CN1982366A - Modified fluorin resin composition and former - Google Patents
Modified fluorin resin composition and former Download PDFInfo
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- CN1982366A CN1982366A CN 200610146886 CN200610146886A CN1982366A CN 1982366 A CN1982366 A CN 1982366A CN 200610146886 CN200610146886 CN 200610146886 CN 200610146886 A CN200610146886 A CN 200610146886A CN 1982366 A CN1982366 A CN 1982366A
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Abstract
The invention provides a modified-fluororesin composition and moulded body with excellent abrasion resistance in high specific pressure and keeping the good performance of original fluororesin. The invention relates to the modified-fluororesin composition, which can be made by mixing polyamide-imide and organic fiber in organic polymer and fluororesin modified by ionizing radiation.
Description
Technical field
The wear resistant under high surface pressure that the present invention relates to be made of modified fluorin resin, the slide unit of creep resistant excellence, sealing member, gasket (packing), air packing (gasket), semi-conductor manufacturing are with the composition and the formed body of container, anchor clamps, pipeline etc.
Background technology
The organic polymer of rubber or plastics is applied to extensive fields, and wherein fluoro-resin is owing to low frictional properties, thermotolerance, electrical specification, resistance to chemical reagents and spatter property (non-polluting) excellence, so be widely used in various uses such as industry, the people's livelihood.But under the slip environment or under high temperature compressed environment, its abrasion and creep strain are big, therefore by add packing materials such as glass fibre or carbon fiber in fluoro-resin, improve abrasion and creep strain.Even but adopt these means, when using under high surface pressure, the wear resistant of fluorin resin composition is also also insufficient, weather resistance aspect existing problems.As its countermeasure, studied the method for in fluoro-resin, adding various packing materials.
Patent documentation 1: the spy opens the 2004-331814 communique
Patent documentation 2: the spy opens the 2004-217758 communique
Summary of the invention
But,, can not say so fully according to different its wear resistants of purposes even added the fluorin resin composition of packing material as mentioned above.
Thereby purpose of the present invention is the wear resistant excellence that is provided under the high surface pressure, and can keep the modified fluorin resin composition and the formed body of the original superperformance of fluoro-resin.
In order to achieve the above object, the invention of summary of the invention 1 is a kind of modified fluorin resin composition, is at organic polymer and carries out with the ionization radioactive rays that mixed polyamide imide and organic fibre form in the fluoro-resin of modification.
The invention of summary of the invention 2 is the modified fluorin resin compositions according to summary of the invention 1 record, the total weight of described modified fluorin resin, polyamidoimide and organic fibre is 10 weight parts～50 weight parts of gross weight, wherein, modified fluorin resin accounts for 5 weight parts～30 weight parts of gross weight, 2 weight parts～15 weight parts that polyamidoimide accounts for gross weight, 3 weight parts～10 weight parts that organic fibre accounts for gross weight.
The invention of summary of the invention 3 is that described organic fibre is a carbon fiber according to the modified fluorin resin composition of summary of the invention 1 or 2 records.
The invention of summary of the invention 4 is the modified fluorin resin compositions according to each record in the summary of the invention 1～3, and described organic fibre is length 1～300 μ m, slenderness ratio 1～500.
The invention of summary of the invention 5 is the modified fluorin resin compositions according to each record in the summary of the invention 1～4, and described organic polymer is more than select from tetrafluoroethylene based polymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) based polymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) based polymer at least a.
The invention of summary of the invention 6 is that described polytetrafluoroethyl-ne alkene copolymer contains 1 mole of % with the second interior composition or a plurality of ternary heterogeneous fluorine monomer according to the modified fluorin resin composition of summary of the invention 5 records.
The invention of summary of the invention 7 is the modified fluorin resin compositions according to each record in the summary of the invention 1～6, and the crystallization heat of described modified fluorin resin is below the 40J/g, and fusing point is below 325 ℃.
The invention of summary of the invention 8 is the modified fluorin resin compositions according to each record in the summary of the invention 1～7, and the fluoro-resin of described modified fluorin resin is more than select from tetrafluoroethylene based polymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) based polymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) based polymer at least a.
The invention of summary of the invention 9 is the modified fluorin resin compositions according to each record in the summary of the invention 1～8, and described modified fluorin resin is with in the atmosphere of inert gases of fluoro-resin below oxygen concn 10torr and be heated under its state more than fusing point with the scope irradiation ionization radioactive rays of illuminated line amount 1kGy～10MGy and obtain.
The invention of summary of the invention 10 is to use the modified fluorin resin composition of each record in the summary of the invention 1～9 and the formed body of moulding.
According to the present invention, can give the abradability of the excellent in resistance under the high surface pressure to modified fluorin resin composition, be very beneficial for widening the range of application of organic polymer.
Embodiment
Embodiments of the present invention are described below in further detail.
