JP2009501326A - Large surface distributed pressure sensor based on polythiophene - Google Patents

Abstract

（Ｉ）
（式中、Ｒ^１とＲ^２は、独立的にＣ_１−Ｃ_１２アルキル基を表すか、任意選択でＣ_１−Ｃ_１２アルキル、Ｃ_２−Ｃ_１２アルケン、ビニレン、ベンジル、フェニル、ハロゲン基によって置換された、または任意選択でＣ_１−Ｃ_１２アルキル基で置換されたエステル、アミノ、アミドもしくはエーテル官能基によって置換されたＣ_１−Ｃ_１２１，ｎ−アルキレン基（ｎ＝１〜１２）を形成する）を有する繰り返し構造を含有するポリチオフェンの層で全面的あるいは部分的に被覆された少なくとも二層のフレキシブル基材と、一個または複数個の絶縁スペーサと、を有する大表面分布型圧力センサに関する。本発明のセンサは、フレキシブルで、製造が容易で、要求に応じて相異なる単層または多層の対称構造を有し得る。In the present invention, at least one layer is represented by the formula (I):

(I)
Wherein R ¹ and R ² independently represent a C ₁ -C ₁₂ alkyl group, or optionally a C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkene, vinylene, benzyl, phenyl, halogen group. A C ₁ -C ₁₂ 1, n-alkylene group (n = 1-12) substituted by an ester, amino, amide or ether functional group substituted by or optionally substituted by a C ₁ -C ₁₂ alkyl group A large surface distributed pressure having at least two layers of a flexible substrate covered entirely or partially with a layer of polythiophene containing a repeating structure having a) and one or more insulating spacers It relates to sensors. The sensor of the present invention is flexible, easy to manufacture, and may have a single-layer or multi-layer symmetric structure as required.

Description

  The present invention relates to a distributed pressure sensor with a large surface area based on polythiophene. More specifically, the present invention relates to a flexible sheet coated with a polythiophene-like compound and assembled into different structures using suitable insulating spacers. Such structures include, in particular, symmetrical structures, single structures, and multilayer structures. The device of the present invention is flexible, easy to manufacture, and uses a polythiophene-type intrinsically conductive polymer as the sensor element.

  Distributed pressure sensors are useful for determining the force or pressure on a soft object, for example, measuring the interface pressure of a person sitting in a chair. For this application, the sensor needs to be flexible in order to strictly follow the curved shape of the chair and to properly measure the applied force. In addition, the sensor must be sufficiently thin so as not to introduce reading errors. This type of sensor usually has a thickness of 0.1 mm to several mm. In order to measure pressure at different points on the surface, the sensor area of each element of the distributed sensor needs to be as small as possible. In general, classification based on the number of sensor elements used can be divided into single sensors and array type sensors consisting of n × n elements. These can be further classified on the basis of output signals into sensors with two output signals (on-off type) and sensors with more than two output signals (analog or digital type sensors).

The performance required for flexible pressure sensors is usually lower than that required for conventional hard material sensors, and measurement inaccuracy of 5% to 10% can be tolerated. A flexible pressure sensor typically consists of a matrix-type array of a series of row and column elements. A flexible pressure sensor consisting of nxn sensor elements provides data relating to the pressure distribution shown on n ² regions of the sensor. This data is collected in the form of an electronic signal by converting the resistance change measurement provided by the sensor element into a voltage or intensity. The data thus obtained is linearized in order to optimize its resolution and simplify its interpretation. In order to improve the measurement accuracy, different sensor elements are calibrated by adjusting corresponding gains and offsets or by establishing a calibration curve. Using the data processed in this way, 2D and 3D pressure maps can be generated in real time.

  Different technologies that exist for the development of distributed pressure sensors may include, among other things, technologies that use changes in air pressure, hydraulic pressure, resistance, and capacity, as well as technologies that use piezoelectric elements. Techniques using piezoelectricity cannot be used for static measurements. This is because current loss occurs in these sensors, and the response signal becomes zero over time. Sensors based on pneumatic and hydraulic technology require very complex assemblies and large thicknesses, which limits their application to flexible sensors. Today, techniques that use resistance and capacitance changes are most commonly used for flexible pressure sensors.

