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WO1999038173A1 - Composition polymere - Google Patents

Composition polymere Download PDF

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Publication number
WO1999038173A1
WO1999038173A1 PCT/GB1999/000205 GB9900205W WO9938173A1 WO 1999038173 A1 WO1999038173 A1 WO 1999038173A1 GB 9900205 W GB9900205 W GB 9900205W WO 9938173 A1 WO9938173 A1 WO 9938173A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
granules
composition
composition according
composite
Prior art date
Application number
PCT/GB1999/000205
Other languages
English (en)
Inventor
David Lussey
Andrew Brian King
Christopher John Lussey
Original Assignee
Peratech Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/GB1998/000206 external-priority patent/WO1998033193A1/fr
Priority claimed from GBGB9806623.6A external-priority patent/GB9806623D0/en
Priority claimed from GBGB9814131.0A external-priority patent/GB9814131D0/en
Application filed by Peratech Ltd. filed Critical Peratech Ltd.
Priority to JP2000528985A priority Critical patent/JP2002501949A/ja
Priority to EP99901767A priority patent/EP1050054B1/fr
Priority to CA002318742A priority patent/CA2318742A1/fr
Priority to DE69935416T priority patent/DE69935416T2/de
Priority to AU21768/99A priority patent/AU2176899A/en
Priority to US09/600,808 priority patent/US6495069B1/en
Publication of WO1999038173A1 publication Critical patent/WO1999038173A1/fr

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Classifications

    • 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
    • H01C7/027—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 conducting or semi-conducting material dispersed in a non-conductive organic material

