CN101335124A - Polymer PTC heat sensitive material obtained by compound extruding method - Google Patents
Polymer PTC heat sensitive material obtained by compound extruding method Download PDFInfo
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- CN101335124A CN101335124A CNA2007100289153A CN200710028915A CN101335124A CN 101335124 A CN101335124 A CN 101335124A CN A2007100289153 A CNA2007100289153 A CN A2007100289153A CN 200710028915 A CN200710028915 A CN 200710028915A CN 101335124 A CN101335124 A CN 101335124A
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Abstract
The invention discloses a method for preparing macromolecule PTC heat sensitive material by utilizing an extrusion laminating method, which comprises the following steps: (1) master batch of the PTC heat sensitive material is prepared as a matter of routine; (2) by adopting the extrusion laminating method, the master batch obtained in step (1) is laminated with metal foil at an extrusion die head by molten resin; (3) the composite membrane obtained in step (2) is cooled on a quenching roller and then wrapped up and parted off to form a semi-manufactured membrane; (4) the composite membrane obtained in step (3) is crosslinked by irradiation. The macromolecule PTC heat sensitive material, prepared by adopting the extrusion laminating method of the invention, is applicable to mechanized production and has low cost and high efficiency. The prepared macromolecule PTC heat sensitive material increases the composite forces of metal electrodes and macromolecule matrixes and can be wrapped up. Furthermore, products can be produced into small ones.
Description
Technical field
The present invention relates to a kind of high molecular PTC heat sensitive material, its preparation method with and uses thereof.
Background technology
As everyone knows, in crystallinity or hemicrystalline high molecular polymer, add the conduction factor, can show positive temperature coefficient (Positive Temperature Coefficient is PTC) characteristic: resistivity can increase fast with the rising of temperature in a relatively shorter temperature range, because high molecular PTC thermistor has lower initial resistance, and nearly 5 orders of magnitude increased sharply in the time faster, can prevent effectively that circuit from breaking down, as short circuit, overlap joint, when situations such as induction take place, avoid producing in the circuit destruction of big electric current to other critical elements in the circuit.After fault was got rid of, the temperature of thermistor descended, and its resistance returns to the low resistance state, does not need manually to change, so macromolecular PTC thermistor is called resettable fuse again.
This temperature switch effect that high molecular PTC heat sensitive material had can be used to many occasions such as circuit overcurrent protection, Automatic Control Temperature Heater.As substitute, be widely applied in the various fields such as communication, computer, automobile, Industry Control, household electrical appliance as disposable fuse; As companion's hot product, as the effect of accompanying-heat cable in many outdoor studies fields such as oil drilling, carried of crude oil, chemical, railway transportation, telecommunications transmission, gardens gardening performance uniqueness.
A kind of method for manufacturing multi-layer combined macromolecular PTC chip is disclosed in the Chinese patent application 200510112415.9.The high polymer PTC chip multi-layer compound structure of this patent application, comprise the high molecular PTC material layer and be compounded in the electrode of material layer outside, wherein, the high molecular PTC material layer can be two layers or more, and can add between each high molecular PTC material layer has the copper sheet layer.Its advantage is: adopt the prepared high molecular PTC thermistor chip of this structure, can effectively reduce the resistance drift after the recovery.But what its preparation method adopted is pressing, that is: this high polymer PTC chip multi-layer compound structure is to suppress by the combination electrode sheet on macromolecule core and top layer to form.These class methods are particularly suitable for preparing the electronic component of monolithic or some, but are not suitable for preparing the PTC materials of electronic components of can reeling.Similar method is also disclosed in the Chinese patent 02137202.0,02137203.9,02145483.3.
Chinese patent application 200610026057 also discloses a kind of high molecular PTC heat sensitive material and preparation method thereof, and it comprises following step:
1. the masterbatch for preparing the PTC thermistor routinely;
2. above-mentioned masterbatch is made film;
3. the film that 2. step is made carries out surface treatment, improves surface tension;
4. plate metal electrode on surface-treated film two sides;
The film that 5. will plate metal electrode carries out cross-linking radiation.
The method of above-mentioned patent application can be prepared the PTC product that can reel, thereby has improved production efficiency of products.But owing to adopt the mode combination electrode of electroplating, the big flow process more complicated of equipment input, and normal compound defective tightness because of metal electrode and polymer matrix, increased the resistance under the thermistor normal temperature, and be difficult to guarantee the uniformity of the coat of metal, resistance between 1-10 Ω, is difficult to reach the instructions for use of thermistor m Ω level usually.
