CN100387649C - Fluororesin compositions - Google Patents
Fluororesin compositions Download PDFInfo
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- CN100387649C CN100387649C CNB2004800320771A CN200480032077A CN100387649C CN 100387649 C CN100387649 C CN 100387649C CN B2004800320771 A CNB2004800320771 A CN B2004800320771A CN 200480032077 A CN200480032077 A CN 200480032077A CN 100387649 C CN100387649 C CN 100387649C
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Abstract
A fluororesin composition which comprises a terminal-stabilized fluororesin and carbon nanotubes; and a fluororesin composition which comprises a fluororesin and carbon nanotubes surface-treated with a fluorochemical surfactant. The compositions are excellent in electrical properties such as conductivity and electrostatic buildup characteristics.
Description
Technical field
The present invention relates to the fluorine resin composition, particularly can be used for having the fluorine resin composition of the conductive material etc. of surface of good resistance.
Background technology
It is in the various uses of representative that the resin combination that contains electroconductive stuffing in the synthetic resins material is used to electronic material etc. as the conductive material with characteristic.
For example, open in the 2003-192914 communique, propose CNT (carbon nano-tube) (carbonnanotube) is used as the electroconductive stuffing that is formed by conductive carbon black in the past the Japanese Patent spy.
Known when CNT (carbon nano-tube) is added into synthetic resins as electroconductive stuffing, as long as the addition of 1/3～1/4 when adding PAN and being the charcoal fiber just can manifest the electroconductibility of equal extent.This is because the electroconductibility of CNT (carbon nano-tube) is higher than carbon series conductive filler in the past, and length-to-diameter ratio (aspect ratio, length-to-diameter) height, therefore easily form network structure in the synthetic resins that mixes, in addition, CNT (carbon nano-tube) is very fine, volume density is little, and the radical of unit weight is many.
In addition, carbon containing is the conductive material of electroconductive stuffing when using as the protecting materials of various electronic materials, electronic installation, electric wire etc., owing to reasons such as frictions, if electroconductive stuffing comes off, then may the detonator circuit short circuit etc. significant problem.
But, it is the very tiny material of size that CNT (carbon nano-tube) is compared with conductive carbon material in the past, the phenomenon of " floating " from resin combination can appear hardly, and it be in apparent good order and condition, intensity big, have the material of spring rate, so possess the feature of rare dropping situations.
In addition, CNT (carbon nano-tube) is the material that only is made of carbon atom, different with carbon black etc., impure hardly, can not change even be exposed under the high temperature during moulding or when using yet, and can not decompose the synthetic resins that mixes, not have gas in the moulding product yet and produce, so used with material as electronic component by expectation.
In addition, also proposed CNT (carbon nano-tube) is mixed technical scheme in the fluorine resin as filler.When CNT (carbon nano-tube) is impregnated in the fluorine resin as filler, can provide the fluorine resin composition of the chemical stability that advantageous property and fluorine resin had that has CNT (carbon nano-tube) concurrently.
The announcement of invention
The present invention relates to the fluorine resin composition, its problem provides conductive characteristic and the good fluorine resin composition of electrostatic charging characteristic that contains in the fluorine resin as in the composition of the CNT (carbon nano-tube) of electroconductive stuffing.
The fluorine resin composition that problem of the present invention can form by the fluorine resin and the CNT (carbon nano-tube) of end group stabilization solves.
In the aforementioned fluorine resin composition, the fluorine resin of end group stabilization is perfluoro alkoxy alkane polymkeric substance or fluorinated ethylene propylene copolymer.
In the aforementioned fluorine resin composition, CNT (carbon nano-tube) is to be selected from individual layer CNT (carbon nano-tube), multi-layer nano carbon pipe, vapor-grown carbon fibers at least a kind.
In addition, problem of the present invention can be that the fluorine resin composition that the surface-treated CNT (carbon nano-tube) of tensio-active agent forms solves by the fusion fluorine resin with through fluorine.
