WO2015140943A1 - 導電性樹脂組成物及び感圧センサ - Google Patents
導電性樹脂組成物及び感圧センサ Download PDFInfo
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- WO2015140943A1 WO2015140943A1 PCT/JP2014/057420 JP2014057420W WO2015140943A1 WO 2015140943 A1 WO2015140943 A1 WO 2015140943A1 JP 2014057420 W JP2014057420 W JP 2014057420W WO 2015140943 A1 WO2015140943 A1 WO 2015140943A1
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- resin composition
- conductive resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
- G01L1/22—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to a conductive resin composition and a pressure sensitive sensor.
- a pressure-sensitive sensor having a plurality of conductors provided apart from each other is known (see, for example, Patent Documents 1 and 2).
- Such a pressure-sensitive sensor functions as a switch when a plurality of conductors come into contact with each other and become conductive when receiving an external force.
- the pressure-sensitive sensor described in Patent Document 1 has a structure in which four linear electrode wires are spirally provided along the inner peripheral surface of a cylindrical insulator so as not to contact each other through a gap. Thus, external forces in all directions can be reliably detected.
- These electrode wires are composed of an electric conductor made of a tin-plated annealed copper stranded wire and a conductive rubber covering the surface thereof. This conductive rubber is disclosed to contain carbon black.
- the cord switch described in Patent Document 2 is a linear pressure-sensitive sensor, and has a structure in which the end portion of a rubber cover that covers the outer periphery of a cylindrical insulator is sealed with a hot-melt resin.
- a hot melt resin as a sealant, the curing time of the sealant can be shortened and a code switch can be manufactured efficiently.
- the plurality of conductors provided in the cord switch are composed of a core wire and a conductive resin covering the surface thereof. Details of this conductive resin are not disclosed.
- a conductive rubber composition that is used as a material for a conductor of a pressure-sensitive sensor and has excellent processability is known (see, for example, Patent Document 3).
- the conductive rubber composition described in Patent Document 3 is a base rubber having a Mooney viscosity ML 1 + 4 (100 ° C.) of 40 or less, in which an ethylene- ⁇ -olefin copolymer and carbon as a conductivity-imparting agent are added. It is.
- One of the objects of the present invention is to have a conductive resin composition that can be manufactured at low cost, suitable for the material of the conductor of the pressure-sensitive sensor, and a conductor made of the conductive resin composition.
- the object is to provide a pressure sensitive sensor.
- an insulator having a hollow portion, and a plurality of conductors provided apart from each other along an inner surface of the insulator facing the hollow portion; And the plurality of conductors are made of a conductive resin composition containing a styrene-based thermoplastic elastomer and carbon.
- Another aspect of the present invention provides a conductive resin composition containing a styrenic thermoplastic elastomer and carbon.
- the pressure sensitive sensor which has a conductor suitable for the material of the conductor of a pressure sensor which can be manufactured at low cost, and the conductor made from the conductive resin composition. Can be provided.
- FIG. 1 is a radial sectional view of a linear pressure sensor according to an embodiment.
- FIG. 2A is a schematic diagram showing an internal state of the conductor at a temperature higher than the melting point of the crystalline polyolefin.
- FIG. 2B is a schematic diagram showing an internal state of the conductor at a temperature lower than the melting point of the crystalline polyolefin.
- FIG. 3 is a graph showing the relationship between the carbon concentration (mass%) and the volume resistivity (Ohm ⁇ cm) in each of the conductive resin compositions according to the examples with and without the crystalline polyolefin. It is.
- FIG. 1 is a radial cross-sectional view of a linear pressure-sensitive sensor 1 according to an embodiment.
- the pressure-sensitive sensor 1 includes an insulator 10 having a hollow portion 13 and a plurality of conductors 11 provided to be separated from each other along an inner surface facing the hollow portion 13 of the insulator 10.
- the conductor 11 covers the core wire 12, and the conductor 11 and the core wire 12 constitute an electrode wire 14 of the pressure sensor 1.
