CN1090087C - Method of making a laminate comprising a conductive polymer composition - Google Patents

Method of making a laminate comprising a conductive polymer composition Download PDF

Info

Publication number
CN1090087C
CN1090087C CN97198230A CN97198230A CN1090087C CN 1090087 C CN1090087 C CN 1090087C CN 97198230 A CN97198230 A CN 97198230A CN 97198230 A CN97198230 A CN 97198230A CN 1090087 C CN1090087 C CN 1090087C
Authority
CN
China
Prior art keywords
laminate
composition
make
mixing arrangement
conductive filler
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
CN97198230A
Other languages
Chinese (zh)
Other versions
CN1231635A (en
Inventor
E·F·楚
D·A·钱德勒
A·巴尼赫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raychem Corp
Original Assignee
Raychem Corp
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
Application filed by Raychem Corp filed Critical Raychem Corp
Publication of CN1231635A publication Critical patent/CN1231635A/en
Application granted granted Critical
Publication of CN1090087C publication Critical patent/CN1090087C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41D—APPARATUS FOR THE MECHANICAL REPRODUCTION OF PRINTING SURFACES FOR STEREOTYPE PRINTING; SHAPING ELASTIC OR DEFORMABLE MATERIAL TO FORM PRINTING SURFACES
    • B41D7/00—Shaping elastic or deformable material, e.g. rubber, plastics material, to form printing surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41K—STAMPS; STAMPING OR NUMBERING APPARATUS OR DEVICES
    • B41K1/00—Portable hand-operated devices without means for supporting or locating the articles to be stamped, i.e. hand stamps; Inking devices or other accessories therefor
    • B41K1/02—Portable hand-operated devices without means for supporting or locating the articles to be stamped, i.e. hand stamps; Inking devices or other accessories therefor with one or more flat stamping surfaces having fixed images
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermistors And Varistors (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

A method of making a laminate from a conductive polymer composition in which a particulate filler is dispersed in a polymeric component. The method comprises the following steps conducted sequentially in a single continuous procedure: (A) loading the polymeric component and the conductive filler into a mixing apparatus; (B) mixing the polymeric component and the conductive filler to form a molten mixture; (C) transporting the mixture from the mixing apparatus through a die; (D) forming a polymeric sheet; and (E) attaching metal foil to a least one side of the sheet to form a laminate. The laminate can be used to prepare circuit protection devices or heaters.