In the aforementioned fluorine resin composition, aforementioned fluorine is that tensio-active agent is to be selected from fluoroalkyl sulfonic acid, fluoroalkyl carboxylic acid and their salt at least a kind.
In addition, by fluorine resin with through fluorine is that the end group of the fluorine resin in the fluorine resin composition that forms of the surface-treated CNT (carbon nano-tube) fusion of tensio-active agent has been realized stabilization, here, the fluorine resin that is preferably the end group stabilization is the aforementioned fluorine resin composition that is selected from perfluoro alkoxy alkane polymkeric substance or fluorinated ethylene propylene copolymer.
By fluorine resin with through fluorine is the fluorine resin composition that the surface-treated CNT (carbon nano-tube) fusion of tensio-active agent forms, because CNT (carbon nano-tube) is that tensio-active agent has carried out mixing with fluorine resin after the surface treatment again with fluorine in advance, so the affinity of CNT (carbon nano-tube) and fluorine resin increases, the rare phenomenon that comes off from fluorine resin, and the affinity between fluorine resin is mutual also increases, and therefore can obtain the higher fluorine resin composition of electroconductibility.
One of fluorine resin composition of the present invention is by forming as the fluorine resin of the end group stabilization of fluorine resin with as the CNT (carbon nano-tube) fusion of electroconductive stuffing, consequently, just can obtain high conductivity with lower CNT (carbon nano-tube) mix proportions, can be used in lower noise electromagnetic shielding material etc.In addition, because its electrostatic charging characteristic is good, the CNT (carbon nano-tube) of using as filler can not come off, and electrostatic charging is few, and therefore can obtain can be as the extremely useful material to high various electronic component materials of reliability requirement etc.
In another fluorine resin composition of the present invention, CNT (carbon nano-tube) is being to mix as electroconductive stuffing after tensio-active agent is handled through fluorine, consequently, just can obtain high conductivity, can be used in lower noise electromagnetic shielding material etc. with lower CNT (carbon nano-tube) blended amount.In addition, because its electrostatic charging characteristic is good, the CNT (carbon nano-tube) of using as filler can not come off, and electrostatic charging is few, and therefore can obtain can be as the extremely useful material to high various electronic component materials of reliability requirement etc.
In addition owing to mix a spot of CNT (carbon nano-tube) and just can obtain required conductive characteristic, so can not have influence on surface property and mechanical characteristics that fluorine resin possesses originally, because of the degree of mixing the processibility decline that filler causes also little.
The best mode that carries out an invention
Below, embodiments of the present invention are described.
One of the present invention's fluorine resin composition is finished according to following discovery, this discovery is: in the fluorine resin composition that with the CNT (carbon nano-tube) is electroconductive stuffing, when the end group of fluorine resin is unstable, the electroconductibility of CNT (carbon nano-tube) obviously descends under the high temperature more than the fusing point of this fluorine resin of processing, and situation is compared therewith, when the end group of fluorine resin has been realized stabilization, can suppress the phenomenon of electroconductibility decline etc.
Fluorine resin is the resin that chemical resistant properties is better than other synthetic resins, and being widely used in has desired field to chemical resistant properties, and thermotolerance is had desired field, the less fields such as liquid contamination that perhaps require the leachable of generations such as plastics to cause.
Particularly the fluoropolymer of the polymerization manufacturing by fluorine monomer may be molded to different shape, therefore is applicable to the manufacturing with the mixing fluorine resin composition that forms of electroconductive stuffing.
Fluorine monomer is when carrying out polymerization, owing to mixed initiator and chain-transfer agent etc., so be subjected to the effect of these reagent or the influence of side reaction, formed the end group of unstable chemcial properties such as amide group, methanol-based, carboxyl in the polymkeric substance of formation inevitably.
