CN101560313A - Flame-retardant master batch, novel macromolecular PTC thermistor containing flame-retardant master batch and manufacturing method thereof - Google Patents
Flame-retardant master batch, novel macromolecular PTC thermistor containing flame-retardant master batch and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant master batch, which comprises a flame retardant and carrier resin uniformly mixed together, wherein the preferred weight ratio of the carrier resin to the flame retardant is 10:90-30:70. The flame-retardant master batch also comprises an antioxidant, a coupling agent and a lubricant which account for 0.5 to 10 percent of the total weight of the flame retardant and the carrier resin. The invention also provides a method for preparing the flame-retardant master batch. The invention also relates to a novel macromolecular PTC thermistor containing the flame-retardant master batch, wherein a PTC chip of the PTC thermistor comprises 20 to 70 percent of the flame-retardant master batch, and the preferred weight percentage of the flame-retardant master batch in the PTC chip is between 30 and 60 percent. The invention also provides a method for manufacturing the novel macromolecular PTC thermistor containing the flame-retardant master batch. The flame-retardant master batch has high concentration of the flame retardant and high flame-retardant efficiency, and is simple to prepare. The novel macromolecular PTC thermistor containing the flame-retardant master batch has high voltage resistance, high PTC strength, superior resistance stability and high efficiency, and is simple and convenient to manufacture.
Description
Technical field
The present invention relates to the thermistor technology field, be particularly related to positive temperature coefficient (Positive temperature coefficient, PTC) electrically conductive composition technical field specifically is meant a kind of fire-retardant master granule, comprises the novel macromolecular PTC thermistor and the manufacture method thereof of this fire-retardant master granule.
Background technology
A certain amount of conducting particles; in filled polymer matrixes such as carbon black, graphite, carbon fiber, metal-powder, metal oxide; the polymer composite that obtains shows (the positive temperaturc coefficient) effect that has positive temperature coefficient PTC; the distinguishing feature of this material is exactly that its resistance varies with temperature and presents nonlinearities change; and in certain temperature range, show unique ptc characteristics; this family macromolecule matrix material with PTC effect can be made into the macromolecular thermosensitive resistor device, as the over-current protecting element of circuit.When lower temperature; the macromolecular thermosensitive resistor device presents lower resistivity; be elevated to it more than high molecular polymer fusing point but work as temperature, during also promptly so-called " shutoff " temperature, resistivity raises suddenly; it is very big that its resistance value becomes; just can make circuit be in a kind of approximate " opening circuit " state in the application circuit, thereby protect other element in the circuit, and after fault is got rid of; the temperature of thermistor descends, and its resistance value can return to the low resistance state again.
At present, high molecular PTC thermistor has been widely applied in the fields such as communication, electronic apparatus, Industry Control, automobile.For some field, use PTC themistor as communication, require it can bear high-voltage, PTC intensity height, advantage that resistance stability is good, otherwise in use have problems such as high electrical breakdown, energising front and back resistance change instability.For addressing this problem, many researchs filler and fire-retardant in the macromolecular thermosensitive resistor device has been arranged.
Fire retardant is of a great variety, can be divided into organic fire-retardant and inorganic combustion inhibitor.Inorganic combustion inhibitor decomposition temperature height, except flame retardant effect was arranged, the kind that the effect that also having suppresses to be fuming generates is mainly used had aluminium hydroxide, magnesium hydroxide, antimonous oxide etc.Aluminium hydroxide is to integrate fire-retardant, press down cigarette, fill the fire retardant of three big functions, does not produce toxic gas under nontoxic, no burn into good stability, the high temperature, and cheap, wide material sources.Magnesium hydroxide decomposes between 340 ℃～490 ℃, and Heat stability is good has good fire-retardant and smoke effect.Magnesium hydroxide fire retardant mechanism as fire retardant in matrix material is: the water outlet of magnesium hydroxide decomposes, absorb a large amount of latent heat simultaneously, thereby the temperature that suppresses material rises, continue its thermolysis and reduce combustionvelocity, this has just reduced the actual withstand temp of matrix material in flame, has to suppress the cooling effect that superpolymer decomposes and inflammable gas produces.The magnesium oxide that decomposes the back generation is good refractory materials, flowing of the supply of cut-out oxygen, prevention inflammable gas, help to improve the ability of resin opposing flame, and the heat decomposition temperature of magnesium hydroxide is up to 340 ℃, therefore magnesium hydroxide is very superior as its flame retardant properties of fire retardant, and the flame retardancy and smoke suppression that can be used for macromolecular materials such as polypropylene, polyethylene, polyvinyl chloride, terpolymer EP rubber and unsaturated polyester is suitable for the higher polyolefin plastics of processing temperature especially.