Description

The autofrettage that contains the laminate of conductive polymer compositions
Background of invention
Invention field
The present invention relates to the method that a kind of manufacturing contains the laminate of conductive polymer compositions and comprises the electric device of this laminate.
Invention is introduced
The conductive polymer compositions that shows PTC (resistance positive temperature coefficient) behavior is quite famous in the electric device such as circuit protection device uses.This composition comprises the polymerization composition and is dispersed in wherein the granular conductive filler such as carbon black or metal.Amount of filler in the composition and type are by the characteristic decision of resistance coefficient required in every kind of application and polymerization composition.The composition that is applicable to circuit protection device has low-resistance coefficient when room temperature, for example less than 100 ohm-cms, generally contain the conductive filler of suitable high-load.When this highly-filled composition when making such as the conventional method of melting mixing, it stands sizable shearing force.This shearing force can produce heat, and it may make depolymerization and cause resistance coefficient to improve.Other shearing force and/or heat exposure are then by causing such as the subsequent processing steps of extruding, melt forming and utilization such as laminating method and electrode link.In the conventional process technology, can in a continuous process, implement such as extruding, but usually with some laminated steps, can disperse fully and make manufacture process be divided into several other steps because wish to guarantee filler in the polymer, just separation steps.The heating of composition, cooling and be subjected to the number of times of shearing force many more, then degraded is many more with the chance that resistance coefficient changes.
Composition use with low-resistance coefficient is optimal in circuit protection device, and it can respond the change of environment temperature and/or current condition.Under normal operation, circuit protection device can be connected with load in circuit and remain under low temperature, the low-resistance state.Yet when it is exposed to the following time of condition of an overcurrent or excess temperature, the resistance of this device increases and the load current that flow in the circuit is stopped.For many application, needed be for during normal running to the minimum that influences that circuitous resistance produced, make the resistance of device low as far as possible.Though the low resistance device can utilize the change of size to make, for example make that interelectrode distance makes very little or make the device district very big, dingus is preferable, and is less and generally have a preferable thermal property because of its space occupied on circuit board.Desire to finish the most common technology of dingus and be to use composition with low-resistance coefficient.The resistance coefficient of conductive polymer compositions can reduce by means of adding more conductive fillers, but the method is as influencing the processing characteristics of composition by the increase of viscosity.Moreover the interpolation of conductive filler generally can reduce the size of PTC unusual (PTCanomaly), and the size that resistance coefficient increased when just composition increased in response to temperature is general in a quite little temperature range.Required PTC unusually by apply voltage and use determined.Therefore, for obtaining having the composition of acceptable size and electric property, essential is to make the processing influence that causes resistance coefficient to increase reach minimum.
Summary of the invention
We have found to utilize a kind of method at present, wherein, in single series-operation, make the laminate that conductive polymer compositions wherein is linked to a metal foil electrode (and preferably being sandwiched between two metal foil electrodes), can prepare and provide low-resistance coefficient, enough PTC are unusual, and the device of good electrical performance.The series-operation of making laminate allows raw material, not in molten polymer and the mixing arrangement of filler composition introducing as extruder, and melt-shaping is laminate, it has reduced the required number of steps of manufacturing installation.Be unlike in the conventional method, wherein raw material is formed to be melted and is mixed and granulation, is dried subsequently and is extruded into sheet material with laminated, and method of the present invention can reduce the pellet drying steps before granulation step and the sheet material forming step.This is meaning in the processing that composition is exposed to less heating and shearing.
The present invention is providing a kind of method with conductive polymer compositions manufacturing laminate aspect first, said composition comprises that (i) polymerization composition reaches the granular conductive filler that (ii) is dispersed in the polymerization composition, and this method comprises
(A) polymerization composition and conductive filler are loaded in the mixing arrangement;
(B) the mixed polymerization composition mixes with conductive filler formation molten state in mixing arrangement
Thing;
(C) the molten state mixture is carried through die head by mixing arrangement;
(D) make the molten state mixture be shaped to polymeric sheet; And
(E) at least one face of metal forming and sheet material is linked to form laminate, step (A) to (E) is sequentially carried out in single series-operation.
Aspect second, the invention provides a kind of electric device, its
(1) comprise (a) resistive element, it is can show the conducting polymer of PTC behavior
Composition is formed, and to have melt temperature be T and said composition comprises (i) m
The polymerization composition, and (ii) be scattered in granular conductive filler in the polymerization composition;
Reach (b) two electrodes, its (i) links with resistive element, (ii) bag
The containing metal paper tinsel and (iii) can be connected with power supply;
(2) resistance R that under 20 ℃, has 20Be 50.0 ohm to the maximum;
(3) the resistance coefficient ρ 20 that has under 20 ℃ is 50.0 ohm-cms to the maximum; And
(4) to comprise the method manufacturing of following steps
(A) polymerization composition and conductive filler are loaded in the mixing arrangement;
(B) the mixed polymerization composition mixes with conductive filler formation molten state in mixing arrangement
Thing;
(C) the molten state mixture is carried through die head by mixing arrangement;
(D) make the molten state mixture form polymeric sheet;
(E) make the two sides of metal forming and sheet material link the formation laminate; And
