WO2013097664A1 - 高分子基导电复合材料及ptc元件 - Google Patents

高分子基导电复合材料及ptc元件 Download PDF

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Publication number
WO2013097664A1
WO2013097664A1 PCT/CN2012/087264 CN2012087264W WO2013097664A1 WO 2013097664 A1 WO2013097664 A1 WO 2013097664A1 CN 2012087264 W CN2012087264 W CN 2012087264W WO 2013097664 A1 WO2013097664 A1 WO 2013097664A1
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Prior art keywords
polymer
conductive composite
based conductive
boride
carbide
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PCT/CN2012/087264
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English (en)
French (fr)
Inventor
杨铨铨
刘正平
方勇
刘玉堂
刘利锋
王炜
高道华
龚炫
王军
Original Assignee
上海长园维安电子线路保护有限公司
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Priority to CN201280027372.2A priority Critical patent/CN103797548B/zh
Priority to JP2014549337A priority patent/JP6598231B2/ja
Priority to US14/369,919 priority patent/US9534102B2/en
Priority to KR1020147021576A priority patent/KR20140114413A/ko
Publication of WO2013097664A1 publication Critical patent/WO2013097664A1/zh

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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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008—Thermistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025—Perovskites, e.g. titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/028—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of organic substances

Definitions

  • the invention relates to a polymer-based conductive composite material and a PTC component, in particular to a polymer-based conductive composite material having low room temperature resistivity, outstanding weather resistance, good withstand voltage performance and resistance reproducibility, and prepared therefrom PTC components.
  • the polymer-based conductive composite material can maintain a low resistance value under normal temperature, and has a characteristic of being sensitive to temperature changes, that is, when an overcurrent or an overheating phenomenon occurs in the circuit, the resistance thereof instantaneously increases to a high resistance value. , the circuit is in an open state, in order to protect the circuit components. Therefore, the high molecular weight based conductive composite material can be connected to the circuit as a material for the current sensing element. Such materials have been widely used in electronic circuit protection components.
  • the polymer-based conductive composite material is generally composed of a polymer and a conductive filler, and the conductive filler is uniformly distributed macroscopically in the polymer substrate.
  • the polymer is generally a polyolefin and a copolymer thereof, for example, polyethylene or ethylene-vinyl acetate copolymer
  • the conductive filler is generally carbon black, metal powder or conductive ceramic powder.
  • the carbon black has a special aggregate structure and has a polar group on the surface thereof, so that the adhesion of the carbon black to the polymer is good, so that the resistance is stable. Sex.
  • the conductive filler of the base conductive composite material and such materials have been greatly developed.
  • the proportion of metal carbide, metal nitride, metal silicide or metal boride ceramic powder added to the polymer-based conductive composite material is large, processing and forming are difficult, and dispersion in the polymer is poor, resulting in no further resistance. reduce.
  • the thickness of the PTC element prepared from metal carbide, metal nitride or metal boride ceramic powder is limited (eg, less than 1.0 mm, 0.8 mm, 0.6 mm, etc.), and the area is further reduced (eg, 1210, 1206, 0805) When the size is 0603, the conductivity cannot meet the requirements, so it is imperative to develop a conductive filler with lower resistivity and excellent oxidation resistance. Summary of the invention
  • the technical problem to be solved by the present invention is to provide a polymer-based conductive composite material having good electrical conductivity and process dispersibility.
  • Still another technical problem to be solved by the present invention is to provide a PTC element prepared by the above polymer-based conductive composite material.
  • the PTC element has low room temperature resistivity, outstanding weather resistance, good withstand voltage performance, and excellent resistance reproducibility.
  • a polymer-based conductive composite material comprising a polymer substrate, a conductive filler and a coupling agent, wherein:
  • the polymer substrate is polyethylene, polypropylene, polyvinylidene fluoride, polyolefin elastomer, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate, ethylene-acrylic acid copolymer And a mixture thereof, which accounts for 20% to 75%, preferably 25% to 70%, more preferably 30% to 65%, of the volume fraction of the polymer-based conductive composite;
  • a conductive filler having a core-shell particle structure, constituting 25% to 80% by volume of the polymer-based conductive composite material, and having a particle diameter of 0.1 ⁇ m to 20 ⁇ m, preferably 0.05 ⁇ m to 50 ⁇ m, more preferably
  • the conductive filler is dispersed in the polymer substrate; the volume resistivity is less than 0.03 ⁇ ., and more preferably less than 0.02 ⁇ ., and preferably less than ⁇ . ⁇ .
  • the coupling agent is 0.5% to 5%, preferably 0.1% to 5%, more preferably 0.5% to 3% by volume of the conductive filler, and the coupling agent is titanate, and the structural formula is:
  • the group is one of an ethyl group, a propyl group, a butyl group, a pentyl group or an isomer thereof
  • the X group is a carboxyl group, a sulfonic acid group, a sulfone group, a phosphate group, a pyrophosphate group.
  • the R 2 group is one of a hexyl group, a heptyl group, an octyl group or an isomer thereof
  • the Y group is one of an acyloxy group and an amino group
  • n Is the functionality of the titanate, lm 4, l ⁇ n ⁇ 3, m, n are integers
  • the coupling agent is a monoalkoxy type titanate coupling agent, monoalkoxy pyrophosphate type A mixture of one or more of a titanate coupling agent, a chelating titanate coupling agent, a coordinating titanate coupling agent, and a quaternary ammonium salt type titanate coupling agent.
  • the structure of the coupling agent is divided into six different functional areas:
  • the function of the functional region I is to couple the inorganic substance to the titanium; the function of the functional region II is to have the transesterification Transfer and cross-linking function; functional zone III is a group connecting titanium center; functional zone IV is a long-chain entangled group of thermoplastic polymer; functional zone V is a reactive group of thermosetting polymer; functional zone VI represents titanate Functionality.
  • the polymer-based conductive composite material may contain other components such as an antioxidant, a radiation crosslinking agent (often referred to as an irradiation accelerator, a crosslinking agent, or a crosslinking accelerator such as triallyl isocyanuric acid). Ester), coupling agent, dispersant, stabilizer, non-conductive filler (such as magnesium hydroxide, calcium carbonate), flame retardant, arc inhibitor or other components. These components usually constitute up to 15% of the total volume of the polymer-based conductive composite, for example 5% by volume.
  • the core-shell particle structure is composed of a core, an outer shell and an intermediate layer, wherein: the inner core is made of tantalum, vanadium, zirconium, titanium, hafnium, molybdenum, niobium, tungsten, chromium or tantalum.
  • composition comprising: a boride, a nitride, a carbide or a silicide of a core material; the intermediate layer being composed of a boride, a nitride, a carbide or a silicide of a core material,
  • the boride, nitride, carbide or silicide constituting the intermediate layer has a different molecular structure from the boride, nitride, carbide or silicide constituting the outer shell.
  • the invention also provides a polymer-based conductive composite material comprising:
  • the polymer substrate is one of polyethylene, polypropylene, polyvinylidene fluoride, polyolefin elastomer, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate, ethylene-acrylic acid copolymer or a mixture thereof, wherein the polyethylene comprises: high density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, etc., accounting for 20% to 75% of the volume fraction of the polymer based conductive composite material , preferably from 25% to 70%, more preferably from 30% to 65%;
  • the particle size of the conductive filler having a core-shell particle structure is preferably 0.05 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 20 ⁇ m; and the volume resistivity is not more than 0.03 ⁇ , preferably not more than 0.02 ⁇ , more preferably not More than ⁇ . ⁇ . ⁇ ; the conductive filler having a core-shell particle structure is composed of a core, an outer shell and an intermediate layer, and accounts for 25% to 80%, preferably 30%, of the volume fraction of the polymer-based conductive composite material. Between -75%, more preferably between 35% and 70%, dispersed in the polymer substrate, wherein
  • the core material is one of cerium, vanadium, zirconium, titanium, hafnium, molybdenum, niobium, tungsten or chromium;
  • the outer shell material is a boride, nitride, carbide or silicidation of the core material.
  • the intermediate layer is composed of a boride, nitride, carbide or silicide of a core material, which constitutes a boride, a nitride, a carbide or a silicide of the intermediate layer and a boride or nitrogen constituting the outer shell.
  • Compounds, carbides or silicides are different compounds.
  • the boride is lanthanum boride, lanthanum diboride, vanadium boride, vanadium diboride, Zirconium diboride, titanium diboride, lanthanum boride, lanthanum diboride, molybdenum boride, molybdenum pentaboride, lanthanum diboride, ditungsten boride, tungsten boride, dichromium boride, boron One of chromium, chromium diboride or chromium triboride.
  • the nitride is one of tantalum nitride, vanadium nitride, zirconium nitride, titanium nitride, tantalum nitride or tantalum nitride.