There is the possibility of reacting in above-mentioned unsettled end group, so the difference because of the purposes of fluorine resin has problems sometimes, in semiconductor fabrication process that requires high stability etc., adopt end group stabilization that these unsettled end groups form by fluoridation by fluorizating agents such as fluorine gas etc. fluorine resin.
The fluorine resin composition of one of the invention described above is also according to following discovery: as the fluorine resin composition, mix CNT (carbon nano-tube) in the fluorine resin by group stabilization endways and given electroconductibility, in this case, blended amount with less CNT (carbon nano-tube), just can under the prerequisite of the rerum natura that does not have influence on fluorine resin, show excellent characteristic aspect conductivity and the electrostatic charging characteristic.
In one of the present invention's fluorine resin preparation of compositions spendable end group stabilization fluorine resin carry out the resin of the fluoridation of end group by fluorizating agent after being polymerization, specifically can exemplify and be selected from tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-1,1-difluoroethylene terpolymer (THV), polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVdF), at least a kind of polychlorotrifluoroethylene (PCTFE) etc.
Wherein, be preferably fluoridized polymkeric substance, more preferably tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA).
In addition, also can mix the end group stabilization simultaneously in the fluorine resin composition of the present invention fluorine resin and the end group fluorine resin of stabilization not.In this case, the end group stabilization the consumption of fluorine resin be preferably more than 1/3 of total mass of used fluorine resin, the end group stabilization consumption more than 1/2 of total mass more preferably of fluorine resin.
The CNT (carbon nano-tube) that can be used for fluorine resin composition of the present invention can exemplify the carbon nanoporous body that individual layer CNT (carbon nano-tube) (SWCNT), multi-layer nano carbon pipe (MWCNT), vapor-grown carbon fibers (VGCF), Carbon Nanohorn (carbonnanohorn) etc. have electroconductibility.
In addition, the diameter of CNT (carbon nano-tube) is preferably 1nm～300nm, and length-to-diameter ratio is more fortunately more than 5.
The mix proportions of the CNT (carbon nano-tube) among the present invention is a benchmark with the overall quality of composition, is preferably more than the 0.1 quality %, and more preferably more than the 1 quality %, but this mix proportions can be adjusted according to the conductive characteristic as the fluorine resin composition of purpose.
In addition, aspect improving dispersed fluorine resin, consider that CNT (carbon nano-tube) can form master batch (master batch) with mixed with resin in advance and use.Be used for master batch formation resin preferably with the identical fluorine resin of fluorine resin composition that finally makes.
One of the present invention's fluorine resin composition can be shaped to the regulation shape by the following method,, after mixed fluorine resin and the CNT (carbon nano-tube), is shaped to the shape of regulation by methods such as extrusion molding method, roll moulding method, injection molding methods according to the rules that is.
The present invention will be described for following illustrative embodiments and comparative example.
Embodiment
In the hopper of biaxial extruder (the system KZW20-25G of テ Network ノ ベ Le Co., Ltd.), supply with fluorine resin particle and CNT (carbon nano-tube) respectively by 2 feeding machines according to the part by weight of table 1.The barrel temperature of biaxial extruder is set at 330 ℃; the mould temperature is set at 340 ℃; with screw rod rotation number 30rpm fluorine resin and CNT (carbon nano-tube) melting mixing are extruded to behind the strand shape, in tank, cooled off, make the particle of diameter 1.5mm, long 3mm again with tablets press.
Sample 5～7th is pre-mixed the particle of fluorine resin PFA450HPJ and 350J, supplies with from feeding machine.Relatively 3 use dry FEP120J as dispersion after, with acetone eccysis tensio-active agent, extrude with the single shaft forcing machine again and be strand shape, handle with tablets press then and the particle that makes.
(mensuration of electric conductivity)
Mix with biaxial extruder, under 350 ℃ hot pressing, be the sheet of thick 0.2mm with 10g gained grain forming, measure meter (Mitsubishi Chemical makes LORESTA-AP) and measure surface resistivity as electric conductivity with high resistivity mensuration meter (the system HIRESTA-IP of Mitsubishi Chemical), low-resistivity, its evaluation result is shown in table 1.