(F) the incised layer plywood forms device, and step (A) to (E) is sequentially carried out in single series-operation.
Detailed Description Of The Invention
The inventive method is used to make the laminate of conductive polymer compositions.Conductive polymer compositions comprises polymerization composition and the granular conductive filler that is dispersed in the polymerization composition.
The branch that aggregates into of composition comprises one or more polymer, and preferred wherein a kind of is the crystalline polymer with at least 20% degree of crystallinity, and degree of crystallinity adopts differential scanning calorimetry not measure under the occupied state at it.Suitable crystalline polymer comprises one or more olefin polymers, particularly such as the polyethylene of high density polyethylene (HDPE); At least a alkene and at least a can with the copolymer of the monomer of its copolymerization ethylene/acrylic acid for example, ethylene/ethyl acrylate, Ethylene/vinyl acetate, and ethylene/butylacrylate copolymer; The fluoropolymer polymer that is shaped such as the fusable links of Kynoar and Tefzel (comprising ter-polymers); And the blend of two or more these polymer.For some application, for reaching, it is desirable to, a kind of crystalline polymer and another kind of as elastomer or the blend of amorphous thermoplastic polymer as pliability or maximum specific physics or the thermal property that exposes temperature to the open air.The melt temperature of polymerization composition is T m, its endothermic peak through differential scanning calorimetry is measured.When surpassing a peak, for example in the polymeric blends example, T mTemperature when being defined as the maximum temperature peak.The polymerization composition generally accounts for the 40-90% (volume) of composition cumulative volume, and the preferably is 45-80% (volume), is in particular 50-75% (volume).
The granular conductive filler that is dispersed in the polymerization composition can be any suitable material, it comprises carbon black, graphite, metal oxide, conduction coated glass or ceramic bead, granular conducting polymer or its combination, and that filler can be is Powdered, pearl, sheet, fibrous or any other suitable shape.The conductive filler amount is a benchmark with the resistance coefficient of required composition and the resistance coefficient of conductive filler itself.For many compositions, conductive filler accounts for the 10-60% (volume) of composition cumulative volume, and the preferably is 20-55% (volume), is in particular 25-50% (volume).
Conductive polymer compositions can contain other component, antioxidant, inert filler, non-conducting filler, radiation crosslinker (being commonly referred to pre-radiation or crosslinking enhancer, for example the cyamelide triallyl), stabilizing agent, dispersant, coupling agent, plumper (CaCO for example for example 3) or other component.General maximum 20% (volumes) that account for total composition of these components.
Composition generally shows positive temperature coefficient (PTC) behavior, that is to say, it increases the resistance coefficient that demonstrates sharp increase with temperature between a quite little temperature range, though method of the present invention can be used for making the composition that it manifests zero-temperature coefficient (ZTC) behavior.In this application, proper noun " PTC " means the R that has 14Value is at least 2.5 and/or be at least 10 R 100The composition or the device of value, and preferable composition or device must have and be at least 6 R 30Value, wherein R 14Be the end of 14 ℃ of scopes and the resistance coefficient ratio that begins to locate, R 100Be the end of 100 ℃ of scopes and the resistance coefficient ratio that begins to locate, and R 30Be the end of 30 ℃ of scopes and the resistance coefficient ratio that begins to locate.Generally speaking, the shown resistance coefficient increase of the composition that can show the PTC behavior that is used in apparatus of the present invention is far longer than these minimum of a values.The preferred person of composition who is used to form apparatus of the present invention between 20 ℃ to (T m+ 5 ℃) have at least 10 during at least one temperature between scope 4PTC unusual, the preferably is at least 10 4.5, special good person is at least 10 5, better person is at least 10 5.5, that is to say that log[is in (T m+ 5 ℃) time the resistance of resistance/in the time of 20 ℃] be at least 4.0, the preferably is at least 4.5, special good person is at least 5.0, better person is at least 5.5.If maximum resistance is lower than (T one m+ 5 ℃) temperature T xIn time, reach, and then PTC is unusually by log (T xThe time resistance/20 ℃ the time resistance) determine.
The resistance coefficient of composition is decided on application and required electric device kind.When using the composition manufacturing to be used in the laminate of circuit protection device; the resistance coefficient ρ 20 that preferred composition has in the time of 20 ℃ is 100 ohm-cms to the maximum; the preferably is 50 ohm-cms to the maximum; better person is 20 ohm-cms to the maximum; special good person is 10 ohm-cms to the maximum; more special good person is 5 ohm-cms to the maximum, and special better person is 2.0 ohm-cms to the maximum, and the most special good person is 1.0 ohm-cms to the maximum.When using composition in heater, the resistance coefficient of preferred conductive polymer compositions is higher, for example is at least 10 2Ohm-cm, the preferably is at least 10 3Ohm-cm.
Suitable conductive polymer compositions is disclosed in United States Patent (USP) 4,237,441 (people such as vanKonynenburg), 4,388,607 (people such as Toy), 4,534,889 (people such as vanKonynenburg), 4,545,926 (people such as Fouts), 4,560,498 (people such as Horsma), 4,591,700 (Sopory) 4,724,417 (people such as Au), 4,774,024 (people such as Deep), 4,935,156 (people such as van Konynenburg), 5,049,850 people such as () Evans, and 5,250,228 people such as () Baigrie, 5,378,407 (people such as Chandlen), 5,451,919 (people such as Chu), and 5,582,770 people such as () Chu, in international publishing sequence number WO 96/29711 (Raychem company, on September 26th, 1996 published) and WO 96/30443 (Raychem company, on October 3rd, 1996 published).
The inventive method comprises five steps, and step (A) is sequentially carried out in single series-operation to (E).Such as other treatment step of heat treatment or radiation, as long as operation is continuous it is carried out between two steps of the present invention.Part in two steps is carried out simultaneously, for example make the conveying of molten state mixture and pass through die head (step C), this die head has the shape (step D) that can make the molten state mixture form polymeric sheet.