  The principle of operation of a resistive sensor is based on the change in electrical resistance that occurs in a material that exhibits a piezoresistive effect when a force or pressure is applied. In the case of capacitive sensors, these operating principles are based on the change in capacitance that occurs when a force or pressure is applied over a structure obtained by sandwiching an elastomeric non-conductor between two parallel plates. This latter type of sensor has the disadvantage that it requires electronics that are extremely precise, highly sensitive and operate stably. This is because the measured change in capacitance is usually less than picofarady. In contrast, resistive type flexible pressure sensors use very simple electronics. The change in resistance is several orders of magnitude, has a high speed that is important for many sensor element arrays, and has little sensitivity to electromagnetic fields (capacitive sensors also have drawbacks in this regard). . As a disadvantage of these conventional sensors, we can emphasize that the sensor characteristics are non-linear and that the sensor response depends on the number of cycles used and the history of the sensor. Furthermore, the response of these sensors usually depends on temperature and relative humidity, so that the signal stability exhibited by the sensors is reduced and the lifetime may not be sufficiently long.

  Generally, a flexible pressure sensor existing in the market is composed of three layers. That is, the outer upper and lower two layers are made of a flexible material (woven fabric or polymer, US Pat. No. 6,155,120 and US Pat. No. 6,501,465) to which conductive wire, usually, Metal wire (US patent application 2003/0173195 and WO 99/39168) or metal particle filled conductive paste (US 6,646,540 and US 6,291,568) or carbon It is coated with black (US Pat. No. 6,597,276 and WO 00/25325), and the intermediate layer is made of a conductive ink type (US Pat. No. 5,652,395 and US Pat. No. 5). , 838,244) or non-conductive elastomer dielectrics (US Pat. No. 5,010,774 and WO 2004/064011). It is those prepared from a material.

  The use of polythiophenes, a family of extremely stable intrinsically conductive polymers that can be processed from aqueous dispersions, as active substances for the manufacture of distributed pressure sensors is also described in the latest technical information. Absent. US Pat. No. 4,959,430 and US Pat. No. 4,987,042 describe different procedures for preparing dispersions based on poly (ethylene-dioxy-thiophene), and US Pat. No. 5,766. 515 and US Pat. No. 5,370,981 describe the use of these as transparent electrodes in electroluminescent devices and the production of electrostatic plastics, respectively.

US Pat. No. 6,155,120 US Pat. No. 6,501,465 US Patent Application Publication No. 2003/0173195 International Publication No. 99/39168 Pamphlet US Pat. No. 6,646,540 US Pat. No. 6,291,568 US Pat. No. 6,597,276 International Publication No. 00/25325 pamphlet US Pat. No. 5,652,395 US Pat. No. 5,838,244 US Pat. No. 5,010,774 International Publication No. 2004/064011 Pamphlet US Pat. No. 4,959,430 US Pat. No. 4,987,042 US Pat. No. 5,766,515 US Pat. No. 5,370,981

  Accordingly, there remains a need for an advanced technology for an alternative large surface distributed pressure sensor that overcomes the shortcomings of the state of the art.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a large surface distributed pressure sensor having at least two layers of a flexible substrate and one or more insulating spacers, at least one layer of which is entirely or partially covered with a polythiophene layer. That is.

  Similarly, an object of the present invention is to provide a method of making the pressure sensor.

（Ｉ）
（式中、Ｒ^１とＲ^２は、独立的にＣ_１−Ｃ_１２アルキル基を表すか、任意選択でＣ_１−Ｃ_１２アルキル、Ｃ_２−Ｃ_１２アルケン、ビニレン、ベンジル、フェニル、ハロゲン基によって置換された、または任意選択でＣ_１−Ｃ_１２アルキル基で置換されたエステル、アミノ、アミドもしくはエーテル官能基によって置換されたＣ_１−Ｃ_１２１，ｎ−アルキレン基（ｎ＝１〜１２）を形成する）を有する繰り返し構造を含有するポリチオフェンの層で全面的あるいは部分的に被覆された少なくとも二層のフレキシブル基材と、一個または複数個の絶縁スペーサと、を有する大表面分布型圧力センサを提供する。 In the present invention, at least one layer is represented by the formula (I):

