KR101650827B1 - Conductive complex composite having piezoresistivity and piezoresistive device using the same - Google Patents
Conductive complex composite having piezoresistivity and piezoresistive device using the same Download PDFInfo
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- KR101650827B1 KR101650827B1 KR1020150053597A KR20150053597A KR101650827B1 KR 101650827 B1 KR101650827 B1 KR 101650827B1 KR 1020150053597 A KR1020150053597 A KR 1020150053597A KR 20150053597 A KR20150053597 A KR 20150053597A KR 101650827 B1 KR101650827 B1 KR 101650827B1
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- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
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Abstract
It can be used as a tactile sensor that can measure the external pressure or detect the area under pressure. It can also be used for various applications such as electronic and electric products, parts, automobiles and machines. And a piezoresistive element using the conductive composite composition.
The conductive composite composition having a piezoresistive characteristic according to the present invention is characterized by comprising 0.05 to 95 parts by weight of a conductive filler, 50 to 1000 parts by weight of a solvent, 0.01 to 5 parts by weight of a plasticizer and 0.01 to 5 parts by weight of a dispersant 0.01 To 5 parts by weight.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive composite composition and a piezoresistive element using the conductive composite composition. More particularly, the present invention relates to a conductive composite composition having a conductive filler added thereto at an optimal composition ratio, A conductive composite composition having a piezoresistive characteristic that can be utilized as a tactile sensor by measuring the external pressure intensity by measuring the strength of the external pressure through the piezoresistance characteristic in which the volume and the electric resistance value are reversibly changed, Device.
Piezoresistive effect refers to a change in the electrical resistance of a material due to external pressure or force. The piezoresistive effect can be classified into positive piezoresistivity and negative piezoresistivity. The positive voltage resistance characteristic indicates that the resistance value increases as the external stress increases , And the negative pressure resistance characteristic means that the resistance value decreases as the external stress increases. Further, the piezoresistance effect is distinguished from the piezoelectric effect which causes a change in the electrical potential because it causes only a change in the electric resistance value.
The piezoresistive sensor is a micro-electro-magnetometer (MEMS) sensor that detects pressure, vibration, and acceleration. The piezoresistive sensor detects pressure, Mechanical-System (MEMS) sensors.
Pressure measurement, which had previously been dependent on mechanical displacement, has begun to be developed as a small and high performance electronic sensor by utilizing the piezoresistive effects of metals, semiconductors, and conductive polymers, The change of the resistance is large, and the position control and the shape of the sensor are simple.
In particular, in the bent surfaces of various industrial equipments such as automobile engines and electric appliances, existing rigid pressure sensors are difficult to perform their functions properly, and in order to detect physical changes such as mutual contact action between operating systems, Development is required.
It is expected that a conductive composite using a rubber or polymer material having a high flexibility and excellent elastic restoration property as a composite substrate will be a good alternative to solve the above problems, and is soft and light in weight It can be applied to various fields.
The related literature is Korean Patent Laid-Open Publication No. 10-2011-0110388 (published on October 10, 2011), which discloses a method for manufacturing a pressure-sensitive device, a pressure-sensitive device manufactured by the method, and a pressure- A method of measuring the pressure by the pressure is described.
An object of the present invention is to provide a conductive composite composition in which a conductive filler is added at an optimal composition ratio to form a conductive composite layer by using a printing method, thereby having a piezoelectric resistance characteristic in which the volume and electric resistance value are reversibly changed according to an external pressure Therefore, it is an object of the present invention to provide a conductive composite composition having a piezoresistive characteristic that can be used as a tactile sensor that measures the external pressure or senses an area where a pressure is applied, and a piezoresistive element using the same.
In order to accomplish the above object, the conductive composite composition according to an embodiment of the present invention comprises 0.05 to 95 parts by weight of a conductive filler, 50 to 1000 parts by weight of a solvent, 0.01 to 5 parts by weight of a plasticizer, And 0.01 to 5 parts by weight of a dispersing agent.
According to an aspect of the present invention, there is provided a piezoresistive element comprising: a conductive composite layer produced by a printing method; A first electrode disposed on a lower surface of the conductive complex layer and patterned in a slit shape along a first direction; And a second electrode disposed on an upper surface of the conductive complex layer and patterned in a slit shape along a second direction intersecting the first direction.