Definitions

  • This invention relates to a polymer composition including a finely divided electrical conductor, particularly comprising such a composition in an advantageous physical form.
  • a polymer composition comprises at least one substantially non- conductive polymer, and at least one electrically conductive filler and is characterized by being in the form of granules.
  • the granules are typically in the size range up to 1mm, especially 0.04 to 0.2mm. Thus 2 the smaller granules behave as powders. These ranges are based on measuring the greater diameter of the granules if not regularly spherical.
  • the granules may be for example in an approximate Poisson size distribution, or sieved to a skewed distribution or a narrow spread (for example, largest granules no greater than 2 x smallest) or classified so that small granules fill the spaces between larger granules .
  • the conductor polymer volumetric ratio (tapped bulk : voidless solid) is suitably at least 3:1 especially in the range 5-15:1.
  • the ratio of conductive medium to polymer small changes will be required to account for differences in relative surface tensions of types and grades of polymer and the various surface energies of the different conductive oxides and other solids present. Changes of this ratio have an effect on the piezo-charge properties, the overall resistance range, the recovery hysteresis and the pressure sensitivity of the granules .
  • Various relationships within the granules are envisaged, for example : a. the conductor particles are fully covered, giving non-conduction under mere gravity, but conduction under applied stress; b.
  • the conductor particles are in mutual contact within granules but do not project outside granules ; 3 c. the conductor particles are out of mutual contact within granules but project outwards, giving inter- granule contact; d. the conductor particles are in mutual inter- granular and intra-granular contact.
  • the conductive material can be one or more metals, other conductive or semiconductive elements and oxides or intrinsically conductive or semiconductive organic or inorganic polymers.
  • the conductive material is suitably selected from powdered forms of the metallic elements or their electrically conductive alloys or reduced oxides either on their own or together.
  • the conducting filler can be the basic element in the unoxidised state; or can be a layer on a carrier core of powder, grains, fibres or other shaped forms.
  • the oxides can be mixtures comprising sintered powders of an oxycompound.
  • the alloy may be for example titanium diboride .
  • the micro-structure of the conductor particles is of 4 substantial importance.
  • dendritic, filamentous, and spiked forms of the conductive materials have been shown to be capable of producing particularly sensitive conductive granules when coated with a polymer such as silicone.
  • the conductor particles are rough- surfaced with smaller and spikier powders producing more sensitive granules.
  • the particles comprise metal having at least one of these characteristics: (i) spiky and/or dendritic surface texture; (ii) filamentary structure, with a three- dimensional chain- like network of spiky beads, the chains being on average 2.5 - 3.5 microns in cross- section and possibly more than 15 - 20 microns in length.
  • these characteristics are present in the conductor particles before mixing with polymer, and mixing is controlled to substantially preserve them.
  • preferred conductor particles comprise carbonyl-derived metallic nickel.
  • Other examples include dendritic copper.
  • the polymer constituent of the granules can be chosen from a wide range of materials, the only limitation being that the polymer or a precursor thereof should be available in a form sufficiently mobile to permit incorporation of conductor particles. In an extreme case it can be a fully or partly cured resin, such as a formaldehyde condensate, epoxy resin, maleimide resin or 3 -dimensional olefin resin. Polymers having 5 flexibility, such as linear thermoplasts, are of more general application. Very suitably the polymer constituent is an elastomer. Since elastomers are preferred in certain composites including the granules, they will be described further below.
  • the invention provides a method of making the granules by mixing conductor particles with liquid-form polymer in granule-forming conditions.
  • the liquid-form polymer may be, for example, a precursor subject to polymerization or to cross-linking during the granule- forming step or later.
  • Liquid-form means sufficiently flowable to undergo mixing with the conductor particles.
  • the polymer may be very viscous.
  • a liquid may be present to modify the viscosity of the polymer as an aid to mixing. It may be added, for example, by pre-mixing with the polymer or with the conductor powder.
  • the liquid should of course be chemically inert with respect to the conductor and polymer.
  • Hydrocarbons such as petroleum distillates, are very suitable .
  • a hydrophobising agent Before or during mixing there may be added a hydrophobising agent. This is believed to act by displacing adsorbed water from the surfaces of the components of the mix, for example the conductor particles, solid additives such as those described below, especially fumed silica, and possibly of newly exposed polymer and newly formed granules .
  • the agent may 6 also act as a lubricant limiting friction at mixer surfaces. Since it can act by formation of very thin, even unimolecular layers, the quantity to be used is very small, for example 10 - 1000 ppm w/w of the mix.