Inorganic combustion inhibitor such as magnesium hydroxide, aluminium hydroxide is used in the high molecular PTC thermistor in a large number, because these fire retardant good flame retardant property, so resistance to pressure and the PTC intensity that improves thermistor is played a role.
At present, the powdered fire retardants that adopt in the high molecular PTC mixture more, because the influence of factors such as state of the art, appointed condition or technological process control, problem such as when using powdery combustion inhibitor, have dispersed bad, poor, dust pollution, flame retardant effect is general and technology is loaded down with trivial details with the consistency of matrix resin.
JP11-283808 discloses a kind of PTC mixture, with 50-90% (parts by weight) unsaturated polyester or ethene is matrix resin, add the carbon black of 5-30%, add＜20% fire retardant simultaneously, the ptc material of making has and has good power on/off stability, change in resistance is less before and after power on/off, but this invention does not relate to the kind and the concrete consumption of fire retardant.CN1182942A discloses a kind of hydrolytic crosslinking method for preparing positive temperature coefficient thermistor, with the surperficial treated fire-retardant anti-electric-arc filler of 5-20% volume parts, i.e. Al (OH)
3And/or Mg (OH)
2Join in the matrix material, improved its anti-rush of current life-span, but fire-retardant anti-electric-arc filler Al (OH) in this patent
3And/or Mg (OH)
2Addition is 20% volume fraction nearly, may exist fire-retardant powder to mix inhomogeneous, bad dispersibility, problem that flame retarding efficiency is low when mixing in matrix, to high voltage withstanding property, the resistance stability generation detrimentally affect of macromolecular thermosensitive resistor device.Mentioned a kind of conductive polymer PTC matrix material among the patent US5227946 of U.S. Raychem company, having added the trade mark is that Hydral 705 is the filler of aluminium hydroxide, also exist to mix inhomogeneous, bad dispersibility, problem that flame retarding efficiency is low.
Summary of the invention
The objective of the invention is to have overcome above-mentioned shortcoming of the prior art, a kind of fire-retardant master granule is provided, comprises the novel macromolecular PTC thermistor and the manufacture method thereof of this fire-retardant master granule, this fire-retardant master granule fire retardant concentration height, flame retarding efficiency height and manufacturing are simple, the novel macromolecular PTC thermistor that comprises this fire-retardant master granule has high voltage withstanding, high PTC intensity and good resistance stability, and make easy, the efficient height.
To achieve these goals, in a first aspect of the present invention, provide a kind of fire-retardant master granule, be characterized in, described fire-retardant master granule comprises fire retardant and the vector resin that mixes.
Preferably, the ratio of the parts by weight of described vector resin and described fire retardant is 10: 90～30: 70.
Preferably, described fire retardant is selected from one or more in magnesium hydroxide, aluminium hydroxide, magnesium oxide, aluminum oxide, the antimonous oxide.
Preferably, described vector resin is selected from one or more in the polymkeric substance, ethylene-propylene copolymer, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer of ethylene-vinyl acetate, ethene, propylene, polyvinylidene difluoride (PVDF).
Preferably, described fire-retardant master granule also comprises oxidation inhibitor, coupling agent and lubricant, described oxidation inhibitor, described coupling agent and the described lubricated 0.5-10% that accounts for described fire retardant and described vector resin gross weight.
More preferably, described oxidation inhibitor is phenols or ester kind antioxidant, and described coupling agent is silane or titante coupling agent, and described lubricant is polyethylene wax or stearic acid.
In a second aspect of the present invention, a kind of manufacture method of above-mentioned fire-retardant master granule is provided, be characterized in, described fire retardant and described vector resin are mediated in kneader, be cooled to room temperature then, pulverize the back extruding pelletization.If fire-retardant master granule also comprises oxidation inhibitor, coupling agent and lubricant, then during fabrication oxidation inhibitor, coupling agent and lubricant and described fire retardant and described vector resin are mediated together.
