CN101353473A - Highly transparent flame-retardant polycarbonate material, film and sheet material products thereof - Google Patents
Highly transparent flame-retardant polycarbonate material, film and sheet material products thereof Download PDFInfo
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- CN101353473A CN101353473A CNA2008100214753A CN200810021475A CN101353473A CN 101353473 A CN101353473 A CN 101353473A CN A2008100214753 A CNA2008100214753 A CN A2008100214753A CN 200810021475 A CN200810021475 A CN 200810021475A CN 101353473 A CN101353473 A CN 101353473A
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Abstract
The invention discloses a high-transparent flame retarding polycarbonate material and a membrane and sheet product thereof. The high-transparent flame retarding polycarbonate material contains polycarbonate and other addition agents, which is characterized in that: the high-transparent flame retarding polycarbonate contains an environment-protecting brominated flame retardant. The high-transparent flame retarding polycarbonate provided by the invention has good flame retardance and good impact resistance; compared with the common heating-emission flame retarding polycarbonate material, the flame retarding polycarbonate also reduces toxicity when being exposed to high temperature. The membrane or sheet material processed by the high-transparent flame retarding polycarbonate has the transparency of higher than 90 percent, and the membrane with flame retarding thickness of 0.25mm reaches the UL94-V0 grade standard.
Description
Technical field
The present invention relates to a kind of highly transparent flame-retardant polycarbonate material and film thereof and sheet material products.This kind highly transparent flame-retardant polycarbonate material flame retarding efficiency height, transparency is good, is used to produce high environmentally-friendly transparent anti-flaming polycarbonate ester film and sheet material.
Background technology
Polycarbonate (PC) is one of widely used five large-engineering plastics, have the mechanics of aggregative equilibrium, electric and resistance toheat, shock strength and the creep resistant with excellence is celebrated the transmittance height especially, mechanical property is good, and particularly impelling strength is best in engineering plastics.Because the premium properties of PC, its goods and intermingling material thereof have obtained to use widely in industries such as electronics, electrical equipment, machinery, automobile, weaving, light industry and buildings.
Polycarbonate (PC) has certain self-extinguishing, can emit CO during burning
2, its flame retardant properties is better than general plastics.But some fire-retardant demanding occasion then needs it further flame-retardant modified.At present in flame-retardant modified, the technology of normal employing is added halogenated flame retardant and phosphorus flame retardant exactly both at home and abroad, and halogenated flame retardant has characteristics such as flame retarding efficiency height, flame retardant properties are good.But some halogen flame exists for environment and the deleterious material of HUMAN HEALTH, particularly in combustion processes.And phosphorus flame retardant seriously causes the physicals of material to descend after adding in the polycarbonate, and the polycarbonate for the processing film-grade shows particularly outstandingly especially.Simultaneously, also there is " bottle strength " phenomenon to a certain extent in the flame retarding efficiency of phosphorus flame retardant, shows the film product that is used to process as thin as a wafer especially, and flame retardant properties can't reach the UL94-VO level.Therefore research and develop the environmental-protection flame-retardant PC with excellent comprehensive performance is the problem of paying much attention to both at home and abroad always.
Fire retardant is that a class can stop polymer materials to be ignited or suppresses the auxiliary agent of propagation of flame, can be divided into addition type and response type according to its using method, and additive flame retardant is widely used because of it is easy to use.At present, the fire retardant that adds in polycarbonate mainly contains halogen flame and phosphorus flame retardant, as tetrabromo-bisphenol, hexabromobenzene, red phosphorus, phosphoric acid ester; The fire retardant that these are conventional, because flame retarding efficiency is low, generally to reach certain fire-retardant requirement, consumption is all bigger, this just will worsen the original good mechanical property of superpolymer base material, electric property and thermostabilitys such as polycarbonate, the cigarette amount or the toxic gas volume that generate when increasing superpolymer burning or pyrolysis inevitably.