  • the carbide is one of tantalum carbide, vanadium carbide, zirconium carbide, titanium carbide, tantalum carbide, molybdenum carbide, tantalum carbide, tungsten carbide, tungsten carbide or trichromium.
  • the silicide is lanthanum silicide, lanthanum trisilicate, lanthanum silicide, vanadium disilicide, zirconium disilide, titanium disilicide, lanthanum trisilide, lanthanum disilicide, molybdenum disilicide, lanthanum disilicide, disilicide One of tungsten, silicon trioxide or chromium disilicate.
  • the polymer-based conductive composite material may contain other auxiliary agents, such as an antioxidant, a radiation crosslinking agent (often referred to as an irradiation accelerator, a crosslinking agent or a crosslinking accelerator such as triallyl isocyanurate). Acid ester), coupling agent, dispersant, stabilizer, non-conductive filler (such as magnesium hydroxide, calcium carbonate), flame retardant, arc inhibitor or other components. These components are typically no greater than 15% of the total volume of the polymer-based conductive composite, such as 10% by volume.
  • auxiliary agents such as an antioxidant, a radiation crosslinking agent (often referred to as an irradiation accelerator, a crosslinking agent or a crosslinking accelerator such as triallyl isocyanurate). Acid ester), coupling agent, dispersant, stabilizer, non-conductive filler (such as magnesium hydroxide, calcium carbonate), flame retardant, arc inhibitor or other components. These components are typically no greater than 15% of the total volume of the polymer-
  • the invention also provides a PTC component prepared by using the above polymer-based conductive composite material, wherein a polymer-based conductive composite material sheet is tightly composited between two metal electrode sheets to form a polymer-based conductive composite material sheet, the metal
  • the electrode sheet includes one of nickel, copper, aluminum or zinc and a composite thereof, such as copper foil, nickel foil, single-sided nickel-plated copper foil, double-sided nickel-plated copper foil, etc., wherein the polymer-based conductive
  • the composite sheet has a thickness of 0.01 to 3.0 mm, preferably 0.05 to 2.0 mm, and is preferably divided into a single element having a planar shape which is perpendicular to a current flowing direction for the convenience of processing.
  • the surface of the metal electrode sheet is not more than 0.3 mm, preferably not more than 0.2 mm, more preferably not more than 0.1 mm, for example, 0.035 mm; and the volume resistivity of the PTC element is not more than ⁇ at 25 ° C ⁇ . ⁇ , preferably less than 0.05 ⁇ . ⁇ , optimally less than 0.02 ⁇ . ⁇ , suitable for metal electrode sheets including nickel, copper, aluminum, zinc and their composites, such as copper foil, nickel foil, single-sided Nickel plating Foil, a double-sided copper foil, nickel-plated, most preferably less than 0.02 ⁇ . ⁇ , and has outstanding weather resistance, excellent withstand voltage performance, reproducibility and excellent resistance PTC intensity.
  • the PTC element made of the material of the present invention has a resistivity at 25 ° C. Therefore, the PTC element of the present invention has a low resistance at 25 ° C, for example, 1.0 ⁇ ⁇ to 10 ⁇ .
  • the single element is a square, triangular, circular, rectangular, circular, polygonal or other irregularly shaped sheet-like structure.
  • the method of the PTC element prepared from the above polymer-based conductive composite material comprises the following steps: 1) Put the polymer substrate, conductive filler and additives (if additives are added) into a hybrid device such as a torque rheometer, an internal mixer, an open mill, a single screw extruder or a twin screw extruder. Melt mixing is carried out at a temperature higher than the melting temperature of the polymer, and then the mixed polymer is processed into a polymer-based conductive composite sheet having a thickness of 0.01 to 3.0 mm by extrusion molding, compression molding or calender molding. Preferably, the thickness is 0.05 to 2.0 mm, and the processing is more preferably 0.1 to 1.0 mm;
  • a composite metal electrode sheet on both sides of a polymer-based conductive composite material sheet wherein the polymer-based conductive composite material sheet is in a molten state, and the electrode sheet is directly pressed against the sheet by a roller.
  • a composite sheet is obtained, and the composite sheet can be processed into a surface mount PTC component by a series of PCB processes such as etching, lamination, drilling, copper plating, tin plating, and dicing, or can be divided into individual components. Connecting other metal parts into strip PTC elements;
  • a method of dividing a composite sheet into individual components includes any method of separating individual components from a composite article, such as die cutting, etching, dicing, and laser cutting.
  • the individual elements have a planar shape, i.e. have two surfaces perpendicular to the direction of current flow, and the distance between the two surfaces is rather thin, i.e. at most 3.0 mm, preferably at most 2.0 mm, particularly preferably at most l .Omm, for example 0.4 mm, to produce a PTC component;
  • Cross-linking and/or heat-treating the PTC element and generally improving the stability of the performance of the PTC element by means of crosslinking and/or heat treatment.
  • Crosslinking can be chemical crosslinking or irradiation crosslinking, for example, using crosslinking accelerators, electron beam irradiation or Co 6Q irradiation.
  • the irradiation dose required for the PTC element is generally less than 100 Mrad, preferably 1-50 Mrad, more preferably 1-20 Mrad; the heat treatment may be annealing, thermal cycling, high and low temperature alternating, such as +85 ° C / -40 ° C high and low temperature Alternating.
  • the temperature environment for the annealing may be any temperature below the decomposition temperature of the polymer substrate, such as a high temperature anneal above the melting temperature of the polymer substrate and a low temperature anneal below the melting temperature of the polymer substrate.
  • the two metal electrode pieces are connected in series to the protected circuit through the conductive member to form a conductive path.
  • Conductive parts or other metal parts can be connected to the metal pads by electroplating, electroless plating, printing, dip soldering, spot welding, reflow soldering or conductive adhesive to connect the PTC into the circuit.
  • the term "metal member” includes any structural member that can be electrically connected to a metal electrode sheet, and can be any shape, for example, a dot shape, a wire shape, a strip shape, a sheet shape, a column shape, other irregular shapes, and a combination thereof.
  • the substrate of the "metal component” may be any electrically conductive metal and alloys thereof such as nickel, copper, aluminum, zinc, tin, and alloys thereof.
  • the PTC element has a low room temperature resistivity as a thermistor element or a transition protection element, Outstanding weather resistance, good withstand voltage performance and resistance reproducibility, high PTC strength.
  • the volume resistivity of the PTC component can be less than 0.02 ⁇ . ⁇ .
  • the invention has the advantages that: the polymer-based conductive composite material has good electrical conductivity and processing and dispersing performance, and the PTC element prepared from the polymer-based conductive composite material has outstanding room temperature resistivity and outstanding weather resistance, and is good. Withstand voltage performance and resistance reproducibility.
  • FIG. 1 is a schematic structural view of a PTC element of the present invention
  • FIG. 2 is a schematic structural view of an embodiment of a PTC component of the present invention.
  • Fig. 3 is a graph showing the resistance-temperature of the thermistor element of Embodiment 6 of the present invention.
  • Examples 1 to 6 are materials of the present invention and PTC elements to which a coupling agent is added.
  • composition of the conductive composite material for preparing the PTC element is:
  • the polymer substrate is a high-density polyethylene having a melting temperature of 134 ° C, a density of 0.953 g/cm 3 , and a volume fraction of 40%;
  • the conductive filler is a core-shell granular structure consisting of an outer shell, an intermediate layer and a core.
  • the outer shell is ditungsten carbide
  • the middle layer is tungsten boride
  • the inner core is metal tungsten
  • the particle size is 2.0 ⁇ m
  • the volume fraction is 60. %.
  • the coupling agent is a monoalkoxy type isopropyl dioleate acyl titanate having a volume fraction of 0.5% by volume of the electrically conductive filler and a density of 0.976 g/cm 3 .
  • the temperature of the internal mixer was set at 180 ° C and the rotation speed was 30 rpm.
  • the polymer was first mixed for 3 minutes, and then the conductive filler was added to continue the mixing for 15 minutes to obtain a polymer-based conductive composite material.
  • the melt-mixed polymer-based conductive composite material is calendered by an open mill to obtain a polymer-based conductive composite material 11 having a thickness of 0.20 to 0.25 mm.
  • the preparation process of the PTC component is as follows:
  • FIG. 1 schematic diagram of the PTC element of the present invention
  • the polymer-based conductive composite material 11 The layer is placed between the two metal electrode sheets 12, 12' which are vertically symmetric, and the metal electrode sheets 12, 12' are tightly bonded to the polymer-based conductive composite material layer 11.
  • the polymer-based conductive composite material 11 and the metal electrode sheets 12, 12' are tightly bonded together by a thermocompression bonding method.