Summary of the invention
The purpose of this invention is to provide high molecular PTC heat sensitive material that a kind of softness can reel and the preparation method that can produce this high molecular PTC heat sensitive material.
For realizing the purpose of foregoing invention, on the one hand, the invention provides a kind of preparation method of the high molecular PTC heat sensitive material that comprises the steps:
1. prepare the needed macromolecule masterbatch of high molecular PTC heat sensitive material;
2. with step 1. the macromolecule masterbatch of gained extrude through extruder, and the molten resin of metal forming being extruded with extruder at the extrusion die place of extruder carries out compoundly, makes composite membrane;
3. the laminated film that 2. step is made cools off on sharp cooling roll, rolling then, cut the semi-finished product film;
4. with step 3. the laminated film of gained carry out cross-linking radiation.
Wherein, 1. step adopts any prior art such as mixer mixing, makes masterbatch with resinous as composition blend granulations such as HDPE, LLDPE, carbon black, antioxidant and other function additives.
Preferably, step 2. in, at the extrusion die place, all compound metal forming that goes up in the molten resin both sides that extruder is extruded.More preferably, step 2. in, adopt the mode of two rollers extruding, molten resin and left and right sides double layer of metal paper tinsel that extruder is extruded is compound.For example, 2. step installs two volume metal formings volumes in advance in the extrusion die both sides, simultaneously in being equipped with the plasticizing system of single screw extrusion machine or double screw extruder, with the masterbatch plastifying fusion of step in 1., reach the extrusion die place through tube connector, compound in die head place metal forming and molten resin.
3. step with also being in the resin of molten condition in the laminated film of step in 2., is cooled off on the chilling roller, and is flattened under the pressure of pressure roller, and rolling is then cut and made the semi-finished product film.The 3. middle chilling roll temperature of step can be controlled between 20～90 ℃.
The 4. described irradiation dose of step can be with reference to existing literature or prior art.Usually with above-mentioned compound thermosensitive film gamma-rays (Co
60) or electron beam to irradiate crosslinked, dosage is 5～100Mrad.
In addition, the extruder that adopted in 2. of step can be single screw extrusion machine or double screw extruder.
On the other hand, the present invention also provides a kind of high molecular PTC heat sensitive material, this high molecular PTC heat sensitive material is to adopt said method laminated film that make, that can reel, this laminated film is compounded with metal forming and forms on macromolecular material, wherein, the thickness of laminated film is 10-300 μ m, and width is 100mm-5m, and metal foil thickness is 5-200 μ m.
Preferably, the thickness of laminated film is that 10-100 μ m is thin; The thickness of metal forming is 10-100 μ m.
Further preferably, on the upper and lower top layer of above-mentioned high molecular PTC heat sensitive material laminated film, all be compounded with metal forming.
The present invention, metal forming can be aluminium foil, Copper Foil, tinfoil paper, also can be other Alloy Foil.
Thermo-sensitive material laminated film of the present invention can be made the PTC thermistor, particularly can be used to make low resistance, undersized thermistor by winding method; The planar graph that also can be made into arbitrary shape is as the heating occasion that is used for pipeline heating, floor heating, electric blanket or other form from the temperature control heating element.
Preparation method of the present invention successfully is applied to filming technology the preparation field of PTC thermo-sensitive material first, and each step among the preparation method is simple, all can realize on existing machinery, so can realize mechanization, suitability for industrialized production, has the high characteristics of efficient.
Compared with prior art, high molecular PTC temperature-sensitive laminated film of the present invention has the following advantages: it is lower that (1) can produce resistance, the thermistor that size is littler; (2) saved the technical process of core sheet surface treatment (as corona); (3) under friendly more environment, make product, avoid producing the environmental contaminants possibility; (4) have outstanding high efficiency, energy savings, cost is more low-cost.Adopt technology production temperature-sensitive laminated film of the present invention, not only operation is few, and the mechanization degree raising, and the production capacity of plant equipment is all bigger, can realize high efficiency, low-cost production.Simultaneously, in laminated film of the present invention, film core and metal electrode have good coating performance.
Description of drawings
Fig. 1 is for adopting a kind of schematic representation of apparatus of extrusion composite technology of the present invention, and among the figure, the implication of each Reference numeral is:
1 parallel dual-screw extruding machine, 2 T pattern heads, 3 fused film
4 metal formings volume (both sides each one), 5 metal formings, 6 pressure rollers
7 sharp cooling rolls, 8 laminated films, 9 deflector rolls
10 nip rollss, 11 wind-up rolls
Embodiment
Further specify the present invention below in conjunction with embodiment, but the present invention is not limited in these concrete execution modes.