Except that the fire retardant of routine, other has the patent documentation report, the very effectively fire retardant that can be used for polycarbonate also has organic aromatic sulfonic acid salt, as aromatic sulfonic acid, arone sulfonic acid, fragrant thiosulfonic acid, aromatic ester sulfonic acid etc. and the basic metal or the alkaline earth salt that have the fragrant sulfone sulfonic acid of electron withdrawing group.This based flame retardant, especially the basic metal or the alkaline earth salt that have the fragrant sulfone sulfonic acid of electron withdrawing group, it is little that its superiority is embodied in required addition, the flame retarding efficiency height, can overcome some shortcomings of conventional polycarbonate flame retardent, but have the problem of easily in polycarbonate, reach capacity addition and its material transparency of reduction.Therefore, for this based flame retardant, only depending on increases addition and makes polycarbonate obtain more excellent flame, with satisfy its some use occasion more high flame retardant to require be infeasible, further improve the flame retardant resistance of polycarbonate and transparent so need seek other approach.
Summary of the invention
The objective of the invention is to solve the problem that prior art exists, provide a kind of efficient, low cigarette, low toxicity, pollution-free, to processing of plastic performance and the physical and mechanical property influence is very little and flame retardant properties is excellent highly transparent flame-retardant polycarbonate material and by the film as thin as a wafer and the sheet material of its processing.
First purpose of the present invention is realized by following technical scheme:
A kind of highly transparent flame-retardant polycarbonate material wherein contains polycarbonate and other auxiliary agent, it is characterized in that: contain the environmental protection bromide fire retardant in the described highly transparent flame-retardant polycarbonate.
The content of environmental protection bromide fire retardant is 1～40% of described polycarbonate weight in the above-mentioned highly transparent flame-retardant polycarbonate, the content of preferred environmental protection bromide fire retardant is 5～30% of polycarbonate weight, and the content of more preferred environmental protection bromide fire retardant is 10～20% of polycarbonate weight.
The content of other auxiliary agent is 0.01～10% of polycarbonate weight in the above-mentioned highly transparent flame-retardant polycarbonate, the content of preferred other auxiliary agent is 0.05～5% of polycarbonate weight, and the content of more preferred other auxiliary agent is 0.1～1% of polycarbonate weight.
The crying out the bromine polycarbonate oligomer or contain the polycarbonate oligomer of the end capped many bromines bisphenol A-type of phenoxy group of the preferred tetrabromo-bisphenol type of described environmental protection fire retarding agent, on the preferred phenoxy group with the polycarbonate oligomer of the tetrabromo-bisphenol type of a plurality of then methyl.
Described polycarbonate is an aromatic copolycarbonate.
Described other auxiliary agent is thermo-stabilizer and releasing agent, and wherein the weight ratio of thermo-stabilizer and releasing agent is 1: 1.
Second purpose of the present invention realized by following technical scheme: a kind of highly transparent flame-retardant polycarbonate film and sheet material is characterized in that: described film and sheet material are made by the described highly transparent flame-retardant polycarbonate of first purpose of the present invention.
Highly transparent flame-retardant polycarbonate provided by the invention has good flame resistance, favorable shock resistance, and when being exposed to high temperature, compare with the common flame-retardant polycarbonate material that is subjected to heat emission, it has also reduced toxicity.By film or the sheet material that the process for processing of this kind highly transparent flame-retardant polycarbonate forms, transparency is more than 90%, and it is that the film of 0.25mm reaches the UL94-V0 grade standard that its flame retardant resistance meets thickness.
The present invention has the following advantages:
1. the high-efficiency environment friendly bromide fire retardant of Tian Jiaing has improved the flame retardant properties of polycarbonate material greatly on the basis that does not influence the material transparency.
2. selected high-efficiency environment friendly bromide fire retardant is bromated polycarbonate oligomer, structurally with polycarbonate very close part is arranged, and has improved the consistency of fire retardant and base material.
3. selected high-efficiency environment friendly bromide fire retardant can satisfy the strictest ROSH index request fully, can not damage human body and environment.
4. adopt the high-efficiency environment friendly bromide fire retardant, the preparation method is simple, and is harmless to environment, and its flame retardant properties is far superior to other traditional halogen systems, phosphorus flame retardant.
High environmentally-friendly transparent fire-retardant polycarbonate of the present invention can be realized by following preparation method:
1. mechanical pre-mixing
Environmental protection brominated flame-retardant, other auxiliary agents of each component are added in the powdery polycarbonate base-material, in high speed mixer, mix.Blended mode and time directly influence the quality of particle and the film of being produced by particle and the surface quality of sheet material.The blended mode adopts low mixing-Gao to mix-low mixed hocketing, so that base-material can mix uniformly and effectively with fire retardant and other auxiliary agents and disperse.