The conductive composite composition having the piezoresistive characteristic and the piezoresistive element using the same according to the present invention are formed so that the filling amount of the conductive filler particles in the polymer composite layer is close to the percolation threshold value, By varying the type of the substrate and the conductive filler particles, the dispersibility of the conductive filler particles, the orientation direction, the shape and size of the conductive filler particles, and the thickness of the conductive composite layer, It is suitable for use as a tactile sensor.
Therefore, the conductive composite composition having the piezoresistive characteristic according to the present invention and the piezoresistive element using the same have a piezoresistive characteristic in which the volume and the electric resistance value are reversibly changed according to the external pressure. Therefore, Not only can it be used as a tactile sensor capable of sensing the area under pressure, but also can be applied to various applications such as electronic and electrical products, parts, automobiles, and machines.
1 is a perspective view illustrating a piezoresistive element having a piezoresistive characteristic according to an embodiment of the present invention.
2 and 3 are cross-sectional views taken along line II-II 'in FIG.
4 is a perspective view illustrating a tactile sensor according to an embodiment of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a conductive composite composition having a piezoresistive characteristic according to a preferred embodiment of the present invention and a piezoresistive element using the same will be described in detail with reference to the accompanying drawings.
The conductive composite composition having a piezoresistive property according to an embodiment of the present invention may include 0.05 to 95 parts by weight of a conductive filler, 50 to 1000 parts by weight of a solvent, 0.01 to 5 parts by weight of a plasticizer, 0.01 to 5 parts by weight of a dispersing agent.
The polymer substrate is nonconductive as the main material of the conductive composite composition. Such polymeric substrates may be selected from the group consisting of polyethylene, high density polyethylene, low density polyethylene, bakelite, neoprene, nylon, polystyrene, polyacrylonitrile, ultra high molecular weight polyethylene, ethylene vinyl acetate, polypropylene, polysulfurethylene, polyacrylates, At least one selected from the group consisting of vinyl butyral, polyvinyl chloride, ethylene propylene rubber (EPDM), polydimethylsiloxane (PDMS), alkyl glycidyl ether, polyfunctional acrylic resin, acryl-urethane copolymer, carboxyl binder and amide binder . ≪ / RTI >
The conductive filler is added to the polymer base material and serves to selectively impart conductivity to the conductive composite layer by the electric tunneling effect. The conductive filler is preferably added in an amount of 0.05 to 95 parts by weight based on 100 parts by weight of the polymer resin. More preferably in an amount of about 10 parts by weight based on the penetration threshold value concentration so as to be a concentration near the penetration threshold value.
When the amount of the conductive filler to be added is less than 0.05 part by weight based on 100 parts by weight of the polymer resin, the addition amount of the conductive filler is insignificant, so that it may be difficult to exhibit the electric tunneling effect properly. Conversely, when the amount of the conductive filler added is more than 95 parts by weight based on 100 parts by weight of the polymer resin, it is not economical since it can act as a factor for raising the manufacturing cost without any additional effect.
Such a conductive filler may be a semiconductor material containing a metal material including Ag, Au, Al, Cu, Pt, Ni and Fe, vanadium oxide and titanium oxide, carbon black, acetylene black, Carbon materials including carbon nanotubes and multi-wall carbon nanotubes.
At this time, the conductive filler preferably has an average particle size of 10 nm to 100 μm. When the average particle size of the conductive filler is less than 10 nm, the dispersion stability may be deteriorated. On the contrary, when the average particle size of the conductive filler exceeds 100 탆, problems such as nozzle clogging may occur during the printing process.
The solvent is selected from the group consisting of polyalcohol, dimethylsulfoxide, N, N-dimethylformamide, ethylene glycol, polyethylene glycol, meso-erythritol, aniline, acetone, methyl ethyl ketone, isopropyl alcohol, butyl alcohol, ethyl alcohol, The solvent is preferably selected from amides, hexanes, toluene, chloroform, cyclohexanone, distilled water, pyridine, methylnaphthalene, octamethylamine, tetraacetamide, hexane, toluene, chloroform, cyclohexanone, distilled water, pyridine, methylnaphthalene, octamethylamine, Furan, dichlorobenzene, dimethylbenzene, trimethylbenzene, nitromethane, and acrylonitrile may be used.
Plasticizers are added for the purpose of lowering the modulus of elasticity. Such plasticizers may include at least one selected from phthalic acid esters, fatty acid esters, polyarylene glycol dielectrics, waxes and glycerin.