The modified fluorin resin that relates in the present embodiment is at organic polymer and carry out with the ionization radioactive rays that mixed polyamide imide and organic fibre form in the fluoro-resin (below be called modified fluorin resin) of modification.
Modified fluorin resin in the modified fluorin resin composition that relates in the present embodiment, polyamidoimide, and the total weight of organic fibre be 10 weight parts～50 weight parts of gross weight, wherein, modified fluorin resin accounts for 5 weight parts～30 weight parts of gross weight, 2 weight parts～15 weight parts that polyamidoimide accounts for gross weight, 3 weight parts～10 weight parts that organic fibre accounts for gross weight.
The organic fibre that uses in the modified fluorin resin composition is preferably carbon fiber, is preferably length 1～300 μ m, slenderness ratio 1～500.The effect of wear resistant if staple length below prescribed value, then is not greatly improved, if surpass prescribed value, then increasing substantially of wear resistant can be impaired.About slenderness ratio (with respect to the ratio of the staple length of Fibre diameter), if below prescribed value, then there is not effectively to improve the effect of wear resistant, and if surpass prescribed value, then dispersed significantly variation, its result causes wear resistant to descend.
The polyamidoimide that uses in the modified fluorin resin composition is considered from dispersed aspect, is preferably Powderedly, and preferred maximum particle diameter is below 200 μ m.If surpass this value, resist and stretch characteristic, especially extensibility significantly descends.
As organic polymer, can enumerate nitrile rubber, viton etc., perhaps plastics such as Resins, epoxy, nylon, aromatic series based polymer, wherein especially preferred fluoro-resin.As fluoro-resin, can enumerate TFE copolymer (PTFE), tetrafluoroethylene-Fluoroalkyloxy trifluoro-ethylene copolymer (PFA), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluor dioxole multipolymer (THF/PDD).
In above-mentioned PTFE, also comprise second composition, for example contain 1 mole below the %, the material that the following polymerized unit by co-polymerized monomers such as perfluor (alkyl vinyl ether), R 1216, (perfluoroalkyl) ethene or chlorotrifluoroethylenes of preferred 0.2 mole of % constitutes.And the situation of above-mentioned fluoro-resin also can contain a spot of the 3rd composition, for example heterogeneous fluorine monomer in its molecular structure.The 3rd composition can be a kind of or two or more.
Preferred its fusing point of modified fluorin resin is below 325 ℃, and the crystallization heat is below the 40J/g, if surpass prescribed value, then wear resistant and creep resistant significantly reduce.When the fluoro-resin that constitutes modified fluorin resin was PFA, preferably its fusing point was below 305 ℃, and the crystallization heat is below the 26J/g; During for FEP, preferably its fusing point is below 275 ℃, and the crystallization heat is below the 11J/g.
Estimate their fusing point and during crystallization heat (thermal property), use differential scanning heat instrument (DSC), between 50～360 ℃ with warming and cooling rate twice intensification and the cooling repeatedly of 10 ℃/min, the endotherm peak temperature of the DSC curve when heated up the second time is as fusing point, the peak area that surrounds from the exothermal peak when lowering the temperature for the second time and baseline, according to JIS K7122, obtain the crystallization heat.
Modified fluorin resin is with in the atmosphere of inert gases of fluoro-resin below oxygen concn 10torr and be heated under its state more than fusing point, for this fluoro-resin with the scope irradiation ionization radioactive rays of illuminated line amount 1kGy～10MGy and make.
As the ionization radioactive rays, can use gamma-rays, electron rays, X ray, neutron line or energetic ion line etc.
When irradiation ionization radioactive rays, fluororesin molding need be heated to it more than crystalline melt point.For example when using PTFE as fluoro-resin, need be heated to than 327 ℃ of high temperature of its fusing point and shine the ionization radioactive rays, and when using PFA, FEP, being heated to than specific fusing point separately is the former 310 ℃, 275 ℃ of high temperature of the latter and shine the ionization radioactive rays.When fluoro-resin being heated to its fusing point when above, the motion of the backbone molecule that constitutes fluoro-resin is come to life, its result can promote intermolecular crosslinking reaction effectively.Just, if superheated can cause the fracture and the decomposition of molecular backbone chain on the contrary, therefore need be in the scope higher 10～30 ℃ than fluoro-resin fusing point heating and temperature control.
In addition, in the modified fluorin resin that present embodiment relates to, also can mix solid lubricants such as molybdenumdisulphide, graphite etc., to improve oilness.
The effect of present embodiment then, is described.
The result that the inventor etc. carry out various researchs in order to improve the wear resistant under high surface pressure finds to pass through and with modified fluorin resin, polyamidoimide and organic fibre, can improve wear resistant significantly, so that finished the present invention.Thereby the modified fluorin resin composition that present embodiment relates to is to add to have mixed polyamidoimide and organic fibre forms in organic polymer and modified fluorin resin.