(I)
Wherein R ¹ and R ² independently represent a C ₁ -C ₁₂ alkyl group, or optionally a C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkene, vinylene, benzyl, phenyl, halogen group. A C ₁ -C ₁₂ 1, n-alkylene group (n = 1-12) substituted by an ester, amino, amide or ether functional group substituted by or optionally substituted by a C ₁ -C ₁₂ alkyl group A large surface distributed pressure having at least two layers of a flexible substrate covered entirely or partially with a layer of polythiophene containing a repeating structure having a) and one or more insulating spacers Provide a sensor.

  Within the context of the present invention, a “large surface distributed pressure sensor” is a sensor capable of measuring the pressure of the entire large surface (greater than 1 cm × 1 cm), In contrast, the sensor is flexible and can be curved.

A completely novel aspect of the present invention is the use of the above polythiophene (hereinafter referred to as “the polythiophene of the present invention”) as a sensor element. Thus, in a specific embodiment of the sensor of the present invention, the R ¹ and R ² groups of the polythiophene form an alkylene group selected from methylene, 1,2-ethylene and 1,3-propylene. In a preferred embodiment, the R ¹ and R ² groups form a 1,2-ethylene group. That is, the preferred polythiophene used in the sensor embodiment of the present invention is poly (ethylene-dioxy-thiophene).

  In another specific embodiment of the sensor of the present invention, the flexible substrate is a flexible plastic sheet. In a preferred embodiment, the flexible plastic sheet is made from a polymer having a high melting point or glass transition temperature, preferably polyethylene terephthalate or polycarbonate. In another preferred embodiment, the flexible plastic sheet is made of plasticized PVC, thermoplastic rubber, fiber, or polymer cloth.

  In another specific embodiment of the sensor of the present invention, the flexible substrate is a sheet of non-plastic material.

  In one preferred embodiment, the flexible substrate is a sheet of cellulose derivative material, preferably a sheet of cellulose paper.

  In another preferred embodiment, the flexible substrate is a sheet of woven material.

  In another preferred embodiment, the flexible substrate is a sheet of flexible glass.

  Surprisingly, it has been found that two flexible sheets coated with the polythiophene of the present invention are brought into contact so that both conductive films are in close proximity to each other (using suitable insulating spacers). ), When establishing a voltage difference between the two films, the current passing through is directly proportional to the pressure applied to the sheet at a given range of pressure, and at very high pressures the current will be constant. It is saturated.

  This effect is the effect used in the present invention for the production of the distributed pressure sensor based on the aforementioned polythiophene, but the rough (and simultaneously viscoelastic) of the used conductive film at the nm level. It can be attributed to the characteristics. The rough characteristics are as shown in FIG. 1 using an atomic force microscope (AFM). As will be described below, the form is caused by including conductive particles (electron conductivity) of the polythiophene and relatively insulating regions of the polyanion used as a dopant. Thus, it is conceivable that as the pressure applied to the polythiophene coated sheet increases, the number of conductive contact points on the nm scale increases to a certain pressure at which the maximum possible number of contact points is reached, and therefore The current value is saturated at that point. When the pressure is relieved by the viscoelastic properties of the film material, the current value will result in a return to roughly the original state since the pressure is gone.

  In order to prevent short circuits (when there is no pressure), an insulating spacer is used when assembling the distributed pressure sensor of the present invention to adjust the pressure range in which the sensor responds in a linear manner. Is convenient. The spacer is preferably made of a suitable stretchable module material that covers the pressure range. Then, the pressure range that the sensor can detect can be controlled based on its thickness and viscoelastic properties.

  Accordingly, in a preferred embodiment, the insulating spacer is silicone, foamed polymer or epoxy resin.

