CN101935418B - Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof - Google Patents
Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof Download PDFInfo
- Publication number
- CN101935418B CN101935418B CN 200910108460 CN200910108460A CN101935418B CN 101935418 B CN101935418 B CN 101935418B CN 200910108460 CN200910108460 CN 200910108460 CN 200910108460 A CN200910108460 A CN 200910108460A CN 101935418 B CN101935418 B CN 101935418B
- Authority
- CN
- China
- Prior art keywords
- acid ester
- titanic acid
- ptc
- ptc material
- 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.)
- Active
Links
Landscapes
- Thermistors And Varistors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a positive temperature coefficient material and a preparation method thereof, and a material-containing thermosensitive resistor and a preparation method thereof. The material is a product formed by melting a mixture and characterized in that: the mixture contains a resin, a titanic acid ester modified conductive filler, a lubricant, a titanic acid ester modified antioxidant and a titanic acid ester modified fire retardant, wherein a three-dimensional conductive network structure is formed in the mixture by the conductive filler. The positive temperature coefficient material provided by the invention has high stability and the output power of the positive temperature coefficient material is reduced along with the increasing times of switch motions, so that the thermosensitive resistor which is prepared by the positive temperature coefficient material provided by the invention has high room temperature resistance stability and positive temperature coefficient (PTC) strength stability after being repeatedly used.
Description
Technical field
The invention relates to a kind of material and contain the resistance of this material and their preparation method, specifically, be about a kind of PTC material and contain the thermistor of this material and their preparation method.
Background technology
Some conductive polymer composites have positive temperature coefficient (PTC) effect, that is, the resistivity of material raises with temperature and increases, and resistivity presents the sudden change of the order of magnitude near critical temperature.The application of high molecular positive temperature coefficient material has been subject to paying close attention to more and more widely, yet the stability of this material remains to be further improved.The subject matter that the restriction PTC material is used has: the room temperature resistivity of (1) PTC material is unstable, is changed along with the thermal cycling that stands in the use procedure by the resistivity of the thermistor of this material preparation; (2) the PTC strength stability is relatively poor, and the output rating of PTC intensity and material increases and rapidly decay with the resistance switch action frequency; (3) can occur resistance negative temperature coefficient (NTC) effect in the temperature range more than being higher than melting point polymer, that is, resistivity of material raises with temperature and reduces.The unstable control that is unfavorable for electric current in the loop of PTC material room temperature resistivity, the decay of PTC intensity and NTC effect have been damaged its performance as protecting component especially.(4) loss of properties on aging of material, reuse and particular surroundings under when using, the performance variation amplitude of PTC material is larger.These shortcomings have reduced application stability and the security as products such as current limiting element, heater elements.Therefore control the stable room temperature resistance of PTC material and good PTC intensity repeatability has very important meaning.
At present, the main method of elimination macromolecular positive temperature coefficient thermosensitive resistor defects is that the high molecular positive temperature coefficient core is carried out radiation crosslinking.But the positive temperature coefficient core is under irradiation, reach higher cross-link intensity and just need higher irradiation dose, so not only increased cost, having limited it promotes the use of, and large irradiation dose also can make the macromolecular material in the positive temperature coefficient core degrade, destroy other component in the material, affect the use properties of PTC material.
CN1655290A discloses a kind of macromolecular positive temperature coefficient thermosensitive resistor, this thermistor is by the polymer substrate and be compound in the pellet electrode on substrate two sides, the insulation layer that is welded in electrode surface lead-in wire shape electrode and is encapsulated in outside surface consists of, and it is characterized in that: original composition and the parts by weight of matrix are as follows:
Polymkeric substance 40-65,
Conductive filler material 30-60,
Processing aid 0.2-10,
Described polymkeric substance is homopolymer or multipolymer, comprise one or more mixtures with arbitrary proportion in polyethylene, polypropylene, ethylene propylene copolymer, ethylene acrylic acid co polymer and the vinylformic acid, described conductive filler material is one or more in nickel powder, copper powder or the carbon black, described processing aid comprises oxidation inhibitor and coupling agent, the weight ratio of oxidation inhibitor and coupling agent is 1: 1.5-2.5, wherein, oxidation inhibitor is vinylformic acid alkoxide compound, and coupling agent is titanic acid ester or silane compound.Although the PTC intensity by the thermistor of this PTC material preparation has obtained certain improvement, but the stability of the room temperature resistivity of this PTC material still can not meet the demands, after repeatedly using, the stability of the PTC intensity of thermistor is still undesirable.
Summary of the invention
Technical problem to be solved by this invention is room temperature resistance stability and PTC strength stability, difference and the loss of properties on aging defective that overcomes posistor resistance after repeatedly using of the PTC material preparation that is prepared by prior art.Manufacture method of the present invention has not only improved the ageing-resistant performance of PTC material, is repeatedly using the little and high thermistor of PTC intensity of rear room temperature resistance drift amplitude but also provide a kind of.
The present inventor finds by great many of experiments, stability and the filler of PTC comprise oxidation inhibitor, the distribution situation of other additives such as stablizer and fire retardant in mixture has much relations, the PTC intensity of the present inventor by the thermistor that will contain resin, after the preparation processes such as moulding, irradiation, make through the conductive filler material of modification, the PTC material that obtains through melting through oxidation inhibitor, lubricant, the titanic acid ester mixture of modification be improved significantly.Wherein compared with prior art, in this mixture, conductive filler material has formed obvious conductive network, infer that reason may be formation and the resin of conductive network, the comprehensive action of the even distribution of antioxidant and even stick modification conductive filler material, this network is so that the thermistor of ptc material preparation is repeatedly using room temperature resistance stability and the PTC intensity of rear resistance all to significantly improve.
The invention provides a kind of PTC material, this material is the product that is formed through melting by a kind of mixture, described mixture contains resin, conductive filler material, lubricant, oxidation inhibitor, fire retardant, wherein, also contain titanic acid ester in the described mixture, conductive filler material consists of three-dimensional conductive network structure in mixture.
The present invention also provides the preparation method of this PTC material, and the method comprises:
1) proportionally weighing titanate coupling agent, Virahol, oxidation inhibitor, dry under vacuum condition after mixing, obtain the oxidation inhibitor of titanic acid ester modification;
2) proportionally weighing titanate coupling agent, Virahol, fire retardant mix, and obtain the fire retardant of titanic acid ester modification after the drying;
3) proportionally weighing titanate coupling agent, isopropyl acid, conductive filler material stir, and obtain the conductive filler material of titanic acid ester modification after dry.
