CN101333299A - Film lamination method and high molecular PTC heat sensitive material prepared by the method - Google Patents
Film lamination method and high molecular PTC heat sensitive material prepared by the method Download PDFInfo
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- CN101333299A CN101333299A CNA2007100289168A CN200710028916A CN101333299A CN 101333299 A CN101333299 A CN 101333299A CN A2007100289168 A CNA2007100289168 A CN A2007100289168A CN 200710028916 A CN200710028916 A CN 200710028916A CN 101333299 A CN101333299 A CN 101333299A
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- ptc heat
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Abstract
The invention discloses a method for preparing macromolecule PTC thermo-sensitive material, including the following steps: 1)preparing a film substrate for PTC thermo-sensitive material normally; 2), dry laminating the film substrate with a metal foil to make a semi-finished film; 3) conducting aging treatment in a thermostatic chamber to the composite film prepared in step 2); 4)conducting radiation crosslinking to the composite film prepared in step 3). Macromolecule PTC thermo-sensitive resistors made through the method are suitable for mechanical production and are low in cost and high in efficiency. The macromolecule PTC thermo-sensitive material made through the method increases the bonding force between a metal electrode and the macromolecule substrate, thus simplifying production process and reducing equipment investment. The macromolecule PTC thermo-sensitive material can be rolled and can be made into small products.
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 safety 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, transportation by railroad, 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 combined electrode sheet on polymer core and top layer to form.These class methods are particularly suitable for preparing the electronic component of monolithic or some amount, 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 galvanized mode combined electrode, the big flow process more complicated of equipment input, and normal compound undertighten because of metal electrode and polymer matrix, increased the resistance under the thermistor normal temperature, and be difficult to guarantee the homogeneity of metal plating, resistance between 1-10 Ω, is difficult to reach the service requirements 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 film substrate of high molecular PTC heat sensitive material;
2. by the dry method composite methods, film substrate that 1. step is made and tinsel are carried out compound, make half-finished laminated film;
3. the laminated film that 2. step is obtained carries out ageing treatment in thermostatic chamber;
4. the laminated film that 3. step is obtained carries out cross-linking radiation.
Wherein, step can be with the masterbatch of selecting for use in 1., through conventional mode such as curtain coating, stretching, blown film, prepare the required film substrate of PTC thermo-sensitive material.
Preferably, the dry method composite methods of step in 2. is Method for bonding, and this method can be coated electro-conductive adhesive by the both sides at film substrate, carries out compound with tinsel then.For example, can pass through coating machine, viscose glue roller and other mode, at the both sides of film substrate coating last layer electro-conductive adhesive.
Wherein, electro-conductive adhesive can be the polyurethane adhesive of two-pack or single component, wherein added carbon black, copper powder, nickel powder, silver powder or polymer conductive filler materials such as other metal powder and polyaniline.For the flowability that realizes that adhesive system is good, wetting ability needs the good certain amount of solvent of proportioning, as dimethylbenzene, acetone, ethyl acetate etc.After coating conductive resin, in the both sides of film substrate compound on tinsel (electrode), make half-finished laminated film.
3. step is placed on constant temperature in the thermostatic chamber, constant humidity after for some time with the laminated film that step obtains in 2., for example 1～7 day, takes out standby.The Controllable Temperature of thermostatic chamber is between 20～90 ℃.
The irradiation dose of step in 4. can be with reference to prior art.Usually with above-mentioned compound thermosensitive film gamma-rays (Co
60) or electron beam to irradiate crosslinked, dosage is 5～100Mrad.
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 aforesaid method laminated film that make, that can reel, this laminated film is compounded with tinsel 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 tinsel 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 tinsel.
The present invention, tinsel 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 unit.
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 mechanize, 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 technological process of core sheet surface treatment (as corona); (3) under friendly more environment, make product, avoid producing the environmental pollutant possibility; (4) have outstanding high-level efficiency, save energy, 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 mechanical means is all bigger, can realize high-level 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 composite dry process of the present invention, and among the figure, the implication of each Reference numeral is:
1 masterbatch film substrate, 2 adhesive solvent grooves, 3 viscose glue rollers
4 deflector rolls, 5 tinsels, 6 supporting rolls
7 pressure rollers, 8 nip rolls, 9 wind-up rolls
10 drying units, 11 pressure rollers
Embodiment
Further specify the present invention below in conjunction with embodiment, but the present invention is not limited in these concrete embodiments.
Wherein, the prescription of the polymer masterbatch that is adopted among each embodiment is as shown in table 1, and the prescription of electro-conductive adhesive is as shown in table 2.