In a third aspect of the present invention, a kind of novel macromolecular PTC thermistor is provided, comprise PTC chip and two metal foil electrode layers, two described metal foil electrode layers are attached to respectively on the two opposite surfaces of described PTC chip, be characterized in that described PTC chip comprises matrix resin, conductive filler material and according to the arbitrary described fire-retardant master granule of claim 1-6.
Preferably, described fire-retardant master granule is the 20-70% of the gross weight of described PTC chip.
More preferably, described fire-retardant master granule is the 30-60% of the gross weight of described PTC chip.
Further, described fire-retardant master granule is the 35-55% of the gross weight of described PTC chip.
Preferably, described matrix resin is selected from one or more in polypropylene, polyethylene, polyvinyl chloride, terpolymer EP rubber and the unsaturated polyester.
More preferably, described polyethylene is selected from one or more in new LDPE (film grade), linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), the ultrahigh molecular weight polyethylene(UHMWPE).
Preferably, described conductive filler material is selected from one or more in carbon black, carbon fiber, metal-powder, the metal oxide.
In a fourth aspect of the present invention, a kind of manufacture method of above-mentioned novel macromolecular PTC thermistor is provided, be characterized in, described matrix resin, described conductive filler material, described fire-retardant master granule melting mixing, cooling or pulverizing back mold pressing under the temperature that is higher than described matrix resin fusing point are obtained described PCT chip, pressing two described metal foil electrode layers obtain crude product respectively on the two opposite surfaces of described PCT chip, and heat-treat and cross-linking radiation.
Preferably, described melting mixing adopts mill, Banbury mixer or twin screw extruder, and described temperature is higher than 30-60 ℃ of described matrix resin fusing point.
Preferably, single screw extrusion machine or thermocompressor are adopted in described mold pressing, and the thickness of described PTC chip is 0.1-2.2mm.
Preferably, thermocompressor hot pressing is adopted in described pressing, and described hot pressed temperature is higher than fusing point 5-40 ℃ of described matrix resin, and pressure is 1-25MPa.
Preferably, described thermal treatment is that described crude product is placed 10min at the above 20-70 of the fusing point of described matrix resin ℃, slow again cool to room temperature, and rate of cooling is not higher than 30 ℃/min.
Preferably, described cross-linking radiation adopts gamma-rays or electron rays, and irradiation dose is 5-100Mrads.
Beneficial effect of the present invention is:
1, fire-retardant master granule of the present invention comprises fire retardant and the vector resin that mixes, and has fire retardant concentration height, good dispersity, and alternative powdered fire retardant has characteristics such as fire retardant concentration height, flame retarding efficiency height and technology thereof are simple;
2, fire-retardant master granule of the present invention is with matrix resin, conductive filler material mixing the time, can directly use, in matrix material, mix easilier, consistency is good, addition can be bigger, need not to make the flame retardant plastics particle after it and the plastics fusion, promptly can make further extrusion molding or molding etc. and be processed into needed product, overcome fire retardant performance in long-time the mixing and progressively descended, taken place easily the aged shortcoming, proof voltage, PTC intensity height and the resistance stability that improves high molecular PTC thermistor had tangible effect well;
3, high molecular PTC thermistor of the present invention has the high fire-retardant master granule of excellent blended fire retardant concentration owing to having introduced, thereby has proof voltage, PTC intensity height and the good characteristics of resistance stability.
Embodiment
In order more to be expressly understood technology contents of the present invention, describe in detail especially exemplified by following examples.
PCT intensity
PTC intensity is defined as resistivity maximum value ρ
MaxElectricalresistivity during with room temperature
RTThe logarithm of ratio, i.e. I
PTC=log (ρ
Max/ ρ
RT).High molecular PTC thermistor is placed baking oven, heat up with the speed of 2 ℃/min, 20～160 ℃ of temperature ranges are measured its resistance and are concerned with variation of temperature.
