibers are arranged.
- the "contact type dispenser" in the present specification is a dispenser of a type in which the discharge portion directly contacts the liquid pool of the conductive fiber dispersion liquid formed on the surface to be coated.
- the discharge unit is configured to discharge the conductive fiber dispersion liquid, for example, by pushing the plunger with pneumatic pressure.
- Examples of the discharge unit include a syringe and a nozzle.
- the relative moving speed of the discharge portion with respect to the base material 11 is preferably 5 mm / sec or more and 500 mm / sec or less.
- the relative moving speed is 5 mm / sec or more, the wet spreading of the conductive fiber 18B can be suppressed, and when it is 500 mm / sec or less, the conductive fiber dispersion liquid can be discharged linearly without running out.
- the relative movement speed is 5 mm / sec or more and 450 mm / sec or less, 5 mm / sec or more and 420 mm / sec or less, 5 mm / sec or more and 400 mm / sec or less, 10 mm / sec or more and 500 mm / sec or less, 10 mm / sec or more and 450 mm / sec or less.
- the "relative moving speed of the ejection portion with respect to the base material” is the relative moving speed in the direction of forming the linear coated portion.
- the distance (coating gap) between the discharged portion and the electrically insulating layer at the time of discharging the conductive fiber dispersion liquid is preferably 5 ⁇ m or more and 80 ⁇ m or less. If the coating gap is 5 ⁇ m or more, the contact between the discharge portion and the electrically insulating layer can be suppressed, and if it is 80 ⁇ m or less, the conductive fiber dispersion liquid can be discharged linearly without running out.
- the coating gap is 5 ⁇ m or more and 70 ⁇ m or less, 5 ⁇ m or more and 60 ⁇ m or less, 5 ⁇ m or more and 50 ⁇ m or less, 10 ⁇ m or more and 80 ⁇ m or less, 10 ⁇ m or more and 70 ⁇ m or less, 10 ⁇ m or more and 60 ⁇ m or less, 10 ⁇ m or more and 50 ⁇ m or less, 15 ⁇ m or more and 80 ⁇ m or less, 15 ⁇ m or more and 70 ⁇ m or less.
- the diameter of the discharge port of the discharge portion is preferably 20 ⁇ m or more and 200 ⁇ m or less.
- the diameter of the discharge port is 20 ⁇ m or more, clogging of the conductive fiber dispersion liquid at the discharge port can be suppressed, and when the diameter is 200 ⁇ m or less, the outflow of the conductive fiber dispersion liquid can be suppressed.
- the diameter of the discharge port is 20 ⁇ m or more and 160 ⁇ m or less, 20 ⁇ m or more and 120 ⁇ m or less, 20 ⁇ m or more and 100 ⁇ m or less, 22 ⁇ m or more and 200 ⁇ m or less, 22 ⁇ m or more and 160 ⁇ m or less, 22 ⁇ m or more and 120 ⁇ m or less, 22 ⁇ m or more and 100 ⁇ m or less, 24 ⁇ m or more and 200 ⁇ m or less, 24 ⁇ m or more and 160 ⁇ m.
- the discharge pressure of the conductive fiber dispersion liquid at the time of discharge of the conductive fiber dispersion liquid is preferably 1 kPa or more and 50 kPa or less.
- the discharge pressure is 1 kPa or more, the conductive fiber dispersion liquid can be discharged without clogging, and when the discharge pressure is 50 kPa or less, excessive pressure can be suppressed from being applied to the conductive fiber dispersion liquid.
- the discharge pressure is 1 kPa or more and 40 kPa or less, 1 kPa or more and 30 kPa or less, 1 kPa or more and 20 kPa or less, 2 kPa or more and 50 kPa or less, 2 kPa or more and 40 kPa or less, 2 kPa or more and 30 kPa or less, 2 kPa or more and 20 kPa or less, 4 kPa or more and 50 kPa or less, 4 kPa or more and 40 kPa or less.
- the drying temperature of the conductive fiber dispersion is preferably 60 ° C. or higher and 200 ° C. or lower.
- the drying temperature of the conductive fiber dispersion liquid is 60 ° C. or higher, for example, the types of base materials that can be used when the conductive fiber dispersion liquid is applied to the three-dimensional surface described later will increase. Further, if the drying temperature of the conductive fiber dispersion is 200 ° C. or lower, the dimensional change of the base material can be suppressed.
- the drying temperature of the conductive fiber dispersion is 60 ° C or higher and 180 ° C or lower, 60 ° C or higher and 160 ° C or lower, 60 ° C or higher and 150 ° C or lower, 80 ° C or higher and 200 ° C or lower, 80 ° C or higher and 180 ° C or lower, 80 ° C or higher and 160 ° C.
- 100 ° C. or higher and 160 ° C. or lower, or 100 ° C. or higher and 150 ° C. or lower is more preferable.
- the resin composition is applied so as to cover the conductive fibers 18A and 18B using a die coater, a dispenser or an inkjet method, and dried to form a coating film.
- the resin composition contains a polymerizable compound and a solvent, but in addition, a polymerization initiator or a reaction inhibitor may be added, if necessary.
- the coating film is irradiated with ionizing radiation such as ultraviolet rays to polymerize (crosslink) the polymerizable compound to cure the coating film to form a resin layer 17 containing the resin portions 17A and 17B shown in FIG. do. As a result, the sensor 10 shown in FIG. 1 is obtained.
- the conductive fiber dispersion liquid containing the conductive fiber 18A and the conductive fiber dispersion liquid containing the conductive fiber 18B are applied by using a dispenser or an inkjet method.
- a dispenser or an inkjet method For example, a spray coating method, a dip coating method, etc.
- These conductive fiber dispersions may be applied by a drop casting method or the like.
- the dispenser or the inkjet method is used, the agglomeration of conductive fibers can be suppressed, fine patterns can be formed, and a coating film having excellent uniformity can be obtained. Therefore, the dispenser or the inkjet method is used.
- the applied coating is particularly preferred.
- the sensor 30 can also be manufactured by, for example, the following method. First, as shown in FIG. 18A, the conductive fiber 18A and the conductive fiber dispersion liquid containing the dispersion medium are applied to the entire first surface 11A of the base material 11 by a coating device such as a die coater. After drying, the conductive fibers 18A are placed.
- the resin composition containing the polymerizable compound and the solvent is applied to the entire surface of the conductive fiber 18A by a coating device such as a die coater, and dried to form a coating film of the resin composition.
- the coating film is irradiated with ionizing radiation such as ultraviolet rays to polymerize (crosslink) the polymerizable compound to cure the coating film to form the resin shown in FIG. 18B to form the resin portion 17C.
- ionizing radiation such as ultraviolet rays to polymerize (crosslink) the polymerizable compound to cure the coating film to form the resin shown in FIG. 18B to form the resin portion 17C.
- ionizing radiation such as ultraviolet rays
- a conductive paste is applied to the surface of the resin portion 17C on the region where the first electrode portion 12A is to be formed by using a screen printing method or the like to form a coating film.
- the conductive paste is cured by heating at a temperature of 80 ° C. or higher and 150 ° C. or lower for a predetermined time to obtain the cured conductive paste 52 shown in FIG. 19 (A).
- the conductive layer 51 and the cured conductive paste 52 are patterned to form the conductive fibers 18A in the shapes of the first conductive portion 12 and the second electrode portion 13A, and the take-out wiring portion is formed.
- Form 15 the regions to be the first conductive portion 12 and the second electrode portion 13A are irradiated with a laser beam (for example, an infrared laser) to etch the conductive layer 51 by dry etching, and the cured conductive paste.
- a laser beam (for example, an infrared laser) is irradiated so that the 52 is located on a part of the surface of the first electrode portion 12A located at the end of the plurality of first electrode portions 12A along the first direction DR1.
- the cured conductive paste 52 is etched.
- the heat of the laser light sublimates the conductive fibers 18A contained in this region.
- the sublimated conductive fiber 18A breaks through the resin portion 17C and is discharged to the outside of the resin portion 17C.
- the conductive layer 51 and the cured conductive paste 52 are patterned by dry etching, but the conductive layer 51 and the cured conductive paste 52 may be patterned by the photolithography method.
- the bridge wiring part is made of an oxide-based material such as ITO, cracks and cracks may occur when the sensor is folded, so good flexibility cannot be obtained.
- the bridge wiring portion 13B contains the conductive fiber 18B, good flexibility can be obtained.
- the bridge wiring portion 13B includes the conductive fiber 18B, but since the conductive fiber 18B is arranged in the resin portion 17B, most of the bridge wiring portion 13B becomes the resin portion 17B. There is. Therefore, the refractive index of the bridge wiring portion 13B is substantially the same as the refractive index of the resin portion 17B. This makes it possible to make the bridge wiring portion invisible.
- the bridge wiring portion 13B includes the conductive fiber 18B which is the same kind of conductive material as the conductive material 18A contained in the second electrode portion 13A, but the conductive fiber 18B is a conductive material. Since it is arranged in the resin portion 17B, most of the bridge wiring portion 13B is the resin portion 17B. Therefore, the refractive index of the bridge wiring portion 13B is substantially the same as the refractive index of the resin portion 17B. As a result, the difference in refractive index between the second electrode portion 13A and the bridge wiring portion 13B can be reduced, so that the bridge wiring portion 13B can be made invisible.
- the second electrode portion and the bridge wiring portion are formed by etching, but if the second electrode portion and the bridge wiring portion are made of the same conductive material, the bridge wiring portion is etched. Since the second electrode portion is also etched, it is difficult to configure the second electrode portion and the bridge wiring portion with the same kind of conductive material.
- the first electrode portion 12A, the wiring portion 12B, the second electrode portion 13A and the bridge wiring portion 13B are formed by applying the conductive fiber dispersion liquid, so that it is necessary to perform patterning by etching. not.
- unnecessary conductive fibers 18A and 18B can be reduced, so that cost can be reduced.
- etching since etching is not required, the number of steps can be reduced and the manufacturing time can be shortened.
- the wall portion 41 is formed between the first conductive portion 12 and the second electrode portion 13A, the migration of the conductive fibers from the first conductive portion 12 and the second electrode portion 13A is carried out on the wall. It can be suppressed by the section 41, whereby an electrical short circuit between the first conductive section 12 and the second electrode section 13A can be suppressed.
- the die coat method or the bar coat method is used when applying the conductive fiber dispersion liquid, but when the conductive layer is formed by using the die coat method or the bar coat method, the conductive fibers are randomly arranged. Become. Therefore, even if the conductive layer is etched to form a patterned linear conductive portion, the conductive fibers are arranged randomly. Further, when the conductive fiber dispersion liquid is applied by a non-contact dispenser or an inkjet method to form a linear conductive portion, although the conductive fibers have a directionality for each droplet, the applied conductivity is obtained. Since there is no directionality in the entire fiber, the conductive fibers in the conductive portion are arranged randomly.
- the conductive fibers in the conductive portion are randomly arranged.
- the linear resistance value is lower than when the conductive fibers are randomly arranged.
- the conductive fiber dispersion liquid containing the conductive fibers 18B is transferred from the discharge portion to the first surface of the base material 11.
- the conductive fibers 18B can be lined up along the moving direction of the ejection portion or the base material 11.
- the discharge portion of the dispenser has a narrow opening, so that when the conductive fiber dispersion liquid is applied, the conductive fibers do not lie down and the longitudinal direction of the conductive fibers 18B is the normal direction of the base material 11. It is considered that this is because the conductive fibers are applied in a state of facing. Therefore, since the line resistance value of the bridge wiring portion 13B can be lowered, the content of the conductive fibers 18B in the bridge wiring portion 13B can be reduced. As a result, it is possible to reduce the cost while realizing the desired line resistance value.
- the conductive portion is formed in a layered shape. Therefore, in order to form the linear conductive portion, patterning by etching is required. .. Since patterning by etching removes an unnecessary portion of the conductive portion, the conductive fibers contained in the portion removed by etching are wasted.
- the conductive fiber dispersion liquid is directly applied linearly, it is not necessary to perform patterning by etching. As a result, the waste of the conductive fibers 18A and 18B can be reduced, so that the cost can be reduced. Further, since etching is not required, the number of steps can be reduced and the manufacturing time can be shortened.
- the line resistance value of the bridge wiring portion 13B can be reduced, and this result.
- the content of conductive fibers 18B in the bridge wiring portion 13B can be reduced. As a result, it is possible to reduce the cost while realizing the desired line resistance value.
- the conductive fiber dispersion liquid is filled between the wall portions 41 to form the first conductive portion 12 and the second electrode portion 13A, it is not necessary to perform patterning by etching. As a result, unnecessary conductive fibers 18A can be reduced, so that cost can be reduced. Further, since etching is not required, the number of steps can be reduced and the manufacturing time can be shortened.
- the migration of the conductive material from the first conductive portion 12 and / or the second electrode portion 13A can be suppressed by the wall portion 41, whereby an electrical short circuit between the first conductive portion 12 and the second conductive portion 13 can be suppressed.
- FIG. 20 is a schematic configuration diagram of an image display device according to the present embodiment.
- the image display device 60 shown in FIG. 20 includes a display element 70, a circularly polarizing plate 80, a sensor 10, and a cover member 90 in this order toward the observer side.
- the sensor 10 functions as a touch panel, and the bridge wiring portion 13B is arranged so as to be closer to the observer side than the first conductive portion 12.
- the display element 70 and the circular polarizing plate 80, the circular polarizing plate 80 and the sensor 10, and the sensor 10 and the cover member 90 are adhered to each other via the adhesive layers 91 to 93.