In step (A), polymerization composition and granular conductive filler are loaded in the mixing arrangement, in a preferable embodiment, Powdered, sheet, fibrous or granular that the shape of polymerization composition and conductive filler can be, it can easily feed in the mixing arrangement.Though these two kinds of components can feed mixing arrangement individually, preferably with polymerization composition and conductive filler under drying regime " premix " for example can utilize blender or such as Henschel TMThe blender premix of blender, with the uniformity of improving component during the addition step with mobile.Other component can be with Powdered, granular or aqueous and polymers compositions and granular component premix, or can add by the difference in operation.It is reinforced to utilize any method to finish, though preferably such as weightlessness (loss-in-weight) feeder of being sold with " K-Tron " trade mark by K-Tron u s company so that guarantee with in the constant speed feeding unit.Though can use comprise be equipped with suitable accessory such as Banbury TMMixer, Brabender TMMixer, and Moriyama TMThe mixing apparatus of other type of mixer comes convey materials finishing required step of the present invention, but the mixing arrangement preferably is an extruder.Suitable extruder comprises single screw extrusion machine, co-rotating twin screw extruder, counter rotating twin screW extruder or reciprocating type single screw extrusion machine, for example Buss TMKneader.When using extruder, various additives for example, such as the crosslinking agent of peroxide, can be added by the porch, downstream of polymerization composition and conductive filler porch continuously.Be unlike in the conventional method, crosslinking agent is added into composition, this will cause crosslinked caking, and this caking is difficult for the uniform sheet material of follow-up formation or other shape, and the inventive method is specially adapted to online chemical crosslinking.Series-operation allows that crosslinking agent just adds by die head before in mass transport.
In step (B), polymerization composition and conductive filler are mixed in mixing arrangement to form the molten state mixture, that is to say that it is that temperature is higher than and aggregates into branch fusion temperature T mMixture, during step (B), make conductive filler, and be dispersed in the polymerization composition such as other component of inorganic filler or pigment.For guaranteeing to reach sufficient mixing and dispersion, the screw rod of extruder can be designed to have mixing or kneading block and transportation section.For example, we find, for co-rotating twin screw extruder, when at least 10% kneading block of total spiro rod length is housed, can produce acceptable dispersion.When using extruder, fully disperse for reaching conductive filler, spiro rod length and its diameter ratio, L/D ratio just, the preferably was at least 10: 1, and better person was at least 15: 1, and special good person was at least 20: 1, and more special good person was at least 30: 1, for example 40: 1.Can utilize electricity or oil that one or more snippets (district) in the mixing arrangement is heated.For discharging the volatile matter that is during mixing produced, vacuum plant and mixing arrangement can be settled through appropriate combination.
In step (C), molten mixture is carried by mixing arrangement passed through die head.Being used in proper noun " die head " in the specification of the present invention means to have and can allow any element in the hole that fused materials passes through.Therefore, die head can be mould, nozzle or has the opening that can make the special shape that fused materials passes through or the object in slit.Can utilize Die-head connecting sleeve for example to make die head directly be connected the exit of mixing arrangement, maybe can utilize such as one or more equipment of gear pump or vacuum plant and it is separated with mixing arrangement.When mixing arrangement was extruder, " conveying " of molten state mixture occurred in during the extruder normal running.If when using the mixing arrangement of other type, then may need the device of other transporting molten attitude mixture.
In step (D), make the molten state mixture form polymeric sheet.This can utilize by the sheet material die head and extrude or utilize calendering molten state mixture, just makes the molten state mixture by becoming sheet material and easily finish to make it thinning between roller or plate.The thickness of calendered sheet is decided by the velocity of rotation of distance between plate or roller and roller.Generally speaking, polymeric sheet thickness is 0.025～3.8 millimeter (0.001～0.150 English inch), and the preferably is 0.051～2.5 millimeter (0.002～0.100 English inch).Polymeric sheet can have any width.Width is decided by the volume and the rolling velocity of die head shape and width or material, and is generally 0.15～0.31 meter (6～12 English inch).
In step (E), laminate is to utilize metal forming to be linked to the one side at least of polymeric sheet and to form, and the preferably is for being linked to the two sides.When laminate was cut into electric device, metal foil layer was as electrode.The thickness of metal forming is generally maximum 0.13 millimeter (0.005 English inch), and the preferably is 0.076 millimeter (0.003 English inch) to the maximum, and special good person is 0.051 millimeter (0.002 English inch) to the maximum, for example 0.025 millimeter (0.001 English inch).The width of metal forming is general approximately identical with polymeric sheet, but for some application, and it is preferable that metal forming is applied with the form of two or many arrowbands, and every arrowband has the width much smaller than polymeric sheet.The proper metal paper tinsel is to comprise nickel, copper, and brass, aluminium, molybdenum reaches alloy, or contains the paper tinsel layer of two or more these materials in identical or different layer.Particularly suitable metal forming is to have the surface that at least one is electroplated, and the preferably is electronickelling or copper.The metal forming that is fit to is disclosed in United States Patent (USP) 4,689,475 (Matthiesen), and 4,800,253 people such as () Kleiner, and among the international publishing sequence number WO 95/34081 (Raychem company, publish December 14 nineteen ninety-five).In preferable embodiment, metal forming contacts with polymeric sheet, subsequently via such as folded roller machine and by roller to impel the paper tinsel layer good laminated on polymer.In addition, allow the sheet cools minimum when withdrawing from die head for making, have between die head and folded roller machine quite little apart from the time preferable, for example less than 0.61 meter (2 English Foot), the preferably is less than 0.31 meter (1 English Foot).For some application, with before metal forming contacts, binding compositions (tack coat just) can be imposed on polymeric sheet with for example spraying or brushing mode in polymeric sheet.Can make laminate from step (E) be wound on the spool or be cut into each sheet spare so that further handle or store.The thickness of laminate is generally 0.076～4.1 millimeter (0.003～0.160 English inch).