  As described above, an anionic group having an action of stabilizing the free positive charge carrier of the polymer chain can be added to the oxidized polythiophene. Thus, in a specific embodiment of the sensor of the present invention, the polythiophene contains an anionic dopant. In a preferred embodiment, the anionic dopant is an inorganic anion, preferably a sulfate, chloride, or bromide anion. In another embodiment, the anionic dopant is an organic anion having a sulfonate or phosphate group, preferably p-toluenesulfonic acid or p-toluenephosphonic acid. In another preferred embodiment, the anionic dopant is a polymeric carboxylic acid, preferably poly (acrylic acid), poly (methacrylic acid) or poly (maleic acid), polymeric sulfonic acid, preferably poly Organic polyanions selected from (styrene sulfonic) acid or poly (vinyl sulfonic acid), or other polymerizable monomers of vinyl carboxylic acid and vinyl sulfonic acid, preferably copolymers of styrene and acrylic or methacrylic monomers. In a further preferred embodiment, the molecular weight of the polyanion is preferably 15,000 to 300,000 daltons.

  Regarding the possible structures in which the present invention can be implemented, the simplest structure is formed by two identical flexible sheets on which polythiophene conductive tracks are deposited, ordered by insulating spacers arranged vertically between both sheets. Separated symmetrical structure. In this case, the height of the spacer must be greater than the height of the polythiophene conductive track. As mentioned above, after the non-conductive insulating spacers are combined in a sandwich or optionally encapsulated, the current intensity is between the top and bottom sheets as shown in FIG. When no pressure is applied, it has the function of preventing electrical contact between the conductive tracks of both sheets.

The pressure sensor configured in this manner provides an electrical signal proportional to the applied pressure, and can obtain pressure distribution data for n ² regions of the sensor by means of a matrix arrangement (n rows × n columns). Become. Furthermore, the detectable pressure range can be modified depending on the viscoelastic properties of the spacer used.

  A variation of the foregoing configuration is to replace one sheet with polythiophene conductive tracks with conductive tracks made from deposits of other conductive materials. Thus, in another embodiment of the sensor of the present invention, a polythiophene conductive track is deposited, a flexible sheet regularly separated by insulating spacers, and the track is deposited with another conductive material. In another embodiment, a single structure formed with two non-conductive flexible sheets is shown.

  Within the context of the present invention, “conductive material” means conductive silver paste, graphite paste, copper type metal material (silver, copper, nickel, etc.), or polypyrrole, polyaniline deposited from solution or dispersion. Or refers to an intrinsically conductive polymer of the polythiophene type.

  Other structures included in the present invention are those obtained using a sheet obtained by uniform deposition (eg, a film) of polythiophene on the sheet.

  Therefore, in a specific embodiment of the present invention, the sensor is composed of three layers. That is, formed from a flexible sheet on which a uniform conductive layer of polythiophene is deposited, a non-conductive flexible sheet on which tracks of conductive material are deposited, and an insulating spacer deposited on the conductive sheet of polythiophene Is done.

  In another specific embodiment, the sensor comprises a flexible sheet deposited with a uniform conductive layer of polythiophene, a non-conductive flexible sheet deposited with a track of conductive material, and a conductive material. It has a three-layer structure formed from insulating spacers deposited on a non-conductive sheet having tracks.

  The structure is formed from a sheet having a uniform deposit of polythiophene, a non-uniform electrically insulating layer or insulating spacer, and a sheet having conductive tracks obtained from the deposition of a conductive material, in particular two electrodes Is a multilayer structure capable of forming The electrical insulation layer can be manufactured by depositing a non-conductive material or a high electrical resistance material on top of any other layer, but the structure, thickness, and viscoelastic coefficient of this electrical insulation layer are Since they may be different, the sensor measurement range can be adapted and optimized in any way based on the above description.

  In another aspect of the invention, a method of making a large surface distributed pressure sensor based on the above description is provided. In this method, polythiophene is deposited, in whole or in part, on a flexible substrate, for example, in the form of a film or in the form of a track, as described above.