- adhesive is a concept including adhesion.
- Examples of the display element 70 include a liquid crystal display element, an organic light emitting diode element (hereinafter, also referred to as an “OLED element”), an inorganic light emitting diode element, a micro LED, a plasma element, and the like.
- the organic light emitting diode element a known organic light emitting diode element can be used.
- the liquid crystal display element may be an in-cell touch panel liquid crystal display element having a touch panel function in the element.
- the circular polarizing plate 80 includes, for example, a first retardation film, an adhesive layer, a second retardation film, an adhesive layer, and a polarizing plate in this order toward the observer side.
- the thickness of the circular polarizing plate 80 is preferably 100 ⁇ m or less from the viewpoint of reducing the thickness.
- the thickness of the circularly polarizing plate 80 is 20 ⁇ m or more and 100 ⁇ m or less, 20 ⁇ m or more and 95 ⁇ m or less, 20 ⁇ m or more and 90 ⁇ m or less, 20 ⁇ m or more and 80 ⁇ m or less, 30 ⁇ m or more and 100 ⁇ m or less, 30 ⁇ m or more and 95 ⁇ m or less, and 30 ⁇ m or more and 90 ⁇ m.
- the thickness of the circularly polarizing plate 80 is determined by photographing the cross section of the circularly polarizing plate 80 using a scanning electron microscope (SEM), measuring the thickness of the circularly polarizing plate 80 at 10 points in the image of the cross section, and measuring the thickness of the circularly polarizing plate 80 at 10 points. It can be obtained by obtaining the arithmetic average value of the thickness at eight points excluding the maximum value and the minimum value in the thickness.
- SEM scanning electron microscope
- the circular polarizing plate 80 may be incorporated into the image display device by either a chip cut method or a roll-to-panel method.
- the chip cutting method is a method in which a circularly polarizing plate having a predetermined size is cut out from a roll-shaped circularly polarizing plate according to the size of an image display device and attached to a cover member such as glass via an adhesive layer.
- the roll-to-panel method is a method in which a roll-shaped circularly polarizing plate is cut while being sent out in a production line of an image display device, and is bonded to a cover member such as glass via an adhesive layer.
- the surface 90A of the cover member 90 is the surface 60A of the image display device 60.
- the cover member 90 may be a cover film made of a cover glass or a resin.
- the cover member 90 is made of flexible glass or flexible resin.
- the flexible resin include a polyimide resin, a polyamide-imide resin, a polyamide resin, a polyester resin (for example, a polyethylene terephthalate resin and a polyethylene naphthalate resin), or a mixture of two or more of these resins. Can be mentioned.
- the adhesive layers 91 to 93 can be composed of a cured product of a liquid ionizing radiation curable adhesive (for example, OCR: Optically Clear Resin) or a pressure-sensitive adhesive (for example, OCA: Optical Clear Adhesive) containing a polymerizable compound. Is.
- a liquid ionizing radiation curable adhesive for example, OCR: Optically Clear Resin
- a pressure-sensitive adhesive for example, OCA: Optical Clear Adhesive
- the conductor is a three-dimensional object having a three-dimensional surface (three-dimensional surface), is provided on the three-dimensional surface, is arranged in the resin portion and the resin portion, is composed of a plurality of conductive fibers, and follows the shape of the three-dimensional surface. It includes a conductive portion including a conductive fiber pattern (first conductive fiber pattern).
- a conductor is not particularly limited as long as it has a conductive fiber pattern that follows the shape of the three-dimensional surface, and examples thereof include the sensor 10. "Following” in this case means that the conductive fiber patterns as a whole are along the three-dimensional surface and are electrically connected. Therefore, each conductive fiber does not have to be along the three-dimensional surface.
- the conductive fiber pattern does not have to be exactly along the shape of the three-dimensional surface, and if it is substantially along the shape, it is assumed to be along the three-dimensional surface. Whether or not the conductive fiber patterns are electrically connected can be confirmed by measuring the linear resistance value. For example, if the linear resistance value of the conductive fiber pattern is 1000000 ⁇ or less, it can be determined that the conductive fiber patterns are electrically connected.
- the use of the conductor is not particularly limited, but the conductor can be incorporated into a sensor, for example, and can be used for various articles (for example, an image display device or a biosensor).
- the use of the sensor is the same as the use of the sensor described in the section of the sensor above.
- the conductor 100 includes a three-dimensional object 101 as shown in FIG.
- the three-dimensional object 101 includes a base material 11, a plurality of first electrode portions 12A provided on the first surface 11A side of the base material 11, and arranged in the first direction DR1, and adjacent first electrodes.
- the first conductive portion 12 having the wiring portion 12B for electrically connecting the portions 12A to each other is provided on the first surface 11A side of the base material 11, is separated from the first conductive portion 12, and intersects with the first direction DR1. It is composed of a plurality of conductive fiber patterns 13A1 arranged in the second direction DR2 and an electrically insulating layer 14 arranged on the wiring portion 12B.
- the three-dimensional object 101 has a three-dimensional surface 101A.
- the three-dimensional surface is not particularly limited, and examples thereof include a three-dimensional surface obtained by combining two planes, a curved surface, a combination of a plane and a curved surface, and a surface having a step. Normally, it is very difficult to apply conductive fibers to a shape having a step of 50 ⁇ m or more, but since it can be applied by application using a dispenser or an inkjet method, the three-dimensional surface has a step of 50 ⁇ m or more. (For example, a step of 1 mm or more or a step of 1 cm or more) may be provided. In FIG.
- both the wiring portion 12B and the conductive fiber pattern 13A1 are formed on the first surface 11A of the base material 11, and the electrical insulating layer 14 is formed on the wiring portion 12B, so that the electrical insulating layer is formed.
- the position of the surface 14A of 14 is higher than the position of the surface 13A11 of the conductive fiber pattern 13A1. Therefore, the surface composed of the surface 14A of the electrically insulating layer 14 and the surface 13A11 of the conductive fiber pattern 13A1 is a three-dimensional surface 101A.
- the upper surface 14A1 is planar, and the side surface 14A2 is substantially parallel to the normal direction DR3 of the base material 11.
- the upper surface 14A1 of the electrical insulating layer 14 may be curved, and the side surface 14A2 may be inclined with respect to the normal direction DR3 of the base material 11.
- the members having the same reference numerals as those in FIG. 3 are the same as the members shown in FIG. 3, and therefore the description thereof will be omitted.
- the conductive portion 102 includes the conductive fiber pattern 102A, in which the conductive fiber pattern 102A straddles the wiring portion 12B and is adjacent to each other so that the adjacent conductive fiber patterns 13A1 are electrically connected to each other. It is formed on the surface 14A of the electrically insulating layer 14 between the surface 13A11 of the textile pattern 13A1 and the conductive fiber pattern 13A1. That is, the conductive portion 102 is a bridge wiring portion 13B. When the conductive portion 102 is the bridge wiring portion 13B, the conductive portion 102 includes the resin portion 17B in addition to the conductive fiber pattern 102A, but the conductive portion includes the conductive fiber pattern. It does not have to have a resin part.
- the three-dimensional object 101 is composed of the base material 11 and the like, but the three-dimensional object 101 is not particularly limited as long as it has a shape having a three-dimensional surface.
- the three-dimensional surface 101A is composed of the surface 14A of the electric insulating layer 14 and the surface 13A11 of the conductive fiber pattern 13A1, but the surface is not particularly limited to this configuration.
- the three-dimensional object may be a plano-convex lens having a convex surface.
- the conductive portion 102 is the bridge wiring portion 13B, but it does not have to be the bridge wiring portion 13B.
- the application of the conductive fiber dispersion liquid is performed while moving the ejection portion of the dispenser or the inkjet device or the three-dimensional object 101, and the ejection portion and the electrical insulating layer 14 are applied. It is preferable to control the distance between the surface 14A of the surface and the surface 13A11 of the conductive fiber pattern 13A1. For example, the distance between the discharge portion of the dispenser and the surface 14A of the electrically insulating layer 14 and the surface 13A11 of the conductive fiber pattern 13A1 may be controlled to be substantially constant.
- the conductive fibers 18A By controlling the distance between the discharge portion and the surface 14A of the electrically insulating layer 14 and the surface 13A11 of the conductive fiber pattern 13A1 when the conductive fiber dispersion liquid is applied, the conductive fibers 18A having an aspect ratio of 5 or more can be obtained. Even when arranged on the three-dimensional surface 101A, the conductive fibers 18A can be arranged without bias, so that the conductive fiber pattern 13B1 can be uniformly formed on the three-dimensional surface 101A. As a result, the conductive fiber pattern 13B1 that follows the three-dimensional surface 101A can be formed.
- the conductor 130 shown in FIG. 22 is incorporated in, for example, a cotton swab-shaped biosensor 120.
- the biosensor 120 includes a conductor 130 and a covering portion 140 that covers a part of the conductor 130.
- the conductor 130 includes a support (three-dimensional object) 131 having a three-dimensional surface 131A, and a conductive fiber pattern 132A provided on the three-dimensional surface 131A, which is composed of a plurality of conductive fibers and follows the shape of the three-dimensional surface 131A. It is provided with a conductive portion 132.
- the covering portion 140 covers the conductive portion 132.
- the biosensor 120 for example, when the inside of the nasal cavity or the oral cavity is wiped with the biosensor 120 and nasal discharge, mucous membrane, saliva or the like adheres to the covering portion 140 as a sample, the sample passes through the covering portion 140 and is introduced into the conductive portion 132. Therefore, it can be used for inspection.
- the conductive portion 132 includes a resin portion (not shown) in addition to the conductive fiber pattern 132A, but if the conductive portion 132 includes the conductive fiber pattern 132A, the conductive portion 132 does not have to have the resin portion. good. Since the conductive fibers constituting the conductive fiber pattern 132A are the same as the conductive fibers 18A, the description thereof will be omitted here.
- the conductors 100, 110 and 130 include the conductive fiber patterns 102A and 132A following the three-dimensional surfaces 101A and 131A, the conductivity corresponding to various three-dimensional surfaces 101A and 131A can be applied. Conductors 100, 110, 130 having fiber patterns 102A, 132A can be obtained. Further, with such conductors 100, 110, and 130, it is possible to obtain performance according to the purpose.
- Silver nanowire dispersion liquid 1 Ethylene glycol as an alcohol solvent, silver nitrate as a silver compound, sodium chloride as a chloride, sodium bromide as a bromide, sodium hydroxide as an alkali metal hydroxide, aluminum nitrate nineahydrate as an aluminum salt, and vinylpyrrolidone as an organic protective agent.
- a copolymer of diallyldimethylammonium nitrate (prepared with 99% by mass of vinylpyrrolidone and 1% by mass of diallyldimethylammonium nitrate, weight average molecular weight 130,000) was prepared.
- Isopropyl alcohol was added to the washed silver nanowires to obtain a silver nanowire dispersion liquid 1.
- the average fiber diameter and the average fiber length of the silver nanowires in the silver nanowire dispersion liquid 1 were measured, the average fiber diameter of the silver nanowires was 45 nm, and the average fiber length was 15 ⁇ m.
- the concentration of silver nanowires in the silver nanowire dispersion liquid 1 was 1.5 mg / ml. Further, the viscosity of the silver nanowire dispersion liquid 1 was 0.08 Pa ⁇ s.
- the average fiber diameter of silver nanowires is 50 images taken at 100,000 to 200,000 times using a transmission electron microscope (TEM) (product name "H-7650", manufactured by Hitachi High-Technologies Corporation), and attached to the TEM.
- the fiber diameters of 100 conductive fibers were actually measured on the imaging screen using the software of the above, and obtained as the arithmetic mean value.
- the acceleration voltage is "100 kV”
- the emission current is "10 ⁇ A”
- the focusing lens diaphragm is "1”
- the objective lens diaphragm is "0”
- the observation mode is "HC”
- spot spot is "Spot”. 2 ".
- the average fiber length of silver nanowires is 100 silver at a magnification of 5 to 20 million times using a scanning electron microscope (SEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.).
- SEM scanning electron microscope
- the fiber length of the nanowires was measured, and the arithmetic average value of 98 of the 100 silver nanowires excluding the maximum value and the minimum value was obtained.
- the signal selection was set to "SE”
- the acceleration voltage was set to "3 kV”
- the emission current was set to "10 ⁇ A”
- the SE detector was set to "mixing".
- the fiber length of silver nanowires is measured by using the SEM function of a scanning electron microscope (SEM) (product name “S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.), and 10 images are taken at a magnification of 5 to 20 million.
- SEM scanning electron microscope
- the fiber length of 100 silver nanowires is measured on the imaging screen by the attached software, and among the fiber lengths of 100 silver nanowires, 98 arithmetic average values excluding the maximum and minimum values are used. I asked.
- a sample table tilted at 45 ° is used, the signal selection is "SE”, the acceleration voltage is "3kV”, the emission current is "10 ⁇ A to 20 ⁇ A”, and the SE detector is "mixed".
- Probe current is "Norm”
- focus mode is "UHR”
- condenser lens 1 is "5.0”
- W. D. was set to “8 mm”
- Til was set to "30 °”.
- the TE detector was removed in advance.
- a measurement sample prepared by the following method was used. First, the silver nanowire dispersion liquid 1 was diluted with ethanol to a concentration of 0.05% by mass or less in accordance with the dispersion medium. Further, one drop of this diluted silver nanowire dispersion liquid 1 is dropped onto a grid mesh with a carbon support film for TEM or STEM observation (Cu grid model number "# 10-1012 Elastic Carbon ELS-C10 STEM Cu100P grid specification").