The power on/off circulation
Energising 1min, outage 2min, writes down the resistance of 25 power on/off circulations of 100 high molecular PTC thermistors front and back, and calculates resistance change rate and extreme difference as a circulation with this.With R
25Be designated as the resistance after the power on/off circulation 25 times, R
0Be the resistance before the power on/off circulation, then resistance change rate Δ R=(R
25-R
0)/R
0Be designated as Δ R as the resistance change rate maximum
Max, the minimum Δ R that is designated as
Min, extreme difference δ=Δ R then
Max-Δ R
Min
The action weather resistance
Under the 600V/3A starting condition, write down the resistance of withstand voltage 1 hour front and back of 100 high molecular PTC thermistors, and calculate resistance change rate and extreme difference.With R
1hrBe designated as the resistance after withstand voltage 1 hour under the 600V/3A starting condition, R
0Be the resistance before the voltage-withstand test, then resistance change rate Δ R=(R
1hr-R
0)/R
0Be designated as Δ R as the resistance change rate maximum
Max, the minimum Δ R that is designated as
Min, extreme difference δ=Δ R then
Max-Δ R
Min
Main raw material
Employed composition of composition such as following table 1 in following embodiment or comparative example:
Table 1PTC composition components
| Composition | Trade(brand)name | Characteristic |
| High density polyethylene(HDPE) | PetroChina Company Ltd. | Density is 0.955g/cm 3, melting index is 130 ℃ of 0.35g/10min fusing points |
| Carbon black | Columbian Chemical Co.； Raven 430 | 80～100ml/100g; Particle diameter 50～100m 2/g |
| Fire-retardant master granule series | Last ocean gloomy chemical industry company limited | Flame retardant agent content 70-90wt% |
| Magnesium hydroxide | Dalian Yatai Science and Technology New Material Co., Ltd. | Specific surface area 20-40m 2/g |
The prescription of the fire-retardant master granule of using among the embodiment is as shown in table 2.Production method is: in kneader, mediate earlier, be cooled to room temperature then, again through being crushed into irregular particle, and then in forcing machine, extrude, cooling, granulation, promptly obtain the fire-retardant master granule of fire retardant concentration up to 70-90wt%.
The feature of table 2 fire-retardant master granule
| Numbering | Carrier | Fire retardant | The weight part ratio of carrier and fire retardant |
| Fire-retardant master granule A | EVA | Mg(OH) 2 | 10∶90 |
| Fire-retardant master granule B | Ethylene-propylene copolymer | Mg(OH) 2 | 10∶90 |
| Fire-retardant master granule C | LDPE | Mg(OH) 2 | 10∶90 |
| Fire-retardant master granule D | Ethylene-ethyl acrylate copolymer | Antimonous oxide | 10∶90 |
| Fire-retardant master granule E | EVA | Mg(OH) 2 | 25∶75 |
| Fire-retardant master granule F | LDPE | Al(OH) 3 | 20∶80 |
| Fire-retardant master granule G | EVA | Mg(OH) 2 | 30∶70 |
Embodiment 1
(density is 0.955g/cm to select the 310g high density polyethylene(HDPE)
3, melting index is 0.35g/10min), 300g carbon black (80～100ml/100g, particle diameter 50～100m
2/ g), 430g fire-retardant master granule A.Carry out mixingly behind above-mentioned each component premix in mill, temperature is 185 ℃, makes the PTC chip; Be that 185 ℃, hot pressing pressure are the upper and lower surface that rides over the PTC chip under the 16MPa with metal electrode in hot pressing temperature on the thermocompressor, obtaining thickness is the macromolecular PTC thermistor crude product of 2mm.The macromolecular PTC thermistor crude product that makes is cut into the small pieces of 5mm * 5mm, in 190 ℃ baking oven, place 5min, then with the speed cool to room temperature of 2 ℃/min.With the small pieces gamma-rays after the thermal treatment is carried out cross-linking radiation, irradiation dose is 17.6Mrads.The baking oven of irradiated small pieces being put into again 190 ℃ is placed 5min then, then with the speed cool to room temperature of 2 ℃/min, promptly obtains novel macromolecular PTC thermistor device of the present invention.
Comparative example 1
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 390g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 2
(density is 0.955g/cm except selecting the 280g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) and 660g fire-retardant master granule A outside, all the other are with embodiment 1.
Comparative example 2
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 590g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 3
(density is 0.955g/cm except selecting the 330g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) and 210g fire-retardant master granule A outside, all the other are with embodiment 1.
Comparative example 3
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 190g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 4
(density is 0.955g/cm except selecting the 300g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and replacing fire-retardant master granule A with 360g fire-retardant master granule B, all the other are with embodiment 1.