4) will there be conductive filler material, the lubricant of resin, titanic acid ester modification, the fire retardant of titanic acid ester modification proportionally to mix, with the mixture heating up melting, add simultaneously the oxidation inhibitor of the titanic acid ester modification of preparation in the step (1), then with gained melts extruding pelletization, obtain PTC material.
The invention provides a kind of posistor, this thermistor comprises conducting base, PTC material and conductive electrode, described PTC material is positioned in the middle of two conducting bases and is attached on the conducting base, described conductive electrode lays respectively on two conducting bases, wherein, described PTC material is PTC material provided by the present invention.
The present invention also provides the preparation method of posistor, the method comprises PTC material is placed two through between the Copper Foils of special processing, hot-forming is three layers of composite core material, this core is heat-treated, and use the irradiation x ray irradiation x, then weld conductive electrode at two conducting bases respectively, wherein, described PTC material is PTC material provided by the invention.
Having good stability of PTC material provided by the invention, the output rating of PTC material is slow with the decay that the switch motion number of times increases, and so that by the thermistor of PTC material provided by the invention preparation, after repeatedly using, resistance has good room temperature resistance stability and PTC strength stability.
Description of drawings
Fig. 1 is provided the PTC material stereoscan photograph by present embodiment 1.
Embodiment
A kind of PTC material, this material is the product that is formed through melting by a kind of mixture, described mixture contains resin, titanic acid ester modification conductive filler material, lubricant, titanic acid ester modification oxidation inhibitor, the agent of titanic acid ester modified flame-retardant, and conductive filler material consists of three-dimensional conductive network structure in mixture.
According to the present invention, wherein, take the gross weight of described mixture as benchmark, the content of described resin is 10%-30%, the content of described titanic acid ester modification conductive filler material is 60-80%, the content of described lubricant is 0-5%, and the content of titanic acid ester modification oxidation inhibitor is 0-2%, and the content of described titanic acid ester modified flame-retardant agent is 1-10%.
In the preferred case, take the gross weight of mixture as benchmark, the content of described resin is 10%-20%, the content of titanic acid ester modification conductive filler material is 70-80%, the content of described lubricant is 0.5-4%, the content of titanic acid ester modification oxidation inhibitor is 0.1-0.5%, and the content of described titanic acid ester modified flame-retardant agent is 1-6%.
In order further to improve performance, can also add linking agent among the present invention, described linking agent is selected from TMPTA, two BP, TATC, TGIC, SR351, the SR350 linking agent can be by commercially available, reach the TMPTA linking agent of chemical company limited such as Shanghai Fang Rui, when using linking agent, take the mixture total weight amount as benchmark, the content of linking agent is 0.5-2%.
Owing to PTC material provided by the invention is the product that a kind of mixture forms through melting, described melt temperature refers to the melt temperature of resin in the mixture, and melt temperature is far below decomposition temperature, thereby has molten state.
According to the present invention, the kind of described resin is conventionally known to one of skill in the art, as, can be selected from one or more in polyvinyl resin, acrylic resin, ethylene propylene copolymer, ethylene acrylic acid co polymer, polyacrylic ester, teflon resin, daiflon, polyvinylidene dichloride resin, polyvinylidene fluoride resin, the fluorinated ethylene propylene.
The kind of described conductive filler material also can be selected from and well known to a person skilled in the art various conductive filler materials, as can for metal-powder or for being selected from one or more and the mixture of metal-powder in carbon black, graphite and the carbon fiber, described metal-powder be selected from one or more in copper, molybdenum, nickel, tungsten and the silver; In described carbon black, graphite and the carbon fiber one or more can play the effect of additional conductive as conducting particles.
Described oxidation inhibitor kind also can be selected from and well known to a person skilled in the art various oxidation inhibitor, as, Vinylstyrene and vulcabond, benzoyl peroxide, quinone oximes compound, polysulphide polymer, urethanum, maleimide derivatives, one or more among B215, B225, SK1908, PDM, the XL-1,1010.
Fire retardant is selected from magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, silicon-dioxide, magnesium hydroxide and aluminium hydroxide, Calucium Silicate powder, Magnesium Silicate q-agent, in glass fibre and the glass powder one or more, fire retardant is various fire retardant known in the field, can obtain by supplier, OL-104/WE and OL-104/LEO type such as LMT, in prescription provided by the present invention except above-mentioned component, can also add as required some auxiliary agents, the kind of these auxiliary agents is conventionally known to one of skill in the art, those skilled in the art can select suitable auxiliary agent as required, to satisfy different needs and to reach best effect.
For example, in order to prevent and to suppress matrix material in the course of processing or in the use procedure, because the factors such as light, heat, oxygen cause too early degraded, can add stablizer.Stablizer can be selected from UV-series product such as Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV531), carbon black, one or more in organic tin stablizer, trisnonyl phenyl phosphite (TNPP), the epoxy soybean oil.Wherein, described organic tin stablizer can be selected from one or more in dibutyl tin laurate, the different monooctyl ester diformazan of dithioglycol ester group ethylidene tin (being called for short ester group tin), ester group tin RWS-784, two (the different monooctyl ester of sulfo-glycolic acid) dioctyltin (being called for short capital tin 8831), two toxilic acid dibutyl tins, the different monooctyl ester dibutyl tin of sulfo-glycol, these auxiliary agents cooperate can play synergistic effect, and result of use is better.
The preparation method of PTC material provided by the invention comprises:
1) proportionally weighing titanate coupling agent, Virahol, oxidation inhibitor, dry under vacuum condition after mixing, obtain the oxidation inhibitor of titanic acid ester modification;
2) proportionally weighing titanate coupling agent, Virahol, fire retardant mix, and obtain the fire retardant of titanic acid ester modification after the drying;
3) proportionally weighing titanate coupling agent, isopropyl acid, conductive filler material stir, and obtain the conductive filler material of titanic acid ester modification after dry.