In addition, the relatively expression comparative example in the table 1.
(mensuration that electrostatic belt is electrical)
After removing 100g sample particulate institute static electrification with static electricity removing device (ア ズ ワ Application system SF-1000), in its polyethylene bag of packing into, sack is expanded tightens mouth, vibrate up and down tempestuously 10 times, judge in the bag particle whether because of static attached on the bag wall.Being designated as of not adhering to is good, and being designated as of adhering to is bad.
In the table 1, PFA450HPJ, PFA440HPJ represent fluorine chemistry Co., Ltd. of Mitsui Du Pont system tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA) of end group stabilization respectively, and FEP100J represents fluorine chemistry Co., Ltd. of Mitsui Du Pont system tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) of end group stabilization.
In addition, PFA350J, PFA340J represent not fluorine chemistry Co., Ltd. of Mitsui Du Pont system tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA) of stabilization of end group respectively, and FEP120J represents not fluorine chemistry dwarf formula commercial firm of the Mitsui Du Pont system tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) of stabilization of end group.
VGCF is the vapor phase process charcoal fiber that clear and electrician makes diameter 150nm, and CNT20 is the CNT (carbon nano-tube) of canbon nanotechresearch institute system diameter 20nm.
Table 1
| PFA450HPJ | PFA440HPJ | FEP100J | PFA350J | PFA340J | FEP120J | VGCF | CNT20 | Electric conductivity (Ω/) | Static characteristic | |
| Sample 1 | 96 | 4 | ＞10 13 | Well | ||||||
| Sample 2 | 95 | 5 | 10 11 | Well | ||||||
| Sample 3 | 94 | 6 | 10 3 | Well | ||||||
| Sample 4 | 93 | 7 | 10 3 | Well | ||||||
| Sample 5 | 63 | 31 | 6 | 10 11 | Well | |||||
| Sample 6 | 47 | 47 | 6 | 10 12 | Well | |||||
| Sample 7 | 31 | 63 | 6 | 10 13 | Well | |||||
| Sample 8 | 98 | 2 | ＞10 13 | Well | ||||||
| Sample 9 | 97 | 3 | 10 13 | Well | ||||||
| Sample 10 | 96 | 4 | 10 5 | Well | ||||||
| Sample 11 | 93 | 7 | 10 5 | Well | ||||||
| Sample 12 | 95 | 5 | 10 5 | Well | ||||||
| Sample 13 | 90 | 10 | 10 0 | Well | ||||||
| Sample 14 | 95 | 5 | 10 4 | Well | ||||||
| Sample 15 | 93 | 7 | 10 0 | Well | ||||||
| Compare 1 | 94 | 6 | ＞10 13 | Bad | ||||||
| Compare 2 | 96 | 4 | ＞10 13 | Bad | ||||||
| Compare 3 | 93 | 7 | ＞10 13 | Bad | ||||||
| Compare 4 | 95 | 5 | ＞10 13 | Bad | ||||||
| Compare 5 | 94 | 6 | ＞10 13 | Bad | ||||||
| Compare 6 | 95 | 5 | ＞10 13 | Bad |
Below, another embodiment of the present invention is described.
In the fluorine resin composition of another CNT (carbon nano-tube) of the present invention as electroconductive stuffing, because CNT (carbon nano-tube) is the processing of tensio-active agent through fluorine in advance, so the affinity of itself and used fluorine resin increases, consequently, blended amount with still less CNT (carbon nano-tube) can provide to have the fluorine resin composition that high conductivity, filler can not come off and possess good processibility and mechanical characteristics.