- this cut-out sensor is used on an SEM sample table having a 45 ° inclination (model number "728-45", manufactured by Nissin EM, inclined sample table 45 °, ⁇ 15 mm ⁇ 10 mm, made of M4 aluminum) using silver paste. It was attached flat to the surface of the table. Further, Pt-Pd was sputtered for 20 to 30 seconds to obtain continuity.
- the viscosity of the silver nanowire dispersion liquid 1 was measured using a vibration viscometer (product name "VM-10A-M", manufactured by Sekonic Corporation). Specifically, the viscosity of the silver nanowire dispersion 1 was measured 10 times in an environment of a temperature of 25 ° C. and a relative humidity of 50%, and among the 10 measured viscosities, 8 viscosities excluding the maximum and minimum values were obtained. The viscosity was determined by determining the arithmetic mean value of.
- Silver nanowire dispersion liquid 2 A silver nanowire dispersion 2 was obtained in the same manner as the silver nanowire dispersion 1 except that the amount of isopropyl alcohol added was larger than that of the silver nanowire dispersion 1 and the viscosity was 0.008 Pa ⁇ s.
- the silver nanowire dispersion liquid 3 was obtained in the same manner as the silver nanowire dispersion liquid 1 except that the amount of isopropyl alcohol added was smaller than that of the silver nanowire dispersion liquid 1 and the viscosity was 30 Pa ⁇ s.
- composition for electrical insulation layer ⁇ Preparation of composition for electrical insulation layer> Each component was blended so as to have the composition shown below to obtain a composition 1 for an electrically insulating layer.
- Composition for Electrical Insulation Layer 1 -Dipentaerythritol hexaacrylate (DPHA): 100 parts by mass-Polymerization initiator (product name "Omnirad 184", manufactured by IGM Resins B.V.): 4.0 parts by mass
- Resin composition 1 -Dipentaerythritol hexaacrylate (DPHA): 100 parts by mass-Polymerization initiator (product name "Omnirad 184", manufactured by IGM Resins B.V.): 4.0 parts by mass-Methyl isobutyl ketone (MIBK): 500 parts by mass
- Resin composition 2 -Dipentaerythritol hexaacrylate (DPHA): 100 parts by mass-Polymerization initiator (product name "Omnirad 184", manufactured by IGM Resins B.V.): 4.0 parts by mass-Methyl isobutyl ketone (MIBK): 2000 parts by mass
- composition for high refractive index layer Each component was blended so as to have the composition shown below to obtain a composition 1 for a high refractive index layer.
- Composition for High Refractive Index Layer 1 -Dipentaerythritol hexaacrylate (DPHA): 14 parts by mass-Zirconium oxide fine particle dispersion (dispersion of zirconium oxide fine particles having an average particle size of 10 to 15 nm dispersed in methyl isobutyl ketone (solid content 32.5%)): 69 parts by mass ⁇
- Polymerization initiator product name “Omnirad 127”, manufactured by IGM Resins B.V.
- MIBK Methyl isobutyl ketone
- composition for low refractive index layer Each component was blended so as to have the composition shown below to obtain a composition 1 for a low refractive index layer.
- DPHA -Dipentaerythritol hexaacrylate
- MIBK methyl Isobutyl Ketone
- Example 1 First, a 48 ⁇ m-thick polyethylene terephthalate film (trade name “Cosmo Shine (registered trademark) A4100”, manufactured by Toyobo Co., Ltd.) having a base layer on one side as a base material was prepared, and the untreated surface side of the polyethylene terephthalate film was prepared.
- the first conductive portion having a plurality of first electrode portions arranged in the first direction and a wiring portion for electrically connecting adjacent first electrode portions, and a first conductive portion separated from the first conductive portion.
- Silver nanowires were arranged using the silver nanowire dispersion liquid 1 in the regions where the plurality of second electrode portions arranged in the second direction orthogonal to the direction were to be formed.
- the silver nanowire dispersion liquid 1 was applied to the shape of the first conductive portion and the shape of the second electrode portion using a dispenser capable of discharging the silver nanowire dispersion liquid to form a coating film. Then, dry air at 40 ° C. was circulated for 15 seconds at a flow rate of 0.5 m / s to the formed coating film, and then dry air at 70 ° C. was further circulated for 30 seconds at a flow rate of 15 m / s for drying. The solvent in the coating film was evaporated by allowing the mixture to evaporate. As a result, silver nanowires were arranged on the surface of the polyethylene terephthalate film in the regions where the first conductive portion and the second electrode portion should be formed, and silver nanowire patterns were formed respectively.
- a silver paste (trade name "DW-520H-14", trade name “DW-520H-14") is used on the silver nanowires which are the first electrode portions at the ends of the plurality of first electrode portions along the first direction using a dispenser. (Made by Toyobo Co., Ltd.) was applied. Next, the silver paste was heated at 130 ° C. for 30 minutes to cure the silver paste to form an take-out wiring portion.
- the composition for the electrical insulating layer was applied on the silver nanowires in the region where the wiring portion of the first conductive portion should be formed by using a dispenser to form a coating film.
- dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- the solvent in the coating film is evaporated by causing the coating film to evaporate, and the coating film is cured by irradiating the coating film with ultraviolet rays so that the integrated light amount is 100 mJ / cm 2 , so that the size is 1 mm ⁇ 2 mm and the film thickness is 300 nm.
- An electrically insulating layer having a refractive index of 1.50 was formed.
- the second electrode portions that straddle the wiring portions and are adjacent to each other on the three-dimensional surface consisting of the surface of the electrically insulating layer and the surface of the silver nanowire pattern in the region where the second electrode portion should be formed are electrically connected to each other.
- a dispenser capable of discharging silver nanowire dispersion liquid in the area where the bridge wiring part to be connected is to be formed while controlling the distance between the discharge part of the dispenser and the surface of the electrically insulating layer and the surface of the silver nanowire pattern.
- the silver nanowire dispersion liquid 1 was applied to the shape of the bridge wiring portion in the second direction orthogonal to the first direction to form a coating film.
- the silver nanowire dispersion liquid 1 was applied under the following conditions. (Discharge condition) ⁇ Discharge pressure: 5 kPa ⁇ Discharge diameter: 100 ⁇ m ⁇ Coating gap: 50 ⁇ m ⁇ PET film moving speed: 1 mm / sec
- Resin composition 1 was applied to form a coating film.
- dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- the solvent in the coating film is evaporated by causing the coating film to be cured, and the coating film is cured by irradiating the coating film with ultraviolet rays so that the integrated light amount is 100 mJ / cm 2 , so that the film thickness is 1000 nm and the refractive index is 1.50.
- a resin layer was formed.
- a first electrode portion made of silver nanowires arranged in the resin portion and the resin portion and a first conductive portion having a wiring portion and a second electrode portion made of silver nanowires arranged in the resin portion and the resin portion.
- a sensor having a second conductive portion having a bridge wiring portion made of silver nanowires arranged in the resin portion and the resin portion.
- the shape of the first electrode portion in the sensor according to the first embodiment was the shape shown in FIG. 1, and the width W1 of the first electrode portion was 4 mm.
- the shape of the wiring portion was strip-shaped, and the refractive index of the wiring portion was 1.50. Further, the width W2 of the wiring portion was 1 mm, and the length of the wiring portion was 0.5 mm.
- the shape of the second electrode portion was the shape shown in FIG. 1, and the width W3 of the second electrode portion was 4 mm.
- the thickness of the silver nanowire pattern constituting the first electrode portion, the wiring portion, and the second electrode portion was 100 nm, respectively.
- the shape of the bridge wiring portion was strip-shaped, and the refractive index of the bridge wiring portion was 1.50.
- the width W4 of the bridge wiring portion was 0.5 mm, the length of the bridge wiring portion was 3 mm, and the thickness T3 of the bridge wiring portion was 1 ⁇ m.
- the thickness of each part or each layer is the maximum value among the measured thicknesses of 10 points by randomly measuring the thickness of 10 points from the cross-sectional photograph of the conductive part taken by using a scanning transmission electron microscope (STEM). The arithmetic mean value of the thickness at 8 points excluding the minimum value was used.
- the specific cross-sectional photograph was taken by the following method.
- a sample for cross-section observation was prepared from the sensor. Specifically, a sample was cut out from the sensor to a size of 2 mm ⁇ 5 mm, placed in a silicone-based embedding plate, an epoxy-based resin was poured, and the entire sample was embedded in the resin. Then, the embedding resin was left at 65 ° C. for 12 hours or more to be cured. Then, using an ultramicrotome (product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.), the delivery thickness was set to 100 nm, and an ultrathin section was prepared.
- Ultramicrotome product name "Ultramicrotome EMUC7", manufactured by Leica Microsystems, Inc.
- the prepared ultrathin section was collected by a mesh with a collodion membrane (150) and used as a sample for STEM. Then, a cross-sectional photograph of a sample for STEM was taken using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Corporation). At the time of taking this cross-sectional photograph, the detector (selection signal) was set to "TE", the acceleration voltage was set to 30 kV, and the emission was set to "10 ⁇ A". The magnification was adjusted appropriately at 5000 to 200,000 times while adjusting the focus and observing whether each layer could be distinguished. The preferred magnification is 10,000 to 50,000 times, more preferably 25,000 to 40,000 times.
- the beam monitor aperture was set to 3
- the objective lens aperture was set to 3
- W. D. was set to 8 mm.
- the thickness of each part and the thickness of each layer were measured by this method.
- the refractive index of each part is determined by taking out the pieces of each part one by one by cutting out from any five places of each part, measuring the refractive index of each of the five pieces taken out by the Becke method, and refracting the five pieces measured. It was calculated as the arithmetic mean of the refractive indexes of the three pieces excluding the maximum and minimum values in the rate. The refractive index of each part was measured by this method not only in Example 1 but also in all subsequent Examples and Comparative Examples.
- "BW” described in the column of refractive index difference shown in Table 1 represents the refractive index of a bridge wiring part
- EL represents the refractive index of an electrically insulating layer.
- Example 2 a sensor was obtained in the same manner as in Example 1 except that the width W4 of the bridge wiring portion was set to 0.8 mm.
- Example 3 a sensor was obtained in the same manner as in Example 1 except that the width W4 of the bridge wiring portion was set to 0.35 mm.
- Example 4 a sensor was obtained in the same manner as in Example 1 except that the width W4 of the bridge wiring portion was set to 0.1 mm.
- a 48 ⁇ m-thick polyethylene terephthalate film (trade name “Cosmo Shine (registered trademark) A4100”, manufactured by Toyobo Co., Ltd.) having a base layer on one side as a base material was prepared, and the untreated surface of the polyethylene terephthalate film was prepared.
- the silver nanowire dispersion liquid 1 was applied to the entire surface using a bar coater to form a coating film.
- dry air at 40 ° C. was circulated for 15 seconds at a flow rate of 0.5 m / s to the formed coating film, and then dry air at 70 ° C. was further circulated for 30 seconds at a flow rate of 15 m / s for drying.
- the solvent in the coating film was evaporated by allowing the mixture to evaporate.
- silver nanowires were placed on the entire surface of the untreated surface of the polyethylene terephthalate film.
- the resin composition 2 was applied using a die coater so as to cover the silver nanowires to form a coating film.
- dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- a resin having a film thickness of 100 nm and a refractive index of 1.6 is obtained by evaporating the solvent in the coating film and irradiating it with ultraviolet rays so that the integrated light amount becomes 100 mJ / cm 2 to cure the coating film. Formed a part.
- a conductive layer containing a resin portion and silver nanowires was formed.
- a silver paste (trade name "DW-520H-14", manufactured by Toyobo Co., Ltd.) was applied to the surface of the resin portion on the region to be the first conductive portion by a screen printing method. The silver paste was then heated at 130 ° C. for 30 minutes to cure the silver paste.
- the laser beam is applied to the region other than the region where the take-out wiring portion should be formed in the cured silver paste, and to the region other than the region where the first conductive portion and the second electrode portion should be formed in the conductive layer under the following conditions. Irradiation was performed to pattern the cured silver paste and conductive layer. When the laser beam was applied to a region other than the region where the take-out wiring portion should be formed in the cured silver paste, the silver paste existing in these regions was sublimated and removed. As a result, the take-out wiring part having the same shape and dimensions as the take-out wiring part in the first embodiment was formed.
- the composition for the electrical insulating layer was applied to the region of the conductive layer where the wiring portion should be formed by using a dispenser to form a coating film.
- dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- the solvent in the coating film is evaporated by allowing the coating film to evaporate, and the coating film is cured by irradiating the coating film with ultraviolet rays so that the integrated light amount is 100 mJ / cm 2 , so that the size is 1 mm ⁇ 2 mm and the film thickness is 500 nm.
- An electrically insulating layer having a refractive index of 1.50 was formed.
- the silver nanowire dispersion liquid can be discharged to the region where the bridge wiring portion should be formed on the three-dimensional surface consisting of the surface of the electrically insulating layer and the surface of the silver nanowire pattern in the region where the second electrode portion should be formed.
- the silver nanowire dispersion liquid 1 was applied to the shape of the bridge wiring portion in the second direction orthogonal to the first direction using a simple dispenser to form a coating film. Then, dry air at 40 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 15 m / s for 30 seconds to dry. The solvent in the coating film was evaporated by allowing the mixture to evaporate. As a result, the silver nanowires were arranged in the region where the bridge wiring portion should be formed, and the silver nanowire pattern was formed.
- Resin composition 1 was applied to form a coating film.
- dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- the solvent in the coating film is evaporated by causing the coating film to be cured, and the coating film is cured by irradiating the coating film with ultraviolet rays so that the integrated light amount is 100 mJ / cm 2 , so that the film thickness is 1000 nm and the refractive index is 1.50.
- a resin layer was formed.
- a first electrode portion made of silver nanowires arranged in the resin portion and the resin portion and a first conductive portion having a wiring portion and a second electrode portion made of silver nanowires arranged in the resin portion and the resin portion.
- a sensor having a second conductive portion having a bridge wiring portion made of silver nanowires arranged in the resin portion and the resin portion.
- the first conductive portion having the first electrode portion and the wiring portion in the sensor according to the fifth embodiment has the same shape and dimensions as the first conductive portion having the first electrode portion and the wiring portion in the first embodiment, and has the same shape and dimensions as the first conductive portion.
- the two electrode portions had the same shape and dimensions as the second electrode portion in Example 1.
- the shape of the bridge wiring portion in the sensor according to the fifth embodiment was strip-shaped, and the refractive index of the wiring portion was 1.50.
- the width W4 of the bridge wiring portion was 0.5 mm
- the length of the bridge wiring portion was 3 mm
- the thickness T3 of the bridge wiring portion was 1 ⁇ m.
- Example 6 a sensor was obtained in the same manner as in Example 1 except that the silver nanowires were arranged in the region where the bridge wiring portion should be formed by the following steps. First, using a contact dispenser (product name "Super ⁇ (registered trademark) CMIII", manufactured by Musashi Engineering Co., Ltd.) on the surface of the electrically insulating layer, the silver nanowire dispersion liquid 1 is applied from the discharge portion of the dispenser under the following conditions. It was discharged so that the line thickness at the time was 182 ⁇ m, and the coating was applied linearly to form a linear coating portion. (Discharge condition) ⁇ Discharge pressure: 5 kPa ⁇ Discharge diameter: 100 ⁇ m ⁇ Coating gap: 50 ⁇ m -PET film moving speed: 20 mm / sec
- Example 7 a sensor was obtained in the same manner as in Example 1 except that the silver nanowires were arranged in the region where the first conductive portion and the second electrode portion should be formed by the following steps. First, on the untreated surface of the polyethylene terephthalate film, a first conductive portion having a plurality of first electrode portions arranged in the first direction and a wiring portion for electrically connecting adjacent first electrode portions, and a first. Composition 1 for wall portions (trade name "U-403B”) is provided on both sides of a region where a plurality of second electrode portions arranged in a second direction orthogonal to the first direction and separated from the conductive portion are to be formed.
- the silver nanowire dispersion liquid 1 was filled between the wall portions by an inkjet method to form a coating film. Then, dry air at 40 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 15 m / s for 30 seconds to dry. The solvent in the coating film was evaporated by allowing the mixture to evaporate. As a result, silver nanowires were placed on the surface of the polyethylene terephthalate film in the regions where the first conductive portion and the second electrode portion should be formed.
- the width of the wall is randomly measured at 10 points from a cross-sectional photograph of the wall taken with a scanning transmission electron microscope (STEM), and the maximum and minimum values are selected from the measured widths of the 10 points.
- the arithmetic mean value of the width of the excluded 8 points was used.
- a specific cross-sectional photograph was taken by the following method. First, a sample for cross-section observation was prepared from the conductive film. Specifically, a sensor cut out to a size of 2 mm ⁇ 5 mm was placed in a silicone-based embedding plate, an epoxy-based resin was poured, and the entire sensor was embedded in the resin. Then, the embedding resin was left at 65 ° C. for 12 hours or more to be cured.
- ultramicrotome product name "Ultramicrotome EMUC7”, manufactured by Leica Microsystems, Inc.
- the delivery thickness was set to 100 nm, and an ultrathin section was prepared.
- the prepared ultrathin section was collected by a mesh with a collodion membrane (150) and used as a sample for STEM.
- a cross-sectional photograph of a sample for STEM was taken using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Corporation).
- STEM scanning transmission electron microscope
- the detector selection signal
- the acceleration voltage was set to 30 kV
- the emission was set to "10 ⁇ A”.
- the magnification was adjusted appropriately at 5000 to 200,000 times while observing whether each layer could be distinguished by adjusting the focus.
- the preferred magnification is 10,000 to 50,000 times, more preferably 25,000 to 40,000 times. If the magnification is increased too much, the pixels at the interface become rough and difficult to understand. Therefore, it is better not to increase the magnification too much when measuring the thickness of the wall portion.
- the beam monitor aperture was set to 3
- the objective lens aperture was set to 3
- W. D. was set to 8 mm.
- the thickness of the wall is randomly measured at 10 points from a cross-sectional photograph of the wall taken with a scanning transmission electron microscope (STEM), and the maximum and minimum values are selected from the measured thicknesses at 10 points.
- STEM scanning transmission electron microscope
- the arithmetic mean value of the thickness of the excluded 8 points was used.
- the cross-sectional photograph when measuring the thickness of the wall portion was taken under the same conditions as the cross-sectional photograph when measuring the width of the wall portion.
- the shapes and widths of the first electrode portion, the wiring portion, and the second electrode portion in the sensor according to the seventh embodiment are the same as the shapes and widths of the first electrode portion, the wiring portion, and the second electrode portion of the first embodiment. there were.
- the sensor according to Comparative Example 1 obtained the sensor in the same manner as in Example 1 except that the steps of arranging the silver nanowires in the region where the bridge wiring portion should be formed and the subsequent steps were as follows.
- rice field Specifically, a tin-doped indium oxide (ITO) layer having a film thickness of 30 nm was formed on the surface of the electrically insulating layer by a sputtering method. After forming the ITO layer, the ITO layer was heated at 150 ° C. for 30 minutes to crystallize the ITO layer. Then, the ITO layer was patterned using a photolithography technique. As a result, a bridge wiring portion having a width of 0.1 mm, a length of 3 mm, and a film thickness of 30 nm made of ITO having a refractive index of 2.00 was formed.
- ITO indium oxide
- the resin composition 1 is applied so as to cover the silver nanowires arranged in the regions where the first electrode portion and the second electrode portion should be formed, and the bridge wiring portion using a die coater. Then, a coating film was formed. Next, dry air at 50 ° C. was circulated through the formed coating film at a flow rate of 0.5 m / s for 15 seconds, and then dry air at 70 ° C. was further circulated at a flow rate of 10 m / s for 30 seconds for drying.
- the solvent in the coating film is evaporated by causing the coating film to be cured, and the coating film is cured by irradiating the coating film with ultraviolet rays so that the integrated light amount is 100 mJ / cm 2 , so that the film thickness is 100 nm and the refractive index is 1.6.
- a resin layer was formed.
- the first electrode portion made of silver nanowires arranged in the resin portion and the resin portion and the first conductive portion having the wiring portion
- the second electrode portion made of silver nanowires arranged in the resin portion and the resin portion.
- a second conductive portion having a bridge wiring portion made of ITO was formed.
- the composition 1 for a high refractive index layer was applied to the surface of the resin layer to form a coating film. Then, the formed coating film was dried at 70 ° C. for 30 seconds and then irradiated with ultraviolet rays at an integrated light amount of 150 mJ / cm2 to be cured to form a high refractive index layer having a film thickness of 50 nm. Next, the composition 1 for the low refractive index layer was applied onto the high refractive index layer to form a coating film. Then, this coating film was dried at 70 ° C.
- a reflection reducing layer composed of a high refractive index layer having a refractive index of 1.66 and a low refractive index layer having a refractive index of 1.48 was formed, and a sensor was obtained.
- Comparative Example 2 In Comparative Example 2, when a sensor was tried to be produced in the same manner as in Example 1 except that the silver nanowire dispersion liquid 2 was used instead of the silver nanowire dispersion liquid 1, the viscosity of the silver nanowire dispersion liquid 2 was increased. Since it was too low, the silver nanowire dispersion liquid 2 flowed down from the three-dimensional surface, and the silver nanowire pattern of the bridge wiring portion could not be formed.
- Comparative Example 3 In Comparative Example 3, when a sensor was tried to be produced in the same manner as in Example 1 except that the silver nanowire dispersion liquid 3 was used instead of the silver nanowire dispersion liquid 1, the viscosity of the silver nanowire dispersion liquid 3 was increased. Because it was too high, the silver nanowire dispersion liquid 3 was clogged when the silver nanowire dispersion liquid 3 was discharged, and the silver nanowire pattern could not be formed.
- ⁇ Flexibility evaluation> (1) Evaluation of Electrical Resistance Value Ratio Before and After Folding Test (FD Test)
- the sensors according to Examples 1 to 7 and Comparative Example 1 were subjected to a folding test to evaluate their flexibility. Specifically, first, rectangular samples 1 and 2 having a length of 125 mm and a width of 50 mm were cut out from the sensor. Here, the sample 1 is cut out so that the longitudinal direction of the sample 1 is the first direction, and the sample 2 is cut out so that the longitudinal direction of the sample 2 is the second direction. rice field.
- silver paste (trade name "DW-520H-14", Toyobo Co., Ltd.) is applied to both ends of the longitudinal surface of each sample 1 and 2 in a length of 10 mm and a width of 50 mm.
- the product was applied and heated at 130 ° C. for 30 minutes to provide a cured silver paste on both ends.
- the measurement distance of the electric resistance value in the samples 1 and 2 provided with the cured silver paste at both ends was 105 mm, and the measurement width was 50 mm.
- the cured silver paste is irradiated with laser light under the following conditions, and in sample 1, as shown in FIG. 6, the silver paste is prepared so that the first conductive portion does not electrically conduct with the second electrode portion.
- the electrical resistance values of Samples 1 and 2 were measured using a tester (product name "Digital M ⁇ Hister 3454-11", manufactured by Hioki Electric Co., Ltd.). Specifically, since the Digital M ⁇ Hister 3454-11 has two probe terminals (red probe terminal and black probe terminal, both of which are pin type), in the sample 1, the red probe terminal is attached to one end. The portion of the cured silver paste provided in the portion is in contact with the portion in contact with the first conductive portion, and the black probe terminal is in contact with the portion of the cured silver paste provided in the other end in contact with the first conductive portion. The electric resistance value was measured.
- the red probe terminal is brought into contact with the portion of the cured silver paste provided at one end in contact with the second conductive portion, and the black probe terminal is provided at the other end for curing.
- the electric resistance value was measured by contacting the portion of the silver paste that was in contact with the second conductive portion.
- the electric resistance value of the first conductive part was measured and the electric resistance value of the second conductive part was measured in the same manner as the sample before the folding test. Then, the electric resistance value ratio, which is the ratio of the electric resistance value of the sample 1 after the folding test to the electric resistance value of the sample 1 before the folding test (the electric resistance value of the sample 1 after the folding test / the electric resistance value of the sample 1 before the folding test). (Electrical resistance value) was calculated.
- the electric resistance value ratio which is the ratio of the electric resistance value of the sample 2 after the folding test to the electric resistance value of the sample 2 before the folding test (the electric resistance value of the sample 2 after the folding test / the electric resistance value of the sample 2 before the folding test). (Electrical resistance value) was calculated.
- new samples 1 and 2 cut out from the sensors according to Examples 1 to 7 in the same manner as described above are attached to the above-mentioned durability tester in the same manner as described above, and the surface of the sample on the substrate side is folded by 180 °. (Test for folding so that the first conductive part is on the outside and the base material is on the inside: outer bending folding test) is performed 100,000 times, and similarly, the electric resistance value of the first conductive part of the sample 1 after the folding test is performed. Was measured to determine the electrical resistance value ratio. Further, the electric resistance value of the second conductive portion of the sample 2 after the folding test was measured, and the electric resistance value ratio was obtained. Then, the result of the folding test was evaluated according to the following criteria.
- the electric resistance value ratio was measured five times at different locations, and was used as the arithmetic mean value of three electric resistance value ratios excluding the maximum value and the minimum value among the five measured electric resistance value ratios.
- the sample before the folding test is installed in the fixed part of the durability tester so that the position to be observed can be easily grasped, and when folded once, as shown in FIG.
- An oil-based pen was used to mark both ends of the bent portion, which are located in the direction orthogonal to the folding direction, to indicate that the bent portion is a bent portion.
- a line connecting the marks at both ends of the bent portion was drawn with an oil-based pen. Then, in observing the bending habit, the entire bent portion, which is a region formed by the marks at both ends of the bent portion and the line connecting the marks, was visually observed.
- the planned observation area (bent part) near the center of the sample should not be touched by hand and no force should be applied. Then, both the inner part and the outer part when folded were observed.
- the observation of the microcracks was performed in a dark field and reflected light at a magnification of 200 times by selecting ring illumination as the illumination of the digital microscope.
- the sample before the folding test was installed in the fixed part of the durability tester so that the position to be observed could be easily grasped, and when folded once, as shown in FIG.
- An oil-based pen was used to mark both ends of the bent portion in a direction orthogonal to the folding direction to indicate that the bent portion was a bent portion.
- the number of observers was 15, and it was determined that the shape of the bridge wiring portion was visually recognized when all the observers visually recognized the shape of the bridge wiring portion.
- the evaluation criteria are as follows. A: The shape of the bridge wiring part was not visible. B: The shape of the bridge wiring portion was visually recognized.
- a haze meter (product name "HM-150", manufactured by Murakami Color Technology Laboratory Co., Ltd.) was used in an environment of a temperature of 23 ° C. and a relative humidity of 50%. , JIS K7136: 2000, and the haze value (total haze value) of the sensor was measured.