The inventive method can utilize two or more mixing arrangement/transmission/building mortion manufacturing to have the laminate more than one deck polymeric sheet, and these devices can be made based on the identical or different polymerization composition and the polymeric sheet of conductive filler.
When laminate comprised the double layer of metal paper tinsel, available its made electric device, particularly circuit protection device.In step (F), device can be cut from laminate.In the present patent application book, employed proper noun " is cut " and is comprised any method that makes device be separated or be isolated by laminate, for example can be as cutting, punching, shearing, cutting, etching and/or disrumpent feelings method described in the international publishing sequence number WO 95/34084 (Raychem company on December nineteen ninety-five 4 published), or any other suitable method.Step (F) can be, but is not necessary for, the part in the independent series-operation of step (A) to (E).Other plain conductor such as wire rod or belt-like form can be linked to foil electrode and be electrically connected to circuit so that make.In addition, can use the thermal output that comes control device such as one or more the element of conductive terminal.These terminals can be such as steel, copper, or the metallic plate shape of brass, and perhaps fin-shaped, their are directly or utilize the intermediate layer such as scolding tin or electroconductive binder to be connected in electrode.Ask for an interview, for example United States Patent (USP) 5,089,801 (people such as Chan) and 5,436,609 (people such as Chan).For some application, will install and directly be linked to circuit board is the preferably.The example of these connecting technologies is shown among international publishing sequence number WO 94/01876 (Raychem company, on January 20th, 1994 published) and the WO 95/31816 (Raychem company, publish November 23 nineteen ninety-five).
For improving the electrical stability of device, make device accept various treatment technologies usually and be preferably, for example crosslinked and/or heat treatment.Crosslinkedly utilize chemical method or use such as electron beam or Co 60The radiation of gamma emitter reaches.Crosslinked degree is decided the requirement of composition on application; but be generally less than 20,000 ten thousand rad-equivalents; and the preferably is littler in fact; just between between 1 to 2,000 ten thousand rad; the preferably is between between 1 to 1,500 ten thousand rad; low-voltage (just less than 60 volts) circuit protection is used, and special good person is between 2 and 1,000 ten thousand rads.Generally speaking, device is crosslinked at least to 200 ten thousand rad-equivalents.The different disposal program description of device is in international publishing sequence number WO 96/29711 (publication on September 26th, 1996).
Device of the present invention is preferably circuit protection device, the resistance R that it generally has in the time of 20 ℃ 20Less than 100 ohm, preferably less than 50 ohm, special good person is less than 20 ohm, and more special good person is less than 10 ohm, and more special good person is less than 5 ohm, and is the most special good for 1 ohm.Because of utilizing the prepared laminate of the inventive method to comprise the conductive polymer compositions that can have low resistance coefficient, so it can be used for making the very low-resistance device that has such as between 0.001 to 0.100 ohm.Heater assembly generally has at least 100 ohm resistance value, and the preferably is at least 250 ohm, and special good person is at least 500 ohm.
Can be regarded as, can be used in the electric device of any kind according to the laminate of the inventive method manufacturing, for example heater or sensor and circuit protection device.
Now use down case description the present invention, wherein example 1,2, and 4,6,8 and 10 is comparative example.Example 1 to 7
For each example, with following component, the percentage by weight based on the weight of total composition by listing in the Table I utilizes Henschel TMBlender mixed three minutes under the 1500rpm rotating speed: PVDF (KF TM1000W, polyvinylidene fluoride, about 177 ℃ of melt temperature, Powdered, can obtain by Kureha), ETFE (Tefzel TMHT 2163, ethylene/tetrafluoroethylene/perfluorinate butylethylene ter-polymers, about 235 ℃ of melt temperature can be obtained by DuPont), CB (Raven TM430, carbon black can be obtained by Columbian Chemicals Co.), TAIC (cyamelide triallyl), and CaCO 3(Atomite TMPowder, calcium carbonate can be obtained by John K.Bice company).Make the dried ingredients of mixing accept two steps of the present invention (comparative) or a step process subsequently.Two step process
To comparative example 1,2,4 and 6, the L/D ratio that the dried ingredients of mixing is introduced screw rod is (ZSK-40 can be obtained by Werner-Pfleiderer) in 40: 1 the co-rotating twin screw extruder, makes it to mix, and is extruded into the line material, and is cut into granular.
For example 1, pellet is in 80 ℃ (175) following drying at least 24 hours, extrudes it through 25 millimeters (1 English inch) single screw extrusion machines of (the 0.375 English inch) diameter nozzle of being furnished with 9.5 millimeters subsequently.Melted material is extruded and is fed the folded roller machine that is positioned at apart from about 25 millimeters of nozzle end (1 English inch) by nozzle.Use folded roller machine material to be rolled into the sheet material of about 0.250 millimeter of thickness (0.010 English inch) and width about 114～152 millimeters (4.5～6.0 English inch), and with electronickelling/Copper Foil (type 31, have the about 0.044 millimeter 1 oz foil plate that (0.0017 English inch) is thick, can obtain by Fukuda) be linked to the two sides of calendered sheet.The gained laminate has the thickness of about 0.34 millimeter (0.0135 English inch).
To example 2,4 and 6, pellet is that to be unkitted kneading member, L/D ratio with rotary mode utilization in the same way be that 40: 1 screw rod is extruded via reverse rotation/co-rotating twin screw extruder (ZSE-27 can be obtained by Leistritz).This extruder is furnished with gear pump and the follow-up nozzle of being furnished with as above that ability is 10 cubic centimetres/commentaries on classics (Pep II type can be obtained by Zenith).Make material to extrude, roll as the same program of example 1, and laminated.One step process