Comparative example 4
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 320g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule B, all the other are with embodiment 1.
Embodiment 5
(density is 0.955g/cm except selecting the 230g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and replace fire-retardant master granule A with 490g fire-retardant master granule E.All the other are with embodiment 1.
Comparative example 5
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 370g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule E, all the other are with embodiment 1.
Embodiment 6
(density is 0.955g/cm except selecting the 210g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and replacing fire-retardant master granule A with 560g fire-retardant master granule E, all the other are with embodiment 1.
Comparative example 6
(density is 0.955g/cm except selecting the 350g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 420g magnesium hydroxide (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule E, all the other are with embodiment 1.
Embodiment 7
(density is 0.955g/cm except selecting the 300g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 480g fire-retardant master granule C (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 8
(density is 0.955g/cm except selecting the 300g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 470g fire-retardant master granule D (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 9
(density is 0.955g/cm except selecting the 220g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 520g fire-retardant master granule F (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
Embodiment 10
(density is 0.955g/cm except selecting the 180g high density polyethylene(HDPE)
3, melting index is 0.35g/10min) outside, and with 580g fire-retardant master granule G (particle diameter 2～15 μ m, specific surface area 20-50m
2/ g) replacing fire-retardant master granule A, all the other are with embodiment 1.
The The performance test results of the foregoing description and Comparative Examples sees Table 3 and table 4:
Table 3 is measured the performance variation of 100 high molecular PTC thermistors before and after 25 power on/off circulations
| Room temperature resistance (Ω) | Room temperature resistivity (Ω cm) | PTC intensity | Average resistance velocity of variation Δ R before and after 25 power on/off circulations, % | Resistance change extreme difference before and after 25 power on/off circulations, % | |
| Embodiment 1 | 7.25 | 9.06 | 7.0 | 12.28 | 8.25 |
| Comparative example 1 | 8.36 | 10.45 | 5.6 | 38.52 | 21.36 |
| Embodiment 2 | 6.14 | 7.68 | 7.3 | 16.29 | 9.55 |
| Comparative example 2 | 7.32 | 9.15 | 5.9 | 31.69 | 20.34 |
| Embodiment 3 | 7.58 | 9.48 | 6.7 | 18.21 | 11.42 |
| Comparative example 3 | 8.14 | 10.18 | 5.4 | 29.24 | 25.63 |
| Embodiment 4 | 6.50 | 8.13 | 6.9 | 15.23 | 7.56 |
| Comparative example 4 | 7.52 | 9.40 | 5.4 | 31.52 | 23.21 |
| Embodiment 5 | 8.21 | 10.26 | 6.7 | 18.76 | 9.65 |
| Comparative example 5 | 9.12 | 11.40 | 5.1 | 15.79 | 32.14 |
| Embodiment 6 | 7.58 | 9.48 | 7.2 | 8.84 | 8.54 |
| Comparative example 6 | 8.25 | 10.31 | 5.4 | 37.70 | 36.52 |
| Embodiment 7 | 932 | 11.65 | 6.5 | 10.73 | 12.25 |
| Embodiment 8 | 7.58 | 9.48 | 6.9 | 11.48 | 15.62 |
| Embodiment 9 | 8.56 | 10.70 | 6.4 | 13.08 | 12.84 |
| Embodiment 10 | 7.85 | 9.81 | 7.1 | 12.99 | 11.32 |
Table 4 is measured the performance variation of 100 high molecular PTC thermistors through following 1 hour front and back of 600V/3A starting condition
By table 3 and 4, can it is evident that, that the novel macromolecular PTC thermistor utensil of manufacturing of the present invention has is high voltage withstanding significantly, PTC intensity and resistance stability characteristic, the adding of described fire-retardant master granule is conspicuous to high voltage withstanding, PTC intensity and the resistance stability that improves PTC themistor.
To sum up, fire-retardant master granule fire retardant concentration height of the present invention, flame retarding efficiency height and manufacturing are simple, the novel macromolecular PTC thermistor that comprises the composition of this fire-retardant master granule has high voltage withstanding, high PTC intensity and good resistance stability, and make easy, the efficient height.
In this specification sheets, the present invention is described with reference to its certain embodiments.But, still can make various modifications and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, specification sheets and accompanying drawing are regarded in an illustrative, rather than a restrictive.