- the haze value is a value measured by the entire sensor. After cutting out a sample having a size of 50 mm ⁇ 100 mm from the sensor, the measurement was performed by installing the sample so that the first conductive portion side was the non-light source side in a state where there were no curls or wrinkles and no fingerprints or dust.
- the haze value was obtained by measuring the haze value five times for one sample and using it as the arithmetic mean value of three haze values excluding the maximum value and the minimum value among the five measured haze values.
- the orientation angle of the silver nanowires is within 0 ° ⁇ 10 ° and the orientation strength is 1.2 or more in the bridge wiring portion, it is assumed that the silver nanowires are lined up in the second direction and the orientation angle is set. If the orientation strength is less than 1.2 within 0 ° ⁇ 10 °, or if the orientation angle is 1.2 or more but the orientation angle exceeds 0 ° ⁇ 10 °, or the orientation angle is 0 ° ⁇ 10 °. When the orientation strength is less than 1.2, it is considered that the silver nanowires are not lined up in the direction in which the bridge wiring portion extends.
- the evaluation criteria were as follows. A: The silver nanowires in the bridge wiring part were lined up along the second direction. B: The silver nanowires in the bridge wiring part were not lined up along the second direction.
- ⁇ Electrical short circuit evaluation> The electrical short circuit of the sensor according to Examples 1 and 7 was evaluated. Specifically, first, a sample having a size of 50 mm ⁇ 50 mm was cut out from the sensor along the first direction and the second direction. Then, using a tester (product name "Digital M ⁇ Hister 3454-11", manufactured by Hioki Electric Co., Ltd.), a current is generated between the first conductive portion and the second conductive portion located next to the first conductive portion. I evaluated whether it would flow. Then, a durability test was conducted in which a voltage of 32 V was applied to the first conductive portion of the sample for 100 hours in an environment of 65 ° C. and a relative humidity of 95%.
- a current is applied to the first conductive part and the second conductive part located next to the first conductive part by using a tester (product name "Digital M ⁇ Histester 3454-11", manufactured by Hioki Electric Co., Ltd.). By evaluating whether or not it flows, it was evaluated whether or not it was electrically short-circuited.
- the evaluation criteria are as follows. A: No current flowed between the first conductive portion and the second conductive portion not only before the durability test but also after the durability test. B: Before the durability test, no current flowed between the first conductive part and the second conductive part, and after the durability test, a slight current flowed between the first conductive part and the second conductive part. , There was no problem in actual use. C: Before the durability test, no current flowed between the first conductive part and the second conductive part, but after the durability test, a current flowed between the first conductive part and the second conductive part.
- the silver nanowire pattern of the wiring portion does not follow the three-dimensional surface and the line resistance value exceeds 1,000,000 ⁇ , it is assumed that the silver nanowire pattern of the bridge wiring portion does not follow the three-dimensional surface.
- Whether or not the silver nanowire pattern of the bridge wiring portion was along the three-dimensional surface was determined from a cross-sectional photograph taken using a scanning transmission electron microscope (STEM).
- STEM scanning transmission electron microscope
- the shooting conditions for the cross-sectional photograph by the scanning transmission electron microscope were the same as the shooting conditions for the cross-sectional photograph described in Example 1. In the linear resistance measurement, first, the same sample as in the folding test was prepared.
- the probe terminal of the tester product name "Digital M ⁇ Hister 3454-11", manufactured by Hioki Electric Co., Ltd.
- the resistance value was measured by.
- the Digital M ⁇ Hister 3454-11 has two probe terminals (red probe terminal and black probe terminal, both pin-shaped), so that the red probe terminal is bridged with one of the cured silver pastes.
- the resistance value was measured by contacting the portion in contact with the wiring portion and contacting the black probe terminal with the portion in contact with the bridge wiring portion in the other cured silver paste.
- the line resistance value of the bridge wiring portion was obtained from the above mathematical formula (2).
- the evaluation criteria were as follows. A: The silver nanowire pattern of the bridge wiring part followed the three-dimensional surface.
- B The silver nanowire pattern of the bridge wiring portion did not follow the three-dimensional surface.
- ⁇ Measurement of average fiber diameter of silver nanowires in the bridge wiring part of the sensor> a scanning transmission electron microscope (STEM, product name "S-4800", manufactured by Hitachi High-Technologies Corporation) was used to determine the average fiber diameter of silver nanowires contained in the bridge wiring portion. It was measured. Specifically, first, a sample is cut out from the sensor to a size of 1 mm ⁇ 10 mm so as to include the bridge wiring part, put it in a silicone-based embedding plate, pour epoxy-based resin, and wrap the entire sample with resin. Bury. Then, the embedding resin was left at 25 ° C. for 12 hours or more to be cured.
- STEM scanning transmission electron microscope
- ultramicrotome EM UC7 product name “Ultramicrotome EM UC7”, manufactured by Leica Microsystems, Inc.
- the delivery thickness was set to 100 nm, and ultrathin sections were prepared.
- the prepared ultrathin section was collected by a mesh with a collodion membrane (150) and used as a sample for STEM.
- a cross-sectional photograph of a sample for STEM was taken using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Corporation).
- STEM scanning transmission electron microscope
- the detector selection signal
- the acceleration voltage was set to 30 kV
- the emission was set to "10 ⁇ A”.
- the magnification was adjusted appropriately at 5000 to 200,000 times while adjusting the focus and observing whether each layer could be distinguished.
- the beam monitor aperture was set to 3
- the objective lens aperture was set to 3
- W. D. was set to 8 mm.
- 10 silver nanowires contained in the bridge wiring part were observed, the shortest diameter (minor diameter) of the silver nanowires was measured, and 3 data from the smallest of the 10 data were measured.
- the arithmetic mean value was obtained using the three data, and the arithmetic mean value was used as the average fiber diameter of silver nanowires.
- ultramicrotome EM UC7 product name “Ultramicrotome EM UC7”, manufactured by Leica Microsystems, Inc.
- the delivery thickness was set to 100 nm, and ultrathin sections were prepared.
- the prepared ultrathin sections were collected with a mesh with a collodion membrane (150 mesh) and used as a sample for STEM.
- a cross-sectional photograph of a sample for STEM was taken using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Corporation).
- STEM scanning transmission electron microscope
- the detector selection signal
- the acceleration voltage is set to "30 kV”
- the emission current is set to "10 ⁇ A”.