  The polythiophenes used in the present invention can be prepared by oxidative polymerization of the corresponding monomers or in situ polymerization methods carried out on the substrate, for example as described in the reference ADVANCED FUNCTIONAL MATERIALS 14, 615-622, 2004. Depending on the method, it has film-forming ability when formed from true solutions, colloidal dispersions, or stable dispersions of fine particles, whether aqueous or solvent based. Preferred solvents include alcohols, methanol, ethanol, and isopropanol, as well as mixtures of these alcohols with water, or other water-miscible organic solvents such as acetone and water. Preferred oxidizing agents include ammonium persulfate, iron trichloride, and iron tosyl. In addition, polymer binders such as poly (vinyl alcohol) and poly (vinyl acetate), and adhesion promoters such as silanes and tackifying resins make it easy to make highly adhesive films on substrates. Can be used to form.

  Thus, in a specific embodiment of the method, the polythiophene is filmed from a true solution, a colloidal dispersion, or a stable dispersion of fine particles, whether aqueous or solvent based, by oxidative polymerization of the corresponding thiophene monomer. As deposited. In these preferred embodiments, polymer-based binders such as poly (vinyl alcohol) or poly (vinyl acetate) and adhesion promoters such as silanes and tackifying resins are It can be used to easily form an adhesive film.

  In another embodiment of the method, the polythiophene is a true solution, colloidal dispersion, or microparticle, whether aqueous or solvent based, by an in situ polymerization method performed on the substrate. The film is deposited as a film from a stable dispersion of

  Forming the film on the flexible substrate can be performed by directly evaporating the liquid after the dispersion or solution is developed (applied) on the substrate by dipping, spraying, spin coating technique or the like.

  Thus, in another embodiment of the method, the polythiophene solution or dispersion is deposited on a flexible substrate by coating, dipping, spraying, spin coating techniques, etc., and later directly evaporating the solvent. Is done by.

  In another embodiment of the method, the polythiophene is a flexible sheet as a track using conventional methods of conductive polymer lithography, selective deposition, by ink jet printing, or by mechanical methods, preferably grinding. Is deposited on the flexible substrate as a track by peeling the conductive material from the substrate.

  In a preferred embodiment, the conductive track forms 2n electrodes corresponding to n sensors.

  In the following, the present invention will be described in three examples, but any case should not be considered as limiting the scope of the present invention.

Example 1
<Preparation of pressure sensor based on symmetrical structure having active area of 5 cm × 5 cm>
A thin layer of 1 cm active area and 175 μm thickness each of poly (ethylene-dioxy-thiophene) containing poly (styrene sulfonic) acid as polyanion (PEDOT-PSS) A pressure sensor was prepared from two flexible sheets of polyethylene terephthalate (PET) coated with 2 μm). The thin layer was deposited from a dispersion with a solids content of 2.5% by oxidative polymerization of ethylene-dioxy-thiophene monomer in water. The sheet was assembled into a symmetrical sandwich type structure using a 0.125 mm thick double sided adhesive insulating spacer (IS) (PET / PEDOT-PSS / IS / PEDOT-PSS / PET). The spacer was arranged as a flat band having a width of 0.5 cm along the edge of the sheet coated with PEDOT-PSS. The device thus assembled showed no signs of current passing through the device when no voltage was applied when a voltage was applied between the sheets. The sensor response measured as current intensity when applying different weights to the sensor surface and applying a voltage difference of 1V between both sheets is shown in FIG.

(Example 2)
<Production of pressure sensor based on a single structure having an active area of 1 cm × 1 cm>
A thin layer (1-2 μm) of 1 cm × 1 cm active area and a thickness of 175 μm, poly (ethylene-dioxy-thiophene) containing poly (styrenesulfonic) acid as polyanion (PEDOT-PSS) ) Was used to produce a pressure sensor from a single flexible sheet of polyethylene terephthalate (PET). The thin layer was deposited from a dispersion with a solids content of 2.5% by oxidative polymerization of ethylene-dioxy-thiophene monomer in water. A matrix of dots of epoxy resin was deposited on this sheet (thickness 15 μm) in one of the structures shown in FIG. Another flexible sheet (polyester) on which two electrodes of conductive material (silver) were deposited was adhered to the sample obtained as described above. The assembled device showed very high electrical resistance (on the order of MΩ) between the two electrodes. The change in sensor resistance when different weights are applied to the sensor surface is shown in FIG.