Table 1 unit: % (weight ratio)
Table 2 unit: % (weight ratio)
Embodiment 1
To make thickness through curtain coating by the masterbatch that table 1 prescription makes is the film substrate of 2.0m for the 30um width, and it is compound to carry out dry method then in device shown in Figure 1.Film substrate is through the coating unit, electro-conductive adhesive (its prescription is as shown in table 2) in the coating of film substrate one side, then at the compound last layer aluminium foil of a side that scribbles electro-conductive adhesive, a compound rear flank adopts above-mentioned same mode at the compound good aluminium foil of the opposite side of film substrate, make half-finished laminated film, this half-finished laminated film was put into 40-80 ℃ thermostatic chamber after 2 days, again with this laminated film electron beam irradiation, dosage is 50～80Mrad, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 2
The prepared masterbatch of table 1 prescription is joined high-low pressure blown film unit, the extruded film pipe blasts pressurized air through vane, makes film pipe inflation, makes it cooling and shaping by formed frame again, flatten the film pipe with collapser then, make thickness and be that 30um, film are wide is the film substrate of 2.0m.This film substrate is through the coating unit, electro-conductive adhesive (its prescription is as shown in table 2) in the side coating of film substrate, then at the compound last layer aluminium foil of a side that scribbles electro-conductive adhesive, a compound rear flank adopts above-mentioned same mode at the compound good aluminium foil of the opposite side of film substrate, makes half-finished laminated film.This half-finished laminated film was put into 40-80 ℃ thermostatic chamber after 2 days, again with this laminated film gamma-rays (Co
60) irradiation, dosage is 50～80Mrad, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 3
To make thickness through curtain coating by the prepared masterbatch of prescription in the table 1 is the film substrate of 2.0m for the 100um width.This film substrate is through the coating unit, electro-conductive adhesive (its prescription is as shown in table 2) in the side coating of film substrate, then at the compound last layer aluminium foil of a side that scribbles electro-conductive adhesive, a compound rear flank adopts above-mentioned same mode at the compound good aluminium foil of the opposite side of film substrate, makes half-finished laminated film.This half-finished laminated film was put into 40-80 ℃ thermostatic chamber after 2 days, and again with this laminated film electron beam irradiation, dosage is 50-80Mrad, promptly makes high molecular PTC thermosensitive film of the present invention.
Embodiment 4
To make thickness through curtain coating by the prepared masterbatch of prescription in the table 1 is the film substrate of 2.0m for the 100um width.This film substrate is through the coating unit, electro-conductive adhesive (its prescription is as shown in table 2) in the side coating of film substrate, then at the compound last layer aluminium foil of a side that scribbles electro-conductive adhesive, a compound rear flank adopts above-mentioned same mode at the compound good aluminium foil of the opposite side of film substrate, makes half-finished laminated film.This half-finished laminated film was put into 40 ℃ thermostatic chamber after 2 days, again with this laminated film gamma-rays (Co
60) irradiation, dosage is 50-80Mrad, 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 5.1m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5500 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 4m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5200 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 7m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5100 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 8m Ω.Be placed in 150 ℃ of baking ovens after 2 minutes, recording its resistance is 5600 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 insulating 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 3:
Table 3
| Embodiment | Normal temperature resistance (m Ω) | 150 ℃ of resistance (Ω) |
| 1 | 4.7 | 1000 |
| 2 | 3.5 | 5800 |
| 3 | 5.1 | 5600 |
| 4 | 6.3 | 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 film substrate of high molecular PTC heat sensitive material;
2. by the dry method composite methods, film substrate that 1. step is made and tinsel are carried out compound, make half-finished laminated film;
3. the laminated film that 2. step is obtained carries out ageing treatment in thermostatic chamber;
4. the laminated film that 3. step is obtained carries out cross-linking radiation.
2, the method for claim 1 is characterized in that, the dry method composite methods of step described in 2. is Method for bonding, and it is to coat electro-conductive adhesive by the both sides at described film substrate, carries out compound with described tinsel then.
3, method as claimed in claim 2 is characterized in that, described electro-conductive adhesive comprises polyurethane adhesive or epoxyn, conductive filler material and the solvent of two-pack or single component.
4, method as claimed in claim 3 is characterized in that, described conductive filler material is carbon black, copper powder, nickel powder, silver powder and/or organism conductive filler material.
5, preparation method as claimed in claim 1 is characterized in that, step 3. described in the temperature of thermostatic chamber be 20～90 ℃, the treatment time of described ageing treatment is 1～7 day.
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 tinsel 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 tinsel.
As claim 6 or 7 described high molecular PTC heat sensitive materials, it is characterized in that 8, described tinsel is aluminium foil, Copper Foil, tinfoil paper or Alloy Foil.
9, preparing thermo-sensitivity resistance or the application in the temperature control heating unit as the described high molecular PTC heat sensitive material of one of claim 6-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100289168A CN101333299A (en) | 2007-06-29 | 2007-06-29 | Film lamination method and high molecular PTC heat sensitive material prepared by the method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100289168A CN101333299A (en) | 2007-06-29 | 2007-06-29 | Film lamination method and high molecular PTC heat sensitive material prepared by the method |
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| CN101333299A true CN101333299A (en) | 2008-12-31 |
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| CNA2007100289168A Pending CN101333299A (en) | 2007-06-29 | 2007-06-29 | Film lamination method and high molecular PTC heat sensitive material prepared by the method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477839A (en) * | 2020-05-26 | 2020-07-31 | 苏州凌威新能源科技有限公司 | Manufacturing method of battery pole piece and battery pole piece |
| CN115056517A (en) * | 2022-03-24 | 2022-09-16 | 浙江大铭新材料股份有限公司 | Manufacturing process of PTC heating film |
-
2007
- 2007-06-29 CN CNA2007100289168A patent/CN101333299A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477839A (en) * | 2020-05-26 | 2020-07-31 | 苏州凌威新能源科技有限公司 | Manufacturing method of battery pole piece and battery pole piece |
| CN115056517A (en) * | 2022-03-24 | 2022-09-16 | 浙江大铭新材料股份有限公司 | Manufacturing process of PTC heating film |
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Open date: 20081231 |