  • the temperature of the thermocompression bonding is 180 ° C, preheating for 5 minutes, then hot pressing at 5 MPa for 3 minutes, then hot pressing at 12 MPa for 10 minutes, and then cold pressing on a cold press for 8 minutes. It is die-cut into a single component of 3*4 mm, and finally two metal pins 13, 13' are respectively connected to the surfaces of the two metal electrode sheets 12, 12' by reflow soldering to form a PTC component.
  • the procedure for preparing the polymer-based conductive composite material and the PTC element was the same as in Example 1, except that the volume fraction of the coupling agent in the conductive composite material was increased from 0.5% by volume of the conductive filler to 1.0%.
  • the procedure for preparing the polymer-based conductive composite material and the PTC element was the same as in Example 1, except that the volume fraction of the coupling agent in the conductive composite material was increased from 0.5% by volume to 1.5% of the volume of the conductive filler.
  • the procedure for preparing the polymer-based conductive composite material and the PTC element was the same as in Example 1, except that the volume fraction of the coupling agent in the conductive composite material was increased from 0.5% by volume of the conductive filler to 2.0%.
  • the procedure for preparing the polymer-based conductive composite material and the PTC element was the same as in Example 1, except that the volume fraction of the coupling agent in the conductive composite material was increased from 0.5% by volume to 2.5% of the volume of the conductive filler.
  • the procedure for preparing the polymer-based conductive composite material and the PTC element is the same as that of the second embodiment, but the coupling agent used is a monoalkoxy type isopropyl trioleate acyl titanate, and the amount added is the volume of the conductive filler. 1.0%, density 1.01 g/cm 3 .
  • Comparative example 1 The procedure for preparing the polymer-based conductive composite material and the PTC element was the same as in Example 3, but no coupling agent was added to the polymer-based conductive composite material.
  • R min in Table 1 represents the resistance of two metal pins 12, 12' on the surface of two metal electrode sheets 12, 12' of the PTC element, and the minimum resistance value of 10 PTC elements;
  • R average represents the resistance of two metal pins 12, 13' on the surface of the two metal electrode sheets 12, 12' of the PTC element, and the average resistance value of 10 PTC elements;
  • R max represents the resistance of two metal pins 12, 13' on the surface of the two metal electrode sheets 12, 12' of the PTC element, which is the maximum resistance value of 10 PTC elements;
  • STDEV represents the standard deviation of 10 PTC components, reflecting the discreteness of the resistance
  • R 100cy d es means that the PTC component is placed in the +85 ° C environment for 30 minutes, then placed in the -40 ° C environment for 30 minutes, so that it is cycled 100 times, and then placed in a temperature environment of 25 ° C for 1 hour. The resistance value obtained.
  • A represents the resistance value measured after the PTC element was subjected to a withstand voltage of 2 hours under a condition of 6 V, 50 A for 2 hours and then placed in a temperature environment of 25 ° C for 1 hour.
  • A represents the resistance value measured after the PTC element was subjected to a withstand voltage of 2 hours under conditions of 12 V and 50 A for 2 hours and then placed in a temperature environment of 25 ° C for 1 hour.
  • the PTC elements of Examples 1 to 6 and Comparative Example 1 can withstand a voltage of 6 V, and the PTC elements of Examples 1 to 6 can withstand a voltage of 12 V, and the PTC element of the comparative example cannot withstand a voltage of 12 V, indicating that the coupling agent is added. It is beneficial to enhance the withstand voltage performance of PTC components. It can be seen from the torque at the time of processing the polymer-based conductive composite material in Table 1, the torque of Examples 1 to 6 to which a certain amount of coupling agent was added was lower than that of the comparative example to which no coupling agent was added, indicating that the coupling agent was added. It is beneficial to improve the molding processability of polymer-based conductive composite materials.
  • the conductive composite material used for the PTC element is added with a coupling agent which can improve the dispersion state of the conductive filler, the conductive network in the composite material is enhanced, and thus the resistance concentration is high.
  • the thickness of the conductive material is 0. 2mn!
  • the thickness of the conductive material is 0. 2mn! ⁇ 2. 0mm, PTC components with small currents such as 1210, 1206, 0805, and 0603.
  • the coupling agent was not added in the following examples, and the formulation and properties are shown in Table 2.
  • the polymer 1 is a high-density polyethylene having a melting temperature of 134 ° C and a density of 0.953 g / cm 3 ;
  • the polymer 2 is a high-density polyethylene having a melting temperature of 135 ° C and a density of 0.954 g / cm.
  • conductive filler 1 is titanium carbide, its Feis particle size is 2.0 ⁇ , density is 4.93 g / cm 3 ;
  • conductive filler 2 is a core-shell structure, the particle size is 2.0 ⁇ , wherein the outer shell is diboride; The middle layer is tungsten boride; the inner core is metal tungsten.
  • the preparation process of the thermistor element is as follows: The temperature of the internal mixer is set at 180 ° C, and the rotation speed is 30 rpm. Minutes, the polymer was first mixed for 3 minutes, and then the conductive filler was added to continue the mixing for 15 minutes to obtain a polymer-based conductive composite. The melt-mixed polymer-based conductive composite material was calendered by an open roll to obtain a polymer-based conductive composite material sheet 11 having a thickness of 0.20 to 0.25 mm.
  • the polymer-based conductive composite material sheet 11 is placed between the upper and lower symmetrical upper and lower metal electrode sheets 12, 13, and the metal electrode sheets 12, 12' are electrically conductive with the polymer base.
  • the composite sheet 11 is tightly bonded.
  • the polymer-based conductive composite sheet 11 and the metal electrode sheets 12, 12' are tightly bonded together by a thermocompression bonding method.
  • the temperature of the thermocompression bonding is 180 ° C, preheating for 5 minutes, then hot pressing at 5 MPa for 3 minutes, then hot pressing at 12 MPa for 10 minutes, and then cold pressing on a cold press for 8 minutes. It is die-cut into a single component of 3*4 mm, and finally two metal pins 13, 13' are connected to the surfaces of the two metal electrode sheets 12, 12' by reflow soldering to form a thermistor element.
  • Fig. 3 is a graph showing the resistance-temperature of the thermistor element of the present embodiment.
  • the thermistor element has a very low resistance value at 25 ° C. As the temperature increases, the resistance rises slowly. When the temperature increases to about 130 ° C, the resistance of the thermistor element changes suddenly, increasing by about 10 orders of magnitude. At this time, the thermistor element is changed from a conductor to an insulator, so that the circuit is in an open state, so as to achieve the purpose of protecting the circuit component.
  • composition of the polymer-based conductive composite material for preparing the thermistor element is the same as that of the embodiment 7.
  • the formulation of the polymer-based conductive composite material of the present embodiment and the electrical characteristics of the thermistor element are as shown in Table 2, but the polymer is prepared.
  • the steps of the base conductive composite sheet and the thermistor element are different, and the steps are:
  • the polymer is ground and mixed with the conductive filler in a mixer for 30 minutes, and then the mixture is added to a twin-screw extruder, melt-mixed at a temperature of 180 ° C to 220 ° C, and then extruded and granulated.
  • Example 10 The formulation of the polymer-based conductive composite material of the present embodiment and the electrical characteristics of the thermistor element are shown in the table. 2 is shown. The steps of preparing the polymer-based conductive composite material and the thermistor element were the same as in Example 7, except that the volume fraction of the polymer 1 was changed from 34% to 38%, and the volume fraction of the conductive filler 2 was changed from 60% to 56%. .
  • Example 10 The formulation of the polymer-based conductive composite material of the present embodiment and the electrical characteristics of the thermistor element are shown in the table. 2 is shown. The steps of preparing the polymer-based conductive composite material and the thermistor element were the same as in Example 7, except that the volume fraction of the polymer 1 was changed from 34% to 38%, and the volume fraction of the conductive filler 2 was changed from 60% to 56%. .
  • Example 10 The steps of preparing the polymer-based conductive composite material and the thermistor element were the same as in Example 7, except that the volume fraction of
  • the formulation of the polymer-based conductive composite of this example and the electrical characteristics of the thermistor element are shown in Table 2.
  • the procedure for preparing the polymer-based conductive composite material and the overcurrent protection member is the same as in Example 7, except that the volume fraction of the polymer 1 is changed from 34% to 38%, and the volume fraction of the polymer 2 is increased from 6% to 10%. , change the volume fraction of the conductive filler 2 from 60% to 52%.
  • the formulation of the polymer-based conductive composite of this comparative example and the electrical characteristics of the thermistor element are shown in Table 2.
  • the procedure for preparing the polymer-based conductive composite material and the overcurrent protection member was the same as in Example 1, except that the conductive filler 2 was changed to the conductive filler 1.
  • the formulation of the polymer-based conductive composite of this comparative example and the electrical characteristics of the thermistor element are shown in Table 2.