- the two conductors 11 come into contact with each other and become conductive, so that the pressure sensor 1 functions as a switch.
- the pressure-sensitive sensor 1 is a linear pressure-sensitive sensor, and is provided in a spiral shape so that the two electrode wires 14 do not contact each other through a gap.
- the structure of the pressure sensor 1 is not limited to such a structure.
- the number of the conductors 11 may be three or more, and the shapes of the insulator 10 and the conductor 11 may be shapes other than a linear shape such as a flat plate shape.
- the core wire 12 is a stranded wire of, for example, a 26-30 AWG silver-plated annealed copper wire.
- the conductor 11 is made of a conductive resin composition containing a styrene-based thermoplastic elastomer and carbon. Styrenic thermoplastic elastomers do not require crosslinking during molding. For this reason, the manufacturing process of the conductor 11 can be simplified and the manufacturing cost can be reduced as compared with the case of using a material that needs to be cross-linked at the time of molding such as EPDM (ethylene propylene diene rubber).
- EPDM ethylene propylene diene rubber
- Styrenic thermoplastic elastomer is a thermoplastic elastomer having styrene blocks at both ends of the molecule.
- the styrenic thermoplastic elastomer include SEBS having styrene blocks at both ends of EB (ethylene-butylene), SEPS having styrene blocks at both ends of EP (ethylene-propylene), or EEP (ethylene-ethylene-propylene).
- SEEPS having styrene blocks at both ends.
- the molecular weight of the styrene-based thermoplastic elastomer is preferably about 100,000 to 200,000. If the molecular weight exceeds 200,000, the surface of the conductor 11 after extrusion may be uneven. This is presumably because if the molecular weight of the styrene-based thermoplastic elastomer is too large, the molecular chains are not easily entangled during kneading, and the dispersibility of crystalline polyolefin and the like to be described later is deteriorated.
- the conductive resin composition constituting the conductor 11 preferably contains a crystalline polyolefin.
- the conductor material can be kneaded in a state where the crystalline polyolefin is in a liquid state.
- crystalline polyolefin crystallizes in the conductor 11 under normal temperature (25 degreeC).
- FIG. 2A is a schematic diagram showing the internal state of the conductor 11 at a temperature higher than the melting point of the crystalline polyolefin.
- a region surrounded by a dotted line in FIG. 2A represents the liquid crystalline polyolefin 21 a in the styrene-based thermoplastic elastomer 20.
- carbon 22 is contained in the styrenic thermoplastic elastomer 20 and the liquid crystalline polyolefin 21a at a temperature higher than the melting point of the crystalline polyolefin.
- FIG. 2B is a schematic diagram showing the internal state of the conductor 11 at a temperature lower than the melting point of the crystalline polyolefin.
- the crystallized crystalline polyolefin 21b shown in FIG. 2B is obtained by crystallizing the liquid crystalline polyolefin 21a with a decrease in temperature.
- the carbon 22 contained in the liquid crystalline polyolefin 21 a is extruded into the styrene-based thermoplastic elastomer 20.
- the carbon 22 is more densely formed and more conductive paths are formed, and the conductivity of the conductor 11 is improved.
- conductivity can be obtained with a smaller amount of carbon 22 than when crystalline polyolefin is not used, the amount of carbon 22 can be reduced, and the manufacturing cost of the conductor 11 can be reduced.
- a crystalline polyolefin having a melting point of 180 ° C. or lower and a normal temperature of 25 ° C. or higher is preferable to use.
- a crystalline polyolefin for example, polypropylene having a melting point of about 140 to 160 ° C., polyethylene having a melting point of about 100 to 140 ° C., EVA (ethylene vinyl acetate copolymer) having a melting point of about 80 ° C. can be used.
- polypropylene which does not have a too large particle size after crystallization, as the crystalline polyolefin because it is easily compatible with styrene-based thermoplastic elastomer and has good dispersibility.