(Example 3)
<Preparation of pressure sensor based on symmetrical structure having active area of 5 cm × 5 cm>
A thin layer of 1 cm active area and a thickness of 105 μm each, comprising poly (ethylene-dioxy-thiophene) and containing poly (styrenesulfonic) acid as a polyanion (PEDOT-PSS) A pressure sensor was produced from two flexible sheets of cellulose paper (CP) coated with 2 μm). The thin layer was deposited from a dispersion with a solids content of 2.5% by oxidative polymerization of ethylene-dioxy-thiophene monomer in water. The sheet was assembled into a symmetrical sandwich type structure using a 0.125 mm thick double-sided adhesive insulating spacer (IS) (CP / PEDOT-PSS / IS / PEDOT-PSS / CP). The spacer was arranged as a flat band having a width of 0.5 cm along the edge of the sheet coated with PEDOT-PSS. The device thus assembled showed no signs of current passing through the device when no voltage was applied when a voltage was applied between the sheets. The sensor response measured as the current intensity when different weights were applied to the sensor surface and a voltage difference of 1 V was applied between both sheets was similar to that obtained with the sensor of Example 1. .

It is a graph of the atomic force microscope (AFM) photograph and microroughness statistics of the surface of a polythiophene type conductive polymer. In the schematic diagram showing the symmetrical structure of the pressure sensor according to the present invention, the white lines represent non-conductive insulating spacers separating the polythiophene conductive tracks. It is a graph which shows the response which appears in the form of electric current intensity when weight is added with respect to the symmetrical structure pressure sensor of this invention described in Example 1. FIG. FIG. 3 represents a different matrix of epoxy resin points useful for making the single structure pressure sensor of the present invention as described in Example 2. It is a graph which shows the resistance change which arises when weight is added with respect to the single structure pressure sensor of this invention described in Example 2. FIG.

Claims (27)

At least one layer is of formula (I):