  • the steps of preparing the polymer-based conductive composite material and the thermistor element are the same as those in Embodiment 7, but changing the conductive filler 2 to the conductive filler 1 and changing the volume fraction of the polymer 1 from 34% to 38%, and the conductive filler 1 The volume fraction changed from 60% to 56%.
  • the formulation of the polymer-based conductive composite of this comparative example and the electrical characteristics of the thermistor element are shown in Table 2.
  • the procedure for preparing the polymer-based conductive composite material and the thermistor element is the same as that of Embodiment 7, but the conductive filler 2 is changed to the conductive filler 1, and the volume fraction of the polymer 2 is changed from 34% to 38%, and the polymer 2 is The volume fraction increased from 6% to 10%, and the volume fraction of the conductive filler 1 was changed from 60% to 52%.
  • the resistance value of the thermistor element is measured by a four-electrode method.
  • the resistance data in Table 2 is the resistance test data after the thermistor element prepared by the polymer-based conductive composite material of the present invention is triggered under the condition of 6V/50A and placed in a 25 V temperature environment for 1 hour. .
  • R in Table 2 represents the resistance before the two metal pins 13, 13' on the surface of the two metal electrode sheets 12, 12' of the thermistor element;
  • Ro represents the two electrode sheets 12 of the thermistor element, 12 'The resistance after soldering the two metal pins 13, 13 ' on the surface;
  • R 25 means that the thermistor element is continuously energized (6V/50A) for 6 seconds, power is off for 60 seconds, so cycle 25 times, then at 25 °C The resistance value measured after being placed in an environment for 1 hour; R 5 .
  • Heat cycle R 1QQey d es indicates that the thermistor element is placed in the +85 °C environment for 30 minutes, then placed in the -40 ° C environment for 30 minutes, so cycle 100 times, then at 25 ° C temperature The resistance value measured after being placed in the environment for 1 hour.
  • High temperature and humidity Rioooh indicates the resistance value of the thermistor element placed in an environment of 85 ° C, 85% RH for 1000 hours and then placed in a temperature environment of 25 ° C for 1 hour.
  • High humidity R ⁇ ooh indicates the resistance value measured after the thermistor element was placed in a 60 V, 95% RH environment for 1000 hours and then placed in a temperature of 25 ° C for 1 hour.
  • 6V/50A/2h means that the thermistor element has a withstand voltage of 2 hours under the condition of 6V, 50A
  • 12V/50A/2h means that the thermistor element has a withstand voltage of 2 hours under the condition of 12V, 50A.
  • the voltage performance OK indicates that the overcurrent protection component does not burn or crack
  • NG indicates that the thermistor component is burned or cracked.
  • the resistance values of the thermistors of Comparative Examples 2 to 4 after being subjected to a current of 6 V/50 A for 100 times were small, indicating that the resistance reproducibility was higher. it is good.
  • the thermistor elements of Examples 7 to 10 and Comparative Examples 2 to 4 were capable of withstanding a voltage of 6 V, and the thermistor elements of Examples 7 to 10 were able to withstand a voltage of 12 V and the thermistor elements of Comparative Examples 2 to 4 Can not withstand the voltage of 12V, indicating that the thermistor element prepared by the core-shell granular structure conductive filler has excellent withstand voltage performance.
  • the thermistor element prepared by the core-shell granular structure conductive filler has excellent PTC strength (the PTC intensity in this paper is equal to the maximum resistivity of the sample in the resistivity-temperature relationship curve and its at room temperature. The logarithmic value of the resistivity ratio).