Wherein, the prescription of the macromolecule masterbatch that is adopted among each embodiment is as shown in table 1:
Table 1 unit: % (weight ratio)
Embodiment 1
To join in the extruder complex group by the masterbatch that prescription, employing conventional method in the table 1 make, equipment therefor as shown in Figure 1.Masterbatch is extruded through double screw extruder and is molten (melt processing temperature is 200～240 ℃), reach extrusion die place (die head place temperature is 190～230 ℃) through tube connector, the two-layer aluminium foil of the molten resin and the left and right sides is compound at the die head place with the mode of two roller extruding, through 30～40 ℃ chilling roller, obtaining thickness is that 50 μ m, width are the film of 1.5m.Again with this thermosensitive film gamma-rays (Co
60) irradiation, dosage is 50～80Mrad, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 2
Raw material in the table 1 directly extruded through single screw rod or double screw extruder then through mixer mixing be molten (melt processing temperature is 200～240 ℃), reach extrusion die place (die head place temperature is 190～230 ℃) through tube connector, the two-layer Copper Foil of the molten resin and the left and right sides is compound at the die head place with the mode of two roller extruding, through 80～100 ℃ chilling roller, obtaining thickness is that 50 μ m, width are the film of 1.5m.With this thermosensitive film electron beam irradiation, dosage is 50～80Mrad again, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 3
Prepared masterbatch in the table 1 is joined in the extruder complex group, masterbatch is extruded through single screw rod or double screw extruder and is molten (melt processing temperature is 200～240 ℃), reach extrusion die place (die head place temperature is 190～230 ℃) through tube connector, the two-layer aluminium foil of the molten resin and the left and right sides is compound at the die head place with the mode of two roller extruding, through 80～100 ℃ chilling roller, obtaining thickness is that 100 μ m, width are the film of 1.0m.Again with this thermosensitive film gamma-rays (Co
60) irradiation, dosage is 50～80Mrad, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 4
Raw material in the table 1 directly extruded through single screw rod or double screw extruder then through mixer mixing be molten (melt processing temperature is 200～240 ℃), reach extrusion die place (die head place temperature is 190～230 ℃) through tube connector, the two-layer Copper Foil of the molten resin and the left and right sides is compound at the die head place with the mode of extruding, through 80～100 ℃ chilling roller, obtaining thickness is that 100 μ m, width are the film of 1.0m.With this thermosensitive film electron beam irradiation, dosage is 50～80Mrad again, promptly makes high molecular PTC thermosensitive film of the present invention.
Test case 1
Embodiment 1 prepared thermosensitive film is cut into length and width respectively is the 5mm square, two lead-in wires of burn-oning on two surfaces are respectively made thermistor.The resistance that records under this resistance normal temperature with resistance meter is 2.～3m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5200 Ω.
Embodiment 2 prepared thermosensitive films are cut into length and width respectively are the 5mm square, two lead-in wires of burn-oning on two surfaces are respectively made thermistor.The resistance that records under this resistance normal temperature with resistance meter is 1m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 3800 Ω.
Embodiment 3 prepared thermosensitive films are cut into length and width respectively are the 5mm square, two lead-in wires of burn-oning on two surfaces are respectively made thermistor.The resistance that records under this resistance normal temperature with resistance meter is 4m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5000 Ω.
Embodiment 4 prepared thermosensitive films are cut into length and width respectively are the 5mm square, two lead-in wires of burn-oning on two surfaces are respectively made thermistor.The resistance that records under this resistance normal temperature with resistance meter is 1m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5100 Ω.
Test case 2
It is 5mm that embodiment 1 and embodiment 2 prepared thermosensitive films are cut into width, the rectangle of long 20mm.Respectively at the different surfaces at two ends two lead-in wires of burn-oning.Again this rectangle and onesize dielectric film polyester film are stacked and reel, obtain wide for 5mm, diameter be the resistance of 3mm.Record resistance under these resistance normal temperature with resistance meter, be placed on again in 150 ℃ of baking ovens after 2 minutes, record its resistance.The result is as shown in table 2:
Table 2
| Embodiment | Normal temperature resistance (m Ω) | 150 ℃ of resistance (Ω) |
| 1 | 0.4 | 1000 |
| 2 | 7.0 | 5800 |
| 3 | 3. | 5600 |
| 4 | 2.3 | 5700 |
Claims (9)
1, a kind of method for preparing high molecular PTC heat sensitive material, this method comprises following step:
1. prepare the needed macromolecule masterbatch of high molecular PTC heat sensitive material;
2. with step 1. the macromolecule masterbatch of gained extrude through extruder, and the molten resin of metal forming being extruded with described extruder at the extrusion die place of described extruder carries out compoundly, makes composite membrane;
3. the laminated film that 2. step is made cools off on sharp cooling roll, rolling then, cut the semi-finished product film;
4. with step 3. the laminated film of gained carry out cross-linking radiation.