- the ratio of the mass of polypropylene contained in the conductor 11 to the mass of carbon contained in the conductor 11 is preferably 0.20 or more and 1.10 or less. When this ratio is 0.20 or more, the conductivity of the conductor 11 can be effectively improved. On the other hand, when this ratio exceeds 1.10, the low temperature elastic modulus of the conductor 11 exceeds a desirable value.
- the polypropylene is preferably a reactor blend type.
- the low temperature elastic modulus of the conductor 11 tends to exceed a desired value.
- Carbon in the conductive resin composition constituting the conductor 11 is added to impart conductivity to the conductor 11.
- the carbon is preferably particulate carbon such as carbon black.
- carbon black is fine particles of carbon having a diameter of about 3 to 500 nm obtained by incomplete combustion of oil or gas.
- conductive carbon black having a structure called a structure in which carbon primary particles are connected is preferable.
- the average particle size of the particulate carbon is smaller than the average particle size of the crystalline polyolefin after crystallization.
- carbon easily moves from the liquid crystalline polyolefin to the styrene thermoplastic elastomer accompanying the crystallization of the crystalline polyolefin, and the conductivity of the conductor 11 is increased. It can be improved effectively.
- the average particle size after crystallization of polypropylene is about 0.1 to 1.0 ⁇ m. For this reason, for example, by using carbon black and polypropylene as carbon and crystalline polyolefin, respectively, the conductivity of the conductor 11 can be effectively improved.
- the mass percentage concentration of carbon in the conductive resin composition constituting the conductor 11 is preferably 18% by mass or more. Thereby, the volume resistivity of the conductor 11 becomes sufficiently small.
- the mass percent concentration of carbon is calculated by multiplying 100 by the value obtained by dividing the mass of carbon by the mass of the entire conductive resin composition (the mass of the conductor 11).
- the insulating resin composition constituting the insulator 10 preferably contains a styrene-based thermoplastic elastomer, like the conductive resin composition constituting the conductor 11. Since the styrenic thermoplastic elastomer does not need to be crosslinked during molding, the manufacturing process of the insulator 10 can be simplified and the manufacturing cost can be reduced.
- the insulating resin composition constituting the insulator 10 and the conductive resin composition constituting the conductor 11 include process oil, and the mass percent concentration of the process oil in the conductive resin composition constituting the conductor 11 is It is preferable that the mass percentage concentration of the process oil in the insulating resin composition constituting the insulator 10 is higher.
- the process oil is an oil that can be added to the insulator 10 and the conductor 11 to increase plasticity or reduce hardness. Further, it functions as a carbon medium in the conductor 11.
- the mass percentage concentration of the process oil in the conductive resin composition constituting the conductor 11 is the insulating resin composition constituting the insulator 10.
- the process oil in the insulator 10 moves into the conductor 11.
- the distance between carbon particles in the conductor 11 increases, and the conductivity of the conductor 11 decreases. Therefore, by making the mass percentage concentration of the process oil in the conductive resin composition constituting the conductor 11 higher than the mass percentage concentration of the process oil in the insulating resin composition constituting the insulator 10, The problem can be suppressed.
- This process oil is preferably a paraffinic oil.
- paraffinic oil composed of linear molecules for example, the low-temperature elastic modulus of the insulator 10 and the conductor 11 exceeds a desirable value as compared with the case of using naphthenic oil or aroma based oil composed of planar molecules. Tend. This is considered to be because oil composed of linear molecules has weaker intermolecular interactions than oil composed of planar molecules, and fluidity is less likely to be lost even at low temperatures.
- the conductor 11 is covered on the surface of the core wire 12 by extrusion molding using an extruder, and two electrode wires 14 are formed.
- the conductor 11 does not contain a material that requires a crosslinking treatment, the crosslinking step is not performed.
- a linear first spacer for forming the central portion of the hollow portion 13 and a linear second spacer for forming the peripheral portion of the hollow portion 13 are provided.