In addition, also find because the chemical structure of the end group of used fluorine resin, the characteristic of gained fluorine resin composition has bigger variation, because the difference of the structure of end group, variation has also taken place in electroconductibility and static characteristic, have the fluorine resin of particular end group by use, good fluorine resin compositions such as electroconductibility can be provided.
Another fluorine resin composition of the present invention, use through fluorine be the CNT (carbon nano-tube) handled of tensio-active agent, with the end group stabilization fluorine resin when mixing, its conductivity, particularly electrostatic charging characteristic are especially good.
As the fluorine that is used for another fluorine resin composition of the present invention is tensio-active agent, can exemplify fluoroalkyl sulfonic acid or its salt, fluoroalkyl carboxylic acid or its salt, specifically can exemplify Perfluorooctane sulfonates potassium, Perfluorooctane sulfonates lithium, potassium perfluorobutane sulfonate etc.
Fluorine in another fluorine resin composition of the present invention is that the treatment process of tensio-active agent can be that the method that tensio-active agent contacts with CNT (carbon nano-tube) is implemented by making fluorine, for example, implement by carrying out drying treatment after CNT (carbon nano-tube) being impregnated in the organic solvent solution that fluorine is a tensio-active agent or the aqueous solution.
Corresponding to total composition, fluorine is that the addition of tensio-active agent is preferably more than the 0.001 quality %, more preferably 0.003 quality % above, below the 5 quality %, be preferably 0.005 quality % above, below the 2 quality %.Addition is not solvent-laden amount.
If addition is less than 0.001 quality %, then can't obtain good electrical conductivity, if more than 5 quality %, then processibility descends.
As the fluorine resin that can be used for another fluorine resin preparation of compositions of the present invention, can exemplify polytetrafluoroethylene (PTFE), tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE), poly(vinylidene fluoride) (PVDF), polychlorotrifluoroethylene (PCTFE), vinylchlorid-trifluoro-ethylene copolymer (ECTFE) etc.
The end group stabilization fluorine resin be the fluorine resin that obtains by polymerization to be carried out the resin that the fluoridation of end group forms with fluorizating agent, specifically can exemplify at least a kind that is selected from tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride terpolymer (THV).
Wherein, be preferably perfluorinated polymers, more preferably tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA).
In addition, also can mix the end group stabilization simultaneously in another fluorine resin composition of the present invention fluorine resin and the end group fluorine resin of stabilization not.For the characteristic of the fluorine resin that made based on the end group stabilization is given full play to, the end group stabilization the consumption of fluorine resin be preferably more than 1/3 of total mass of fluorine resin, the end group stabilization consumption more than 1/2 of total mass more preferably of fluorine resin.
The CNT (carbon nano-tube) that can be used for another fluorine resin composition of the present invention can exemplify the carbon nanoporous body that individual layer CNT (carbon nano-tube) (SWCNT), multi-layer nano carbon pipe (MWCNT), vapor-grown carbon fibers (VGCF), Carbon Nanohorn etc. have electroconductibility.
In addition, the diameter of CNT (carbon nano-tube) is preferably 1nm～300nm, and length-to-diameter ratio is more fortunately more than 5.
The mix proportions of the CNT (carbon nano-tube) in another fluorine resin composition of the present invention is a benchmark with the overall quality of composition, be preferably more than the 0.1 quality %, more preferably more than the 1 quality %, but this mix proportions can be adjusted according to the conductive characteristic as the fluorine resin composition of purpose.
In addition, aspect improving dispersed fluorine resin, consider that CNT (carbon nano-tube) can form master batch with mixed with resin in advance and use.Be used for master batch formation resin preferably with the identical fluorine resin of fluorine resin composition that finally makes.
Another fluorine resin composition of the present invention can be shaped to the regulation shape by the following method,, after mixed fluorine resin and the CNT (carbon nano-tube), is shaped to the shape of regulation by methods such as extrusion molding method, roll moulding method, injection molding methods according to the rules that is.
Further the present invention will be described for following illustrative embodiments and comparative example.