- each layer could be distinguished.
- the aperture is set to "beam monitor aperture 3"
- the objective lens aperture is set to "3”
- W. D. was set to "8 mm”.
- the above-mentioned cross-sectional photographs of 10 places taken in this way were prepared.
- each cross-sectional photograph is enlarged to the pixel level, and in each cross-sectional photograph, the number of pixels showing the silver nanowires located on the polyethylene talreflate film side from the position of half the thickness of the bridge wiring portion and the number of pixels of the bridge wiring portion.
- the above ratio obtained from each cross-sectional photograph is taken as the abundance ratio of silver nanowires located on the polyethylene tale phthalate film side from the position of half the thickness of the bridge wiring portion, and the arithmetic mean value of the abundance ratio obtained from each cross-sectional photograph is taken.
- the arithmetic mean value was 55% or more, it was considered to be unevenly distributed on the polyethylene terephthalate film side.
- the evaluation criteria are as follows. A: Silver nanowires were unevenly distributed on the polyethylene sauce phthalate film side from the position of half the thickness of the bridge wiring portion.
- B The silver nanowires were not unevenly distributed on the polyethylene sauce phthalate film side from the position of half the thickness of the bridge wiring portion.
- the results are shown in Tables 1 and 2 below.
- the results of the electrical resistance value ratio shown in Table 1 are the results when the inward bending folding test is performed, and the results of the electrical resistance value ratio shown in Table 2 are the results of the outward bending folding test. It is the result when I went.
- the silver nanowires in the bridge wiring portion were lined up along the second direction, so that the electric resistance value was lower than that of the first embodiment. ..
- silver nanowires can be reduced from the bridge wiring portion in the sensor according to the sixth embodiment, so that the cost can be reduced while realizing the desired line resistance value and surface resistance value.
- the width of the bridge wiring portion was less than 0.35 mm, so that the bridge wiring portion was disconnected when static electricity of 2 kV was applied.
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Abstract
Description
[1]基材と、前記基材の第1面側に設けられた第1導電部と、前記基材の前記第1面側に設けられ、かつ前記第1導電部から離間した第2導電部とを備えるセンサーであって、前記第1導電部が、第1方向に配置された複数の第1電極部と、隣り合う前記第1電極部同士を電気的に接続する配線部とを有し、前記第2導電部が、前記第1方向と交差する第2方向に配置された複数の第2電極部と、前記配線部を跨ぎ、かつ隣り合う前記第2電極部同士を電気的に接続するブリッジ配線部とを有し、前記ブリッジ配線部が、樹脂部と、前記樹脂部中に配置された導電性繊維とを含む、センサー。
図1に示されるセンサー10は、基材11と、基材11の第1面11A側に設けられた第1導電部12と、基材11の第1面11A側に設けられ、かつ第1導電部12から離間した第2導電部13と、後述する配線部12Bとブリッジ配線部13Bの間に設けられた電気絶縁層14と、後述する第1電極部12Aに電気的に接続された取出配線部15とを備えている。なお、センサー10は、後述する導電体の一例である。
(折り畳み条件)
・往復速度:80rpm(回毎分)
・試験ストローク:60mm
・屈曲角度:180°
基材11としては、特に限定されないが、用途によっては光透過性を有することが好ましい。例えば、センサー10が光学用途に用いられる場合には、基材は光透過性を有することが好ましい。本明細書における「光透過性」とは、光を透過させる性質を意味する。また「光透過性」とは、必ずしも透明である必要はなく、半透明であってもよい。
第1導電部12は、電気的に導通可能な部分である。第1導電部12の表面抵抗値から導通を判断する場合には、第1導電部12の表面抵抗値が2000Ω/□未満であれば、第1導電部12から電気的な導通が得られていると判断できる。第1導電部12の表面抵抗値は、以下のようにして求めるものとする。まず、折り畳み試験を行う際のサンプルS1を作製する。サンプルS1を得た後、温度23±5℃および相対湿度30%以上70%以下の環境下で、硬化した銀ペースト21にテスター(製品名「Digital MΩ Hitester 3454-11」、日置電機株式会社製)のプローブ端子を接触させることによって抵抗値を測定する。具体的には、Digital MΩ Hitester 3454-11は、2本のプローブ端子(赤色プローブ端子および黒色プローブ端子、両方ともピン形)を備えているので、赤色プローブ端子を一方の硬化した銀ペースト21における第1導電部12と接触している部分に接触させ、かつ黒色プローブ端子を他方の硬化した銀ペースト21における第1導電部12と接触している部分に接触させて抵抗値を測定する。そして、以下の数式(1)から、第1導電部12の表面抵抗値を求めるものとする。
Rs=R×(CW×CN/CL) …(1)
上記式(1)中、Rsは表面抵抗値(Ω/□)であり、Rは測定された抵抗値(Ω)であり、CWは第1導電部1本の線幅(μm)であり、CNは第1導電部の本数であり、CLは第1導電部の線長(μm)である。
RL=R×CN …(2)
上記式(2)中、RLは線抵抗値(Ω)であり、Rは測定された抵抗値(Ω)であり、CNは導電部の本数である。
第1電極部12Aの形状は、特に限定されず、例えば、四角形状、菱形状等であってもよい。第1電極部12Aの幅W1(電極幅)は、指の接触面積(約10mmφ)以下であることが必要であるので、10mm以下であることが好ましい。第1電極部12Aの幅W1は、0.35mm以上10mm以下、0.35mm以上9mm以下、0.35mm以上8.5mm以下、0.35mm以上8mm以下、0.5mm以上10mm以下、0.5mm以上9mm以下、0.5mm以上8.5mm以下、0.5mm以上8mm以下、0.7mm以上10mm以下、0.7mm以上9mm以下、0.7mm以上8.5mm以下、または0.7mm以上8mm以下であってもよい。
樹脂部17Aは、導電性繊維18Aを覆うものである。樹脂部17Aで導電性繊維18Aを覆うことにより、第1電極部12Aおよび第2電極部13Aからの導電性繊維18Aの脱離を防ぎ、かつ第1電極部12Aおよび第2電極部13Aの耐久性や耐擦傷性を向上させることができる。
導電性繊維18Aは樹脂部17A中に複数本存在している。第1電極部12Aは電気的に導通可能となっているので、第1電極部12Aの厚み方向において導電性繊維18A同士が接触している。
配線部12Bも第1方向DR1(図1参照)に沿って延びている。配線部12Bは、図3に示されるように第1電極部12Aと同様に導電性繊維18Aを含んでいるが、導電性繊維18Aとして金属ナノワイヤを使用すると、静電気の集中によって金属ナノワイヤが断線するおそれがある。このような断線を抑制するために、配線部12Bの幅W2(ネック幅)は、0.35mm以上であることが好ましい。配線部12Bの幅W2は、上記断線をより抑制する観点および第1電極部12Aの面積を確保する観点から、0.35mm以上5.0mm以下、0.35mm以上4.5mm以下、0.35mm以上4.0mm以下、0.4mm以上5.0mm以下、0.4mm以上4.5mm以下、0.4mm以上4.0mm以下、0.45mm以上5.0mm以下、0.45mm以上4.5mm以下、0.45mm以上4.0mm以下、0.5mm以上5.0mm以下、0.5mm以上4.5mm以下、または0.5mm以上4.0mm以下であることが好ましい。
第2導電部13は、電気的に導通可能な部分である。第2導電部13の表面抵抗値、線抵抗値、厚みT2(図3参照)は、第1電極部12Aの表面抵抗値、線抵抗値、厚みT1と同様であるので、説明を省略するものとする。
第2電極部13Aの形状は、特に限定されず、例えば、四角形状、菱形状等であってもよい。第2電極部13Aの幅W3(電極幅)は、指の接触面積(約10mmφ)以下であることが必要であるので、10mm以下であることが好ましい。第2電極部13Aの幅W3は、0.35mm以上10mm以下、0.35mm以上9mm以下、0.35mm以上8.5mm以下、0.35mm以上8mm以下、0.5mm以上10mm以下、0.5mm以上9mm以下、0.5mm以上8.5mm以下、0.5mm以上8mm以下、0.7mm以上10mm以下、0.7mm以上9mm以下、0.7mm以上8.5mm以下、または0.7mm以上8mm以下であってもよい。
ブリッジ配線部13Bも第2方向DR2(図1参照)に沿って延びている。ブリッジ配線部13Bは、樹脂部17Bと、樹脂部17B中に配置された導電性繊維18B(第2導電性繊維)とを含んでいる。樹脂部17Bは、樹脂部17Aと同様であり、導電性繊維18Bは、導電性繊維18Aと同様であるので、説明は省略するものとする。また、ブリッジ配線部13Bは、第2方向DR2に沿って延びているので、ブリッジ配線部13Bは、複数の導電性繊維18Bからなり、第2方向DR2に沿って延びた導電性繊維パターン13B1(図3参照)を含んでいる。
電気絶縁層14は、配線部12Bとブリッジ配線部13Bの間に設けられている。このような電気絶縁層14を設けることにより、配線部12Bとブリッジ配線部13Bの接触を抑制できるので、第1導電部12と第2導電部13が電気的に短絡することを抑制できる。
取出配線部15は、第1電極部12Aと電気的に接続されている。具体的には、取出配線部15は、第1方向DR1に沿って配置された複数の第1電極部12Aのうち末端にある第1電極部12Aに電気的に接続されている。図1に示される取出配線部15は、第1電極部12Aと基材11上に形成されている。
センサー10は、第1電極部12Aおよび第2電極部13Aの導電性繊維18Aは樹脂部17Aで覆われているが、図10に示されるセンサー30のように第1電極部12Aおよび第2電極部13Aの導電性繊維18Aは樹脂部17A、17Cで覆われていてもよい(図11、図12参照)。樹脂部17Cの厚みは、40nm以上100nm以下であることが好ましい。第1導電部12をロールトゥーロールで形成する場合、導電性繊維18Aが樹脂部で覆われていない状態で、導電性繊維18Aを配置した基材11を巻き取ると、導電性繊維18Aが剥がれるおそれがある。これに対し、樹脂部17Cの厚みが40nm以上であれば、導電性繊維18A上に樹脂部17Cを形成した積層体を巻き取れば、上記のような導電性繊維18Aの剥がれを抑制することができる。また、樹脂部17Cの厚みが薄ければ薄いほど、導電性繊維18Aが樹脂部17Cから露出する。このため、樹脂部17Cの厚みが100nm以下であれば、樹脂部17Cの厚みが薄いので、導電性繊維18Aにおいて樹脂部17Cから露出する部分が増え、これにより第1導電部12と取出配線部15の接触抵抗値を低下させることができる。
壁部41は、第1導電部12と第2電極部13Aの充填をガイドする機能を有するとともに、第1導電部12と第2電極部13Aとの間の電気的な短絡を抑制する機能を有する。壁部41は、電気絶縁性材料から構成されている。電気絶縁性材料としては、樹脂が挙げられる。樹脂としては、特に限定されないが、電気絶縁層の欄で説明した樹脂が挙げられる。
センサー10は、例えば、以下のようにして作製することができる。まず、図15(A)に示されるように、基材11の第1面11Aにおける第1導電部12および第2電極部13Aを形成すべき領域に、ディスペンサやインクジェット法を用いて、導電性繊維18Bおよび分散媒を含む導電性繊維分散液を塗布し、乾燥させて、第1導電部12および第2電極部13Aを形成すべき領域に導電性繊維18Aを配置する。
センサー30は、例えば、以下の方法によって作製することも可能である。まず、図18(A)に示されるように、基材11の第1面11A全体に、ダイコーター等の塗布装置によって、導電性繊維18Aおよび分散媒を含む導電性繊維分散液を塗布し、乾燥させて、導電性繊維18Aを配置する。
図20に示される画像表示装置60は、観察者側に向けて、表示素子70と、円偏光板80と、センサー10と、カバー部材90とをこの順で備えている。センサー10は、タッチパネルとして機能し、ブリッジ配線部13Bが第1導電部12よりも観察者側となるように配置されている。表示素子70と円偏光板80の間、円偏光板80とセンサー10との間、センサー10とカバー部材90との間は、接着層91~93を介して接着されている。本明細書における「接着」とは粘着を含む概念である。
表示素子70としては、液晶表示素子、有機発光ダイオード素子(以下、「OLED素子」と称することもある。)、無機発光ダイオード素子、マイクロLED、プラズマ素子等が挙げられる。有機発光ダイオード素子としては、公知の有機発光ダイオード素子を用いることができる。また、液晶表示素子は、タッチパネル機能を素子内に備えたインセルタッチパネル液晶表示素子であってもよい。
円偏光板80は、外光反射を抑制する機能を有するので、表示素子としてOLED素子を用いる場合に、円偏光板80は、特に有効である。円偏光板80は、例えば、観察者側に向けて、第1位相差フィルムと、接着層と、第2位相差フィルムと、接着層と、偏光板とを、この順で備えている。
カバー部材90の表面90Aは、画像表示装置60の表面60Aとなっている。カバー部材90は、カバーガラスまたは樹脂からなるカバーフィルムであってもよい。画像表示装置60が、屈曲性を有する場合には、カバー部材90は屈曲性を有するガラスや屈曲性を有する樹脂から構成されていることが好ましい。屈曲性を有する樹脂としては、例えば、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、ポリエステル系樹脂(例えば、ポリエチレンテレフタレート樹脂やポリエチレンナフタレート樹脂)、またはこれらの樹脂を2以上混合した混合物等が挙げられる。
接着層91~93は、重合性化合物を含む液状の電離放射線硬化性接着剤(例えば、OCR:Optically Clear Resin)の硬化物や粘着剤(例えば、OCA:Optical Clear Adhesive)から構成することが可能である。