- the periphery of the four second spacers and the two electrode wires 14 twisted around the first spacer is covered with the insulator 10 by extrusion molding.
- the hollow portion 13 is formed by pulling out the first spacer and the second spacer.
- the pressure sensor 1 is formed by the above steps.
- the manufacturing process of the pressure sensitive sensor disclosed in Japanese Patent No. 3275767 can be used as the manufacturing process of the pressure sensitive sensor 1 of the present embodiment.
- the cross-linking treatment at the time of molding the conductor 11 or the conductor 11 and the insulator 10 is not performed.
- a pressure sensitive sensor can be produced at low cost by forming a conductor using a conductive resin composition suitable for the material of the conductor of the pressure sensitive sensor and capable of being produced at low cost. Can be obtained.
- the Mooney viscosity was measured at 180 ° C. by a method according to JIS K6300-1. The value after 7 minutes of residual heat and 4 minutes (ML 7 + 4 (180 ° C.)) was taken as Mooney viscosity.
- the volume resistivity was measured for the conductive resin composition samples 1 to 16 molded into a sheet by a method (four-terminal four-probe method) according to JIS K7194.
- the Shore A hardness was measured by a method based on ASTM D2240 on the conductive resin composition samples 1 to 16 molded into a sheet shape.
- the low temperature elastic modulus was measured at a frequency of 10 Hz and ⁇ 30 ° C. by a method according to JIS K7244-4.
- the electrode wire used for evaluation of the extrusion appearance has a structure in which a core wire, which is a stranded wire of a 26 AWG silver-plated annealed copper wire, is covered with a conductor made of samples 1 to 16 of the conductive resin composition, and the outer diameter is 1.0 mm.
- Tables 1 and 2 below show the compositions of the conductive resin compositions of Samples 1 to 16 and the results of each evaluation for Samples 1 to 16.
- Tables 1 and 2 represents the mass (kg) of carbon, crystalline polyolefin, process oil, and styrene thermoplastic elastomer contained in the conductive resin composition of each sample.
- the middle row of Tables 1 and 2 shows the total mass (kg) of materials in the conductive resin composition of each sample, the carbon concentration (% by mass), the ratio of the mass of the crystalline polyolefin to the mass of carbon, the crystalline polyolefin And the total concentration (mass%) of carbon and carbon, and process oil concentration (mass%).
- Ketjen Black EC600JD as carbon is carbon black manufactured by Ketjen Black International Co., Ltd.
- Wellnex RGF4VM as a crystalline polyolefin is a reactor blend type polypropylene manufactured by Nippon Polypro Co., Ltd., having a density of 0.89 g / cm 3 , an MFR (Melt Flow Rrate) of 6.0 g / 10 min, and a flexural modulus of 280 MPa. It is.
- PM580X as a crystalline polyolefin is a block polypropylene manufactured by Sun Allomer Co., Ltd., having a density of 0.9 g / cm 3 , an MFR of 5.0 g / 10 min, and a flexural modulus of 1300 MPa.
- Lucant HC-40 as a process oil is an ethylene- ⁇ olefin copolymer oligomer manufactured by Mitsui Chemicals, and has a kinematic viscosity at 100 ° C. of 40 mm 2 / s.
- PW-380 as a process oil is a mineral oil manufactured by Idemitsu Kosan Co., Ltd., having a naphthene component of 27%, a paraffin component of 73%, and a kinematic viscosity of 30 mm 2 / s.
- Septon 4055 as a styrenic thermoplastic elastomer is SEEPS manufactured by Kuraray Co., Ltd., which has a styrene component of 30% and a molecular weight of 130,000.
- Septon 4099 as a styrenic thermoplastic elastomer is SEEPS manufactured by Kuraray Co., Ltd., having a styrene component of 30% and a molecular weight of 320,000.
- Irganox 1010 as an antioxidant is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by BASF, and is a heat aging test of a pressure sensor described later. In order to eliminate the influence of oxidative degradation.