4) will there be the conductive filler material of resin, titanic acid ester modification, the lubricant of titanic acid ester modification, the fire retardant of titanic acid ester modification proportionally to mix, with the mixture heating up melting, add simultaneously the oxidation inhibitor of the titanic acid ester modification of preparation in the step (1), then with gained melts extruding pelletization, obtain PTC material.
Wherein the technique in the step (1) is specifically seen lower:
A) take by weighing oxidation inhibitor and be positioned in the vacuum drying oven oven dry after, grinding with mortar is that ponderable quantity uses;
B) in proportion weighing titanic acid ester even summation Virahol, in beaker, titanic acid ester even summation Virahol is fully mixed, guarantee at the bottom of the beaker or sidewall does not have till the residual titanic acid ester, oxidation inhibitor is added in the solvent for preparing, fully stir, after oxidation inhibitor is uniformly dispersed, in vacuum drying oven, dry.
Concrete steps are as follows in the step (2); Under the temperature that is higher than 5-20 ℃ of oxidation inhibitor fusing point, with the above-mentioned oxidation inhibitor of handling well and polyethylene, polypropylene, polyvinylidene difluoride (PVDF), voltalef, the polyvinylidene dichloride resin, polyvinylidene fluoride resin, after one or more take by weighing in proportion in the polyfluoroethylene resins etc., mixing in the SU-70 of Su Yan scientific ﹠ technical corporation type Banbury mixer, obtain mixture, this mixture is taken out, pulverize, obtain the mixture powder, the conductive filler material of titanic acid ester modification is led in weighing in proportion, with conductive filler material, mineral filler with obtain the mixture powder, secondary extrusion moulding in SJSH-30 type forcing machine obtains PTC material provided by the present invention.
Polyethylene in the PTC material, polypropylene, polyvinylidene difluoride (PVDF), the thermal oxidation process of the organic compound such as daiflon, polyvinylidene dichloride resin, polyvinylidene fluoride resin, fluorinated ethylene propylene is a series of free chain reaction, under the effect of heat, light or oxygen, the chemical bond fracture of organic molecule generates active free radical and hydroperoxide.Hydroperoxide generation decomposition reaction also generates hydrocarbon oxyradical and hydroxyl radical free radical.These free radicals can cause a series of free chain reaction, cause structure and the character generation fundamental change of organic compound.The effect of oxidation inhibitor is to eliminate the free radical that has just produced, and perhaps impels the decomposition of hydroperoxide, stops the carrying out of chain reaction.The oxidation inhibitor that can eliminate free radical has compound and the derivatives thereof such as aromatic amine and hindered phenol, is called primary antioxidant; The oxidation inhibitor of energy hydroperoxide decomposition has phosphorous and organic compound sulfur-bearing, is called auxiliary antioxidant.Antioxidant 1010 and B225 that the present invention uses are produced by U.S. big lake company, this oxidation inhibitor is through after the above-mentioned processing, can eliminate free radical again can hydroperoxide decomposition, and after method provided by the invention is processed, the group activity of oxidation inhibitor is stronger, in a single day organic compound occurs owing to temperature in the PTC base material, and oxygen or other reasons cause the organism thermooxidizing in the base material, and the anti-oxidant action of this processing just significantly embodies.In addition, the processing temperature of general oxidation inhibitor is all far above the optimal process temperature of the resins such as the polyethylene in the PTC material base material, polypropylene, ethylene propylene copolymer, ethylene acrylic acid co polymer and vinylformic acid, there is excess Temperature, resin is easily degraded, temperature is excessively low, and oxidation inhibitor disperses inhomogeneous, and adds together man-hour with conductive filler material, excessive temperature can make the conductive filler material oxidation, causes deterioration in material properties.The present inventor by a large amount of experiments repeatedly checking PTC material through after above-mentioned processing and the working method of the present invention, oxidation inhibitor disperses more even in the polymkeric substance such as polyethylene, agglomeration obviously reduces, and so better inhibition polymkeric substance is heated or other elements and the generation of the signs of degradation that produces.In addition, insulating material and conductive filler material obviously consist of a conductive network in the PTC material.During normal circumstances work, conducting particles forms conductive network and conducting in polymkeric substance, and break down when causing that temperature raises when circuit, polymeric matrix generation volumetric expansion etc., the network that conducting particles forms by slowly separately, resistance refers to increase, conductive network is standby to be destroyed, resistance value sharply increases thereupon, and namely matrix material presents the PTC phenomenon.
According to method of the present invention take the gross weight of described mixture as benchmark, the content of described resin is 10%-30%, the content of described titanic acid ester modification conductive filler material is 60-80%, the content of described lubricant is 0-5%, the content of titanic acid ester modification oxidation inhibitor is 0-1%, and the content of described titanic acid ester modified flame-retardant agent is 0-10%.
In the preferred case take the gross weight of described mixture as benchmark, the content of described resin is 10%-20%, the content of titanic acid ester modification conductive filler material is 70-80%, the content of described lubricant is 0.5-4%, the content of titanic acid ester modification oxidation inhibitor is 0-1%, and the content of described titanic acid ester modified flame-retardant agent is 0-6%.
According to method of the present invention, the process that will contain the mixture heating up melting of resin, conductive filler material, lubricant, oxidation inhibitor, fire retardant and titanic acid ester can be carried out in the various device known in the art, as, at mixing facilities, such as mixed melting in Banbury mixer or the mill, also can be in twin screw extruder mixed melting, the preferred process that also is included in mixing facilities or the twin screw extruder gained melts extruding pelletization is conventionally known to one of skill in the art with method, condition and the equipment used of mixture extruding pelletization.
The temperature of the mixture heating up melting of the oxidation inhibitor of the described lubricant that makes the conductive filler material that contains resin, titanic acid ester modification, titanic acid ester modification, titanic acid ester modification, the fire retardant of titanic acid ester modification is for being not less than at least 150 ℃, be preferably 160-200 ℃, the time of heating and melting is not particularly limited, as long as guarantee the abundant mixing of above-mentioned raw materials and heating and melting, generally, the time of described heating and melting is 10-30 minute, is preferably 20 minutes.
The preparation method of mixture can adopt and well known to a person skilled in the art the whole bag of tricks, obtains mixture as each component is mixed, and preferably evenly obtains this mixture in stirrer for mixing.The condition and the method that stir are conventionally known to one of skill in the art, and those skilled in the art's instruction according to the present invention is easy to select suitable agitation condition and method.