(I)
Wherein R ¹ and R ² independently represent a C ₁ -C ₁₂ alkyl group, or optionally a C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkene, vinylene, benzyl, phenyl, halogen group. A C ₁ -C ₁₂ 1, n-alkylene group (n = 1-12) substituted by an ester, amino, amide or ether functional group substituted by or optionally substituted by a C ₁ -C ₁₂ alkyl group And at least two layers of a flexible substrate covered entirely or partially with a layer of polythiophene containing a repeating structure having
One or more insulating spacers;
A large surface distribution type pressure sensor characterized by comprising: 2. The large surface distributed pressure sensor according to claim 1, wherein R ¹ and R ^{2 of the} polythiophene form an alkylene group selected from methylene, 1,2-ethylene and 1,3-propylene. Large surface distributed pressure sensor. The large surface distribution type pressure sensor according to claim 2, wherein R ¹ and R ^{2 of the} polythiophene form a 1,2-ethylene group.   2. The large surface distribution type pressure sensor according to claim 1, wherein the flexible base material is a flexible plastic sheet.   5. A large surface distribution type pressure sensor according to claim 4, wherein the flexible plastic sheet is manufactured from a polymer having a high melting point or a high glass transition temperature, preferably polyethylene terephthalate or polycarbonate. Mold pressure sensor.   5. The large surface distribution type pressure sensor according to claim 4, wherein the flexible plastic sheet is manufactured from plasticizer-added PVC, thermoplastic rubber, fiber or polymer woven fabric. .   2. The large surface distribution type pressure sensor according to claim 1, wherein the flexible base material is a sheet made of a non-plastic material.   The large surface distribution type pressure sensor according to claim 7, wherein the flexible base material is a sheet of a cellulose derivative material.   9. The large surface distribution type pressure sensor according to claim 8, wherein the flexible base material is a sheet of cellulose paper.   8. The large surface distribution type pressure sensor according to claim 7, wherein the flexible base material is a sheet of a woven material.   8. The large surface distribution type pressure sensor according to claim 7, wherein the flexible substrate is a sheet of flexible glass.   2. The large surface distribution type pressure sensor according to claim 1, wherein the insulating spacer is made of silicone, foamed polymer, or epoxy resin.   2. The large surface distribution type pressure sensor according to claim 1, wherein the polythiophene contains an anionic dopant.   14. The large surface distribution type pressure sensor according to claim 13, wherein the anionic dopant is an inorganic anion, preferably a sulfate, chloride or bromide anion.   The large surface distributed pressure sensor according to claim 13, wherein the anionic dopant is an organic anion having a sulfonate or phosphate group, preferably p-toluenesulfonic acid or p-toluenephosphonic acid. Surface distribution type pressure sensor.   14. The large surface distributed pressure sensor according to claim 13, wherein the anionic dopant is a polymer carboxylic acid, preferably poly (acrylic acid), poly (methacrylic acid), poly (maleic acid), or polymer sulfone. Selected from acids, preferably poly (styrene sulfonic acid) or poly (vinyl sulfonic acid), or vinyl carboxylic acid and vinyl sulfonic acid and other polymerizable monomers, preferably copolymers of styrene and acrylic or methacrylic monomers A large surface distributed pressure sensor characterized by being an organic polyanion.   The large surface distribution type pressure sensor according to claim 16, wherein the polyanion used has a molecular weight of 15,000 to 300,000 daltons.   2. The large surface distributed pressure sensor according to claim 1, wherein the large surface distributed pressure sensor is formed by two identical flexible sheets on which polythiophene conductive tracks are deposited, and regularly separated by an insulating spacer vertically disposed between the two sheets. Large surface distribution type pressure sensor characterized by having a symmetrical structure.   2. The large surface distributed pressure sensor according to claim 1, wherein a polythiophene conductive track is deposited, a single flexible sheet regularly separated by an insulating spacer, and a track of another conductive material is deposited. A large surface distributed pressure sensor having a single structure formed of a conductive flexible sheet.   The large surface distribution type pressure sensor according to claim 1, wherein a flexible sheet on which a uniform conductive layer of polythiophene is deposited, a non-conductive flexible sheet on which tracks of conductive material are deposited, and a conductive material of polythiophene A large surface distributed pressure sensor having a three-layer structure formed of an insulating spacer deposited on the substrate.   The large surface distribution type pressure sensor according to claim 1, wherein a flexible sheet on which a uniform conductive layer of polythiophene is deposited, a non-conductive flexible sheet on which tracks of conductive material are deposited, and a track of conductive materials A large-surface distributed pressure sensor characterized by having a three-layer structure formed of insulating spacers deposited on a non-conductive sheet comprising   A method for producing a large surface distributed pressure sensor according to claims 1 to 21, wherein the polythiophene is a true solution, a colloidal dispersion, regardless of whether it is an aqueous solution or a solvent base, by oxidative polymerization of the corresponding thiophene monomer. Or a method for producing a large surface distributed pressure sensor, wherein the film is deposited as a film from a stable dispersion of fine particles on the flexible substrate.   23. A method according to claim 22, wherein a polymer binder of the poly (vinyl alcohol) or poly (vinyl acetate) type and an adhesion promoter of the silane or tackifying resin type are used, and the flexible substrate is highly advanced. A method characterized in that an adhesive film is easily formed.   22. A method of making a large surface distributed pressure sensor according to claims 1-21, wherein the polythiophene is prepared by an in situ oxidative polymerization method on the flexible substrate, an aqueous solution and a solvent base. Regardless of the method, a method for producing a large-surface-distributed pressure sensor, comprising depositing a true solution, a colloidal dispersion, or a stable dispersion of fine particles as a film on the flexible substrate.   25. A method for producing a large surface distributed pressure sensor according to claim 22-24, wherein the polythiophene solution or dispersion is deposited on the flexible substrate by coating, dipping, spraying, spin coating techniques, etc. A large surface distribution type pressure sensor manufacturing method characterized by directly evaporating a solvent with   22. A method of making a large surface distributed pressure sensor according to claims 1-21, wherein the polythiophene is tracked using conventional methods of conductive polymer lithography, selective deposition, by inkjet printing, Alternatively, a method for producing a large surface distributed pressure sensor, characterized in that the conductive material is peeled off from the flexible sheet by a mechanical method, preferably grinding, and is deposited as a track on the flexible substrate.   27. The method of claim 26, wherein the conductive track forms 2n electrodes corresponding to n sensors.

Images