  • Examples of the agent are liquid hydrocarbons carrying groups favouring chemisorption on metals, and fluorocarbons .
  • the granules are made by coating conductive particles with a layer of polymer in a controlled mixing regime that imparts only sufficient force to the components of the mix to achieve the coating process and avoids additional force which has been found to have a degrading effect on the electrical properties of the final polymer.
  • the relationship between filler, binder, mixing energy, time, rate of shear, temperature and pressure determine the particle size-distribution and electro-mechanical properties of the resulting granule. It appears likely that the conductor particles act as a nuclei for granule formation.
  • Such mixing is preferably at a low level of shear, so that the conductor particles remain structurally intact.
  • a dish-granulator, blunger, coaxial cylinder mixer (rotary ablation) can be used.
  • the total shear can be of the same order as in the production of bulk composition but applied at greater intensity for a shorter time.
  • Granule formation is preferably accompanied by some cross-linking of the polymer.
  • the polymer formulation 7 is chosen and the conditions of mixing are controlled so that breakage of the mixture into granules is synchronized with cross-linkage of the polymer sufficient for a non-sticky state. This is especially convenient using RTV silicone.
  • the process may if desired be controlled to produce a precursor of the granules in which the polymer may be subjected to further cross-linking to develop elastomerism.
  • Use of HTV silicone affords more scope in making such precursors.
  • the silicone very suitably is one subject to high shrinkage for example by 10 - 20% on cross- linking. This makes possible a relatively high conductor to polymer volume ratio in granules without an inconveniently high ratio at the start of mixing.
  • silicone content of the mix is increased, sensitivity is decreased and agglomeration increases.
  • silicone may be applied to previously made granules of lower silicone content .
  • This pressure affects the time taken to achieve the granulated state and is important to the coating thickness, the eventual size of the granule and the amount of agglomeration between individual granules . Too much pressure produces destructive shear forces .
  • the resulting granules can be comminuted to provide a 8 desired range. They can be screened to separate the different sized agglomerations if required. Different sized granules show different sensitivities; granule sizes can be separated and remixed in different proportions to alter the final sensitivity of the granule composite. It has also been found possible to combine different conductive materials, conductive, semi-conductive or non-conductive powders, prior to the granule-forming agglomeration/coating process to obtain the required conduction or other electrical and mechanical properties in the final granule form.
  • the invention provides also a composite comprising the granules.
  • the granules can be used by containing them in a device which limits peripheral movement but allows the input of an electrical or mechanical pressure in order to activate it . They may be mixed with or coated onto other bulk or foamed polymers to form solid, semi-flexible or flexible composite structures.
  • the granules can be extruded or pressed into sheet, pellet or fibre form or can be cast into moulds. In the course of the shaping process they can be milled or cryogenically powdered. Energy imparted during mixing and moulding the polymer composition in the uncured state may, however, affect the physical and electrical performance of the composite.
  • the granules may be associated with a containing means.
  • a containing means This may be a fibre 9 or sheet, for example of polymer fibre film, plate or cloth and may carry granules on one or both faces .
  • the polymer sheet may already contain or carry conductor particles as described for example in Example 7 of the co-pending application.
  • the sheet may comprise or carry an adhesive for the granules.
  • precursor granules (as specified above) can be pressed into the surface or surfaces of the un-cross-linked carrier polymer and permanently bonded to the carrier polymer when it is cross-linked. This produces a pressure sensitive or EM screening layer on the carrier polymer.
  • the granules are associated with a three-dimensional matrix.
  • the matrix may be electrically non-conducting, but could be composed, for example, of polymer having conductor particles dispersed in it , such as described in the co- pending application or in prior-published documents.
  • Several variants of this type are possible, for example:
  • matrix material may enter spaces between granules or may be just a containment bag.
  • the polymer composition in a composite structure for generation, detection and relay of electrical signals internal connectivity is provided in the form of an integrated electrically conductive member for example a layer such as metal film or sheet especially continuous metallised cloth, typically polyester based.
  • the cloth increases the tactile sensitivity (increase in resistance drop versus mass loading) of the conductive polymer composition by providing a hard fibre anvil for elastomeric distortion and provides an electron bridge between zones of low resistance within the composite.
  • the conductive polymer composition can be bonded to or formed on the conductive member.