- the target value for each evaluation is a value required as a material for the conductor of the electrode wire of the pressure sensor.
- the mark “ ⁇ ” in the column of the extrusion appearance indicates that almost no unevenness was confirmed on the appearance, the mark “ ⁇ ” indicates that slight unevenness was confirmed, and the mark “ ⁇ ” indicates that the practical use is difficult. This means that the unevenness of the is confirmed.
- Samples 1 to 10 are samples that showed good results in evaluation of volume resistivity, Mooney viscosity, low temperature elastic modulus, and extrusion appearance.
- Samples 11 to 16 are samples that showed unsatisfactory results in at least one of evaluation of volume resistivity, Mooney viscosity, low temperature elastic modulus, and extrusion appearance.
- sample 3 When comparing sample 3 and sample 7, the type of crystalline polyolefin contained was different, and sample 3 was superior in low-temperature elastic modulus. This is considered to be because the sample 3 contains a reactor blend type polypropylene and the sample 7 contains a block polypropylene.
- Samples 11 to 14 have low volume resistivity because they do not contain crystalline polyolefin.
- Table 2 shows that the volume resistivity decreases for the samples 11 to 14 as the carbon concentration increases, but the sample 14 having the highest carbon concentration also has a volume resistivity higher than those of the samples 1 to 9.
- FIG. 3 is a graph showing the relationship between the carbon concentration (mass%) and the volume resistivity (Ohm ⁇ cm) when the conductive resin composition contains crystalline polyolefin and when it does not contain.
- Plot mark “ ⁇ ” is the value of Samples 3, 6, 9, and 10 and represents the relationship when the conductive resin composition contains crystalline polyolefin.
- the plot mark “ ⁇ ” is the value of samples 11 to 14, and represents the relationship when the conductive resin composition does not contain crystalline polyolefin.
- Sample 15 contains crystalline polyolefin, and the target volume resistivity is obtained, but the low-temperature elastic modulus exceeds the target value. This is considered to be because the ratio of the mass of the crystalline polyolefin to the mass of carbon in the sample 15 is too large.
- the ratio of the mass of polypropylene to the mass of carbon in sample 15 is 1.20, and the ratio of the mass of polypropylene to the mass of carbon in samples 1 to 8 in which the target low-temperature elastic modulus was obtained is 0.20 or more and 1 Since it is 0.000 or less, it is considered that the ratio of the mass of polypropylene to the mass of carbon in the conductive resin composition is preferably about 0.20 or more and 1.10 or less.
- Sample 16 contains crystalline polyolefin, and the ratio of the mass of the crystalline polyolefin to the mass of carbon is 0.20, which is the same as that of sample 1, but the low-temperature elastic modulus exceeds the target value. This is considered to be due to the fact that the process oil contained in the sample 16 contains a naphthene component.
- the samples A to H of the pressure-sensitive sensor are double insulators provided with a hollow portion and spaced apart from each other along the inner surface of the hollow portion. It has two electrode lines with a spiral structure.
- the shape of the hollow portion is the same as that of the pressure-sensitive sensor 1 shown in FIG. Samples 3, 5, 6, 12, and 16 were used as electrode wires.
- the distance between the two electrode wires is 1.8 mm, and the outer diameter of the insulator is 5.0 mm.
- Table 3 shows the compositions of the three types of insulating resin compositions used for the insulators of Samples A to H and the concentration (mass%) of the process oil.
- Clayton RP6935 as a styrene-based thermoplastic elastomer is SEBS manufactured by Clayton Co., Ltd., having a styrene component of 58% and a molecular weight of 200,000.
- Softon 1200 as heavy calcium carbonate is heavy calcium carbonate manufactured by Bihoku Flour Industry, and has a particle size of 1.8 ⁇ m and an oil absorption of 36 cc / 100 g.
- Table 4 shows the conductive resin compositions of the conductors of samples A to H, the types of insulating resin compositions of the insulators, and the results of each evaluation for samples A to H.