  • the polymer-based conductive composite material used in the thermistor elements of Embodiments 7 to 10 of the present invention has a low room temperature resistivity and excellent weather resistance because it contains a conductive filler having a core-shell type granular structure having a very low electrical resistivity. Performance, good withstand voltage performance, excellent resistance reproducibility and PTC strength.
  • the thickness of the current-carrying area is 1210.
  • the thickness of the current-carrying area is 1210.
  • the thickness of the current-carrying area is 1210.
  • the thickness of the current-carrying area is 1210.
  • the thickness of the current-carrying area is 1210. , 1206, 0805, 0603 and other small size models of thermistor components.

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Abstract

一种高分子基导电复合材料及PTC元件，所述高分子基导电复合材料包含：高分子基材的体积分数为20%-75%；导电填料的体积分数为25%-80%，具有核壳式颗粒结构，分散于所述高分子基材中；偶联剂为钛酸酯偶联剂，占所述导电填料体积的0%-5%。以及利用所述高分子基导电复合材料制备的PTC元件，包含至少两个金属电极片（12，12'），高分子基导电复合材料（11）与所述金属电极片（12，12'）之间紧密结合。由该高分子基导电复合材料制备的PTC元件具有低室温电阻率、突出的耐候性能，良好的耐电压性能和电阻再现性。

Description

高分子基导电复合材料及 PTC元件
技术领域
本发明涉及一种高分子基导电复合材料及 PTC元件， 尤其是一种具有低室 温电阻率、突出的耐候性能， 良好的耐电压性能和电阻再现性的高分子基导电复 合材料及由其制备的 PTC元件。
背景技术
高分子基导电复合材料在正常温度下可维持较低的电阻值， 具有对温度变 化反应敏锐的特性， 即当电路中发生过电流或过高温现象时，其电阻会瞬间增加 到一高阻值， 使电路处于断路状态， 以达到保护电路元件的目的。 因此可把高分 子基导电复合材料连接到电路中， 作为电流传感元件的材料。此类材料已被广泛 应用于电子线路保护元器件上。
高分子基导电复合材料一般由聚合物和导电填料复合而成， 导电填料宏观 上均匀分布于所述高分子基材中。聚合物一般为聚烯烃及其共聚物， 例如： 聚乙 烯或乙烯-醋酸乙烯共聚物等， 而导电填料一般为碳黑、 金属粉或导电陶瓷粉。 对于以碳黑作导电填料的高分子基导电复合材料，由于碳黑特殊的聚集体结构且 其表面具有极性基团， 使碳黑与聚合物的附着性较好， 因此具有良好的电阻稳定 性。 但是， 由于碳黑本身的导电能力有限， 无法满足低电阻的要求。 以金属粉为 导电填料的高分子基导电复合材料，具有极低的电阻，但是因为金属粉容易氧化， 需要对导电复合材料进行包封， 以阻止因金属粉在空气中氧化而造成的电阻升 高， 而经过包封的 PTC元件的体积不能有效降低， 难以满足电子元器件小型化 的要求。 为得到较低的电阻值， 同时克服金属粉易氧化的弊端， 行业内逐渐趋向 以金属碳化物、 金属氮化物、 金属硅化物或金属硼化物陶瓷粉（如碳化钛）作为 低阻值高分子基导电复合材料的导电填料， 且此类材料已经有了长足的发展。但 添加于高分子基导电复合材料中的金属碳化物、金属氮化物、金属硅化物或金属 硼化物陶瓷粉的比例较大， 加工成型困难， 在聚合物中分散不佳， 导致其电阻无 法进一步降低。
另外， 但由金属碳化物、 金属氮化物或金属硼化物陶瓷粉制备的 PTC元件 的厚度被限制（如小于 1.0mm, 0.8mm, 0.6mm等），且面积进一步缩小（如 1210， 1206， 0805， 0603 等尺寸） 时， 其导电性就无法满足要求， 因此开发具有更低 电阻率且具有优良抗氧化性能的导电填料势在必行。 发明内容
本发明所要解决的技术问题在于提供一种具有良好的导电性能和加工分散 性的高分子基导电复合材料。
本发明所要解决的再一技术问题在于：提供上述高分子基导电复合材料制备 的 PTC元件。 该 PTC元件具有低室温电阻率、 突出的耐候性能、 良好的耐电压 性能、 优良的电阻再现性。
本发明所述技术问题通过下述技术方案实现： 一种高分子基导电复合材料， 包含高分子基材、 导电填料和偶联剂， 其中：
(a) 所述高分子基材为聚乙烯、 聚丙烯、 聚偏氟乙烯、 聚烯烃弹性体、 环 氧树脂、 乙烯 -醋酸乙烯共聚物、 聚甲基丙烯酸甲酯、 乙烯-丙烯酸共聚物中的一 种及其混合物， 占所述高分子基导电复合材料的体积分数的 20%〜75%， 优选为 25%-70%之间， 更优为 30%-65%之间；
(b) 导电填料， 具有核壳式颗粒结构， 占所述高分子基导电复合材料的体 积分数的 25%〜80%， 其粒径为 0.1μιη〜20μιη， 优选为 0.05μιη〜50μιη， 更优为 0.1μιη〜20μιη， 且体积电阻率小于 0.03Ω.ιη， 更优为小于 0.02Ω.ιη， 最优为小于 Ο.ΟΙΩ.ιη, 所述导电填料分散于所述高分子基材中；
(c)偶联剂占导电填料体积的 0. 05%〜5%，优选 0.1%〜5%，更优选为 0.5%〜 3%, 所述的偶联剂为钛酸酯， 其结构式为：
Figure imgf000004_0001
其中， 基团为乙基、 丙基、 丁基、 戊基或它们的同分异构体中的一种， X 基团为羧基、 磺酸基、 砜基、 磷酸酯基、 焦磷酸酯基、 亚磷酸酯基中的一种， R2基团为己基、 庚基、 辛基或它们的同分异构体中的一种， Y基团为酰氧基、 氨 基中的一种， n为钛酸酯的官能度， l m 4， l^n^3, m、 n均为整数， 所述偶 联剂为单烷氧基型钛酸酯偶联剂、单烷氧基焦磷酸酯型钛酸酯偶联剂、螫合型钛 酸酯偶联剂、配位型钛酸酯偶联剂、季铵盐型钛酸酯偶联剂中的一种或多种的混 合物。
具体的， 偶联剂的结构中划分成 6个不同的功能区：
I II III IV V VI
Figure imgf000004_0002
其中， 功能区 I的作用是使无机物与钛偶联； 功能区 II的作用是具有酯基转 移和交联功能； 功能区 III为连接钛中心的基团； 功能区 IV为热塑性聚合物的长链 纠缠基团；功能区 V为热固性聚合物的反应基团；功能区 VI代表钛酸酯的官能度。
所述高分子基导电复合材料可含有其他组分， 如抗氧剂、辐射交联剂（常称 为辐照促进剂、 交联剂或交联促进剂， 例如三烯丙基异氰脲酸酯） 、 偶联剂、 分 散剂、 稳定剂、 非导电性填料（如氢氧化镁， 碳酸钙） 、 阻燃剂、 弧光抑制剂或 其他组分。 这些组分通常至多占高分子基导电复合材料总体积的 15%， 例如 5% 体积百分比。
在上述方案基础上，所述核壳式颗粒结构由内核、外壳和中间层组成，其中： 所述内核由钽、 钒、 锆、 钛、 铌、 钼、 铪、 钨、 铬或铍之中的一种组成； 所 述外壳由内核物质的一种硼化物、氮化物、碳化物或硅化物组成； 所述中间层由 内核物质的一种硼化物、氮化物、碳化物或硅化物组成， 所述组成中间层的硼化 物、 氮化物、 碳化物或硅化物与组成外壳的硼化物、 氮化物、 碳化物或硅化物具 有不同的分子结构。
本发明还提供一种高分子基导电复合材料， 其包含：
聚合物基材， 为聚乙烯、 聚丙烯、 聚偏氟乙烯、 聚烯烃弹性体、 环氧树脂、 乙烯 -醋酸乙烯共聚物、 聚甲基丙烯酸甲酯、 乙烯-丙烯酸共聚物中的一种或其混 合物， 其中， 聚乙烯包括： 高密度聚乙烯、 低密度聚乙烯、 线性低密度聚乙烯、 超高分子量聚乙烯等， 占所述聚合物基导电复合材料的体积分数的 20%〜75%， 优选为 25%-70%， 更优为 30%-65%；
具有核壳式颗粒结构的导电填料的粒径优选为 0.05μιη〜50μιη， 更优为 0.1μιη〜20μιη; 体积电阻率不大于 0.03Ω.ιη， 优选为不大于 0.02Ω.ιη， 更优为不 大于 Ο.ΟΙΩ.ιη;所述具有核壳式颗粒结构的导电填料由内核、外壳和中间层组成， 占所述聚合物基导电复合材料的体积分数的 25%〜80%， 优选为 30%-75%之间， 更优为 35%-70%之间， 分散于所述聚合物基材中， 其中，
所述的内核物质为钽、 钒、 锆、 钛、 铌、 钼、 铪、 钨或铬之中的一种； 所述的外壳物质为内核物质的一种硼化物、 氮化物、 碳化物或硅化物组成； 所述的中间层由内核物质的一种硼化物、氮化物、碳化物或硅化物组成， 组 成中间层的硼化物、 氮化物、 碳化物或硅化物与组成外壳的硼化物、 氮化物、 碳 化物或硅化物为不同的化合物。