Claims (20)
1. a fire-retardant master granule is characterized in that, described fire-retardant master granule comprises fire retardant and the vector resin that mixes.
2. fire-retardant master granule according to claim 1 is characterized in that, the ratio of the parts by weight of described vector resin and described fire retardant is 10: 90～30: 70.
3. fire-retardant master granule according to claim 1 is characterized in that described fire retardant is selected from one or more in magnesium hydroxide, aluminium hydroxide, magnesium oxide, aluminum oxide, the antimonous oxide.
4. fire-retardant master granule according to claim 1, it is characterized in that described vector resin is selected from one or more in the polymkeric substance, ethylene-propylene copolymer, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate glycidyl ester copolymer of ethylene-vinyl acetate, ethene, propylene, polyvinylidene difluoride (PVDF).
5. fire-retardant master granule according to claim 1 is characterized in that described fire-retardant master granule also comprises oxidation inhibitor, coupling agent and lubricant, described oxidation inhibitor, described coupling agent and the described lubricated 0.5-10% that accounts for described fire retardant and described vector resin gross weight.
6. fire-retardant master granule according to claim 5 is characterized in that, described oxidation inhibitor is phenols or ester kind antioxidant, and described coupling agent is silane or titante coupling agent, and described lubricant is polyethylene wax or stearic acid.
7. the manufacture method of a fire-retardant master granule according to claim 1 is characterized in that, described fire retardant and described vector resin are mediated in kneader, is cooled to room temperature then, pulverizes the back extruding pelletization.
8. novel macromolecular PTC thermistor, comprise PTC chip and two metal foil electrode layers, two described metal foil electrode layers are attached to respectively on the two opposite surfaces of described PTC chip, it is characterized in that described PTC chip comprises matrix resin, conductive filler material and according to the arbitrary described fire-retardant master granule of claim 1-6.
9. novel macromolecular PTC thermistor according to claim 8 is characterized in that, described fire-retardant master granule is the 20-70% of the gross weight of described PTC chip.
10. novel macromolecular PTC thermistor according to claim 9 is characterized in that, described fire-retardant master granule is the 30-60% of the gross weight of described PTC chip.
11. novel macromolecular PTC thermistor according to claim 10 is characterized in that, described fire-retardant master granule is the 35-55% of the gross weight of described PTC chip.
12. novel macromolecular PTC thermistor according to claim 8 is characterized in that, described matrix resin is selected from one or more in polypropylene, polyethylene, polyvinyl chloride, terpolymer EP rubber and the unsaturated polyester.
13. novel macromolecular PTC thermistor according to claim 12, it is characterized in that described polyethylene is selected from one or more in new LDPE (film grade), linear low density polyethylene, medium-density polyethylene, high density polyethylene(HDPE), the ultrahigh molecular weight polyethylene(UHMWPE).
14. novel macromolecular PTC thermistor according to claim 8 is characterized in that, described conductive filler material is selected from one or more in carbon black, carbon fiber, metal-powder, the metal oxide.
15. the manufacture method of a novel macromolecular PTC thermistor according to claim 8, it is characterized in that, described matrix resin, described conductive filler material, described fire-retardant master granule melting mixing, cooling or pulverizing back mold pressing under the temperature that is higher than described matrix resin fusing point are obtained described PCT chip, pressing two described metal foil electrode layers obtain crude product respectively on the two opposite surfaces of described PCT chip, and heat-treat and cross-linking radiation.
16. the manufacture method of novel macromolecular PTC thermistor according to claim 15 is characterized in that, described melting mixing adopts mill, Banbury mixer or twin screw extruder, and described temperature is higher than 30-60 ℃ of described matrix resin fusing point.
17. the manufacture method of novel macromolecular PTC thermistor according to claim 15 is characterized in that, single screw extrusion machine or thermocompressor are adopted in described mold pressing, and the thickness of described PTC chip is 0.1-2.2mm.
18. the manufacture method of novel macromolecular PTC thermistor according to claim 15 is characterized in that, thermocompressor hot pressing is adopted in described pressing, and described hot pressed temperature is higher than fusing point 5-40 ℃ of described matrix resin, and pressure is 1-25MPa.