- Samples A to D are samples that showed good results in all four types of evaluation.
- samples E to H are samples that showed poor results in at least one evaluation.
- Samples E, F and H have ON resistance values after heat aging exceeding the target values.
- the process oil concentration contained in the insulating resin composition was higher than the process oil concentration contained in the conductive resin composition, and the process oil transferred from the insulator to the conductor. It is thought that.
- the conductive resin composition which comprises a conductor is the sample 12 with a large volume resistivity, the sample G has shown an unsatisfactory result in any evaluation of ON resistance and ON resistance after heat aging. .
- An insulator (10) having a hollow portion (13) and a plurality of conductors (11) provided apart from each other along an inner surface facing the hollow portion (13) of the insulator (10). And the plurality of conductors (11) are made of a conductive resin composition containing a styrene-based thermoplastic elastomer and carbon.
- the ratio of the mass of polypropylene contained in the conductive resin composition to the mass of carbon contained in the plurality of conductors (11) is 0.20 or more and 1.10 or less.
- Pressure sensor (1) The ratio of the mass of polypropylene contained in the conductive resin composition to the mass of carbon contained in the plurality of conductors (11) is 0.20 or more and 1.10 or less.
- the pressure sensor (1) according to any one of [1] to [5], wherein the insulator (10) is made of an insulating resin composition containing a styrene-based thermoplastic elastomer.
- the insulating resin composition and the conductive resin composition include a process oil, and the mass percent concentration of the process oil in the conductive resin composition is higher than the mass percent concentration of the process oil in the insulating resin composition.
- the pressure sensor (1) according to [8].
- the insulator (10) is cylindrical, and the plurality of conductors (11) extend spirally in the longitudinal direction of the insulator (10) along the inner surface of the insulator (10).
- the pressure-sensitive sensor (1) according to any one of [5].
- a conductive resin composition comprising a styrene-based thermoplastic elastomer, carbon, and crystalline polyolefin.
- the resin composition used for the conductor or insulator includes an antioxidant, an anti-aging agent, an ozone deterioration preventing agent, a metal chelator, a difficulty, and the like without departing from the requirements of [1] to [20].