2. melting mixing
The mixture that high-speed mixing is good is put into the twin screw extruder melt blending and is extruded, and the temperature in each district of forcing machine is controlled between 220 ℃～300 ℃.Screw speed is controlled at 15～45 rev/mins.The temperature in each district of forcing machine is most important for the quality of raw material particle, and the too high meeting of temperature causes the particle jaundice, and the too low meeting of temperature causes the raw material particle to produce a large amount of brilliant points when producing film, influences productivity and quality product.Simultaneously, control the pumped vacuum systems of forcing machine in process of production, the purpose that vacuumizes is to extract out the low molecular weight volatile material in the fusion plastification particle, the existence of low molecular weight volatile material can cause separating out on the production mould surface in the film production process, the surface quality of a large amount of accumulation back final film of influence and sheet material.
3. cooling and dicing
Melt blended material extrudes after room-temperature water bath cooling back pelletizing.It is pure inclusion-free that water coolant requires.Simultaneously, in continuous flow procedure, owing to the temperature of water coolant can raise along with the lengthening of production time, too high water temperature is unfavorable for cooling off the silk moulding pelletizing of being extracted out by forcing machine, therefore, in process of production, requires to control well the temperature of water coolant.
Embodiment
For making your auditor and the public can further understand feature of the present invention and beneficial effect thereof, the spy is described in detail as follows the specific embodiment of the present invention in conjunction with the embodiments:
Embodiment 1:
By weight percentage, the highly transparent flame-retardant polycarbonate of present embodiment comprises following composition and content:
Powdery polycarbonate 100
Environmental protection brominated flame-retardant 5
Thermo-stabilizer 0.25
Releasing agent 0.25
Embodiment 2:
By weight percentage, the highly transparent flame-retardant polycarbonate of present embodiment comprises following composition and content:
Powdery polycarbonate 100
Environmental protection brominated flame-retardant 10
Thermo-stabilizer 0.25
Releasing agent 0.25
Embodiment 3:
By weight percentage, the highly transparent flame-retardant polycarbonate of present embodiment comprises following composition and content:
Powdery polycarbonate 100
Environmental protection brominated flame-retardant 15
Thermo-stabilizer 0.25
Releasing agent 0.25
Embodiment 4:
By weight percentage, the highly transparent flame-retardant polycarbonate of present embodiment comprises following composition and content:
Powdery polycarbonate 100
Environmental protection brominated flame-retardant 20
Thermo-stabilizer 0.25
Releasing agent 0.25
Highly transparent flame-retardant polycarbonate in the above embodiments can be realized by following preparation method:
1. mechanical pre-mixing
Embodiment powdery polycarbonate raw material, environmental protection brominated flame-retardant, other auxiliary agents of each component in the comparative example are added carry out pre-mixing in the high-speed mixing agitator, the rotating speed of high speed blender is more than 1500rpm, because all add composition and all are Powdered, can reach the effect that mixes so stir after a little while, long mixing may cause batch mixing caking phenomenon to occur because temperature rises.
2. melt blending
Extrude carrying out melt blending in the parallel parallel dual-screw extruding machine of the direct adding of the material that mixes.The temperature in each district of forcing machine will be controlled between 250～300 ℃, and screw speed is controlled at 60～70% of main frame specified speed.
3. cooling and dicing
Melt blended material cools off from the water-bath that forcing machine is extruded back inlet chamber temperature, gets final product through the plastic grain cutting machine blank then.
In order to investigate the flame retardant properties of highly transparent flame-retardant polycarbonate material provided by the invention, and compare with the pure polycarbonate and the flame retardant properties of having added the polycarbonate of fire retardant, with the molten fire-retardant polycarbonate pellet that mixes gained and pure polycarbonate pellet behind heat-wind circulate drying, produce the PC film and the standard batten of making that thickness is 0.25mm and 0.5mm through special film line and carry out the combustionproperty test, adopt comprehensive vertical combustion instrument by the program test of ISO1210-1992 specified standards, test result is as shown in the table:
Really we can find out to tie me by the sample test of comparative example and embodiment: the flame retardant properties of not adding the sample of fire retardant is the V-2 level, the fire-retardant rank of material itself just, the amount and the fire-retardant rank of adding fire retardant are proportional, but too much interpolation can bring the cost aspect to raise.