Embodiment
Proportioning according to the frozen composition of table 2 record is to add CNT (carbon nano-tube) in the tensio-active agent at the fluorine of table 2 record, fully stirs the back and makes its drying in 110 ℃.
In the hopper of biaxial extruder (the system KZW20-25G of テ Network ノ ベ Le Co., Ltd.), supply with fluorine resin particle and CNT (carbon nano-tube) respectively by 2 feeding machines according to the part by weight of table 2.The barrel temperature of biaxial extruder is set at 330 ℃; the mould temperature is set at 340 ℃; with screw rod rotation number 30rpm fluorine resin and CNT (carbon nano-tube) melting mixing are extruded to behind the strand shape, in tank, cooled off, make the particle of diameter 1.5mm, long 3mm again with tablets press.
Relatively 10 use dry FEP120J as dispersion after, with methyl alcohol eccysis tensio-active agent, extrude with the single shaft forcing machine again and be strand shape, handle with tablets press then and the diameter 1.5mm that makes, the particle of long 3mm.
In the table 2, relatively represent comparative example.
(mensuration of electric conductivity)
Mix with biaxial extruder, under 350 ℃ hot pressing, be the sheet of thick 0.2mm with 10g gained grain forming, measure meter (Mitsubishi Chemical makes L0RESTA-AP) and measure surface resistivity as electric conductivity with high resistivity mensuration meter (the system HIRESTA-IP of Mitsubishi Chemical), low-resistivity, its evaluation result is that unit is shown in table 2 with Ω/.
(mensuration that electrostatic belt is electrical)
With static electricity removing device (ア ズ ワ Application system SF-1000) remove 100g sample particle with static after, in its polyethylene bag of packing into, sack is expanded tightens mouth, vibrate up and down tempestuously 10 times, judge in the bag particle whether because of static attached on the bag wall.Being designated as of not adhering to is good, and being designated as of adhering to is bad.
In the table 2, PFA350J, PFA450J, PFA340J, PFA420J represent fluorine chemistry Co., Ltd. of Mitsui Du Pont system tetrafluoroethylene-fluoroalkyl vinyl ether co-polymer (PFA) respectively, and PFA450J, PFA420J represent the multipolymer of end group stabilization.
In addition, FEP100J, FEP120J represent fluorine chemistry Co., Ltd. of Mitsui Du Pont system tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) respectively.FEP100J represents the multipolymer of end group stabilization.
In addition, ETFEC88AX represents Asahi Glass Co., Ltd's system tetrafluoroethylene-ethylene copolymer (ETFE).
Numeric representation forms the weight proportion of branch admittedly.
In the tensio-active agent, SA1 represents Perfluorooctane sulfonates potassium, in the methanol solution of 4 quality % CNT (carbon nano-tube) is handled; SA2 represents the Perfluorooctane sulfonates lithium, in the methanol solution of 4 quality % CNT (carbon nano-tube) is handled; SA3 represents perfluorinated butane sulfonic acid lithium, in the aqueous solution of 4 quality % CNT (carbon nano-tube) is handled.
The weight proportion that the solid formation of numeric representation tensio-active agent divides.
CNT represents CNT (carbon nano-tube), and VGCF represents that clear and electrician makes the vapor phase process charcoal fiber of diameter 150nm, and CNT20 represents the CNT (carbon nano-tube) of canbon nanotech research institute system diameter 20nm.
Numeric representation forms the weight proportion of branch admittedly.
Table 2
The possibility of utilizing on the industry
Fluororesin composition of the present invention is owing to used CNT as electroconductive stuffing, simultaneously as fluorine resin used the end group stabilisation fluorine resin, so conductive characteristic, the particularly good fluororesin composition of electrostatic charging characteristic can be provided, can be used for the good electric material of the electrical characteristics such as electric conductivity and static characteristic, the manufacturing of electronic material. In addition, fluororesin composition of the present invention is the CNT that surfactant is processed owing to having used through fluorine, so conductive characteristic, the particularly good fluororesin composition of electrostatic charging characteristic can be provided, can be used for the good electric material of the electrical characteristics such as electric conductivity and static characteristic, the manufacturing of electronic material.