在上述方案基础上，所述的硼化物为硼化钽、二硼化钽、硼化钒、二硼化钒、 二硼化锆、 二硼化钛、 硼化铌、 二硼化铌、 硼化二钼、 五硼化二钼、 二硼化铪、 硼化二钨、 硼化钨、 硼化二铬、 硼化铬、 二硼化铬或三硼化五铬之中的一种。
所述的氮化物为氮化钽、 氮化钒、 氮化锆、 氮化钛、 氮化铌或氮化铪中的一 种。
所述的碳化物为碳化钽、 碳化钒、 碳化锆、 碳化钛、 碳化铌、 碳化二钼、 碳 化铪、 碳化钨、 碳化二钨或二碳化三铬之中的一种。
所述的硅化物为二硅化钽、 三硅化五钽、 硅化三钒、 二硅化钒、 二硅化锆、 二硅化钛、 三硅化五钛、 二硅化铌、 二硅化钼、 二硅化铪、 二硅化钨、 硅化三铬 或二硅化铬之中的一种。
所述高分子基导电复合材料中可含有其他助剂， 如抗氧剂、辐射交联剂（常 称为辐照促进剂、 交联剂或交联促进剂， 例如三烯丙基异氰脲酸酯） 、 偶联剂、 分散剂、 稳定剂、 非导电性填料（如氢氧化镁， 碳酸钙） 、 阻燃剂、 弧光抑制剂 或其他组分。 这些组分通常不大于聚合物基导电复合材料总体积的 15%， 例如 10%体积百分比。
本发明还提供采用上述高分子基导电复合材料制备的 PTC元件， 由聚合物 基导电复合材料片材紧密复合在两片金属电极片之间构成聚合物基导电复合材 料片材，所述的金属电极片包括镍、铜、铝或锌中的一种及其复合物，例如铜箔、 镍箔、 单面镀镍铜箔、 双面镀镍铜箔等， 其中， 所述的聚合物基导电复合材料片 材的厚度为 0.01〜3.0mm， 优选为 0.05〜2.0mm， 为了加工的方便更优为， 被分 割成具有平面形状的单个元件，所述单个元件即有与电流流过方向垂直的两个表 面， 所述金属电极片的厚度不大于 0.3mm， 优选厚度不大于 0.2mm， 更优是不 大于 0.1mm，例如， 0.035mm;在 25 °C时 PTC元件的体积电阻率不大于 Ο. ΙΩ. η, 优选小于 0.05Ω. η， 最优为小于 0.02Ω. η， 适用于金属电极片的材质包括镍、 铜、 铝、 锌及其复合物， 例如铜箔、 镍箔、 单面镀镍铜箔、 双面镀镍铜箔等， 最 优为小于 0.02Ω. η， 且具有突出的耐候性能、 良好的耐电压性能， 优良的电阻 再现性和 PTC强度。用本发明材料制得的 PTC元件， 在 25 °C的电阻率因此本发 明的 PTC元件在 25 °C的电阻很低， 例如 1.0ιη Ω〜10 ιηΩ。
所述单个元件为正方形、 三角形、 圆形、 矩形、 环形、 多边形或其它不规则 形状的片状结构。
由上述高分子基导电复合材料制备的 PTC元件的方法包括下述步骤： 1 ) 将聚合物基材、 导电填料和添加剂 （如果有添加剂的情况下） 投入转矩 流变仪、 密炼机、 开炼机、 单螺杆挤出机或双螺杆挤出机等混合设备， 在高于聚 合物熔融温度以上的温度下进行熔融混合， 然后将混合好的聚合物通过挤出成 型、模压成型或压延成型加工成厚度为 0.01〜3.0mm的聚合物基导电复合材料片 材， 优选厚度为 0.05〜2.0mm， 为了加工的方便更优为 0.1〜1.0mm;
2) 在聚合物基导电复合材料片材的两面复合金属电极片， 方法是所述的聚 合物基导电复合材料片材还处于熔融状态时通过滚筒直接将电极片紧密压合在 片材的二面获得复合片材， 复合好的片材可以通过蚀刻、 层压、 钻孔、 沉铜、 镀 锡和划片等一系列 PCB工艺加工成表面贴装式 PTC元件， 也可以分割成单个元 件后连接其他金属部件加工成条状 PTC元件；
3 ) 把复合片材分割成单个元件的方法包括从复合制品上分离出单个元件的 任何方法， 例如冲切、 刻蚀、 划片和激光切割。 所述单个元件具有平面形状， 即 有与电流流过方向垂直的两个表面， 且两个表面之间的距离相当薄， 即至多 3.0mm, 优选地是至多 2.0mm， 特别优选的是最多 l.Omm, 例如 0.4mm， 制得 PTC元件；
4) 对所述的 PTC元件进行交联和 /或热处理， 通常可借助交联和 /或热处理 的方法来提高 PTC元件性能的稳定性。 交联可以是化学交联或辐照交联， 例如 可利用交联促进剂、 电子束辐照或 Co6Q辐照来实现。 PTC元件所需的辐照剂量 一般小于 lOOMrad, 优选为 l-50Mrad， 更优为 l-20Mrad; 热处理可以是退火、 热循环、 高低温交变， 例如 +85°C/-40°C高低温交变。 所述退火的温度环境可以 是聚合物基材分解温度以下的任何温度，例如高于聚合物基材熔融温度的高温退 火和低于聚合物基材熔融温度的低温退火。
所述的 PTC元件中的， 两个金属电极片通过导电部件串接于被保护电路中 形成导电通路。 导电部件或称其他金属部件， 可以通过电镀、 化学镀、 印刷、 浸 焊、 点焊、 回流焊或导电粘合剂连接在金属电极片上， 从而将 PTC连接进电路 中。 术语"金属部件"包括任何能与金属电极片导通的结构部件， 它可以是任何 形状， 例如， 点状， 线状、 带状、 片状、 柱状、其他不规则形状及它们的组合体。 所述 "金属部件" 的基材可为任何能导电的金属及其合金， 如镍、 铜、 铝、 锌、 锡及其合金。
所述的 PTC元件作为热敏电阻元件或过渡保护元件， 具有低室温电阻率、 突出的耐候性能， 良好的耐电压性能和电阻再现性， PTC强度高。 在 25 °C时， PTC元件的体积电阻率可达小于 0.02Ω. η。
本发明的优越性在于： 高分子基导电复合材料导电性能和加工分散性能良 好， 由该高分子基导电复合材料制备的 PTC元件在具有低室温电阻率的同时， 仍具有突出的耐候性能， 良好的耐电压性能和电阻再现性。
下面结合附图和具体实施例对本发明作进一步的详细说明。
附图说明
图 1为本发明 PTC元件的结构示意图；
图 2 为本发明 PTC元件实施例的结构示意图；
图 3是本发明实施例 6的热敏电阻元件的电阻-温度曲线图。
图中标号说明：
11一高分子基导电复合材料； 12， 12' —金属电极片；
13， 13 ' —金属导电部件。
具体实施方式
实施例 1至 6为添加偶联剂的本发明材料及 PTC元件。
实施例 1
制备 PTC元件的导电复合材料的组成为：
( a)高分子基材为高密度聚乙烯，其熔融温度为 134°C，密度为 0.953g/cm3， 体积分数为 40%;
(b) 导电填料为核壳式颗粒结构， 由外壳、 中间层和内核组成， 外壳为硼 化二钨， 中间层为硼化钨， 内核为金属钨， 粒径为 2.0μιη， 体积分数为 60%。
( c) 偶联剂为单烷氧基型异丙基二油酸酰氧基钛酸酯， 体积分数为导电填 料体积的 0.5%， 密度 0.976g/cm3。
将密炼机温度设定在 180°C， 转速为 30转 /分钟， 先加入聚合物密炼 3分钟 后， 然后加入导电填料继续密炼 15分钟， 得到一高分子基导电复合材料。 将熔 融混合好的高分子基导电复合材料通过开炼机压延，得到厚度为 0.20-0.25mm的 高分子基导电复合材料 11。
PTC元件的制备过程如下：
请参阅图 1 (本发明的 PTC元件的示意图） ， 将高分子基导电复合材料 11 层置于上下对称的两金属电极片 12， 12' 之间， 金属电极片 12， 12' 与高分子 基导电复合材料层 11紧密结合。 通过热压合的方法将高分子基导电复合材料 11 和金属电极片 12， 12' 紧密结合在一起。热压合的温度为 180°C，先预热 5分钟， 然后以 5MPa的压力热压 3分钟， 再以 12MPa的压力热压 10分钟， 然后在冷压 机上冷压 8分钟， 以模具将其冲切成 3*4mm的单个元件， 最后通过回流焊的方 法将两个金属引脚 13， 13 ' 分别连接在两个金属电极片 12， 12' 表面， 形成一 PTC元件。
本实施例的 PTC元件的电性能如表 1所示。
实施例 2
制备高分子基导电复合材料及 PTC元件的步骤与实施例 1相同， 但将导电复 合材料中偶联剂的体积分数由占导电填料体积的 0.5%增加到 1.0%。
本实施例的 PTC元件的电性能如表 1所示。
实施例 3
制备高分子基导电复合材料及 PTC元件的步骤与实施例 1相同， 但将导电复 合材料中偶联剂的体积分数由占导电填料体积的 0.5%增加到 1.5%。
本实施例的 PTC元件的电性能如表 1所示。
实施例 4
制备高分子基导电复合材料及 PTC元件的步骤与实施例 1相同， 但将导电复 合材料中偶联剂的体积分数由占导电填料体积的 0.5%增加到 2.0%。
本实施例的 PTC元件的电性能如表 1所示。
实施例 5
制备高分子基导电复合材料及 PTC元件的步骤与实施例 1相同， 但将导电复 合材料中偶联剂的体积分数由占导电填料体积的 0.5%增加到 2.5%。
本实施例的 PTC元件的电性能如表 1所示。
实施例 6
制备高分子基导电复合材料及 PTC元件的步骤与实施例 2相同， 但采用的偶 联剂为单烷氧基型异丙基三油酸酰氧基钛酸酯， 添加量为导电填料体积的 1.0%， 密度 1.01g/cm3。
本实施例的 PTC元件的电性能如表 1所示。
比较例 1 制备高分子基导电复合材料及 PTC元件的步骤与实施例 3相同， 但高分子基 导电复合材料中不添加任何偶联剂。
本实施例的 PTC元件的电性能如表 1所示。
表 1中的 Rmin表示 PTC元件的两个金属电极片 12， 12'表面上焊上两个金属引 脚 13， 13 ' 之后的电阻， 为 10个 PTC元件的最小电阻值；
Raverage表示 PTC元件的两个金属电极片 12， 12'表面上焊上两个金属引脚 13， 13 ' 之后的电阻， 为 10个 PTC元件的平均电阻值；