19. the manufacture method of novel macromolecular PTC thermistor according to claim 15, it is characterized in that, described thermal treatment is that described crude product is placed 10min at the above 20-70 of the fusing point of described matrix resin ℃, slow again cool to room temperature, and rate of cooling is not higher than 30 ℃/min.
20. the manufacture method of novel macromolecular PTC thermistor according to claim 15 is characterized in that, described cross-linking radiation adopts gamma-rays or electron rays, and irradiation dose is 5-100Mrads.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100520912A CN101560313A (en) | 2009-05-26 | 2009-05-26 | Flame-retardant master batch, novel macromolecular PTC thermistor containing flame-retardant master batch and manufacturing method thereof |
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|---|---|---|---|
| CNA2009100520912A CN101560313A (en) | 2009-05-26 | 2009-05-26 | Flame-retardant master batch, novel macromolecular PTC thermistor containing flame-retardant master batch and manufacturing method thereof |
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| CN101885873A (en) * | 2010-05-05 | 2010-11-17 | 深圳市联嘉祥科技股份有限公司 | Semi-conductive ethylene vinyl acetate (EVA) plastic for shielding and production method thereof |
| CN102093617A (en) * | 2010-12-30 | 2011-06-15 | 合肥工业大学 | Method for preparing composite conductive polyethylene carbon black material with improved positive temperature coefficient performance |
| CN102492170A (en) * | 2011-12-20 | 2012-06-13 | 广州市聚赛龙工程塑料有限公司 | Antimony trioxide master batch and preparation method thereof |
| CN102533161A (en) * | 2011-12-19 | 2012-07-04 | 庄晓曦 | Flame-retarding pressure-sensitive adhesive and preparation method thereof |
| CN103304938A (en) * | 2013-05-24 | 2013-09-18 | 安邦电气集团有限公司 | PTC (Positive Temperature Coefficient) thermistor base material and preparation method thereof |
| CN103465386A (en) * | 2013-09-18 | 2013-12-25 | 长园集团股份有限公司 | Preparation method of halogen-free and red-phosphorus-free flame-retardant heat shrinkable material |
| CN104693580A (en) * | 2015-03-18 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant masterbatch for ethylene-propylene-diene monomer and preparation method of halogen-free flame-retardant masterbatch |
| CN104774439A (en) * | 2015-04-29 | 2015-07-15 | 湖北三江船艇科技有限公司 | Additive type flame-retarded resin and making method thereof |
| CN105111569A (en) * | 2015-10-11 | 2015-12-02 | 江苏五信新材料科技有限公司 | Preparation method of antimony trioxide flame-retardant master batch |
| CN105206362A (en) * | 2014-06-23 | 2015-12-30 | 深圳市万瑞和电子有限公司 | Voltage-withstanding overcurrent self-recovery protector and production technology thereof |
| CN105206361A (en) * | 2014-06-23 | 2015-12-30 | 深圳市万瑞和电子有限公司 | Thermistor core material and production technology thereof |
| CN105936728A (en) * | 2016-06-21 | 2016-09-14 | 河北见喜新材料科技股份有限公司 | Manufacturing method of ultra-dispersed flame-retardant master batch |
| CN105989936A (en) * | 2016-07-07 | 2016-10-05 | 惠州市聚鼎电子有限公司 | Preparation method for PTC (Positive Temperature Coefficient) heat-sensitive material |
| CN106009355A (en) * | 2016-08-10 | 2016-10-12 | 安徽省宁国天成电工有限公司 | Graphene enhanced organosilicon/modified polystyrene composite PTC core material |
| CN107674332A (en) * | 2017-10-24 | 2018-02-09 | 江苏中鹏新材料股份有限公司 | A kind of environmental protection flame retardant master batch and preparation method thereof, application, fire proofing |
| CN110128787A (en) * | 2019-05-14 | 2019-08-16 | 武汉博奇玉宇环保股份有限公司 | A kind of glass fiber reinforced plastics composite material and preparation method thereof |
| CN111372335A (en) * | 2018-12-26 | 2020-07-03 | 弈禔股份有限公司 | Conductive heat-generating material and module using the same |