This preparation method's concrete steps are as follows:
(1) oxidation inhibitor modification
A) an amount of oxidation inhibitor being dried 120-180min in vacuum drying oven under vacuum tightness-0.1-0.09MPa grinds broken for subsequent use with mortar;
B) with titanate coupling agent NDZ-201 with organic solvent dilutings such as Virahol or toluene, in the oxidation inhibitor of drying in adding to a), after stirring fully in vacuum tightness be-0.1-0.09MPa again, in temperature 70-90 ℃ the vacuum drying oven, oven dry 120-180min;
C) under the temperature that is higher than 5-50 ℃ of oxidation inhibitor fusing point, with the polyethylene in the above-mentioned oxidation inhibitor of handling well and the PTC base material, polypropylene, polyvinylidene difluoride (PVDF), the mixing certain hour of one or several insulating material in daiflon, polyvinylidene dichloride, poly(vinylidene fluoride), the fluorinated ethylene propylene etc., taking-up is for subsequent use after pulverizing.
The weight ratio 0.01-0.5 of oxidation inhibitor, titanic acid ester, organic solvent: 1-2: 5-20 in the said process wherein.
(2) modification of conductive filler material
A) an amount of conductive metal powder is dried 180-240min in vacuum drying oven under vacuum tightness-0.1-0.09MPa
B) the weighing titanate coupling agent NDZ-201 organic solvent dilutings such as Virahol, methyl ether or dimethylbenzene, Dilution ratio 1: 20, in the conducting metal of drying in adding to a), be-0.1-0.09MPa in vacuum tightness again after fully stirring with high mixer, in temperature 70-90 ℃ ℃ the vacuum drying oven, oven dry 180-240min
(3) will contain the mixture heating up melting of fire retardant of conductive filler material, lubricant, the titanic acid ester modification of resin, titanic acid ester modification, it is even that the conductive filler material that adds oxidation inhibitor, the titanic acid ester modification of the titanic acid ester modification of preparation in the step (1) joins high-speed mixer and mixing, obtain mixture, wherein, the temperature and time of blended under agitation is conventionally known to one of skill in the art, for example, blended under agitation is at room temperature carried out usually, the time of blended under agitation can be 1-30 minute, and the rotating speed of blended under agitation is 200-2500 rev/min; Under the preferable case, under 800-1200 rev/min rotating speed, stirred 5-10 minute first, and then stirring obtained mixture in 3-5 minute under 1500-2000 rev/min rotating speed.
(4) with the mixture melting, the extruding pelletization that obtain.Wherein, described mixture melting, extruding pelletization can be adopted in Banbury mixer or the mill, extrude and be ground into particle 160-200 ℃ of lower melting mixing; Also can adopt twin screw extruder, be 32 in length-to-diameter ratio: 1-52: 1, and screw speed 150-500 rev/min; Described twin screw extruder generally is divided into 5 sections from the feed end to the discharge end, from the feed end to the discharge end, each zone temperatures is set as respectively 170-200 ℃, 175-200 ℃, 180-200 ℃, 180-200 ℃, 180-200 ℃ successively, and the vacuum tightness of each section is to mix and extruding pelletization under the condition of 0.02 to 0.09 MPa.Vacuum tightness in this specification sheets refers to the absolute value (absolute pressure is less than barometric point) of the difference of absolute pressure and barometric point.
The structure of described posistor is conventionally known to one of skill in the art, as, described thermistor generally comprises conducting base, PTC material and conductive electrode, described PTC material is positioned in the middle of two conducting bases and is attached on the conducting base, and described conductive electrode lays respectively on two conducting bases.According to the present invention, except described PTC material was PTC material provided by the invention, being chosen as of other parts of thermistor was conventionally known to one of skill in the art.For example, described conducting base can be for the used conventional conducting base of various thermistors, and such as tinsel or nickel screen, what adopt in the specific embodiments of the present invention is the nickel plating Copper Foil.Described conductive electrode uses nickel strap as conductive electrode usually.
Under the preferable case, oxidized in order to prevent thermistor, described thermistor surface also comprises resin film layer, the kind of described resin film layer and thickness are conventionally known to one of skill in the art, for example, the thickness of described resin film layer is generally the 0.1-3.0 millimeter, is preferably the 0.25-1.0 millimeter.Described resin film layer can be for various oxidation resistant resins, such as Resins, epoxy or paraffin etc.
The preparation method of described posistor comprises PTC material is placed between two conducting bases, be shaped to three layers of composite core material, this core is heat-treated, and use the irradiation x ray irradiation x, then weld conductive electrode at two conducting bases respectively, except described PTC material was PTC material provided by the invention, the preparation method of described thermistor and condition were conventionally known to one of skill in the art.
Under the preferable case, it is oxidized to prevent thermistor that the method also is included in described thermistor surface formation Resins, epoxy rete, described method at thermistor surface formation Resins, epoxy rete can adopt any method that well known to a person skilled in the art, as with as described in epoxy resin solution be coated in thermistor surface, perhaps with thermistor directly in epoxy resin solution dipping take out after for some time.The thickness that the time chien shih of the coated weight of epoxy resin solution or dipping is formed at the Resins, epoxy rete of thermistor surface is the 5-100 micron, is preferably the 10-50 micron.
The method of described moulding is conventionally known to one of skill in the art, the hot-forming method of preferred employing, described hot-forming method can be carried out in press molding machine, the condition of hot pressing comprises the pressure of hot pressing, the temperature of hot pressing and the time of hot pressing, the pressure of described hot pressing can be the 1-10 MPa, is preferably the 5-10 MPa; The temperature of hot pressing can be 160-220 ℃, is preferably 180-200 ℃; The time of hot pressing can be 5-30 minute, is preferably 8-20 minute.
The purpose that three layers of composite core material that form are heat-treated is in order better to eliminate the stress of PTC material in three layers of composite core material with the further intensity of improving PTC material, described heat treated condition is conventional heat-treat condition, comprise heat treated temperature and heat treated time, generally speaking, under 50-100 ℃ thermal treatment temp, placed 1-20 hour, and be preferably 10-20 and namely can reach heat treated purpose.