導電体は、立体表面(三次元表面)を有する立体物と、立体表面に設けられ、樹脂部と、樹脂部中に配置され、複数の導電性繊維からなり、かつ立体表面の形状に追随した導電性繊維パターン(第1導電性繊維パターン)とを含む導電部を備えている。このような導電体としては、立体表面の形状に追随した導電性繊維パターンを備えていれば、特に限定されないが、例えば、上記センサー10が挙げられる。この場合の「追随」とは、導電性繊維パターンが全体として立体表面に沿い、かつ電気的に繋がっていることを意味する。したがって、各々の導電性繊維は立体表面に沿っていなくともよい。また、導電性繊維パターンは、立体表面の形状に厳密に沿っている必要はなく、概ね沿っていれば、立体表面に沿っているものとする。導電性繊維パターンが電気的に繋がっているか否かは、線抵抗値を測定することで確認することができる。例えば、導電性繊維パターンの線抵抗値が1000000Ω以下であれば、導電性繊維パターンが電気的に繋がっていると判断できる。
(銀ナノワイヤ分散液1)
アルコール溶媒としてエチレングリコール、銀化合物として硝酸銀、塩化物として塩化ナトリウム、臭化物として臭化ナトリウム、アルカリ金属水酸化物として水酸化ナトリウム、アルミニウム塩として硝酸アルミニウム九水和物、有機保護剤としてビニルピロリドンとジアリルジメチルアンモニウムナイトレイト(diallyldimethylammonium nitrate)のコポリマー(ビニルピロリドン99質量%、ジアリルジメチルアンモニウムナイトレイト1質量%でコポリマー作製、重量平均分子量130,000)を用意した。
銀ナノワイヤ分散液1よりもイソプロピルアルコールの添加量を多くして、粘度を0.008Pa・sとしたこと以外は、銀ナノワイヤ分散液1と同様にして、銀ナノワイヤ分散液2を得た。
銀ナノワイヤ分散液1よりもイソプロピルアルコールの添加量を少なくして、粘度を30Pa・sとしたこと以外は、銀ナノワイヤ分散液1と同様にして、銀ナノワイヤ分散液3を得た。
下記に示す組成となるように各成分を配合して、電気絶縁層用組成物1を得た。
(電気絶縁層用組成物1)
・ジペンタエリスリトールヘキサアクリレート(DPHA):100質量部
・重合開始剤(製品名「Omnirad184」、IGM Resins B.V.社製):4.0質量部
下記に示す組成となるように各成分を配合して、樹脂組成物を得た。
(樹脂組成物1)
・ジペンタエリスリトールヘキサアクリレート(DPHA):100質量部
・重合開始剤(製品名「Omnirad184」、IGM Resins B.V.社製):4.0質量部
・メチルイソブチルケトン(MIBK):500質量部
・ジペンタエリスリトールヘキサアクリレート(DPHA):100質量部
・重合開始剤(製品名「Omnirad184」、IGM Resins B.V.社製):4.0質量部
・メチルイソブチルケトン(MIBK):2000質量部
下記に示す組成となるように各成分を配合して、高屈折率層用組成物1を得た。
(高屈折率層用組成物1)
・ジペンタエリスリトールヘキサアクリレート(DPHA):14質量部
・酸化ジルコニウム微粒子分散液(平均粒径10~15nmの酸化ジルコニウム微粒子をメチルイソブチルケトンに分散させた分散液(固形分32.5%)):69質量部
・重合開始剤(製品名「Omnirad127」、IGM Resins B.V.社製):1.0質量部
・メチルイソブチルケトン(MIBK):1000質量部
下記に示す組成となるように各成分を配合して、低屈折率層用組成物1を得た。
(低屈折率層用組成物1)
・ジペンタエリスリトールヘキサアクリレート(DPHA)(製品名「KAYARAD DPHA」、日本化薬株式会社製):3.5質量部
・中実シリカ微粒子分散液(平均粒径10~15nmの中実シリカ微粒子をメチルイソブチルケトンに分散させた分散液(固形分30%)):21.7質量部
・重合開始剤(製品名「Omnirad127」、IGM Resins B.V.社製):0.7質量部
・メチルイソブチルケトン(MIBK):1000質量部
まず、基材としての片面に下地層を有する厚さ48μmのポリエチレンテレフタレートフィルム(商品名「コスモシャイン(登録商標)A4100」、東洋紡株式会社製)を準備し、このポリエチレンテレフタレートフィルムの未処理面側における、第1方向に配置された複数の第1電極部および隣り合う第1電極部同士を電気的に接続する配線部を有する第1導電部と、第1導電部と離間し、かつ第1方向と直交する第2方向に配置された複数の第2電極部とを形成すべき領域に、それぞれ銀ナノワイヤ分散液1を用いて、銀ナノワイヤを配置した。具体的には、まず、銀ナノワイヤ分散液を吐出可能なディスペンサを用いて、銀ナノワイヤ分散液1を第1導電部の形状および第2電極部の形状に塗布して、塗膜を形成した。その後、形成した塗膜に対して、0.5m/sの流速で40℃の乾燥空気を15秒間流通させた後、さらに15m/sの流速で70℃の乾燥空気を30秒間流通させ、乾燥させることにより塗膜中の溶剤を蒸発させた。これにより、ポリエチレンテレフタレートフィルムの表面に、第1導電部と第2電極部を形成すべき領域に銀ナノワイヤを配置して、それぞれ銀ナノワイヤパターンを形成した。
(吐出条件)
・吐出圧:5kPa
・吐出口径:100μm
・コーティングギャップ:50μm
・PETフィルム移動速度:1mm/秒
実施例2においては、ブリッジ配線部の幅W4を0.8mmとしたこと以外は、実施例1と同様にして、センサーを得た。
実施例3においては、ブリッジ配線部の幅W4を0.35mmとしたこと以外は、実施例1と同様にして、センサーを得た。
<実施例4>
実施例4においては、ブリッジ配線部の幅W4を0.1mmとしたこと以外は、実施例1と同様にして、センサーを得た。
まず、基材としての片面に下地層を有する厚さ48μmのポリエチレンテレフタレートフィルム(商品名「コスモシャイン(登録商標)A4100」、東洋紡株式会社製)を準備し、このポリエチレンテレフタレートフィルムの未処理面の全面にバーコーターを用いて銀ナノワイヤ分散液1を塗布して、塗膜を形成した。その後、形成した塗膜に対して、0.5m/sの流速で40℃の乾燥空気を15秒間流通させた後、さらに15m/sの流速で70℃の乾燥空気を30秒間流通させ、乾燥させることにより塗膜中の溶剤を蒸発させた。これにより、ポリエチレンテレフタレートフィルムの未処理面の全面に銀ナノワイヤを配置した。
(レーザー光照射条件)
・種類:YVO4
・波長:1064nm
・パルス幅:8~10ns
・周波数:100kHz
・スポット径:30μm
・パルスエネルギー:16μJ
・加工速度:1200mm/s
実施例6においては、ブリッジ配線部を形成すべき領域に以下のような工程で銀ナノワイヤを配置したこと以外は、実施例1と同様にして、センサーを得た。まず、電気絶縁層の表面に接触式ディスペンサ(製品名「SuperΣ(登録商標)CMIII」、武蔵エンジニアリング株式会社製)を用いて、以下の条件で、ディスペンサの吐出部から銀ナノワイヤ分散液1を塗布時の線厚が182μmとなるように吐出させて、線状に塗布し、直線状の塗工部を形成した。
(吐出条件)
・吐出圧:5kPa
・吐出口径:100μm
・コーティングギャップ:50μm
・PETフィルム移動速度:20mm/秒
実施例7においては、第1導電部および第2電極部を形成すべき領域に以下のような工程で銀ナノワイヤを配置したこと以外は、実施例1と同様にして、センサーを得た。まず、ポリエチレンテレフタレートフィルムの未処理面における、第1方向に配置された複数の第1電極部および隣り合う第1電極部同士を電気的に接続する配線部を有する第1導電部と、第1導電部と離間し、かつ第1方向と直交する第2方向に配置された複数の第2電極部とを形成すべき領域の両側に、それぞれ壁部用組成物1(商品名「U-403B」、ケミテック株式会社製)を用いて、フレキソ印刷法によって塗布して、塗膜を形成した。そして、形成した塗膜に対して、0.5m/sの流速で40℃の乾燥空気を15秒間流通させた後、さらに15m/sの流速で70℃の乾燥空気を30秒間流通させ、乾燥させることにより塗膜中の溶剤を蒸発させた。その後、紫外線を積算光量が100mJ/cm2になるように照射して塗膜を硬化させることにより、図13に示される形状の電気絶縁性の複数の壁部を形成した。壁部の幅は30μmであり、壁部の厚みは1μmであった。
比較例1に係るセンサーは、ブリッジ配線部を形成すべき領域に銀ナノワイヤを配置する工程およびそれ以降の工程を、以下のようにしたこと以外は、実施例1と同様にして、センサーを得た。具体的には、電気絶縁層の表面に、スパッタリング法により膜厚30nmのスズドープ酸化インジウム(ITO)層を形成した。ITO層を形成した後、ITO層を150℃で30分間加熱してITO層を結晶化させた。その後、フォトリソグラフィー技術を利用して、ITO層をパターニングした。これにより、屈折率が2.00のITOからなる幅0.1mm、長さ3mm、および膜厚30nmのブリッジ配線部を形成した。
比較例2においては、銀ナノワイヤ分散液1の代わりに銀ナノワイヤ分散液2を用いたこと以外は、実施例1と同様にして、センサーの作製を試みたところ、銀ナノワイヤ分散液2の粘度が低すぎたために、立体表面から銀ナノワイヤ分散液2が流れ落ちてしまい、ブリッジ配線部の銀ナノワイヤパターンを形成することができなかった。
比較例3においては、銀ナノワイヤ分散液1の代わりに銀ナノワイヤ分散液3を用いたこと以外は、実施例1と同様にして、センサーの作製を試みたところ、銀ナノワイヤ分散液3の粘度が高すぎたために、銀ナノワイヤ分散液3の吐出の際に銀ナノワイヤ分散液3が詰まってしまい、銀ナノワイヤパターンを形成することができなかった。
(1)折り畳み試験(FD試験)前後の電気抵抗値比評価
実施例1~7および比較例1に係るセンサーにおいて、折り畳み試験を行い、フレキシブル性を評価した。具体的には、まず、縦125mm×横50mmの長方形状のサンプル1、2をセンサーから切り出した。ここで、サンプル1は、サンプル1の長手方向が第1方向となるように切り出されたものであり、サンプル2は、サンプル2の長手方向が第2方向となるように切り出されたものであった。
(レーザー光照射条件)
・種類:YVO4
・波長:1064nm
・パルス幅:8~10ns
・周波数:100kHz
・スポット径:30μm
・パルスエネルギー:16μJ
・加工速度:1200mm/s
(折り畳み条件)
・往復速度:80rpm(回毎分)
・試験ストローク:60mm
・屈曲角度:180°
A:いずれの折り畳み試験においても、電気抵抗値比が1.5以下であった。
B:いずれの折り畳み試験においても、電気抵抗値比が1.5を超え、3以下であった。
C:いずれかの折り畳み試験において、電気抵抗値比が3を超えていた。
実施例1~7に係るセンサーにおいて、折り畳み試験後の外観を観察して、センサーの屈曲部に折り癖が生じているか評価した。折り畳み試験は、折り畳み試験前後の電気抵抗値比評価の欄に記載されている方法によって行われた。折り癖の観察は、温度23℃および相対湿度50%の環境下で、目視で行った。折り癖の観察の際には、白色照明の明室(800ルクス~2000ルクス)で、屈曲部を透過光および反射光によって満遍なく観察するともに、折り畳んだときに屈曲部における内側であった部分および外側であった部分を両方観察した。折り癖の観察においては、観察すべき位置が容易に把握できるように、折り畳み試験前のサンプルを耐久試験機の固定部に設置し、1回折り畳んだときに、図8に示したように、屈曲部における折り畳み方向に直交する方向に位置する両端に、屈曲部であることを示す目印を油性ペンで付けておいた。また、折り畳み試験後に、折り畳み試験後に耐久試験機から取り外した状態で、屈曲部の上記両端の目印同士を結んだ線を油性ペンで引いておいた。そして、折り癖の観察においては、屈曲部の上記両端の目印とこの目印同士を結ぶ線とで形成される領域である屈曲部全体を目視観察した。なお、折り畳み試験前における各センサーの屈曲部となる領域を観察したところ、折り癖は観察されなかった。評価基準は、以下の通りであった。
A:いずれの折り畳み試験後においても、センサーに折り癖が観察されなかった。
B:いずれの折り畳み試験後において、センサーに折り癖が若干観察されたが、実使用上問題のないレベルであった。
C:いずれかの折り畳み試験後において、センサーに折り癖が明確に観察された。
実施例1~7に係るセンサーにおいて、折り畳み試験後の外観を観察して、センサーの屈曲部にマイクロクラックが生じているか評価した。折り畳み試験は、折り畳み試験前後の電気抵抗値比評価の欄に記載されている方法によって行われた。マイクロクラックの観察は、温度23℃および相対湿度50%の環境下で、デジタルマイクロスコープ(製品名「VHX-5000」、キーエンス株式会社製)を用いて行った。具体的には、まず、折り畳み試験後のサンプルをゆっくり広げ、マイクロスコープのステージにテープでサンプルを固定した。このとき、折り癖が強い場合には、観察部分がなるべく平らになるようにする。ただし、サンプルの中央付近の観察予定領域(屈曲部)は手で触れず、力が加わらない程度する。次いで、折り畳んだときの内側となる部分および外側となる部分を両方観察した。マイクロクラックの観察は、デジタルマイクロスコープの照明としてリング照明を選択し、倍率200倍で、暗視野および反射光で行った。マイクロクラックの観察においては、観察すべき位置が容易に把握できるように、折り畳み試験前のサンプルを耐久試験機の固定部に設置し、1回折り畳んだときに、図9に示したように、屈曲部における折り畳み方向と直交する方向に位置する両端に、屈曲部であることを示す目印を油性ペンで付けておいた。また、折り畳み試験後に、折り畳み試験後に耐久試験機から取り外した状態で、屈曲部の上記両端の目印同士を結んだ線を油性ペンで引いておいた。そして、マイクロクラックの観察においては、マイクロスコープ視野範囲の中心が屈曲部の中央となるようにマイクロスコープの位置を合わせた。なお、折り畳み試験前における各センサーの屈曲部となる領域を観察したところ、マイクロクラックは観察されなかった。評価基準は、以下の通りであった。
A:いずれの折り畳み試験後においても、センサーにマイクロクラックが観察されなかった。
B:いずれかの折り畳み試験後において、センサーにマイクロクラックが若干観察されたが、実使用上問題のないレベルであった。
C:いずれの折り畳み試験後において、センサーにマイクロクラックが明確に観察された。
実施例1~7および比較例1に係るセンサーにおいて、ブリッジ配線部の形状が視認される否か評価した。具体的には、まず、センサーから100mm×100mmの大きさのサンプルを切り出した。そして、1200Luxの室内環境下において、このサンプルをブリッジ配線部が上側となるように配置して、白色LED灯(型番「Reach-18A」、プライム・スター株式会社製)下で目視によりブリッジ配線部の形状が視認されるか否かの評価を行った。目視観察は、センサーの法線方向を基準(0°)として、あらゆる角度(-180°~180°)から行われた。観察者は、15人とし、全ての観察者がブリッジ配線部の形状が視認された場合に、ブリッジ配線部の形状が視認されたと判断した。評価基準は以下の通りとした。
A:ブリッジ配線部の形状が視認されなかった。
B:ブリッジ配線部の形状が視認された。
実施例1~7および比較例1に係るセンサーにおいて、ヘイズメーター(製品名「HM-150」、株式会社村上色彩技術研究所製)を用いて、温度23℃および相対湿度50%の環境下で、JIS K7136:2000に従ってセンサーのヘイズ値(全ヘイズ値)を測定した。ヘイズ値は、センサー全体で測定したときの値である。センサーから50mm×100mmの大きさのサンプルを切り出した後、カールや皺がなく、かつ指紋や埃等がない状態で、第1導電部側が非光源側となるように設置して測定された。ヘイズ値は、サンプル1枚に対してヘイズ値を5回測定し、測定された5つのヘイズ値中、最大値と最小値を除いた3つのヘイズ値の算術平均値とした。
実施例1、6に係るセンサーにおけるブリッジ配線部中の銀ナノワイヤが、第2方向に沿って並んでいるか評価した。具体的には、まず、センサーから5mm×5mmの大きさのサンプルを切り出した。そして、走査透過型電子顕微鏡(製品名「S-4800(TYPE2)」、株式会社日立ハイテクノロジーズ製)のSEM機能を用い、サンプルにおけるブリッジ配線部の写真を1000倍~6000倍にて10枚撮影した。そして、ブリッジ配線部の各写真において、上記表面繊維配向解析プログラム(V.8.03)を用いて配向角度および配向強度を算出した。そして、ブリッジ配線部において、銀ナノワイヤの配向角度が0°±10°以内で、かつ配向強度が1.2以上である場合には、第2方向に銀ナノワイヤが並んでいるとし、配向角度が0°±10°以内であるが配向強度が1.2未満である場合または配向角度が1.2以上であるが配向角度が0°±10°を超える場合または配向角度が0°±10°を超え配向強度が1.2未満である場合には、ブリッジ配線部が延びる方向に銀ナノワイヤが並んでいないとした。評価基準は、以下の通りとした。
A:ブリッジ配線部中の銀ナノワイヤが、第2方向に沿って並んでいた。