| CN112094449A (en) * | 2020-09-16 | 2020-12-18 | 东莞市竞沃电子科技有限公司 | Curie point adjustable PTC polymer conductive composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101885873B (en) * | 2010-05-05 | 2013-01-23 | 深圳市联嘉祥科技股份有限公司 | Semi-conductive ethylene vinyl acetate (EVA) plastic for shielding and production method thereof |
| CN101885873A (en) * | 2010-05-05 | 2010-11-17 | 深圳市联嘉祥科技股份有限公司 | Semi-conductive ethylene vinyl acetate (EVA) plastic for shielding and production method thereof |
| CN102093617A (en) * | 2010-12-30 | 2011-06-15 | 合肥工业大学 | Method for preparing composite conductive polyethylene carbon black material with improved positive temperature coefficient performance |
| CN102093617B (en) * | 2010-12-30 | 2012-06-27 | 合肥工业大学 | Method for preparing composite conductive polyethylene carbon black material with improved positive temperature coefficient performance |
| CN102533161A (en) * | 2011-12-19 | 2012-07-04 | 庄晓曦 | Flame-retarding pressure-sensitive adhesive and preparation method thereof |
| CN102492170B (en) * | 2011-12-20 | 2014-01-29 | 广州市聚赛龙工程塑料有限公司 | Preparation method of antimony trioxide master batch |
| CN102492170A (en) * | 2011-12-20 | 2012-06-13 | 广州市聚赛龙工程塑料有限公司 | Antimony trioxide master batch and preparation method thereof |
| CN103304938A (en) * | 2013-05-24 | 2013-09-18 | 安邦电气集团有限公司 | PTC (Positive Temperature Coefficient) thermistor base material and preparation method thereof |
| CN103304938B (en) * | 2013-05-24 | 2016-03-16 | 安邦电气集团有限公司 | PTC thermistor base material and preparation method thereof |
| CN103465386A (en) * | 2013-09-18 | 2013-12-25 | 长园集团股份有限公司 | Preparation method of halogen-free and red-phosphorus-free flame-retardant heat shrinkable material |
| CN105206361A (en) * | 2014-06-23 | 2015-12-30 | 深圳市万瑞和电子有限公司 | Thermistor core material and production technology thereof |
| CN105206362A (en) * | 2014-06-23 | 2015-12-30 | 深圳市万瑞和电子有限公司 | Voltage-withstanding overcurrent self-recovery protector and production technology thereof |
| CN104693580A (en) * | 2015-03-18 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant masterbatch for ethylene-propylene-diene monomer and preparation method of halogen-free flame-retardant masterbatch |
| CN104774439A (en) * | 2015-04-29 | 2015-07-15 | 湖北三江船艇科技有限公司 | Additive type flame-retarded resin and making method thereof |
| CN105111569A (en) * | 2015-10-11 | 2015-12-02 | 江苏五信新材料科技有限公司 | Preparation method of antimony trioxide flame-retardant master batch |
| CN105936728A (en) * | 2016-06-21 | 2016-09-14 | 河北见喜新材料科技股份有限公司 | Manufacturing method of ultra-dispersed flame-retardant master batch |
| CN105936728B (en) * | 2016-06-21 | 2018-04-24 | 河北见喜新材料科技股份有限公司 | A kind of ultra-dispersed flame retarding function master batch manufacture method |
| CN105989936A (en) * | 2016-07-07 | 2016-10-05 | 惠州市聚鼎电子有限公司 | Preparation method for PTC (Positive Temperature Coefficient) heat-sensitive material |
| CN106009355A (en) * | 2016-08-10 | 2016-10-12 | 安徽省宁国天成电工有限公司 | Graphene enhanced organosilicon/modified polystyrene composite PTC core material |
| CN107674332A (en) * | 2017-10-24 | 2018-02-09 | 江苏中鹏新材料股份有限公司 | A kind of environmental protection flame retardant master batch and preparation method thereof, application, fire proofing |
| CN111372335A (en) * | 2018-12-26 | 2020-07-03 | 弈禔股份有限公司 | Conductive heat-generating material and module using the same |
| CN110128787A (en) * | 2019-05-14 | 2019-08-16 | 武汉博奇玉宇环保股份有限公司 | A kind of glass fiber reinforced plastics composite material and preparation method thereof |
| CN112094449A (en) * | 2020-09-16 | 2020-12-18 | 东莞市竞沃电子科技有限公司 | Curie point adjustable PTC polymer conductive composite material and preparation method thereof |
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