Described cross-linking radiation to be chosen as the art personnel known, the crosslinked cohesive strength that can improve polymkeric substance, water tolerance, the performances such as thermotolerance, tensile strength and chemically-resistant.For PTC material, irradiation can improve high molecular polymer cross-linking radiation degree, eliminates the NTC phenomenon and improves PTC intensity, can adopt various irradiation rays that core is carried out irradiation, general common employing gamma-rays (Co
60) or electron rays core is carried out irradiation so that each material is further crosslinked in the core.The irradiation dose of described irradiation ray is generally the 10-20 megarad.
Below will the present invention is described in detail by specific embodiment.
Embodiment 1
Present embodiment is used for illustrating the preparation of PTC material of the present invention and thermistor.
Take the weight of PTC material as benchmark, polyvinyl chloride with 13%, 80% titanic acid ester modification conduction nickel powder, 1% titanic acid ester modification phosphorous acid ester sodium, 1% paraffin, the modified oxidized calcium of 5% titanic acid ester joins in the high mixer of SHR-10A type of Bora machine works, in the lower mixing of room temperature (25 ℃), under 800 rev/mins rotating speed, stirred 10 minutes first, and then stirring obtained mixture in 3 minutes under 2000 rev/mins rotating speed.
Wherein the oxidation inhibitor preparation process of titanic acid ester modification is as follows: a) oxidation inhibitor is dried 120-180min in vacuum drying oven under vacuum tightness-0.1-0.09MPa and grind broken for subsequent use with mortar; B) with titanate coupling agent NDZ-201 with organic solvent dilutings such as Virahol or toluene, in the oxidation inhibitor of drying in adding to a), after stirring fully in vacuum tightness be-0.1-0.09MPa again, in temperature 70-90 ℃ the vacuum drying oven, oven dry 120-180min; Oxidation inhibitor wherein: titanic acid ester: the ratio of Virahol is 0.5: 1: 20, obtains the oxidation inhibitor of titanic acid ester modification;
The preparation process of titanic acid ester modification nickel powder is as follows: the nickel powder of a) inciting somebody to action is dried 120-180min under vacuum tightness-0.1-0.09MPa in vacuum drying oven; B) with titanate coupling agent NDZ-201 with organic solvent dilutings such as Virahol or toluene, in the nickel powder of drying in adding to a), after stirring fully in vacuum tightness be-0.1-0.09MPa again, in temperature 70-90 ℃ the vacuum drying oven, oven dry 120-180min, obtain the nickel powder of titanic acid ester modification, wherein nickel powder: titanic acid ester: the ratio of Virahol is 100: 1: 20;
Being prepared as follows of titanic acid ester modified flame-retardant agent: a) fire retardant is dried 120-180min in vacuum drying oven under vacuum tightness-0.1-0.09MPa and grind broken for subsequent use with mortar; B) with titanate coupling agent NDZ-201 with organic solvent dilutings such as Virahol or toluene, in the fire retardant of drying in adding to a), after stirring fully in vacuum tightness be-0.1-0.09MPa again, in temperature 70-90 ℃ the vacuum drying oven, oven dry 120-180min, obtain the fire retardant of titanic acid ester modification, wherein fire retardant: titanic acid ester: the ratio of Virahol is 100: 1: 20.
Mixture obtained above is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.With the adjustment of rotational speed to 400 of screw rod rev/min, from the feed end to the discharge end, be divided into 5 sections, each zone temperatures is controlled at respectively: 170 ℃; 175 ℃, 180 ℃, 185 ℃, 185 ℃; The vacuum keep of each section is 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain PTC material V1.
Two conducting base nickel plating Copper Foils are placed in the mould, and above-mentioned PTC material placed the nickel plating Copper Foil, on thermocompressor, 180 ℃ of lower preheatings 10 minutes, then hot-forming is three layers of composite core material, with the thermal treatment 16 hours in 80 ℃ vacuum chamber of gained core, and with gamma-rays (Co
60) these three layers of composite core materials are carried out radiation crosslinking, irradiation dose 15 megarads.
With punch press these three layers of composite core materials are tailored into the small pieces that are of a size of 3 millimeters * 3 mm in sizes at last, and respectively at two conducting base welding conductive electrode nickel straps, then cover conductive electrode with adhesive tape, at last at epoxy resin solution (bisphenol A type epoxy resin 128, Wuxi anti-impregnating material of a specified duration company buys) in dipping 2 minutes, and 60 ℃ lower dry 30 minutes, form 25 microns Resins, epoxy rete on its surface, make positive temperature coefficient thermistor T1.
Embodiment 2
Present embodiment is used for illustrating the preparation of PTC material of the present invention and thermistor.
This enforcement has adopted the method identical with embodiment to prepare the PTC material difference, take the weight of PTC material as benchmark, polyvinyl chloride with 10%, 80% titanic acid ester modification conduction nickel powder, 0.5% titanic acid ester modification potassium stearate, 5% stearic acid, 4.5% titanic acid ester modifying titanium dioxide joins in the SHR-10A type high mixer of Bora machine works, in the lower mixing of room temperature (25 ℃), under 800 rev/mins rotating speed, stirred 10 minutes first, and then stirring obtained mixture in 3 minutes under 2000 rev/mins rotating speed.
Mixture obtained above is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.With the adjustment of rotational speed to 400 of screw rod rev/min, from the feed end to the discharge end, be divided into 5 sections, each zone temperatures is controlled at respectively: 170 ℃; 175 ℃, 180 ℃, 185 ℃, 185 ℃; The vacuum keep of each section is 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain PTC material V2.
To be placed in the homemade mould through two conducting base nickel plating Copper Foils of special processing, and above-mentioned PTC material placed the nickel plating Copper Foil, on thermocompressor, 180 ℃ of lower preheatings 10 minutes, hot-forming is three layers of composite core material, with the thermal treatment 16 hours in 80 ℃ vacuum chamber of gained core, and with gamma-rays (Co
60) these three layers of composite core materials are carried out radiation crosslinking, irradiation dose 15 megarads.
With punch press these three layers of composite core materials are tailored into the small pieces that are of a size of 3 millimeters * 3 mm in sizes at last, and respectively at two conducting base welding conductive electrode nickel straps, then cover conductive electrode with adhesive tape, at last at epoxy resin solution (bisphenol A type epoxy resin 128, Wuxi anti-impregnating material of a specified duration company buys) in dipping 2 minutes, and 60 ℃ lower dry 30 minutes, form 25 microns Resins, epoxy rete on its surface, make positive temperature coefficient thermistor T2.