Claims (4)
1. the fluorine resin composition is characterized in that, fusion fluorine resin and be the surface-treated CNT (carbon nano-tube) of tensio-active agent and forming through fluorine.
2. fluorine resin composition as claimed in claim 1, its feature also be, fluorine is that tensio-active agent is to be selected from fluoroalkyl sulfonic acid, fluoroalkyl carboxylic acid and their salt at least a kind.
3. fluorine resin composition as claimed in claim 1, its feature are that also fluorine resin is the resin of end group stabilization.
4. fluorine resin composition as claimed in claim 3, its feature are that also the fluorine resin of end group stabilization is the resin that is selected from perfluoro alkoxy alkane polymkeric substance or fluorinated ethylene propylene copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP372251/2003 | 2003-10-31 | ||
| JP2003372251A JP2005133002A (en) | 2003-10-31 | 2003-10-31 | Fluororesin composition |
| JP384006/2003 | 2003-11-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1875064A CN1875064A (en) | 2006-12-06 |
| CN100387649C true CN100387649C (en) | 2008-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800320771A Expired - Fee Related CN100387649C (en) | 2003-10-31 | 2004-10-28 | Fluororesin compositions |
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| JP (1) | JP2005133002A (en) |
| CN (1) | CN100387649C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591724C (en) * | 2005-06-30 | 2010-02-24 | 日信工业株式会社 | Fiber composite material and its manufacturing method |
| JP4898331B2 (en) * | 2006-07-20 | 2012-03-14 | 日信工業株式会社 | Carbon fiber composite material |
| JP5374047B2 (en) * | 2008-01-07 | 2013-12-25 | 日信工業株式会社 | Carbon fiber composite material |
| JP2012130557A (en) * | 2010-12-22 | 2012-07-12 | Junkosha Co Ltd | Medical tube containing contrast medium |
| CN102504451B (en) * | 2011-12-11 | 2014-02-26 | 浙江大学 | Preparation method of fluororesin/nanocomposite material |
| CN111684008A (en) * | 2018-02-09 | 2020-09-18 | 东邦化成株式会社 | Conductive welding material and method for producing same |
| WO2020130144A1 (en) * | 2018-12-21 | 2020-06-25 | ダイキン工業株式会社 | Fluoropolymer composition, molded article, and injection molded article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902444A (en) * | 1988-03-18 | 1990-02-20 | E. I. Dupont De Nemours And Company | Conductive fluoropolymers |
| JP2000281855A (en) * | 1999-04-01 | 2000-10-10 | Mitsubishi Chemicals Corp | Fluorine-based polymer composition and electroconductive belt comprising the same |
| JP2003192914A (en) * | 2001-12-28 | 2003-07-09 | Mitsubishi Plastics Ind Ltd | Thermoplastic resin molding excellent in electroconductivity |
-
2003
- 2003-10-31 JP JP2003372251A patent/JP2005133002A/en active Pending
-
2004
- 2004-10-28 CN CNB2004800320771A patent/CN100387649C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902444A (en) * | 1988-03-18 | 1990-02-20 | E. I. Dupont De Nemours And Company | Conductive fluoropolymers |
| JP2000281855A (en) * | 1999-04-01 | 2000-10-10 | Mitsubishi Chemicals Corp | Fluorine-based polymer composition and electroconductive belt comprising the same |
| JP2003192914A (en) * | 2001-12-28 | 2003-07-09 | Mitsubishi Plastics Ind Ltd | Thermoplastic resin molding excellent in electroconductivity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005133002A (en) | 2005-05-26 |
| CN1875064A (en) | 2006-12-06 |
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