- a flame retardant, a colorant, a foaming agent, a lubricant, a stabilizer, a filler, a compatibilizing agent, and a reinforcing agent can be appropriately added.
- a conductive resin composition that can be manufactured at low cost, suitable for a conductor material of a pressure-sensitive sensor, and a pressure-sensitive sensor having a conductor made of the conductive resin composition.
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Abstract
Description
(感圧センサの構成)
図1は、実施の形態に係る線状の感圧センサ1の径方向の断面図である。
以下に、感圧センサ1の製造方法の一例について説明する。
本実施の形態によれば、感圧センサの導電体の材料に適した、低コストで製造することのできる導電性樹脂組成物を用いて導電体を形成することにより、低コストで感圧センサを得ることができる。
組成の異なる16種の導電性樹脂組成物の試料1~16を形成し、体積抵抗率(Ohm・cm)、ムーニー粘度、ショアA硬度、及び低温(-30℃)下における弾性率(MPa)ついてそれぞれ評価した。その後、導電性樹脂組成物の試料1~16を押出成形により芯線に被覆して電極線を形成し、電極線の外観である押出外観について評価した。
次に、電極線の導電体の導電性樹脂組成物の組成、及び絶縁体の絶縁性樹脂組成物の組成の異なる8種の感圧センサの試料A~Hを形成し、ON抵抗(Ohm)、100℃、1000時間の加熱老化試験後のON抵抗(Ohm)、ON荷重(N)、低温(-30℃)下におけるON荷重(N)についてそれぞれ評価した。
次に、前述の実施の形態から把握される技術思想について、実施の形態における符号等を援用して記載する。ただし、以下の記載における各符号等は、特許請求の範囲における構成要素を実施の形態に具体的に示した部材等に限定するものではない。
10…絶縁体
11…導電体
12…芯線
13…中空部
14…電極線
20…スチレン系熱可塑性エラストマ
21a、21b…結晶性ポリオレフィン
22…カーボン
Claims (22)
- 中空部を有する絶縁体と、
前記絶縁体の前記中空部に面する内面に沿って、互いに離間して設けられた複数の導電体と、
を有し、
前記複数の導電体は、スチレン系熱可塑性エラストマ及びカーボンを含む導電性樹脂組成物からなる、感圧センサ。 - 前記導電性樹脂組成物は、結晶性ポリオレフィンを含む、
請求項1に記載の感圧センサ。 - 前記結晶性ポリオレフィンは、25℃以上かつ180℃以下の融点を有する、
請求項2に記載の感圧センサ。 - 前記結晶性ポリオレフィンは、ポリプロピレンである、
請求項3に記載の感圧センサ。 - 前記導電性樹脂組成物に含まれる前記ポリプロピレンの質量の、前記複数の導電体に含まれる前記カーボンの質量に対する比が、0.20以上かつ1.10以下である、
請求項4に記載の感圧センサ。 - 前記導電性樹脂組成物の体積抵抗率が1.0Ohm・cm以下である、
請求項1乃至5のいずれか1項に記載の感圧センサ。 - 前記導電性樹脂組成物における前記カーボンの質量パーセント濃度が18質量%以上である、
請求項1乃至5のいずれか1項に記載の感圧センサ。 - 前記絶縁体は、スチレン系熱可塑性エラストマを含む絶縁性樹脂組成物からなる、
請求項1乃至5のいずれか1項に記載の感圧センサ。 - 前記絶縁性樹脂組成物及び前記導電性樹脂組成物は、プロセスオイルを含み、
前記導電性樹脂組成物における前記プロセスオイルの質量パーセント濃度が、前記絶縁性樹脂組成物における前記プロセスオイルの質量パーセント濃度よりも高い、
請求項8に記載の感圧センサ。 - 前記プロセスオイルは、パラフィン系オイルである、
請求項9に記載の感圧センサ。 - 前記カーボンは、粒子状である、
請求項1乃至5のいずれか1項に記載の感圧センサ。 - 前記カーボンの平均粒径が前記結晶性ポリオレフィンの平均粒径よりも小さい、
請求項2乃至5のいずれか1項に記載の感圧センサ。 - 前記絶縁体は、筒状であり、
前記複数の導電体は、前記絶縁体の前記内面に沿って、前記絶縁体の長手方向に螺旋状に延びる、
請求項1乃至5のいずれか1項に記載の感圧センサ。 - スチレン系熱可塑性エラストマ、カーボン、及び結晶性ポリオレフィンを含む、導電性樹脂組成物。
- 前記結晶性ポリオレフィンは、25℃以上かつ180℃以下の融点を有する、
請求項14に記載の導電性樹脂組成物。 - 前記結晶性ポリオレフィンは、ポリプロピレンである、
請求項15に記載の導電性樹脂組成物。 - 前記ポリプロピレンの質量の、前記カーボンの質量に対する比が、0.20以上かつ1.10以下である、
請求項16に記載の導電性樹脂組成物。 - 体積抵抗率が1.0Ohm・cm以下である、
請求項14乃至17のいずれか1項に記載の導電性樹脂組成物。 - 前記カーボンの質量パーセント濃度が18質量%以上である、
請求項14乃至17のいずれか1項に記載の導電性樹脂組成物。 - パラフィン系オイルを含む、
請求項14乃至17のいずれか1項に記載の導電性樹脂組成物。 - 前記カーボンは、粒子状である、
請求項14乃至17のいずれか1項に記載の導電性樹脂組成物。 - 前記カーボンの平均粒径が前記結晶性ポリオレフィンの平均粒径よりも小さい、
請求項14乃至17のいずれか1項に記載の導電性樹脂組成物。
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