Embodiment 3
Present embodiment is used for illustrating the preparation of PTC material of the present invention and thermistor.
Originally be that embodiment adopts method identical among the embodiment 1 to prepare PTC material, difference is, take the gross weight of PTC material as benchmark, Graphite Powder 99 is led in polyacrylic ester with 25%, 70% titanic acid ester modification, 1% titanic acid ester modification oxidation inhibitor B215,1.5% Zinic stearas, 2.5% titanic acid ester modified zinc oxide joins in the SHR-10A type high mixer of Bora machine works, in the lower mixing of room temperature (25 ℃), under 800 rev/mins rotating speed, stirred 10 minutes first, and then stirring obtained mixture in 3 minutes under 2000 rev/mins rotating speed.
Mixture obtained above is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.With the adjustment of rotational speed to 400 of screw rod rev/min, from the feed end to the discharge end, be divided into 5 sections, each zone temperatures is controlled at respectively: 170 ℃; 175 ℃, 180 ℃, 185 ℃, 185 ℃; The vacuum keep of each section is 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain PTC material V3.
To be placed in the homemade mould through two conducting base nickel plating Copper Foils of special processing, and above-mentioned PTC material placed the nickel plating Copper Foil, on thermocompressor, 180 ℃ of lower preheatings 10 minutes, hot-forming is three layers of composite core material, with the thermal treatment 16 hours in 80 ℃ vacuum chamber of gained core, and with gamma-rays (Co
60) these three layers of composite core materials are carried out radiation crosslinking, irradiation dose 15 megarads.
With punch press these three layers of composite core materials are tailored into the small pieces that are of a size of 3 millimeters * 3 mm in sizes at last, and respectively at two conducting base welding conductive electrode nickel straps, then cover conductive electrode with special adhesive tape, at last at epoxy resin solution (bisphenol A type epoxy resin 128, Wuxi anti-impregnating material of a specified duration company buys) in dipping 2 minutes, and 60 ℃ lower dry 30 minutes, form 25 microns Resins, epoxy rete on its surface, make positive temperature coefficient thermistor T3.
Embodiment 4
Present embodiment is used for illustrating the preparation of PTC material of the present invention and thermistor.
Present embodiment adopts the method identical with embodiment 1 to prepare PTC material, difference is that volume take PTC material is as benchmark, polyvinylidene dichloride resin with 10%, 80% titanic acid ester modified carbon black, 1% titanic acid ester modification oxidation inhibitor XL-1,4% stearic acid, 5% titanic acid ester modified aluminas joins in the SHR-10A type high mixer of Bora machine works, in the lower mixing of room temperature (25 ℃), under 800 rev/mins rotating speed, stirred 10 minutes first, and then stirring obtained mixture in 3 minutes under 2000 rev/mins rotating speed.
Mixture obtained above is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.With the adjustment of rotational speed to 400 of screw rod rev/min, from the feed end to the discharge end, be divided into 5 sections, each zone temperatures is controlled at respectively: 170 ℃; 175 ℃, 180 ℃, 185 ℃, 185 ℃; The vacuum keep of each section is 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain PTC material V4.To be placed in the homemade mould through two conducting base nickel plating Copper Foils of special processing, and above-mentioned PTC material placed the nickel plating Copper Foil, on thermocompressor, 180 ℃ of lower preheatings 10 minutes, hot-forming is three layers of composite core material, with the thermal treatment 16 hours in 80 ℃ vacuum chamber of gained core, and with gamma-rays (Co
60) these three layers of composite core materials are carried out radiation crosslinking, irradiation dose 15 megarads.
With punch press these three layers of composite core materials are tailored into the small pieces that are of a size of 3 millimeters * 3 mm in sizes at last, and respectively at two conducting base welding conductive electrode nickel straps, then cover conductive electrode with special adhesive tape, at last at epoxy resin solution (bisphenol A type epoxy resin 128, Wuxi anti-impregnating material of a specified duration company buys) in dipping 2 minutes, and 60 ℃ lower dry 30 minutes, form 25 microns Resins, epoxy rete on its surface, make positive temperature coefficient thermistor T4.
Embodiment 5
Present embodiment is used for illustrating the preparation of PTC material of the present invention and thermistor.
Present embodiment adopts embodiment 1 identical method to prepare the PTC material difference, take the weight of PTC material as benchmark, polyvinyl chloride with 20%, 70% titanic acid ester modification conduction tungsten powder, 0.5% modification antioxidant BHT, 4.5% calcium stearate, the magnesium hydroxide of 5% titanic acid ester modification joins in the SHR-10A type high mixer of Bora machine works, in the lower mixing of room temperature (25 ℃), under 800 rev/mins rotating speed, stirred 10 minutes first, and then stirring obtained mixture in 3 minutes under 2000 rev/mins rotating speed.
Mixture obtained above is sent in the twin screw compounding forcing machine (SJSH-30 type, Nanjing Rubber-Plastic Machinery Plant) the length-to-diameter ratio L of forcing machine: D=36: 1, screw diameter is 53 millimeters of Φ.With the adjustment of rotational speed to 400 of screw rod rev/min, from the feed end to the discharge end, be divided into 5 sections, each zone temperatures is controlled at respectively: 170 ℃; 175 ℃, 180 ℃, 185 ℃, 185 ℃; The vacuum keep of each section is 0.05 to 0.08 MPa; Under these conditions, through melt extruding granulation, obtain PTC material V5.
To be placed in the homemade mould through two conducting base nickel plating Copper Foils of special processing, and above-mentioned PTC material placed the nickel plating Copper Foil, on thermocompressor, 180 ℃ of lower preheatings 10 minutes, hot-forming is three layers of composite core material, with the thermal treatment 16 hours in 80 ℃ vacuum chamber of gained core, and with gamma-rays (Co
60) these three layers of composite core materials are carried out radiation crosslinking, irradiation dose 15 megarads.
With punch press these three layers of composite core materials are tailored into the small pieces that are of a size of 3 millimeters * 3 mm in sizes at last, and respectively at two conducting base welding conductive electrode nickel straps, then cover conductive electrode with adhesive tape, at last at epoxy resin solution (bisphenol A type epoxy resin 128, Wuxi anti-impregnating material of a specified duration company buys) in dipping 2 minutes, and 60 ℃ lower dry 30 minutes, form 25 microns Resins, epoxy rete on its surface, make positive temperature coefficient thermistor T5.