  • the composite may be a simple device for switching on or off when deformed, more complicated electrical circuits may be built into the layer, for example, of the metallised cloth structure.
  • the metal coated fabric is typically manufactured by application of metal by vapour deposition, sputtering or similar means to a woven polyester cloth.
  • Electrical circuits analogous to those etched onto a conventional printed circuit board, may be created by masking and etching the pre-metallised cloth or preferably by masking the target cloth at the point of metallisation.
  • the metal coating will only be 11 deposited where the mask allows and by this process a conductive circuit layout can be produced.
  • Composites incorporating the circuit cloth show true flexibility, are solid state and may be made extremely sensitive to touch or other operating forces . They may be used for digital and analogue switching and control, may incorporate PTC load control or heat production capability and have the capacity to carry substantial electric currents.
  • a particularly useful one comprises conductive granules and includes means for the input of electrical and/or mechanical deformation to activate it .
  • the sheet or matrix would comprise ohmic conductor (s) connecting the granule assembly electrically.
  • the granules can also be used as a conductive component of other conductive and electromagnetic shielding materials either alone or in combination with other powders or granules or other non-conductive, semiconductive or conductive materials.
  • Granule-coated surfaces can be particularly sensitive to applied pressure, increasing in pressure sensitivity with increasing surface loading.
  • Granules on their own and granule-coated surfaces can show a drop in electrical resistance of more than 10 12 ohms with an applied force within the range 0.01 - 6 N/cm 2 .
  • hydrophobising agent as above 12 described, present when an assembly of the granules is being set up.
  • Composites containing the granules as a film or heterogeneous mixture with other polymers and materials tend to show greater repeatability, sensitivity and linearity of resistance change than can be obtained with bulk pressure sensitive polymer compositions as in the co-pending application. Like the bulk composition, the granules return to a quiescent resistance state when the operating force is removed.
  • the polymer constituent is an elastomer, especially having the general properties: i) low surface energy typically in the range 15 - 50 dyne/cm but especially 22 - 30 dyne/cm; ii) a surface energy of wetting for hardened elastomer higher than its uncured liquid; iii) a low energy of rotation (close to zero) giving extreme flexibility; iv) excellent pressure sensitive tack both to the filler particles and electrical contacts to which the composite may be attached - that is, possess a high ratio of viscous to elastic properties at time spans comparable to bonding times (fraction of a second) ; v) high on the triboelectric series as a positive charge carrier (conversely, will not carry negative charge on its surface) ; vi) chemically inert, fire extinguishing and 13 effective as a barrier to oxygen and air ingress.
  • Silicone elastomer rubbers are typically but not exclusively based on polydimethylsiloxane, polysilamine and allied silicone backbone polymers, with leaving groups, cross-linkers and cure systems based on:
  • the elastomer can be mixtures comprising cured elastomers selected from the group comprising one, two or more component silicones, one, two or more component polygermanes and polyphosphazines and at least one silicone agent. In such polymer mixtures, the silicone component exceeds other polymer components .
  • additives are included with the silicone for the purpose of modifying the physical and/or electrical properties of the uncured or cured polymer composition.
  • Such additives can include at least one property modifier from the group comprising: alkyl and hydroxyalkycellulose , carboxymethylcellulose , hydroxyethylcellulose, hydroxypropylcellulose, polyacrylamide, polyethylene glycol, poly (ethylene oxide) , polyvinyl alcohol, polyvinylpyrrolidone, starch and its modifications, calcium carbonate, fumed silica, 14 silica gel and silicone analogues and at least one silica analogue or silicone analogue modifier. Fumed silica is an example of a modifier as commonly used in elastomer technology.
  • a silicone system is manufactured from high strength room temperature cured fumed silica loaded (RTV) silicone polymer.
  • RTV room temperature cured fumed silica loaded
  • Another example uses high temperature cured HTV silicone filled with fumed silica to provide interstitial structure, useful strength, pressure tack and life, cross-linked at an elevated temperature in the presence of a peroxide or other catalyst, that may typically but not exclusively be 2,4 dichloro dibenzoyl peroxide .
  • HTV products may be stored for prolonged periods in the uncured state prior to processing into sheet, rod, foam, fibre, press moulded or other forms.
  • Another usable class of elastomer is the natural or synthetic hydrocarbon rubbers. Especially for matrix material, such rubber may be introduced in latex form.
  • the resulting composites may display a piezo-charge affect and will change their inherent electrical resistance in response to both pressure and strain forces.
  • Working resistance is around the range 10 12 to 15
  • the composites have excellent current carrying capability; typically a 2mm thick sample of the composite on a heat-sink can control AC or DC currents of 3A/cm 2 .