2, the method for claim 1 is characterized in that, step 2. in, at described extrusion die place, the compound metal forming that goes up in the molten resin both sides that described extruder is extruded.
3, method as claimed in claim 2 is characterized in that, step 2. in, adopt the mode of two rollers extruding, molten resin and left and right sides double layer of metal paper tinsel that described extruder is extruded is compound.
4, the method for claim 1 is characterized in that, the chilling roll temperature of step described in 3. is 20～90 ℃.
5, the method for claim 1 is characterized in that, the extruder that step is adopted in 2. is single screw extrusion machine or double screw extruder.
6, a kind of high molecular PTC heat sensitive material, it is characterized in that, the laminated film that described high molecular PTC heat sensitive material makes, can reel by the described method of one of claim 1-5, this laminated film is compounded with metal forming and forms on macromolecular material, wherein, the thickness of described laminated film is 10-300 μ m, and width is 100mm-5m; Described metal foil thickness is 5-200 μ m.
7, high molecular PTC heat sensitive material as claimed in claim 6 is characterized in that, the upper and lower top layer of described laminated film all is compounded with described metal forming.
As claim 6 or 7 described high molecular PTC heat sensitive materials, it is characterized in that 8, described metal forming is aluminium foil, Copper Foil, tinfoil paper or Alloy Foil.
9, preparing thermal sensitivity resistance or the application in the temperature control heating element as the described high molecular PTC heat sensitive material of one of claim 6-8.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100289153A CN101335124A (en) | 2007-06-29 | 2007-06-29 | Polymer PTC heat sensitive material obtained by compound extruding method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100289153A CN101335124A (en) | 2007-06-29 | 2007-06-29 | Polymer PTC heat sensitive material obtained by compound extruding method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423952A (en) * | 2011-08-31 | 2012-04-25 | 常州日月机械有限公司 | Production method and device of waterproof rolled material |
| CN102511066A (en) * | 2009-09-29 | 2012-06-20 | 整合公司 | Positive temperature coefficient heating elements and their manufacturing |
| CN102522171A (en) * | 2011-12-31 | 2012-06-27 | 上海长园维安电子线路保护股份有限公司 | PTC (positive temperature coefficient) ring production method |
| CN110791000A (en) * | 2019-09-29 | 2020-02-14 | 芜湖凯龙电子科技有限公司 | Preparation method of novel PPTC (polymeric positive temperature coefficient) for double-matrix lithium battery |
| CN115416325A (en) * | 2022-09-01 | 2022-12-02 | 马栋才 | Continuous production line for automobile foot pads |
-
2007
- 2007-06-29 CN CNA2007100289153A patent/CN101335124A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102511066A (en) * | 2009-09-29 | 2012-06-20 | 整合公司 | Positive temperature coefficient heating elements and their manufacturing |
| US20120175362A1 (en) * | 2009-09-29 | 2012-07-12 | Erik Mikkelsen | Positive Temperature Coefficient Heating Elements and Their Manufacturing |
| US9392645B2 (en) | 2009-09-29 | 2016-07-12 | Conflux Ab | Positive temperature coefficient heating elements and their manufacturing |
| EP2483896A4 (en) * | 2009-09-29 | 2017-08-02 | Conflux AB | Positive temperature coefficient heating elements and their manufacturing |
| CN102423952A (en) * | 2011-08-31 | 2012-04-25 | 常州日月机械有限公司 | Production method and device of waterproof rolled material |
| CN102522171A (en) * | 2011-12-31 | 2012-06-27 | 上海长园维安电子线路保护股份有限公司 | PTC (positive temperature coefficient) ring production method |
| CN110791000A (en) * | 2019-09-29 | 2020-02-14 | 芜湖凯龙电子科技有限公司 | Preparation method of novel PPTC (polymeric positive temperature coefficient) for double-matrix lithium battery |
| CN115416325A (en) * | 2022-09-01 | 2022-12-02 | 马栋才 | Continuous production line for automobile foot pads |
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Open date: 20081231 |