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation prior art PTC material and thermistor
Method according to the disclosed embodiment 1 of CN1655290A prepares PTC material, and note is PV2, and employing and embodiment 1 identical method prepares the reference thermistor by this material, remembers and is TC1.
Embodiment 6-10
This embodiment explanation is carried out performance test to the thermistor that the PTC material that is made by method of the present invention prepares.Test result is as shown in table 1.
Under room temperature (25 ℃), the resistance value with BS-VR type internal resistance test device is tested respectively the PTC thermistor R1-R8 that is prepared by embodiment 1-8 is designated as R0
Room temperatureAnd use the test of ZC-46 type high resistant instrument to test respectively PTC thermistor R1-R8 in the resistance value of turn-offing under the temperature (about 124 ℃), be designated as R0
Peak value
Then with above-mentioned PTC thermistor R1-R8 as in the baking oven, 124 ℃ of fusing-off temperatures that at room temperature heat up and be higher than thermistor with 5 ℃/minute speed, reach 140 ℃, naturally be cooled to again room temperature as a circulation, and repeat above-mentioned circulation 200 times, again test according to the method described above described thermistor turn-off under the temperature resistance value and in abundant cooled resistance value, be designated as respectively R1
Peak valueAnd R1
Room temperature
And calculate the PTC intensity of described thermistor according to following formula.
PTC intensity=1g (R
Peak value/ R
Room temperature)
In the formula: R
The peak temperatureBe the resistance value of material under fusing-off temperature;
R
Room temperatureBe material resistance value at room temperature.
The result is as shown in table 1.
Comparative Examples 2
This Comparative Examples explanation is carried out performance test to the thermistor that the positive temperature coefficient that is made by existing method prepares.
Method according to embodiment 9-16 is carried out performance test to thermistor, and different is, test be the thermistor TC1 that the method by Comparative Examples 1 prepares.The result is as shown in table 1.
| The embodiment numbering | The resistance numbering | Initial p TC intensity | PTC intensity after 200 circulations | Resistance change rate (%) under the room temperature after 200 circulations | PTC change rate of strength (%) after 200 circulations |
| Embodiment 6 | T1 | 10.1164 | 10.0060 | 28.358 | 1.091 |
| Embodiment 7 | T2 | 10.1024 | 9.9914 | 27.941 | 1.099 |
| Embodiment 8 | T3 | 10.1059 | 9.9918 | 28.358 | 1.129 |
| Embodiment 9 | T4 | 10.1199 | 10.0015 | 29.851 | 1.170 |
| Embodiment 10 | T5 | 10.0972 | 9.9741 | 27.536 | 1.219 |
| Comparative Examples 1 | TC1 | 10.03044 | 9.7488 | 71.233 | 2.808 |
Can find out according to the data in the upper table 1, compare with the reference thermistor that is made by reference method, the velocity of variation of the resistance value that the thermistor that adopts PTC material of the present invention to prepare at room temperature records before recycling according to the method described above the room temperature resistance value after 200 times and using is significantly less than the velocity of variation of reference thermistor, and the velocity of variation of the PTC intensity of resistance also is significantly less than the velocity of variation of reference thermistor before and after 200 circulations of thermistor provided by the invention, thus explanation, the thermistor that is prepared by PTC material provided by the invention has good room temperature resistance stability and PTC strength stability, and can find out clearly that from Fig. 1 the prepared PTC material of the present invention has three-dimensional conductive network.
Claims (8)
1. PTC material, this material is the product that is formed through melting by a kind of mixture, it is characterized in that, described mixture contains resin, titanic acid ester modification conductive filler material, lubricant, titanic acid ester modification oxidation inhibitor, the agent of titanic acid ester modified flame-retardant, titanic acid ester modification conductive filler material consists of three-dimensional conductive network structure in mixture, wherein, take the gross weight of described mixture as benchmark, the content of described resin is 10%-30%, the content of described titanic acid ester modification conductive filler material is 60-80%, the content of described lubricant is 1-5%, and the content of titanic acid ester modification oxidation inhibitor is 0.1-0.5%, and the content of described titanic acid ester modified flame-retardant agent is 1-10%.
2. PTC material according to claim 1, wherein, the conductive filler material of described titanic acid ester modification conductive filler material is selected from metal-powder, perhaps conductive filler material is selected from one or more and the mixture of metal-powder in carbon black, graphite and the carbon fiber, and described metal-powder is selected from one or more in copper, molybdenum, nickel, tungsten and the silver.
3. PTC material according to claim 1, wherein, described resin is selected from one or more in polyvinyl resin, acrylic resin, ethylene propylene copolymer, ethylene acrylic acid co polymer, polyacrylic ester, teflon resin, daiflon, polyvinylidene dichloride resin, polyvinylidene fluoride resin, the polyfluoroethylene resin.
4. PTC material according to claim 1, wherein the fire retardant of titanic acid ester modified flame-retardant agent is selected from one or more in magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, silicon-dioxide, titanium dioxide, magnesium hydroxide and the aluminium hydroxide; The antioxidant of described titanic acid ester modification oxidation inhibitor is selected from one or more in phenolic compound, amine compound, organosulfur compound and the bi-ester of phosphite, and lubricant is selected from one or more in paraffin, stearic acid, calcium stearate, the Zinic stearas.
5. the preparation method of the described PTC material of claim 1 is characterized in that, the method comprises:
1) proportionally weighing titanate coupling agent, Virahol, oxidation inhibitor, dry under vacuum condition after mixing, obtain the oxidation inhibitor of titanic acid ester modification;
2) proportionally weighing titanate coupling agent, Virahol, fire retardant mix, and obtain the fire retardant of titanic acid ester modification behind the dry solvent;
3) proportionally weighing titanate coupling agent, Virahol, conductive filler material stir, and obtain the conductive filler material of titanic acid ester modification after dry;
4) will there be conductive filler material, the lubricant of resin, titanic acid ester modification, the fire retardant of titanic acid ester modification proportionally to mix, with the mixture heating up melting, add simultaneously the oxidation inhibitor of the titanic acid ester modification of preparation in the step (1), then with gained melts extruding pelletization, obtain PTC material
The weight ratio of titanate coupling agent, Virahol, oxidation inhibitor is 0.1-1: 1-20 in the step (1): 1,
The weight ratio of titanate coupling agent, Virahol, fire retardant is 0.1-2: 1-20 in the step (2): 1,
The weight ratio of titanate coupling agent, Virahol, conductive filler material is 0.1-1: 1-20 in the step (3): 1.