Such a plasticizer is preferably added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polymer base material. When the amount of the plasticizer to be added is less than 0.01 part by weight based on 100 parts by weight of the polymer base material, the elastic modulus is so high that the change in capacitance is induced to decrease the contact sensitivity. On the contrary, when the amount of the plasticizer to be added is more than 5 parts by weight based on 100 parts by weight of the polymer base material, there arises a problem of matrix hardening or a problem of resilience due to elasticity, which may easily break or deform.
The dispersant is added for the purpose of improving the flow characteristics of the paste. Such dispersing agents may include at least one selected from the group consisting of acrylic acid type, fatty acid type, sulfonic acid type, phosphoric acid ester type, sulfuric acid ester type, polyarylene glycol type and amine type dispersing agent.
Such a dispersant is preferably added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polymer base material. When the addition amount of the dispersing agent is less than 0.01 part by weight based on 100 parts by weight of the polymer base material, there is a possibility that the effect of the addition is not properly exhibited. On the other hand, if the addition amount of the dispersing agent is more than 5 parts by weight based on 100 parts by weight of the polymer base material, it can not be economical because it can only increase the manufacturing cost without increasing the effect.
When the conductive composite composition having the above composition is formed by using the printing method, since the volume resistivity and the electric resistance value are reversibly changed according to the external pressure, the strength of the external pressure can be measured, It can be used as a tactile sensor that can sense the area under pressure.
In this case, the material having the piezoresistive characteristic includes a metal, a semiconductor, a conductive polymer, and a conductive composite, and a conductive composite made of a rubber or a polymer as a substrate has high flexibility and excellent elastic recovery It has the advantage that it can be applied to curved surfaces and it can be used repeatedly in dynamic products.
The conductive composite layer composed of the conductive particles and the polymer resin of the non-conductive substrate functions as an important parameter for the resistance of the conductive filler particles and the current flow path between the first and second electrodes, , The resistance across one particle, and the number of particles that generate the current flow path determine the total resistance value of the conductive composite layer.
When stress is applied to the conductive composite layer, the difference in compressibility between the conductive filler particles and the polymer substrate causes a change in distance between the conductive filler particles, resulting in a change in resistance. In particular, because the conductive filler particles have a much lower compressive modulus than the polymeric substrate of the nonconductive substrate, the deformation of the polymeric substrate shortens the distance between the conductive filler particles, and the tunneling current flows through the particle spacing Resulting in a change in the electrical resistance value of the conductive composite layer.
In particular, one of the important factors in the conductive composite layer is the percolation threshold, which is the concentration at which the polymeric substrate of the nonconductive substrate becomes conductive. When the conductive filler particles are three-dimensionally uniformly dispersed in the conductive composite layer, a current flow path connecting the first and second electrodes with respect to the filling amount of the specific conductive filler particles is generated, The electrical conductivity of the conductive filler particles is changed from the insulating region to the conductive region, and the electrical resistance value changes suddenly. The filling amount of the conductive filler particles is referred to as the penetration threshold value.
In the conductive composite layer, the penetration threshold value is significantly changed depending on the kind of the polymer substrate and the conductive filler particles, and the dispersion property of the conductive filler particles filled in the conductive composite layer, the orientation direction, the particle shape and size, And the like.
In order to be used as a tactile sensor having a piezoresistive characteristic, such as a measuring device for measuring stress or load, a piezoresistive characteristic with a very high change rate of an electrical resistance value according to a pressure change is required. In order to fabricate a tactile sensor having a resistance characteristic that is sensitive to such a stress change, a characteristic that the electric conductivity of the conductive complex layer transitions from the insulating region to the conductive region should be used in proportion to the magnitude of the stress applied to the material.
Therefore, it is preferable to form the polymer composite layer so that the amount of the conductive particles filled in the polymer composite layer is close to the percolation threshold, and the kind of the polymer resin and the conductive filler particles, the dispersibility of the conductive filler particles, And the thickness of the conductive composite layer are the main factors determining the penetration threshold value. Therefore, it is important to form a conductive composite layer considering the correlation therebetween.
Hereinafter, a piezoresistive element having a piezoresistive characteristic according to an embodiment of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a perspective view showing a piezoresistive element having a piezoresistive characteristic according to an embodiment of the present invention, and FIGS. 2 and 3 are cross-sectional views taken along the line II-II 'in FIG.