Rmax表示 PTC元件的两个金属电极片 12， 12' 表面上焊上两个金属引脚 13， 13 ' 之后的电阻， 为 10个 PTC元件的最大电阻值；
STDEV表示 10个 PTC元件的标准偏差， 反映电阻的离散性；
表示 PTC元件持续通电（6V/50A) 6秒后， 在 25 °C的温度环境里放置 1小时 后所测得的电阻值；
Rioo表示 PTC元件持续通电 （6V/50A) 6秒后， 断电 60秒， 如此循环 100次， 然后在 25 °C的温度环境里放置 1小时后所测得的电阻值。
R100cydes表示 PTC元件在 +85 °C环境中放置 30分钟，然后在 -40 °C环境中放置 30 分钟， 如此循环 100次， 然后在 25 °C的温度环境里放置 1小时后所测得的电阻值。
R6V/5。A表示 PTC元件在 6V， 50A的条件下耐压 2小时，然后在 25 °C的温度环境 里放置 1小时后所测得的电阻值。
Ri2v/5。A表示 PTC元件在 12V， 50A的条件下耐压 2小时， 然后在 25 °C的温度环 境里放置 1小时后所测得的电阻值。
表 1
Figure imgf000010_0001
耐候性 热 循 环
8.5 8.4 8.0 8.2 9.1 9.6 10.7 能 Rioocycies(mohm)
耐压性 R6v/50A(mohm) 16.0 15.6 14.6 17.2 17.8 18.5 20.4 能 Ri2v/50A(mohm) 18.6 19.0. 18.8 20.1 22.4 24.1 击穿 加工性
扭矩 CN.m) 45.3 42.5 40.4 42.6 44.1 46.2 48.8 能 从表 1可以看出： 实施例 1至 6和比较例具有相同体积分数的结晶性聚合物和 导电填料，但实施例 1〜6中均添加了一定量的偶联剂，其成品电阻值比未添加偶 联剂的比较例要低， 并且电阻离散性要小， 说明偶联剂的加入有助于导电填料在 高分子基体中的分散。 实施例 3中， 在相同导电填料体积分数的情况下， 当偶联 剂的体积分数为 1.5%时， PTC元件具有最低的电阻。实施例 1〜6和比较例 1的 PTC 元件均能承受 6V电压， 实施例 1〜6中的 PTC元件能承受 12V电压而比较例的 PTC 元件不能承受 12V的电压，说明偶联剂的添加有利于增强 PTC元件的耐电压性能。 从表 1中高分子基导电复合材料加工时的扭矩可以看出， 添加了一定量偶联剂的 实施例 1至 6的扭矩比未添加偶联剂的比较例要低，说明偶联剂的加入有利于改善 高分子基导电复合材料的成型加工性能。
本发明实施例 1〜6中， 由于 PTC元件所使用的导电复合材料添加了可以改 善导电填料分散状态的偶联剂，增强了复合材料中的导电网络， 因此具有较高的 电阻集中度。且所使用的导电填料具有核壳式颗粒结构， 不易被氧化， 无需通过 包封的方式来保护高分子基导电复合材料， 因此可以制备厚度为 0. 2mn！〜 2. 0mm, 承载电流面积为 1210、 1206、 0805、 0603等小尺寸的 PTC元件。
以下的实施例中未加入偶联剂， 配方及性能见表 2。
实施例 7
制备热敏电阻元件的聚合物基导电复合材料的配方如表 2所示。其中，聚合 物 1为高密度聚乙烯， 其熔融温度为 134°C， 密度为 0.953g/cm3; 聚合物 2为高 密度聚乙烯， 其熔融温度为 135 °C， 密度为 0.954g/cm3; 导电填料 1为碳化钛， 其费氏粒径为 2.0μιη，密度为 4.93 g/cm3 ;导电填料 2为核壳式结构，粒径为 2.0μιη， 其中， 外壳为硼化二钨； 中间层为硼化钨； 内核为金属钨。
热敏电阻元件的制备过程如下： 将密炼机温度设定在 180°C， 转速为 30转 / 分钟， 先加入聚合物密炼 3分钟后， 然后加入导电填料继续密炼 15分钟， 得到 一聚合物基导电复合材料。将熔融混合好的聚合物基导电复合材料通过开炼机压 延， 得到厚度为 0.20〜0.25mm的聚合物基导电复合材料片材 11。
本发明的热敏电阻元件的如图 1所示， 聚合物基导电复合材料片材 11置于 上下对称的上下金属电极片 12、 13之间， 金属电极片 12、 12' 与聚合物基导电 复合材料片材 11紧密结合。 通过热压合的方法将聚合物基导电复合材料片材 11 和金属电极片 12、 12'紧密结合在一起。热压合的温度为 180°C，先预热 5分钟， 然后以 5MPa的压力热压 3分钟， 再以 12MPa的压力热压 10分钟， 然后在冷压 机上冷压 8分钟， 以模具将其冲切成 3*4mm的单个元件， 最后通过回流焊的方 法将两个金属引脚 13、 13 ' 连接在两个金属电极片 12、 12' 表面， 形成一热敏 电阻元件。
图 3是本实施例的热敏电阻元件的电阻-温度曲线图。 热敏电阻元件在 25°C 时具有很低的电阻值， 随着温度的增加， 电阻缓慢上升， 当温度增加到 130°C左 右时， 热敏电阻元件的电阻发生突变， 增加约 10个数量级， 此时热敏电阻元件由 导体变成绝缘体， 使电路处于断路状态， 以达到保护电路元件的目的。
实施例 8
制备热敏电阻元件的聚合物基导电复合材料的组成与实施例 7相同，本实施 例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2所示，但制 备聚合物基导电复合材料片材及热敏电阻元件的步骤不同， 步骤为：
将聚合物磨粉后与导电填料在混合器中干态混合 30分钟， 然后将混合料加 入双螺杆挤出机中， 在 180°C-220°C的温度下熔融混合后挤出造粒， 形成聚合物 基导电复合材料粒料； 将聚合物基导电复合材料粒料加入另一双螺杆挤出机中， 在 180°C〜220°C的温度下通过挤出机模头将聚合物基导电复合材料挤出成熔融 状态的聚合物基导电复合材料片材 11， 聚合物基导电复合材料片材 11与对称的 上、 下两金属电极片 12、 12' 通过热压辊牵引热压而紧密结合在一起， 然后将 它们裁剪成 110*200mm大小的芯材， 通过模具将其冲切成 3*4mm的单个元件， 最后通过回流焊的方法将两个金属引脚 14、 15连接在上、下金属电极片 12、 12' 表面， 形成一热敏电阻元件。
实施例 9
本实施例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2所示。制备聚合物基导电复合材料及热敏电阻元件的步骤与实施例 7相同，但将 聚合物 1的体积分数由 34 %变为 38 %， 将导电填料 2的体积分数由 60 %变为 56 %。 实施例 10
本实施例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2所示。制备聚合物基导电复合材料及过电流保护元件的步骤与实施例 7相同，但 将聚合物 1的体积分数由 34 %变为 38 %，将聚合物 2的体积分数由 6 %增加到 10 %， 将导电填料 2的体积分数由 60 %变为 52 %。
比较例 2
本比较例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2 所示。 制备聚合物基导电复合材料及过电流保护元件的步骤与实施例 1相同， 但 将导电填料 2改为导电填料 1。
比较例 3
本比较例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2 所示。 制备聚合物基导电复合材料及热敏电阻元件的步骤与实施例 7相同， 但将 导电填料 2改为导电填料 1，将聚合物 1的体积分数由 34 %变为 38 %，将导电填料 1 的体积分数由 60 %变为 56 %。
比较例 4
本比较例的聚合物基导电复合材料的配方和热敏电阻元件的电气特性如表 2 所示。 制备聚合物基导电复合材料及热敏电阻元件的步骤与实施例 7相同， 但将 导电填料 2改为导电填料 1，聚合物 2的体积分数由 34 %变为 38 %，将聚合物 2的体 积分数由 6 %增加到 10 %，将导电填料 1的体积分数由 60 %变为 52 %。其中热敏电 阻元件的电阻值是用四电极法进行测量得到。
结果分析： 表 2中的电阻数据为由本发明的聚合物基导电复合材料制备的热 敏电阻元件在 6V/50A的条件下触发后， 在 25 V的温度环境里放置 1小时后的电阻 测试数据。
表 2中的 R表示热敏电阻元件的两个金属电极片 12、 12 ' 表面上焊上两个金 属引脚 13、 13 ' 之前的电阻； Ro表示热敏电阻元件的两个电极片 12、 12 ' 表面上 焊上两个金属引脚 13、 13 '之后的电阻； 表示热敏电阻元件持续通电（6V/50A) 6秒后， 在 25 °C的温度环境里放置 1小时后所测得的电阻值； R25表示所述热敏电 阻元件持续通电 （6V/50A) 6秒后， 断电 60秒， 如此循环 25次， 然后在 25 °C的温 度环境里放置 1小时后所测得的电阻值; R5。表示热敏电阻元件持续通电 ( 6V/50A) 6秒后， 断电 60秒， 如此循环 50次， 然后在 25 °C的温度环境里放置 1小时后所测得 的电阻值； RIQQ表示热敏电阻元件持续通电 （6V/50A) 6秒后， 断电 60秒， 如此 循环 100次，然后在 25 °C的温度环境里放置 1小时后所测得的电阻值。热循环（Heat cycle) R1QQeydes表示热敏电阻元件在 +85 °C环境中放置 30分钟， 然后在 -40°C环境 中放置 30分钟， 如此循环 100次，然后在 25 °C的温度环境里放置 1小时后所测得的 电阻值。 高温高湿 （High temperature and humidity) Rioooh表示热敏电阻元件在 85 °C， 85%RH的环境中放置 1000个小时， 然后在 25 °C的温度环境里放置 1小时后 所测得的电阻值。高湿（ High humidity ) R^ooh表示热敏电阻元件在 60 V， 95%RH 的环境中放置 1000个小时， 然后在 25 °C的温度环境里放置 1小时后所测得的电阻 值。耐电压性能中， 6V/50A/2h表示热敏电阻元件在 6V， 50A的条件下耐压 2小时， 12V/50A/2h表示热敏电阻元件在 12V， 50A的条件下耐压 2小时， 耐电压性能 OK 表示过电流保护元件不烧不裂， NG表示热敏电阻元件烧毁或裂开。