The dry ingredient that mixes is introduced with in the ZSE-27 extruder that rotary mode uses in the same way, and in its screw-rod structure, 11% of total screw rod length is kneading member.Screw rod has 40: 1 L: the D ratio.As example 2,4 and 6, extruder is furnished with gear pump and nozzle.Make mixing of materials, and with example 2,4 and 6 identical programs make mixed material via gear pump and nozzle extrude, roll, and laminated.The preparation of device
For example 2 to 7, utilize electron beam radiating layer plywood to 7.5 1,000,000 rad total amounts in a series-operation of 3.5 million electron volts.Subsequently with scolding tin (used soft soldering temperature is about 250 ℃) coat plywood in a series-operation, and go out the device of 11 * 15 millimeters (0.43 * 0.59 English inch) sizes by laminate.The copper conductor of the 20 AWG tin coating that 25 millimeters of two treaties (1 English inch) are long is connected in device, and makes device carry out temperature cycles six times by 40 ℃ to 160 ℃ to the 40 ℃ speed with 10 ℃/minute, and the residence time that at every turn circulates under the extreme temperature is 30 minutes.
For example 1, will have as above that the device of size is downcut by laminate, carry out radiation and it does not imposed scolding tin applying with individual slices.Link lead as mentioned above, and make device as above carry out temperature cycles.
Table I
Example 1 * 2 * 3 4 * 5 6 * 7
Composition is represented (density is with the expression of gram/cubic centimetre) with weight %
PVDF(1.76) 52.90 52.90 52.90 58.20 58.20 56.43 56.43
ETFE(1.70) 5.89 5.89 5.89 6.47 6.47 6.27 6.27
CB(1.8) 37.23 37.23 37.23 31.35 31.35 33.32 33.32
TAIC(1.158) 2.00 2.00 2.00 2.00 2.00 2.00 2.00
CaCO 3(2.71) 1.98 1.98 1.98 1.98 1.98 1.98 1.98
Process 2 2 1 2 1 2 1
*The comparative example device to test
In the time of 20 ℃, measure the resistance of device, and calculate its resistance coefficient.The resistance of device is by device is placed baking oven to the feature measurement of temperature, and is measuring its resistance every one section in 20 to 200 to 20 ℃ temperature range.The height that PTC is unusual, PTC decides with log (resistance/20 175 ℃ the time ℃ time resistance) after first time temperature cycles.
The result who is shown in the Table II has pointed out that the device that produces with the inventive method has lower initial resistance than the device that produces with conventional method.In addition, the PTC that device was had that produces with the inventive method unusually still is similar to conventional method manufacturing person, even contain less conductive filler in the composition of apparatus of the present invention also is (example 5 compares with example 6, and example 7 compares with example 2) like this.
Table II
Example 1 * 2 * 3 4 * 5 6 * 7
R 0(mohm) 17.9 14.6 10.9 38.3 23.7 26.1 15.6
ρ 20(ohm-cm) 1.11 0.95 0.71 2.49 1.54 1.69 1.01
PTC (10 years) 4.1 4.4 3.9 5.5 5.5 5.3 4.5
*Comparative example example 8 to 11
Following as expressed in weight percent and component that list in the Table III is mixed in the Henschel blender: HDPE (Petrothene TMLB832, the high density polyethylene (HDPE) with about 135 ℃ of melt temperatures can be obtained by Quantum Chemical Corp), EBA (Enathene TM705-009, the positive butyl ester copolymer of ethylene/acrylic acid with about 105 ℃ of melt temperatures can be obtained by Quantum Chemical Corp), and CB (Raven 430).Make the dry ingredient of mixing accept two step process or a step process subsequently.Two step process
For comparative example 8 and 10, the dry ingredient that mixes is introduced in the Buss kneader (reciprocating type single screw extrusion machine) of 70 millimeters (2.75 English inch), make its mixing, be extruded into the line material, and be cut into granular.Have and do not have kneading member and L: the D ratio is 40: 1 a screw rod and in the ZSE-27 extruder of operation down of rotary mode in the same way, with as the mode in the example 2, at its exit assembling gear pump.Make gear pump and sheet material die head binding with 152 millimeters (6 English inch) wide and 0.038 millimeter (0.0015 English inch) thick opening.Pellet is extruded by die head forming polymeric sheet, and polymeric sheet is pulled to folded roller machine by die head, the distance of itself and die lip is about 12.7 millimeters (0.5 English inch), and has and be heated to about 155 ℃ rubber-coated roller.Make as the nickel/Copper Foil described in the example 1 laminated on polymeric sheet.The gained laminate has the thickness of about 0.127 millimeter (0.005 English inch).One step process
For example 9 and 11, the dry ingredient that mixes is introduced with in the ZSE-27 extruder that rotary mode uses in the same way, in its screw-rod structure, 11% of total spiro rod length is kneading member and L: the D ratio is 40: 1.Material is mixed in extruder, and utilize the gear pump in example 8, described, die head, and laminated method make it to extrude continuously and laminated.The preparation of device
Laminate is applied with scolding tin in a series-operation (about 220 ℃ of the soft soldering temperature of use), go out the device that is of a size of 5 * 12 millimeters (0.20 * 0.47 English inch) by laminate.Device is exposed to about 4 seconds of temperature of 185 to 215 ℃, in this operation, heat-treats.Utilize Co subsequently 60Gamma emitter makes device be cross-linked into 1,000 ten thousand rads.Utilize Reflow Soldering to make to be of a size of the nickel wire line of 0.13 * 5 * 13.5 millimeters (0.005 * 0.2 * 0.5 English inch) to be linked on the electrode on device two sides, make device from-40 ℃ to 85 ℃ between, and under extreme temperature resident 30 minutes clock times, carry out temperature cycles six times.Device to test
Except that PTC unusually 20 to 160 to 20 ℃ temperature range measurements, device is to test as above-mentioned method.For circulation for the second time, the unusual height of PTC is in 105 ℃, 125 ℃, and under 140 ℃ of three different temperatures with log (in T y℃ the time the resistance of resistance/in the time of 20 ℃) determine, wherein y is for measuring temperature.(in the time of 140 ℃, measuring) near the actual fusing point of conductive polymer compositions.The result who is shown in the Table III points out that it is unusual that it can reach similar PTC, but for manufacturing with a step series-operation but not with the composition that traditional two step process (comparative example 8 and 9) manufacture, have much lower resistance value.
Table III
Example 8 * 9 10 * 11
Composition is represented (density is with the expression of gram/cubic centimetre) with weight %
HDPE(0.954) 5.0 5.0 4.8 4.8
EBA(0.922) 45.0 45.0 43.0 43.0
CB(1.8) 50.0 50.0 52.2 52.2
R 0(mohm) 44.6 33.4 28.6 22.8
PTC 105 5.42 4.73 4.35 3.76
PTC 125 8.95 8.12 7.50 6.62
PTC 140 9.35 8.28 7.64 6.73
*Comparative example