1 to 3, a
The conductive
The conductive
The
It is preferable that the conductive
The
Each of the first and
A pressure can be applied to the first electrode or the second electrode of the piezoresistive element having the above-described configuration. Fig. 2 shows a state in which no pressure is applied to the piezoresistive element. Respectively.
3, when the
That is, when the
As the intensity of the
In particular, the
Accordingly, the changing current or resistance is measured through the
4 is a perspective view illustrating a tactile sensor according to an embodiment of the present invention.
Referring to FIG. 4, a conductive
When a
As described above, the conductive composite composition having the piezoresistive characteristic and the piezoresistive element using the same according to the embodiment of the present invention have a composition ratio such that the filling amount of the conductive filler particles in the polymer composite layer is close to the percolation threshold In addition, by changing the type of the polymer substrate and the conductive filler particles of the polymer composite layer, the dispersibility of the conductive filler particles, the orientation direction, the shape and size, and the thickness of the conductive composite layer, Is very suitable for use as a tactile sensor.
Therefore, the conductive composite composition having the piezoresistive characteristic according to the present invention and the piezoresistive element using the same have a piezoresistive characteristic in which the volume and the electric resistance value are reversibly changed according to the external pressure. Therefore, Not only can it be used as a tactile sensor capable of sensing the area under pressure, but also can be applied to various applications such as electronic and electrical products, parts, automobiles, and machines.
Example
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
1. Manufacture of piezoresistive element
Example 1
A conductive composite composition consisting of 30 parts by weight of a conductive filler, 700 parts by weight of a solvent, 3 parts by weight of a plasticizer and 2 parts by weight of a dispersant was coated on a PET film to a thickness of 3 mm with respect to 100 parts by weight of a polymer substrate, Lt; 0 > C for 1 hour to prepare a conductive composite layer.
Next, a first metal layer was formed on the lower surface of the conductive composite layer to a thickness of 0.3 mm, and then the first metal layer was patterned by wet etching to form a first electrode having a slit shape along the first direction.
Next, after removing the PET film, a second metal layer is formed on the upper surface of the conductive complex layer to a thickness of 0.3 mm, and then the second metal layer is patterned by wet etching to form a slit shape along the second direction intersecting the first direction A second electrode having a thickness of 100 nm was formed to produce a piezoresistive element.
Example 2
Resistive elements were prepared in the same manner as in Example 1, except that conductive composite compositions consisting of 60 parts by weight of a conductive filler, 600 parts by weight of a solvent, 3 parts by weight of a plasticizer and 2 parts by weight of a dispersing agent were used for 100 parts by weight of a polymer substrate .
Example 3
Resistive elements were prepared in the same manner as in Example 1 except that conductive composite compositions consisting of 80 parts by weight of a conductive filler, 900 parts by weight of a solvent, 3 parts by weight of a plasticizer and 2 parts by weight of a dispersant were used for 100 parts by weight of a polymer substrate .
2. Property evaluation
Table 1 shows the results of physical properties evaluation of the piezoresistive devices according to Examples 1 to 3.
[Table 1]
As shown in Table 1, the resistivity of the piezoresistive device according to Examples 1 to 3 was measured. As the pressure increased, the electric tunneling effect was increased. As a result, the amount of current increased and the resistivity decreased .
The conductive filler was added in an amount of 30 parts by weight based on 100 parts by weight of the polymer base material and the conductive filler was added in an amount of 60 parts by weight and 80 parts by weight based on 100 parts by weight of the polymer base material, 3 shows that the resistivity is remarkably decreased.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. These changes and modifications may be made without departing from the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.
100: Resistive element
120: conductive composite layer
122: nonconductive elastic substrate
124: Conductive filler
140: first electrode
160: Second electrode
Claims (16)
Conductive filler: 0.05 to 95 parts by weight,
Solvent: 50 to 1000 parts by weight,
0.01 to 5 parts by weight of a plasticizer, and
0.01 to 5 parts by weight of a dispersing agent,
Wherein the plasticizer comprises at least one selected from phthalic acid ester, fatty acid ester, polyarylene glycol dielectric, wax and glycerin,
Wherein the dispersant comprises at least one selected from the group consisting of acrylic acid type, fatty acid type, sulfonic acid type, phosphoric acid ester type, sulfuric acid ester type, polyarylene glycol type and amine type dispersant.