表 2
Figure imgf000014_0001
Rioocycies(mohm)
高的温度和湿度
7.8 6.6 8.6 9.2 9.4 7.3 8.5 高湿度
7.2 6.0 7.9 8.6 7.8 8.2 8.6 耐电压性能
6V/50A/2h OK OK OK OK OK OK OK
12V/50A/2h OK OK OK OK NG NG NG 从表 2可以看出： 实施例 7〜8和比较例 2; 实施例 9和比较例 3 ; 实施例 10和比 较例 4分别具有相同体积分数的导电填料，但实施例 7〜10中所用导电填料为核壳 式颗粒结构，其成品电阻值比使用非核壳式颗粒结构的碳化钛作导电填料的比较 例 2〜4要小。 实施例 7〜10中的热敏电阻元件经过 6V/50A电流冲击 100次后， 其 电阻值相对比较例 2〜4经过 6V/50A电流冲击 100次后的电阻值小， 说明其电阻再 现性较好。 实施例 7〜10和比较例 2〜4中的热敏电阻元件均能承受 6V电压， 实施例 7〜 10中的热敏电阻元件能承受 12V电压而比较例 2〜4中的热敏电阻元件不能承受 12V的电压， 说明以核壳式颗粒结构导电填料制备的热敏电阻元件具有优良的耐 电压性能。 从图 3可以看出， 以核壳式颗粒结构导电填料制备的热敏电阻元件具 有优异的 PTC强度（本文中 PTC强度等于样品在电阻率 -温度关系曲线中的最大电 阻率与其在室温时的电阻率比值的对数值）。
本发明实施例 7〜10中的热敏电阻元件所使用的聚合物基导电复合材料由 于包含电阻率非常低的具有核壳式颗粒结构的导电填料， 具有很低的室温电阻 率、 优良的耐候性能、 良好的耐电压性能、 优异的电阻再现性和 PTC强度。 且所 使用的导电填料具有核壳式颗粒结构， 不易被氧化，无需通过包封的方式来保护 聚合物基导电复合材料， 因此可以制备厚度为 0. 2mm〜2. 0mm,承载电流面积为 1210、 1206、 0805、 0603等小尺寸型号的热敏电阻元件。
本发明的内容和特点已揭示如上， 然而前面叙述的本发明仅仅简要地或只 涉及本发明的特定部分，本发明的特征可能比在此公开的内容涉及的更多。因此， 本发明的保护范围应不限于实施例所揭示的内容，而应该包括在不同部分中所体 现的所有内容的组合， 以及各种不背离本发明的替换和修饰， 并为本发明的权利 要求书所涵盖

Claims

权 利 要 求
1、 一种高分子基导电复合材料， 包含高分子基材、 导电填料和偶联剂， 其 特征在于：
( a) 所述高分子基材为聚乙烯、 聚丙烯、 聚偏氟乙烯、 聚烯烃弹性体、 环 氧树脂、 乙烯 -醋酸乙烯共聚物、 聚甲基丙烯酸甲酯、 乙烯-丙烯酸共聚物中的一 种及其混合物， 占所述高分子基导电复合材料的体积分数的 20%〜75%；
(b) 导电填料， 具有核壳式颗粒结构， 占所述高分子基导电复合材料的体 积分数的 25%〜80%， 其粒径为 0.1μιη〜20μιη， 且体积电阻率小于 10_2Ω.ιη， 所 述导电填料分散于所述高分子基材中；
( c) 偶联剂占导电填料体积的 0. 05%〜5%， 所述偶联剂为钛酸酯偶联剂， 为单烷氧基型钛酸酯偶联剂、单烷氧基焦磷酸酯型钛酸酯偶联剂、螫合型钛酸酯 偶联剂、配位型钛酸酯偶联剂、季铵盐型钛酸酯偶联剂中的一种或多种的混合物。
2、 根据权利要求 1所述的高分子基导电复合材料， 其特征在于， 所述核壳 式颗粒结构由内核、外壳和中间层组成， 其中， 所述内核由钽、钒、锆、钛、铌、 钼、 铪、 钨、 铬或铍之中的一种组成； 所述外壳由内核物质的一种硼化物、 氮化 物、 碳化物或硅化物组成； 所述中间层由内核物质的一种硼化物、 氮化物、 碳化 物或硅化物组成， 所述的组成中间层的化合物与组成外壳的化合物不同。
3、 根据权利要求 2所述的高分子基导电复合材料， 其特征在于， 所述硼化 物为硼化钽、 二硼化钽、 硼化钒、 二硼化钒、 二硼化锆、 二硼化钛、 硼化铌、 二 硼化铌、 硼化二钼、 五硼化二钼、 二硼化铪、 硼化二钨、 硼化钨、 硼化二铬、 硼 化铬、 二硼化铬或三硼化五铬之中的一种。
4、 根据权利要求 2所述的高分子基导电复合材料， 其特征在于， 所述氮化 物为氮化钽、 氮化钒、 氮化锆、 氮化钛、 氮化铌或氮化铪中的一种。
5、 根据权利要求 2所述的高分子基导电复合材料， 其特征在于， 所述碳化 物为碳化钽、 碳化钒、 碳化锆、 碳化钛、 碳化铌、 碳化二钼、 碳化铪、 碳化钨、 碳化二钨或二碳化三铬之中的一种。
6、 根据权利要求 2所述的高分子基导电复合材料， 其特征在于， 所述硅化 物为二硅化钽、 三硅化五钽、 硅化三钒、 二硅化钒、 二硅化锆、 二硅化钛、 三硅 化五钛、 二硅化铌、 二硅化钼、 二硅化铪、 二硅化钨、 硅化三铬或二硅化铬之中 的一种。
7、一种高分子基导电复合材料， 包含聚合物基材和导电填料， 其特征在于： 所述的聚合物基材为聚乙烯、 聚丙烯、 聚偏氟乙烯、 聚烯烃弹性体、 环氧树 脂、 乙烯 -醋酸乙烯共聚物、 聚甲基丙烯酸甲酯、 乙烯 -丙烯酸共聚物中的一种或 其混合物， 占所述聚合物基导电复合材料的体积分数的 20%〜75%；
所述的导电填料具有核壳式颗粒结构的导电填料， 粒径为 0.1μιη〜20μιη， 体积电阻率不大于 0.03Ω.ιη， 所述具有核壳式颗粒结构的导电填料由内核、 外壳 和中间层组成， 占所述聚合物基导电复合材料的体积分数的 25%〜80%， 分散于 所述聚合物基材中， 其中，
所述的内核物质为钽、 钒、 锆、 钛、 铌、 钼、 铪、 钨或铬之中的一种； 所述的外壳物质为内核物质的一种硼化物、 氮化物、 碳化物或硅化物组成； 所述的中间层由内核物质的一种硼化物、氮化物、碳化物或硅化物组成， 组 成中间层的硼化物、 氮化物、 碳化物或硅化物与组成外壳的硼化物、 氮化物、 碳 化物或硅化物为不同的化合物。
8、 根据权利要求 7所述的高分子基导电复合材料， 其特征在于， 所述硼化 物为硼化钽、 二硼化钽、 硼化钒、 二硼化钒、 二硼化锆、 二硼化钛、 硼化铌、 二 硼化铌、 硼化二钼、 五硼化二钼、 二硼化铪、 硼化二钨、 硼化钨、 硼化二铬、 硼 化铬、 二硼化铬或三硼化五铬之中的一种。
9、 根据权利要求 7所述的高分子基导电复合材料， 其特征在于， 所述氮化 物为氮化钽、 氮化钒、 氮化锆、 氮化钛、 氮化铌或氮化铪中的一种。
10、根据权利要求 7所述的高分子基导电复合材料， 其特征在于， 所述碳化 物为碳化钽、 碳化钒、 碳化锆、 碳化钛、 碳化铌、 碳化二钼、 碳化铪、 碳化钨、 碳化二钨或二碳化三铬中的一种。
11、根据权利要求 7所述的高分子基导电复合材料， 其特征在于， 所述硅化 物为二硅化钽、 三硅化五钽、 硅化三钒、 二硅化钒、 二硅化锆、 二硅化钛、 三硅 化五钛、 二硅化铌、 二硅化钼、 二硅化铪、 二硅化钨、 硅化三铬或二硅化铬之中 的一种。
12、根据权利要求 1至 11之一所述高分子基导电复合材料制备的 PTC元件， 由两个金属电极片间夹高分子基导电复合片材构成，所述金属电极片与所述高分 子基导电复合片材料之间紧密结合，其中，所述的高分子基导电复合材料片材的 厚度为 0.01〜3.0mm， 被分割成具有平面形状的单个元件， 所述单个元件即有与 电流流过方向垂直的两个表面， 所述金属电极片的厚度不大于 0.3mm， 在 25°C 时 PTC元件的体积电阻率不大于 0.02Ω. η。
13、根据权利要求 12所述高分子基导电复合材料制备的 PTC元件， 其特征 在于： 所述单个元件为正方形、 三角形、 圆形、 矩形、 环形、 多边形或其它不规 则形状的片状结构。
14. 根据权利要求 12或 14所述的 PTC元件的制备方法， 包括下述步骤：
1 ) 将聚合物基材和导电填料在高于聚合物熔融温度以上的条件下进行熔融 混合，然后将混合好的聚合物通过挤出成型、模压成型或压延成型加工成厚度为 0.01〜3.0mm的聚合物基导电复合材料片材；
2) 在聚合物基导电复合材料片材还处于熔融状态时通过滚筒直接将电极片 紧密压合在该片材的二面获得复合片材；
3 ) 把复合片材通过冲切、 刻蚀、 划片或激光切割分割成单个元件， 所述单 个元件具有平面形状， 即有与电流流过方向垂直的两个表面， 且两个表面之间的 距离不大于 3.0mm制成 PTC元件；
4) 对 PTC元件进行交联和 /或热处理。
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