  • the initial application of pressure or force to a sample of the high-resistance composite results in the generation of an electrostatic charge; increasing the pressure or force decreases the electrical resistance of the composite.
  • the composites can be flexible and can reassert themselves when the force or pressure is removed. As this occurs the electrical resistance will increase towards a quiescent value and a pronounced electrostatic charge will develop.
  • the electrostatic effect can provide digital switching indications or provide a voltage source.
  • the electrical resistance change can provide an analogue of the applied pressure or force.
  • the resistance range can be used to provide digital switching especially but not essentially at its upper and lower limits.
  • Sensitive versions of composite which are close to conduction can be changed into a fully conducting state by applying an electrostatic charge, typically that generated by a piezoelectric spark generator and greater than 0.5kV.
  • the composite consists of the granules held within a matrix.
  • the conductive particles are of such a size distribution as to provide for a close packed structure with interstitial particle infilling.
  • Voids present in the bulk conductor powder 16 become infilled with elastomer during mixing and conductor particles become set in close proximity during curing.
  • the elastomer will have a low surface energy relative to the powder phase and uncured liquid surface energy less than cured elastomer surface energy.
  • Such polymer compositions will include silicones, polygermanes and polyphosphazines . In the stressed state the distortion takes place such that the average entrapped inter- particle distance decreases. For metal particles this corresponds to an increase in electrical conductivity, for other types of particle other effects may be generated (change in ferromagnetism, piezoelectricity, ionic conduction, etc.).
  • the assembly of granules is capable of carrying significant electrical current.
  • Up to 30 amps continuous load has been carried by a 2 x 2cm conductor to date when in a compressed state.
  • This unique property may be explained by the fact that in the compressed state conduction occurs principally through the metal bridges described above. So for the purpose of explaining conduction the materials are best described in terms of a heterogeneous mixture in which the insulative encapsulant dominates electrical property in the quiescent state; and tending towards that of the conductor bridges (having a local resistivity tending to that of the conductor typically 1 - 1000 microhm-cm) , in the compressed state (typically having a bulk resistivity greater than 1 milliohm-cm) .
  • Electron conduction is further confined to the conductor filler by the inability of the encapsulant to hold negative 'electron' charge (typically the encapsulant is the optimal positive triboelectric charge carrier) .
  • the encapsulant is the optimal positive triboelectric charge carrier
  • the statistical chance of bridge formation is directly related to composite thickness.
  • both the sensitivity to distortion and current carrying capability increase with reduction in thickness with the thinnest films limited by the filler size distribution.
  • the 18 filler size distribution will typically limit thickness to >10 - 40 microns.
  • the composite By incorporation of zirconium particles (or other ionic conducting materials) into a silicone elastomer, within and/or between granules, the composite may be made to conduct both electrons and, in the presence of gaseous oxygen, oxygen ions.
  • control of bulk material stress for example by the incorporation of static or externally resonated "stress grids' into the bulk composition
  • conduction of electrons and oxygen may be made to occur in different planes or different parts of the bulk structure.
  • Such properties may be of particular interest in the design of fuel cell systems. It has also been found that internal ohmic heating may affect the internal structure of the composite.
  • ohmic heating switches by virtue of the PTC effect between conducting and insulating states in a composition that is under little or no compressive force.
  • This effect allows these polymer compositions to be used as switches or fuses which switch sharply to a high resistance state in response to excess current and which, because of their elastomeric nature, will return to a conductive state without the removal of power when the current flow returns to a set value.
  • This PTC effect can also be used in self-regulating heating elements where heat levels can be set by applying mechanical pressure to keep the polymer composition close to its PTC point at the required temperature.
  • the polymer composition will maintain a relatively steady temperature by cycling in and out of the PTC phase.
  • the composition has wide temperature tolerance and good thermal conductivity.
  • a nickel powder used in the invention was INCO Type 287 which has the following properties: beads are on average 2.5 - 3.5 microns in cross-section; chains may be more than 15 - 20 microns in length. It is a filamentary powder with a three-dimensional chain- like network of spiky beads having a high surface area . 20
  • the sizes of the particles are substantially all under 100 microns, preferably at least 75% w/w being in the range 4.7 to 53 microns.
  • the particle size distribution (in microns and by weight) is as follows (in rounded % figures): 2.4 - 3%, 3.4 - 5%, 4.7 - 7%, 6.7 - 10%, 9.4
  • Nickel powders also made by the carbonyl process usable in the invention are : Type 123 : bulk density 1.6 - 2.6 g/cm 2 ; equiaxial shape, spiked irregular surface;