The flame retardant resistance of thin-film material is directly related with the thickness of himself, the film of the different thickness of the raw material production that same recipe is formed, and flame retardant resistance becomes inverse relationship with thickness, thin more material, flame retardant resistance is poor more, reach the flame retardant resistance of same levels, the just essential addition that strengthens fire retardant.
It can also be seen that from example selected fire retardant can not influence the transmittance of material itself, the transmittance that how much can't make material of addition descends, and particularly is applied in and requires high transmission rate base material aspect, seems particularly important.
The interpolation of other auxiliary agents be prevent material in the course of processing since factors such as heat, oxidation cause material to turn to be yellow and make other degradation of material.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that content is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (13)
1. a highly transparent flame-retardant polycarbonate material wherein contains polycarbonate and other auxiliary agent, it is characterized in that: contain the environmental protection bromide fire retardant in the described highly transparent flame-retardant polycarbonate.
2. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described environmental protection bromide fire retardant is 1～40% of described polycarbonate weight.
3. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described environmental protection bromide fire retardant is 5～30% of described polycarbonate weight.
4. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described environmental protection bromide fire retardant is 10～20% of described polycarbonate weight.
5. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described other auxiliary agent is 0.01～10% of polycarbonate weight.
6. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described other auxiliary agent is 0.05～5% of polycarbonate weight.
7. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: the content of described other auxiliary agent is 0.1～1% of polycarbonate weight.
8. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: described environmental protection bromide fire retardant is bromated polycarbonate oligomer.
9. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: described environmental protection bromide fire retardant is the polycarbonate oligomer of many bromines bisphenol A-type.
10. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: described environmental protection bromide fire retardant is the polycarbonate oligomer of tetrabromo-bisphenol type.
11. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: described polycarbonate is an aromatic copolycarbonate.
12. highly transparent flame-retardant polycarbonate material according to claim 1 is characterized in that: described other auxiliary agent is thermo-stabilizer and releasing agent, and the weight ratio of wherein said thermo-stabilizer and releasing agent is 1: 1.
13. highly transparent flame-retardant polycarbonate film and sheet material, it is characterized in that: described film and sheet material are made by the described highly transparent flame-retardant polycarbonate of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100214753A CN101353473A (en) | 2008-08-04 | 2008-08-04 | Highly transparent flame-retardant polycarbonate material, film and sheet material products thereof |
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| CNA2008100214753A CN101353473A (en) | 2008-08-04 | 2008-08-04 | Highly transparent flame-retardant polycarbonate material, film and sheet material products thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781449A (en) * | 2010-03-16 | 2010-07-21 | 苏州奥美光学材料有限公司 | Polycarbonate film with highlight black surface |
| CN101824215A (en) * | 2010-05-10 | 2010-09-08 | 苏州奥美光学材料有限公司 | Polycarbonate film applied to speaker network for electronic appliances and manufacturing method thereof |
| CN107541035A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High fire-retardance polycarbonate film material and its products formed |
| CN107541034A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High tenacity fire-retardant polycarbonate thin-film material and its products formed |
-
2008
- 2008-08-04 CN CNA2008100214753A patent/CN101353473A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781449A (en) * | 2010-03-16 | 2010-07-21 | 苏州奥美光学材料有限公司 | Polycarbonate film with highlight black surface |
| CN101824215A (en) * | 2010-05-10 | 2010-09-08 | 苏州奥美光学材料有限公司 | Polycarbonate film applied to speaker network for electronic appliances and manufacturing method thereof |
| CN101824215B (en) * | 2010-05-10 | 2015-05-20 | 苏州奥美光学材料有限公司 | Polycarbonate film applied to speaker network for electronic appliances and manufacturing method thereof |
| CN107541035A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High fire-retardance polycarbonate film material and its products formed |
| CN107541034A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High tenacity fire-retardant polycarbonate thin-film material and its products formed |
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Open date: 20090128 |