6. method according to claim 5, wherein, the temperature of described heating and melting is 160-200 ℃.
7. posistor, this thermistor comprises two conducting bases, PTC material and two conductive electrodes, described PTC material is positioned in the middle of two conducting bases and is attached on the conducting base, described two conductive electrodes are connected with tin cream with two conducting bases respectively, it is characterized in that described PTC material is PTC material claimed in claim 1.
8. the preparation method of the described posistor of claim 7, the method comprises PTC material is placed between two conducting bases, be shaped to three layers of composite core material, this core is heat-treated, and use the irradiation x ray irradiation x, then weld conductive electrode at two conducting bases respectively, it is characterized in that, described PTC material is PTC material claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910108460 CN101935418B (en) | 2009-06-30 | 2009-06-30 | Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910108460 CN101935418B (en) | 2009-06-30 | 2009-06-30 | Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101935418A CN101935418A (en) | 2011-01-05 |
| CN101935418B true CN101935418B (en) | 2013-05-29 |
Family
ID=43389003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910108460 Active CN101935418B (en) | 2009-06-30 | 2009-06-30 | Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101935418B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333388B (en) * | 2013-05-29 | 2016-08-10 | 安徽琦迅强电子科技有限公司 | A kind of metallocene PE is PTC high-molecular conductive material of major ingredient and preparation method thereof |
| CN103333386B (en) * | 2013-05-29 | 2016-08-10 | 安徽琦迅强电子科技有限公司 | A kind of High-temperature resistance PTC polymer conductive material and preparation method thereof |
| CN104867636B (en) * | 2015-06-11 | 2016-06-15 | 郑州轻工业学院 | A kind of semistor and preparation method thereof |
| CN106158176B (en) * | 2016-06-18 | 2018-03-27 | 芜湖长启炉业有限公司 | PTC resistor based on polyaniline and preparation method thereof |
| CN107522986A (en) * | 2017-10-13 | 2017-12-29 | 广东美晨通讯有限公司 | A kind of handset shell material and its mobile phone shell and preparation method |
| CN108164893B (en) * | 2018-01-15 | 2020-10-13 | 太原理工大学 | Preparation method of wear-resistant conductive PTFE/Cu composite material |
| CN113715223B (en) * | 2021-08-18 | 2023-08-15 | 厦门赛尔特电子有限公司 | Method for improving resistance value reduction of plug-in type PPTC finished product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140318A (en) * | 1995-06-08 | 1997-01-15 | Abb研究有限公司 | Positive temp. coefficient resistance |
| CN1730541A (en) * | 2005-08-12 | 2006-02-08 | 陕西师范大学 | Macromolecule material for automatic recovery fuse and its preparation method |
-
2009
- 2009-06-30 CN CN 200910108460 patent/CN101935418B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140318A (en) * | 1995-06-08 | 1997-01-15 | Abb研究有限公司 | Positive temp. coefficient resistance |
| CN1730541A (en) * | 2005-08-12 | 2006-02-08 | 陕西师范大学 | Macromolecule material for automatic recovery fuse and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101935418A (en) | 2011-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935418B (en) | Positive temperature coefficient material and preparation method thereof, and material-containing thermosensitive resistor and preparation method thereof | |
| CN101465185B (en) | Positive temperature coefficient material and thermistor containing the material and preparation method therefore | |
| CN102558638B (en) | Positive temperature coefficient material, preparation method thereof and thermistor containing positive temperature coefficient material | |
| US20230183539A1 (en) | A composite phase change material and its method of preparation thereof | |
| CN104130492A (en) | One-step silicane cross-linked polyethylene cable material and preparation method thereof | |
| KR20200060306A (en) | Mixture with non-crosslinking resin for preparing insulation layer of power cable | |
| KR20200011947A (en) | Reactive Formulation of Ethylene Vinyl Acetate | |
| CN115322472B (en) | Semiconductive shielding material based on compound resin and preparation method and application thereof | |
| CN113881133A (en) | High-voltage cable semiconductive shielding material with conductive carbon black efficiently dispersed and preparation method thereof | |
| CN102167858A (en) | Positive temperature coefficient material, preparation method thereof and thermistor containing material | |
| CN102140194A (en) | Material with positive temperature coefficient, preparation method thereof and thermosensitive resistor having same | |
| CN102050977B (en) | PTC material and preparation method thereof, and material-containing thermistor and preparation method thereof | |
| CN115216082A (en) | Stripping strength improved semi-conductive shielding material, preparation method, product and cable | |
| KR101864413B1 (en) | Anti-oxidant semi-conductive polymer compound self-regulating heating cable therein and a manufacturing method | |
| CN103665529A (en) | Semi-conductive internal shielding material composition, semi-conductive internal shielding material and manufacturing method thereof, as well as medium and low-pressure and 110KV cable | |
| CN114015148A (en) | Method for preparing high-voltage cable semiconductive shielding material by using low-impurity conductive carbon black | |
| CN102723153A (en) | PTC (positive temperature coefficient) core material with positive temperature coefficient characteristics and preparation method and application thereof | |
| CN102260385B (en) | Positive temperature coefficient material and thermistor containing same | |
| CN1222743A (en) | Posistor of laminar polymer | |
| JP2000508832A (en) | Method for producing positive temperature coefficient material | |
| KR100767058B1 (en) | Manufacturing method of ptc polymer sheet-electrode assembly | |
| JP3699514B2 (en) | Cross-linked polyethylene insulated power cable and method for producing the same | |
| CN112094449A (en) | Curie point adjustable PTC polymer conductive composite material and preparation method thereof | |
| KR100330920B1 (en) | Overcurrent protecting ptc polymer fuse and process for manufacturing that | |
| WO2023065429A1 (en) | Method for preparing semi-conductive shielding material used for high-voltage cable from low-impurity conductive carbon black |
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 |