  • Type 210 apparent density less than 0.5g/cm 2 ; filamentary powder of average particle size 0.5 - 1.0 microns; Type 255 : bulk density 0.5 - 0.65g/cm 2 ; filamentary powder with 3 - dimensional chain-like network of very spiky beads cross-section 2 - 3 microns; chain length 20 - 25 microns;
  • the conductor particles have a bulk density less than one third of their solid density.
  • the composition may be usefully employed in association with the anode or cathode construction of an electrochemical cell based on lithium, manganese, nickel, cobalt, zinc, mercury, silver or other battery chemistry including organic chemistry. Either or both the electrodes may be exchanged or coated with the polymer composition to give the following advantages:
  • the cell could incorporate its own integral pressure switch which, for example, could be operated by the pressure normally used to hold the cell in place in the battery compartment. By this means, self-discharge or short circuiting of the cell could be reduced or eliminated whilst the cell was in an unstressed storage state;
  • the integral pressure switch could simplify circuit design and permit new applications by eliminating the need for external switches
  • (iii) as the polymer composition can be manufactured without metal, it is possible to construct a wholly plastic electrochemical cell.
  • Pressure sensitive polymer composition can also be used without direct involvement in the cell chemistry by positioning the composition on external casings or non- reacting surfaces of electrodes. Switching of the polymer composition could be initiated by externally applied mechanical pressure such as finger pressure or 22 spring pressure from within a battery compartment . This could form a switch for controlling external circuits including battery check circuits.
  • compositions include: Mechanical Transducers, both relative and absolute, for measuring pressure, load, displacement, torque, elongation, mass and volume change, acceleration, flow, vibration and other mechanically induced changes.
  • Figs.1(a) and 1(b) are graphs showing the variation/dependence of resistance with applied pressure for the granules according to the invention. 23
  • Granules were prepared from:
  • ALFAS Industries RTV silicone type 2000 4g [This weight ratio corresponds approximately to a nickel : polymer volume ratio of 7 : 1 based on the tapped bulk volume of the nickel and the voidless volume of the silicone]
  • the silicone as a soft lump was placed in the bottom of a RETSCH RM100 motorized mixer having a steel mortar and a porcelain rotary pestle.
  • the nickel powder was placed around the lump of silicone.
  • the pestle was lowered under hand control with an approximate 1mm clearance from the wall of the mortar. This machine subjects the mixture to rotary ablation. In about 5 min ⁇ tes the silicone coated the nickel particles and in so doing became resolved into granules having the following size distribution % w/w in microns:
  • Example 1 The procedure of Example 1 was repeated using: ALFAS Industries RTV silicone type 1000 6g INCO nickel powder 287 30g corresponding to a nickel : polymer ingredient volume ratio of approximately 5 : 1. Although the ratio is lower than in Example 1, the characteristic shrinkage on cross-linking of the grade of silicone used, resulted in granules electrically conductive without applied pressure. The shrinkage seems to be a product of the loss of volatile components at cross-linking. ALFAS 1000 contains 12% of volatile substances. ALFAS 2000 contains 4% of volatile substances.
  • Such granules are for example of especial value in conductive adhesives, EM screening and PTC devices.
  • Example of a conductor based on the granules a test piece conductor was made by loading a sample of the granules prepared in Example 1 into a test cell consisting of a washer of silicone rubber sponge 12mm in diameter, 3mm thick and with a hole 6mm in diameter, resting on an electrically conductive surface 25 as lower electrode. A conductive plate was placed on top of the washer to form an upper electrode. The electrodes were connected via a constant-current 10 volt supply and a 20M ohm high- impedance buffer amplifier to a Picoscope ADC 100 signal processor and recording device.
  • test cell To allow measured amounts of force to be applied to the test cell, it was placed on the platen of a load testing device, namely a Lloyd Instruments LRX fitted with a 100N maximum force resolver. Slowly increasing pressure was applied to the cell and its resistance was recorded and represented graphically by the signal processor. Runs were carried out at two levels of current:
  • test cell of Example 3 was compressed with a static loading of approximately 3N, a current of 10 microAmps was passed through the test cell and its resistance, calculated from the potential difference (PD) across the cell, was 100K Ohms. Keeping the voltage and applied pressure constant, the current was 26 increased to 100 microAmps. The measured PD now showed the resistance of the cell to have dropped to 50K ohms.
  • Example 1 was repeated with the difference that the starting materials were:
  • Example 1 was repeated with the difference that, before being added to the mixer, the nickel powder was sprayed with an aerosol of the fluorocarbon hydrophobising agent WD40 (RTM) .
  • the granules were tested as in Examples 3 and 4 and found to be substantially more sensitive than those prepared without the WD40.
  • Granules made as in Example 1 were formulated as follows :
  • the gel was split in two and applied through a stencil onto:

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  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

Cette composition polymère comprend au moins un polymère essentiellement non conducteur et au moins une charge électroconductrice et se présente sous la forme de granules, lesquels ont de préférence une grosseur allant jusqu'à 1 mm et plus préférablement comprise entre 0,04 mm et 0,2 mm, le rapport de volume entre le conducteur et le polymère étant de préférence compris entre 3/1 et 15/1.
PCT/GB1999/000205 1998-01-23 1999-01-21 Composition polymere WO1999038173A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2000528985A JP2002501949A (ja) 1998-01-23 1999-01-21 ポリマー組成物
EP99901767A EP1050054B1 (fr) 1998-01-23 1999-01-21 Composition polymere
CA002318742A CA2318742A1 (fr) 1998-01-23 1999-01-21 Composition polymere
DE69935416T DE69935416T2 (de) 1998-01-23 1999-01-21 Polymerzusammensetzung
AU21768/99A AU2176899A (en) 1998-01-23 1999-01-21 Polymer composition
US09/600,808 US6495069B1 (en) 1998-01-30 1999-01-21 Polymer composition

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
PCT/GB1998/000206 WO1998033193A1 (fr) 1997-01-25 1998-01-23 Composition polymere
GBPCT/GB98/00206 1998-01-23
GBGB9806623.6A GB9806623D0 (en) 1998-03-28 1998-03-28 Conductive structures within conductive polymerse
GB9806623.6 1998-03-28
GB9814131.0 1998-06-30
GBGB9814131.0A GB9814131D0 (en) 1998-06-30 1998-06-30 Polymeric sensing materials

Publications (1)

Publication Number Publication Date
WO1999038173A1 true WO1999038173A1 (fr) 1999-07-29

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PCT/GB1999/000205 WO1999038173A1 (fr) 1998-01-23 1999-01-21 Composition polymere

Country Status (6)

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EP (1) EP1050054B1 (fr)
JP (1) JP2002501949A (fr)
CN (1) CN1149588C (fr)
AU (1) AU2176899A (fr)
CA (1) CA2318742A1 (fr)
WO (1) WO1999038173A1 (fr)