The polymer substrate
A polyolefin such as polyethylene, high density polyethylene, low density polyethylene, bakelite, neoprene, nylon, polystyrene, polyacrylonitrile, ultra high molecular weight polyethylene, ethylene vinyl acetate, polypropylene, polysulfurethylene ethylene, polyacrylate, polyurethane, Those containing at least one selected from polyvinyl chloride, ethylene propylene rubber (EPDM), polydimethylsiloxane (PDMS), alkyl glycidyl ether, polyfunctional acrylic resin, acryl-urethane copolymer, carboxyl-based binder and amide-based binder Wherein the conductive composite composition has a piezoresistive property.
The conductive filler
A semiconductor material comprising a metal material including Ag, Au, Al, Cu, Pt, Ni and Fe, vanadium oxide and titanium oxide, carbon black, acetylene black, Wherein the carbon nanotubes contain at least one selected from the group consisting of carbon materials including carbon nanotubes and multi-wall carbon nanotubes.
The conductive filler
And having an average particle size of 10 nm to 100 탆.
The solvent
But are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, isopropyl alcohol, isopropyl alcohol, butyl alcohol, isopropyl alcohol, The organic solvent is selected from the group consisting of hexane, toluene, chloroform, cyclohexanone, distilled water, pyridine, methylnaphthalene, octamethylamine, tetraacetamide, hexane, toluene, chloroform, cyclohexanone, distilled water, pyridine, methylnaphthalene, octamethylamine, Wherein the conductive composite composition comprises at least one selected from the group consisting of dichlorobenzene, dimethylbenzene, trimethylbenzene, nitromethane, and acrylonitrile.
A first electrode disposed on a lower surface of the conductive complex layer and patterned in a slit shape along a first direction; And
And a second electrode disposed on the upper surface of the conductive complex layer and patterned in a slit shape along a second direction crossing the first direction,
The conductive composite composition is composed of 0.05 to 95 parts by weight of a conductive filler, 50 to 1000 parts by weight of a solvent, 0.01 to 5 parts by weight of a plasticizer, and 0.01 to 5 parts by weight of a dispersant, based on 100 parts by weight of a polymeric base material,
Wherein the plasticizer comprises at least one selected from phthalic acid ester, fatty acid ester, polyarylene glycol dielectric, wax and glycerin,
Wherein the dispersing agent comprises at least one selected from the group consisting of an acrylic acid type, a fatty acid type, a sulfonic acid type, a phosphoric acid ester type, a sulfuric acid ester type, a polyarylene glycol type and an amine type dispersant.
The conductive composite layer
And has a thickness of 0.1 占 퐉 to 5 mm.
Each of the first and second electrodes
And has a thickness of 0.1 占 퐉 to 1 mm.
Each of the first and second electrodes
PEDOT, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene and polystyrene sulfonate, and a metal including Ag, Pt, Pd, Ni and Ag-Pb alloy Lt; / RTI >
When an external force is applied to the first electrode or the second electrode,
Wherein the conductive composite layer is compressed in a direction in which the external force is applied and an electric tunneling effect is generated between the conductive filler particles in the compressed region to apply a current between the first and second electrodes. device.
Due to the electrical tunneling effect,
And a current of 1mA to 100A is supplied between the first and second electrodes.
Wherein the tactile sensor is provided with the piezoresistive element alone to measure an area where the pressure is applied.
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| CN111982362A (en) * | 2020-08-25 | 2020-11-24 | 工科思维技术(深圳)有限公司 | Method for preparing high-sensitivity flexible piezoresistive sensor based on fracture microstructure |
| CN111982362B (en) * | 2020-08-25 | 2022-12-20 | 工科思维技术(深圳)有限公司 | Method for preparing high-sensitivity flexible piezoresistive sensor based on fracture microstructure |
| CN112374490A (en) * | 2020-10-31 | 2021-02-19 | 华南理工大学 | Three-dimensional porous graphene/polyurethane flexible stress-strain sensor and preparation method thereof |
| CN112374490B (en) * | 2020-10-31 | 2022-08-16 | 华南理工大学 | Three-dimensional porous graphene/polyurethane flexible stress-strain sensor and preparation method thereof |
| KR20230102850A (en) | 2021-12-30 | 2023-07-07 | 현대자동차주식회사 | Preparing method for conductive composite, conductive composite and ppiezoresistive device using the same |
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