B:ブリッジ配線部中の銀ナノワイヤが、第2方向に沿って並んでいなかった。
実施例1、7に係るセンサーの電気的短絡を評価した。具体的には、まず、センサーから第1方向および第2方向に沿って50mm×50mmの大きさのサンプルを切り出した。そして、テスター(製品名「Digital MΩ Hitester 3454-11」、日置電機株式会社製)を用いて、第1導電部と、第1導電部の隣に位置する第2導電部との間に電流が流れるか否か評価した。その後、65℃および相対湿度95%の環境下で、サンプルの第1導電部に32Vの電圧を100時間印加する耐久性試験を行った。耐久性試験後、テスター(製品名「Digital MΩ Hitester 3454-11」、日置電機株式会社製)を用いて、第1導電部と、第1導電部の隣に位置する第2導電部に電流が流れるか否かを評価することによって電気的に短絡しているか否かを評価した。評価基準は以下の通りとした。
A:耐久性試験前のみならず、耐久性試験後も第1導電部と第2導電部との間に電流が流れなかった。
B:耐久性試験前においては第1導電部と第2導電部の間に電流が流れず、また耐久性試験後においては第1導電部と第2導電部の間に電流が若干流れたが、実使用上問題ないレベルであった。
C:耐久性試験前においては第1導電部と第2導電部の間に電流が流れなかったが、耐久性試験後においては第1導電部と第2導電部の間に電流が流れた。
実施例1~7において、ブリッジ配線部の銀ナノワイヤパターンが、電気絶縁層の表面および第2電極部の銀ナノワイヤパターンの表面からなる立体表面に追随しているか否かを、評価した。追随評価は、走査透過型電子顕微鏡(STEM)を用いて撮影された断面写真と、線抵抗値測定とから判断した。具体的には、ブリッジ配線部の銀ナノワイヤパターンが立体表面に沿っており、かつ線抵抗値が1000000Ω以下である場合を、ブリッジ配線部の銀ナノワイヤパターンが立体表面に追随していたとし、ブリッジ配線部の銀ナノワイヤパターンが立体表面に沿っておらず、また線抵抗値が1000000Ωを超える場合を、ブリッジ配線部の銀ナノワイヤパターンが立体表面に追随していないとした。ブリッジ配線部の銀ナノワイヤパターンが立体表面に沿っているか否かは、走査透過型電子顕微鏡(STEM)を用いて撮影された断面写真から判断された。走査透過型電子顕微鏡による断面写真の撮影条件は、実施例1に記載されている断面写真の撮影条件と同様とした。線抵抗値測定においては、まず、折り畳み試験時と同様のサンプルを作製した。サンプルを得た後、温度23℃および相対湿度50%の環境下で、硬化した銀ペーストにテスター(製品名「Digital MΩ Hitester 3454-11」、日置電機株式会社製)のプローブ端子を接触させることによって抵抗値を測定した。具体的には、Digital MΩ Hitester 3454-11は、2本のプローブ端子(赤色プローブ端子および黒色プローブ端子、両方ともピン形)を備えているので、赤色プローブ端子を一方の硬化した銀ペーストにおけるブリッジ配線部と接触している部分に接触させ、かつ黒色プローブ端子を他方の硬化した銀ペーストにおけるブリッジ配線部と接触している部分に接触させて抵抗値を測定した。そして、上記の数式(2)から、ブリッジ配線部の線抵抗値を求めた。評価基準は、以下の通りとした。
A:ブリッジ配線部の銀ナノワイヤパターンが立体表面に追随していた。
B:ブリッジ配線部の銀ナノワイヤパターンが立体表面に追随していなかった。
実施例1~7に係るセンサーにおいて、ブリッジ配線部の静電気評価を行った。具体的には、センサーからブリッジ配線部を含むように10mm×150mmの大きさのサンプルを5枚切り出した後、それぞれのサンプルにおいてブリッジ配線部に電子銃で2kVを印加して、ブリッジ配線部の断線の有無を評価した。評価基準は、以下の通りとした。
A:サンプル全てに断線が無かった。
B:サンプル1枚~4枚に断線が無かった。
C:サンプル5枚全てが断線していた。
実施例1~7に係るセンサーにおいて、走査透過型電子顕微鏡(STEM、製品名「S-4800」、株式会社日立ハイテクノロジーズ製)を用いて、ブリッジ配線部に含まれる銀ナノワイヤの平均繊維径を測定した。具体的には、まず、センサーからブリッジ配線部を含むように1mm×10mmの大きさにサンプル切り出し、それをシリコーン系の包埋板に入れ、エポキシ系樹脂を流し込み、サンプル全体を樹脂にて包埋する。その後、包埋樹脂を25℃で12時間以上放置して、硬化させた。その後、ウルトラミクロトーム(製品名「ウルトラミクロトーム EM UC7」、ライカ マイクロシステムズ社製)を用いて、送り出し厚み100nmに設定し、超薄切片を作製した。作製した超薄切片をコロジオン膜付メッシュ(150)にて採取し、STEM用サンプルとした。その後、走査透過型電子顕微鏡(STEM)(製品名「S-4800(TYPE2)」、株式会社日立ハイテクノロジーズ製)を用いて、STEM用サンプルの断面写真を撮影した。この断面写真の撮影の際には、検出器(選択信号)を「TE」、加速電圧を30kV、エミッションを「10μA」にした。倍率については、フォーカスを調節しコントラストおよび明るさを各層が見分けられるか観察しながら5000倍~20万倍で適宜調節した。なお、断面写真の撮影の際には、さらに、ビームモニタ絞りを3にし、対物レンズ絞りを3にし、またW.D.を8mmにした。そして、撮影された断面の画像においてブリッジ配線部に含まれる10個の銀ナノワイヤを観察し、銀ナノワイヤの最も短い径(短径)をそれぞれ測定し、その10データ中、小さい方から3つのデータを選び、その3つのデータを用いて算術平均値を求め、その算術平均値を銀ナノワイヤの平均繊維径とした。
実施例1~7に係るセンサーにおいて、ブリッジ配線部中の銀ナノワイヤが、全体として、ブリッジ配線部中においてブリッジ配線部の厚みの半分の位置よりポリエチレンタレフタレートフィルム側に偏在しているか否か調べた。具体的には、まず、センサーから断面観察用のサンプルを作製した。詳細には、センサーからブリッジ配線部を含むように2mm×5mmにサンプルを切り出し、サンプルをシリコーン系の包埋板に入れ、エポキシ系樹脂を流し込み、サンプル全体を樹脂にて包埋した。その後、包埋樹脂を65℃で12時間以上放置して、硬化させた。その後、ウルトラミクロトーム(製品名「ウルトラミクロトーム EM UC7」、ライカ マイクロシステムズ社製)を用いて、送り出し厚み100nmに設定し、超薄切片を作製した。作製した超薄切片をコロジオン膜付メッシュ(150メッシュ)にて採取し、STEM用サンプルとした。その後、走査透過型電子顕微鏡(STEM)(製品名「S-4800(TYPE2)」、日立ハイテクノロジーズ社製)を用いて、STEM用サンプルの断面写真を撮影した。この断面写真の撮影の際には、検出器(選択信号)を「TE」、加速電圧を「30kV」、エミッション電流を「10μA」にしてSTEM観察を行う倍率については倍率2.5万倍~5万倍でフォーカスを調節し、コントラストおよび明るさを各層が見分けられるよう適宜調節した。また、断面写真の撮影の際には、さらに、アパーチャーを「ビームモニタ絞り3」、対物レンズ絞りを「3」にし、またW.D.を「8mm」にした。そして、このように撮影した10箇所の上記断面写真を用意した。次いで、各断面写真を画素レベルまで拡大し、各断面写真において、ブリッジ配線部の厚みの半分の位置よりポリエチレンタレフタレートフィルム側に位置する銀ナノワイヤが表示されている画素の個数およびブリッジ配線部の厚みの半分の位置よりブリッジ配線部の表面側に位置する銀ナノワイヤが表示されている画素の個数を数え、銀ナノワイヤが表示されている画素の全個数に対する上記半分の位置よりポリエチレンタレフタレートフィルム側に位置する銀ナノワイヤが表示されている画素の個数の割合を求めた。なお、銀ナノワイヤが表示されている画素が上記半分の位置に跨っている場合には、各画素において、上記半分の位置からポリエチレンタレフタレートフィルム側に存在している部分と、この位置からブリッジ配線部の表面側に存在している部分とに分けて、分けた部分の面積比に基づいて1画素を分けるものとした。そして、各断面写真から求めた上記割合を、ブリッジ配線部の厚みの半分の位置よりポリエチレンタレフタレートフィルム側に位置する銀ナノワイヤの存在割合とし、各断面写真から求めた存在割合の算術平均値を求め、この算術平均値が55%以上のときをポリエチレンテレフタレートフィルム側に偏在しているとした。評価基準は以下の通りとした。
A:ブリッジ配線部の厚みの半分の位置よりポリエチレンタレフタレートフィルム側に銀ナノワイヤが偏在していた。
B:ブリッジ配線部の厚みの半分の位置よりポリエチレンタレフタレートフィルム側に銀ナノワイヤが偏在していなかった。
11…基材
11A…表面
12…第1導電部
12A…第1電極部
12B…配線部
13…第2導電部
13A…第2電極部
13B…ブリッジ配線部
17…樹脂層
17A、17B…樹脂部
18A、18B…導電性繊維
100、110、130…導電体
101…立体物
101A、131A…立体表面
102、132…導電部
102A、132A…導電性繊維パターン
Claims (19)
- 基材と、前記基材の第1面側に設けられた第1導電部と、前記基材の前記第1面側に設けられ、かつ前記第1導電部から離間した第2導電部とを備えるセンサーであって、
前記第1導電部が、第1方向に配置された複数の第1電極部と、隣り合う前記第1電極部同士を電気的に接続する配線部とを有し、
前記第2導電部が、前記第1方向と交差する第2方向に配置された複数の第2電極部と、前記配線部を跨ぎ、かつ隣り合う前記第2電極部同士を電気的に接続するブリッジ配線部とを有し、
前記ブリッジ配線部が、樹脂部と、前記樹脂部中に配置された導電性繊維とを含む、センサー。 - 基材と、前記基材の第1面側に設けられた第1導電部と、前記基材の前記第1面側に設けられ、かつ前記第1導電部から離間した第2導電部とを備えるセンサーであって、
前記第1導電部が、第1方向に配置された複数の第1電極部と、隣り合う前記第1電極部同士を電気的に接続する配線部とを有し、
前記第2導電部が、前記第1方向と交差する第2方向に配置された複数の第2電極部と、前記配線部を跨ぎ、かつ隣り合う前記第2電極部同士を電気的に接続するブリッジ配線部とを有し、
前記第2電極部が導電性材料を含み、
前記ブリッジ配線部が、樹脂部と、前記樹脂部中に配置され、かつ前記第2電極部に含まれる前記導電性材料と同種の導電性材料とを含む、センサー。 - 前記第2電極部の前記導電性材料および前記ブリッジ配線部の前記導電性材料が、導電性繊維である、請求項2に記載のセンサー。
- 前記第2電極部の幅が10mm以下である、請求項1または2に記載のセンサー。
- 前記ブリッジ配線部の幅が0.35mm以上である、請求項1または2に記載のセンサー。
- 前記第1電極部および前記第1導電部の前記配線部が、それぞれ導電性繊維を含む、請求項1または2に記載のセンサー。
- 前記配線部と前記ブリッジ配線部の間に設けられた電気絶縁層をさらに備える、請求項1または2に記載のセンサー。
- 前記ブリッジ配線部と前記電気絶縁層の屈折率差の絶対値が、0.08以下である、請求項7に記載のセンサー。
- 請求項1または2に記載のセンサーを備える、物品。
- 前記物品が、画像表示装置である、請求項9に記載の物品。
- 基材の第1面側における、第1方向に配置された複数の第1電極部および隣り合う前記第1電極部同士を電気的に接続する配線部を有する第1導電部と、前記第1導電部と離間し、かつ前記第1方向と交差する第2方向に配置された複数の第2電極部とを形成すべき領域に、それぞれ第1導電性繊維を配置する工程と、
前記配線部を形成すべき領域に配置された前記第1導電性繊維を覆うように電気絶縁層を形成する工程と、
前記電気絶縁層上における、前記配線部を跨ぎ、かつ隣り合う前記第2電極部同士を電気的に接続するブリッジ配線部を形成すべき領域に、第2導電性繊維を配置する工程と、
前記第1導電性繊維および前記第2導電性繊維を覆う樹脂層を形成する工程と
を備える、センサーの製造方法。 - 前記第1導電性繊維を配置する工程が、前記基材の前記第1面側に樹脂部と前記第1導電性繊維とを含む導電層を形成する工程と、前記導電層における、前記第1導電部と前記第2電極部を形成すべき領域以外の領域に存在する少なくとも前記第1導電性繊維を除去する工程とを備える、請求項11に記載のセンサーの製造方法。
- 前記第2電極部の幅が10mm以下である、請求項11に記載のセンサーの製造方法。
- 前記ブリッジ配線部の幅が0.35mm以上である、請求項11に記載のセンサーの製造方法。
- 立体表面を有する立体物と、
前記立体表面に設けられ、複数の導電性繊維からなり、かつ前記立体表面の形状に追随した第1導電性繊維パターンを含む導電部と
を備える、導電体。 - 前記立体物が、基材と、前記基材の第1面側に設けられ、第1方向に配置された複数の第1電極部、および隣り合う前記第1電極部同士を電気的に接続する配線部を有する第1導電部と、前記基材の前記第1面側に設けられ、前記第1導電部から離間し、かつ前記第1方向と交差する第2方向に配置され、複数の導電性繊維からなる第2導電性繊維パターンと、前記配線部上に設けられた電気絶縁層とを備え、
前記立体表面が、前記電気絶縁層の表面と、前記第2導電性繊維パターンの表面とから構成されており、
前記第1導電性繊維パターンが、前記配線部を跨ぎ、隣り合う前記第2導電性繊維パターン同士が電気的に接続されるように、隣り合う前記第2導電性繊維パターンの前記表面と前記第2導電性繊維パターン間の前記電気絶縁層の前記表面に形成されている、請求項15に記載の導電体。 - 請求項15に記載の導電体を備える、センサー。
- 請求項17に記載のセンサーを備える、物品。
- 前記物品が、画像表示装置である、請求項18に記載の物品。
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Citations (5)
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JP2010231288A (ja) * | 2009-03-26 | 2010-10-14 | Seiko Epson Corp | タッチパネルとその製造方法及び表示装置並びに電子機器 |
US20110148780A1 (en) * | 2009-12-21 | 2011-06-23 | Lu Ying-Chi | Touch panel and fabricating method thereof |
JP2011254046A (ja) * | 2010-06-04 | 2011-12-15 | Fujifilm Corp | 三次元曲面構造体の製造方法 |
WO2013151052A1 (ja) * | 2012-04-04 | 2013-10-10 | 日立化成株式会社 | 導電パターンの形成方法及び導電パターン基板 |
JP2015056068A (ja) * | 2013-09-12 | 2015-03-23 | 株式会社アルバック | タッチパネルおよびタッチパネルの製造方法 |
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- 2021-09-29 JP JP2022554055A patent/JPWO2022071422A1/ja active Pending
- 2021-09-29 US US18/247,375 patent/US20230418424A1/en active Pending
- 2021-09-29 WO PCT/JP2021/035938 patent/WO2022071422A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010231288A (ja) * | 2009-03-26 | 2010-10-14 | Seiko Epson Corp | タッチパネルとその製造方法及び表示装置並びに電子機器 |
US20110148780A1 (en) * | 2009-12-21 | 2011-06-23 | Lu Ying-Chi | Touch panel and fabricating method thereof |
JP2011254046A (ja) * | 2010-06-04 | 2011-12-15 | Fujifilm Corp | 三次元曲面構造体の製造方法 |
WO2013151052A1 (ja) * | 2012-04-04 | 2013-10-10 | 日立化成株式会社 | 導電パターンの形成方法及び導電パターン基板 |
JP2015056068A (ja) * | 2013-09-12 | 2015-03-23 | 株式会社アルバック | タッチパネルおよびタッチパネルの製造方法 |
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JPWO2022071422A1 (ja) | 2022-04-07 |
US20230418424A1 (en) | 2023-12-28 |
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