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WO2002099822A3 (fr) * 2001-06-07 2003-03-06 Peratech Ltd Dispositif d'analyse
WO2005029514A1 (fr) * 2003-09-20 2005-03-31 Peratech Limited Materiaux a conductance variable
US7093499B2 (en) 2004-12-21 2006-08-22 Delphi Technologies, Inc. Force sensor, strain sensor and methods for measuring same
US7145432B2 (en) * 2000-05-18 2006-12-05 Canesis Network Ltd. Flexible switching devices
WO2008022031A2 (fr) 2006-08-11 2008-02-21 Mastercard International Inc. Carte de paiement de proximité avec commutateur actionné par l'utilisateur et procédés de réalisation de la carte
GB2441733A (en) * 2006-09-18 2008-03-19 Powered Triangle Ltd Footwear display comprising a display
WO2008046988A2 (fr) 2006-10-13 2008-04-24 Computer Masters International Dispositif de signalisation de touches pour la pratique de l'escrime sans fil
WO2008135787A1 (fr) 2007-05-04 2008-11-13 Peratech Limited Composition polymère
GB2462920A (en) * 2008-08-29 2010-03-03 Peratech Ltd Electrically responsive composite material for transducers
US7837123B2 (en) 2007-09-10 2010-11-23 Mastercard International, Inc. Identification token and method of making identification token
US7857202B2 (en) 2006-08-11 2010-12-28 Mastercard International, Inc. Method and apparatus for a contactless smartcard incorporating a pressure sensitive switch
US7992779B2 (en) 2007-09-10 2011-08-09 Mastercard International, Inc. Method for use in association with identification token and apparatus including identification token
US7997498B2 (en) 2006-09-08 2011-08-16 Mastercard International, Inc. Identification of installable card
US8167198B2 (en) 2006-11-06 2012-05-01 Mastercard International, Inc. Method, apparatus, assembly and kit for identification token
WO2012076612A1 (fr) 2010-12-08 2012-06-14 Condalign As Procédé d'assemblage de particules conductrices dans des chemins conducteurs et capteurs ainsi formés
US8226013B2 (en) 2007-10-26 2012-07-24 Mastercard International, Inc. Method and apparatus for use in providing an identification token
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US10783514B2 (en) 2007-10-10 2020-09-22 Mastercard International Incorporated Method and apparatus for use in personalizing identification token
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US8286862B2 (en) 2007-12-28 2012-10-16 Mastercard International, Inc. Methods and apparatus for use in association with security parameter
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US8794532B2 (en) 2008-12-29 2014-08-05 Mastercard International Incorporated Methods and apparatus for use in association with identification token
US8812402B2 (en) 2009-01-05 2014-08-19 Mastercard International Incorporated Methods, apparatus and articles for use in association with token
US8684261B2 (en) 2009-01-20 2014-04-01 Mastercard International Incorporated Methods, apparatus, computer program products and articles for use in providing human understandable indication of account balance
US8587422B2 (en) 2010-03-31 2013-11-19 Tk Holdings, Inc. Occupant sensing system
US9007190B2 (en) 2010-03-31 2015-04-14 Tk Holdings Inc. Steering wheel sensors
US8725230B2 (en) 2010-04-02 2014-05-13 Tk Holdings Inc. Steering wheel with hand sensors
US8983732B2 (en) 2010-04-02 2015-03-17 Tk Holdings Inc. Steering wheel with hand pressure sensing
EP3598122A1 (fr) 2010-12-08 2020-01-22 Condalign AS Procédé d'assemblage de particules conductrices dans des trajets conducteurs et capteurs ainsi formés
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US9727031B2 (en) 2012-04-13 2017-08-08 Tk Holdings Inc. Pressure sensor including a pressure sensitive material for use with control systems and methods of using the same
US9696223B2 (en) 2012-09-17 2017-07-04 Tk Holdings Inc. Single layer force sensor
DE102013202375A1 (de) * 2013-02-14 2014-08-14 Zumtobel Lighting Gmbh Schaltelement mit triboelektrischem Element
US10667755B2 (en) 2013-09-16 2020-06-02 Sensing Tex, S.L. Textile piezoresistive sensor and heartbeat and/or respiratory rate detection system
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WO2015036647A1 (fr) * 2013-09-16 2015-03-19 Sensing Tex, S.L. Capteur textile piézorésistif et système de détection du rythme cardiaque et/ou respiratoire
WO2018128583A1 (fr) 2017-01-04 2018-07-12 Mas Innovation (Private) Limited Ensemble bouton tactile pouvant être porté
US10935445B2 (en) 2017-01-04 2021-03-02 Mas Innovation (Private) Limited Wearable touch button assembly
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GB2561609B (en) * 2017-04-21 2019-12-18 Peratech Holdco Ltd Method of producing agglomerates for inclusion in a composite material
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EP1050054B1 (fr) 2007-03-07
JP2002501949A (ja) 2002-01-22
CN1291338A (zh) 2001-04-11

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