Claims (9)

1. make the method for laminate by conductive polymer compositions for one kind, said composition comprises (i) polymerization composition and (ii) is dispersed in granular conductive filler in the polymerization composition, and this method comprises:
(A) polymerization composition and conductive filler are loaded in the mixing arrangement;
(B) in mixing arrangement mixed polymerization composition and conductive filler to form the molten state mixture;
(C) the molten state mixture is carried through die head by mixing arrangement;
(D) make the molten state mixture be shaped to polymeric sheet; And
(E) make at least one side that metal forming is attached at this sheet material forming laminate,
Step (A) to (E) is carried out in single continuous program in regular turn.
2. according to the process of claim 1 wherein that mixing arrangement is an extruder.
3. according to the method for claim 2, wherein said extruder is single screw extrusion machine, rotary in the same way double screw extruder, reverse rotation formula double screw extruder or reciprocating type single screw extrusion machine.
4. according to the process of claim 1 wherein that die head is a nozzle.
5. according to the process of claim 1 wherein that die head directly is linked to the exit of mixing arrangement.
6. make metal forming be attached at the two sides of sheet material according to the process of claim 1 wherein that step (E) comprises.
7. according to the process of claim 1 wherein that the conductive polymer compositions in laminate has the resistance coefficient of maximum 20 ohm-cms.
8. according to the method for claim 7, wherein the conductive polymer compositions in laminate has the resistance coefficient of maximum 10 ohm-cms.
9. according to the process of claim 1 wherein that polymeric sheet has the thickness of 0.025～3.8 millimeter (0.001～0.150 English inch), and by extruding or rolling formation.
CN97198230A 1996-08-01 1997-07-30 Method of making a laminate comprising a conductive polymer composition Expired - Lifetime CN1090087C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69175196A 1996-08-01 1996-08-01
US08/691,751 1996-08-01

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN01117188A Division CN1326197A (en) 1996-08-01 2001-04-21 Electric device

Publications (2)

Publication Number Publication Date
CN1231635A CN1231635A (en) 1999-10-13
CN1090087C true CN1090087C (en) 2002-09-04

Family

ID=24777820

Family Applications (2)

Application Number Title Priority Date Filing Date
CN97198230A Expired - Lifetime CN1090087C (en) 1996-08-01 1997-07-30 Method of making a laminate comprising a conductive polymer composition
CN01117188A Pending CN1326197A (en) 1996-08-01 2001-04-21 Electric device

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN01117188A Pending CN1326197A (en) 1996-08-01 2001-04-21 Electric device

Country Status (8)

Country Link
EP (1) EP0918638A1 (en)
JP (1) JP2000515448A (en)
KR (1) KR20000029763A (en)
CN (2) CN1090087C (en)
AU (1) AU3742997A (en)
CA (1) CA2261895A1 (en)
TW (1) TW343423B (en)
WO (1) WO1998005503A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306323B1 (en) * 1997-07-14 2001-10-23 Tyco Electronics Corporation Extrusion of polymers
US6589299B2 (en) * 2001-02-13 2003-07-08 3M Innovative Properties Company Method for making electrode
KR100381920B1 (en) * 2001-02-16 2003-04-26 엘지전선 주식회사 Chemical crosslinking process of PTC using a laminator
KR100378927B1 (en) * 2001-02-16 2003-04-07 엘지전선 주식회사 Method for overcurrent protecting PTC polymer fuse
KR100436582B1 (en) * 2001-11-10 2004-06-19 엘지전선 주식회사 The chemical crosslinking method of PTC composite using a press
CN102522171A (en) * 2011-12-31 2012-06-27 上海长园维安电子线路保护股份有限公司 PTC (positive temperature coefficient) ring production method
US20170004946A1 (en) * 2015-06-30 2017-01-05 Tyco Electronics Corporation Conductive Composite and Circuit Protection Device Including a Conductive Composite
CN106455296A (en) * 2016-10-17 2017-02-22 上海长园维安电子线路保护有限公司 Circuit protection component
CN113826174A (en) 2018-11-23 2021-12-21 上海利韬电子有限公司 PPTC compositions and devices with low thermal deration and low process jump

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237441A (en) * 1978-12-01 1980-12-02 Raychem Corporation Low resistivity PTC compositions
US4769901A (en) * 1986-03-31 1988-09-13 Nippon Mektron, Ltd. Method of making PTC devices
EP0311142A2 (en) * 1981-04-02 1989-04-12 Raychem Corporation Radiation cross-linking of ptc conductive polymers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390489A (en) * 1977-12-19 1983-06-28 Allied Corporation Method of shaping thermoplastic compositions on aluminum foil support
US5174924A (en) * 1990-06-04 1992-12-29 Fujikura Ltd. Ptc conductive polymer composition containing carbon black having large particle size and high dbp absorption
JPH04247602A (en) * 1991-02-01 1992-09-03 Fujikura Ltd Manufacture of ptc thermistor
GB2301223B (en) * 1995-05-26 1999-04-21 Johnson Electric Sa Polymeric type positive temperature coefficient thermistors
EP0845148B1 (en) * 1995-08-15 2000-01-19 Bourns Multifuse (Hong Kong), Ltd. Surface mount conductive polymer devices and method for manufacturing such devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237441A (en) * 1978-12-01 1980-12-02 Raychem Corporation Low resistivity PTC compositions
EP0311142A2 (en) * 1981-04-02 1989-04-12 Raychem Corporation Radiation cross-linking of ptc conductive polymers
US4769901A (en) * 1986-03-31 1988-09-13 Nippon Mektron, Ltd. Method of making PTC devices

Also Published As

Publication number Publication date
CA2261895A1 (en) 1998-02-12
AU3742997A (en) 1998-02-25
JP2000515448A (en) 2000-11-21
CN1326197A (en) 2001-12-12
EP0918638A1 (en) 1999-06-02
WO1998005503A1 (en) 1998-02-12
CN1231635A (en) 1999-10-13
KR20000029763A (en) 2000-05-25
TW343423B (en) 1998-10-21

Similar Documents

Publication Publication Date Title
CN1097829C (en) Conductive polymer composition and device
US4591700A (en) PTC compositions
CN1230837C (en) Electrically conductive polymer composition
CN1111876C (en) Electrical device
US5451919A (en) Electrical device comprising a conductive polymer composition
US6221282B1 (en) Electrical devices comprising conductive polymer compositions
US4980541A (en) Conductive polymer composition
US4334351A (en) Novel PTC devices and their preparation
CN100343925C (en) PTC conductive composition containing a low molecular weight polyethylene processing aid
US6104587A (en) Electrical device comprising a conductive polymer
JPH0159684B2 (en)
KR102044107B1 (en) Conductive Polymer Compositions, Conductive Polymer Sheets, Electrical Components, and Methods for Making the Same
US5554679A (en) PTC conductive polymer compositions containing high molecular weight polymer materials
CN103797548A (en) Macromolecule-based conductive composite material and ptc element
CN1090087C (en) Method of making a laminate comprising a conductive polymer composition
US4318881A (en) Method for annealing PTC compositions
EP0803879B1 (en) Conductive polymer composition
CN113826174A (en) PPTC compositions and devices with low thermal deration and low process jump
GB2033707A (en) Conductive polymer compositions of an electrical device
MXPA99001160A (en) Method of making a laminate comprising a conductive polymer composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20020904