About modified fluorin resin because of and the reason that significantly improves with polyamidoimide and organic fibre wear resistant still indeterminate, but be estimated as, by combination modified fluorin resin and polyamidoimide, on the slipping plane respective material, form transfer film easily, and by combination polyamidoimide and organic fibre, the Young's modulus of whole composition rises, and suppressed the distortion under the high surface pressure, play the effect that increases the weight of centrostigma simultaneously, its result has reduced the load to block (formed body of modified fluorin resin composition).Because the effect that increases substantially wear resistant has been given play in these complementary effects.
As with the organic fibre of polyamidoimide and usefulness, most preferably the reason of carbon fiber is, when for the imido composition of mixed polyamide in fluoro-resin, when formative stage high temperature burns till, the part of polyamidoimide is thermal decomposited, and produces the space easily on formed body, and its result causes mechanical characteristics to descend easily, but by and with polyamidoimide and carbon fiber, can suppress to produce the space.Still indeterminate about the detailed reason that suppresses the generation space, but be considered to, carbon fiber has the polyamidoimide of inhibition pyrolysated effect.
As mentioned above, by mixed polyamide imide and organic fibre in organic polymer and modified fluorin resin, can access when keeping the original good characteristic of fluoro-resin to be low frictional properties, thermotolerance, electrical specification, resistance to chemical reagents and spatter property (non-polluting) modified fluorin resin composition that the wear resistant under the high surface pressure is also excellent.
And by in having the mould of the shape set arbitrarily, the modified fluorin resin composition to set arbitrarily that the above-mentioned present embodiment of pressure forming relates to can obtain the modified fluorin resin formed body.About the purposes of this modified fluorin resin formed body, can expect to be applied to purposes widely such as slide unit, sealing member, gasket, air packing, the relevant manufacture component (container, anchor clamps, pipeline) of semi-conductor.
Embodiment
Below in conjunction with embodiment and comparative example, specifically describe the present invention.
In oxygen concn 1torr, nitrogen atmosphere, 340 ℃ temperature, (the Asahi Glass corporate system, trade(brand)name: P-192), irradiation 100kGy electron rays (acceleration voltage 2MeV) carries out modification to PTFE.With injector-type mill its micro mist is broken into median size 20 μ m.
Make up this modified ptfe (modified fluorin resin), PTFE (organic polymer), polyamidoimide (median size 30 μ m, maximum particle diameter 80 μ m), and carbon fiber (organic fibre), mix and make various mixtures (embodiment 1～4 and comparative example 1～3).Composition at the various mixtures of table 1 expression.Using mixing tank, all is under 15 ℃ the condition, to mix these materials in material temperature and atmosphere temperature.Carbon fiber is to use two kinds of carbon fiber A (Fibre diameter 5 μ m, staple length 50 μ m, slenderness ratio 10) and carbon fiber B (Fibre diameter 5 μ m, staple length 100 μ m, slenderness ratio 20).The mixture of embodiment 4 is except these materials, also to comprise molybdenumdisulphide (Dow Corning Corporation's system, the trade(brand)name: Mo Like Z) of 2 weight parts.
Table 1
Use level is a weight part
| Form | Embodiment | Comparative example | |||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| PTFE modified ptfe polyamidoimide carbon fiber A carbon fiber B molybdenumdisulphide | 75 10 10 5 | 65 10 15 10 | 65 20 5 10 | 67 11 10 10 2 | 80 10 10 | 80 15 5 | 75 15 10 |
Polyamidoimide: median size 30 μ m, maximum particle diameter 80 μ m
Carbon fiber A: Fibre diameter 5 μ m, staple length 50 μ m, slenderness ratio 10
Carbon fiber B: Fibre diameter 5 μ m, staple length 100 μ m, slenderness ratio 20
Molybdenumdisulphide: Mo Like Z (Dow Corning Corporation)
When using various mixtures to make formed body, be to use unburned connection in embodiment 1 and the comparative example 1, other then use hot-forming method.Use the mould of φ 45 * high 80mm in the compressed moulding, carry out compressed moulding with the pressure of 50MPa at normal temperature.Then, be under atmospheric pressure to burn till in unburned connection with 360 ℃ * 2 hours, make the formation of lots body, on the other hand, in hot-forming method, then after burning till, take out together with mould at normal temperatures, with forming pressure 20MPa compressed moulding, make the formation of lots body.Each formation of lots body for making like this cuts, and makes each test film.
The characteristic of following evaluation gained test film (tight, sliding properties are arranged).Wherein, the mensuration number that is used to estimate each characteristic is, gets three points for each test film, with its arithmetical mean as mean value.Characteristic at each test film of table 2 expression.
About tight is arranged, be the sheet that downcuts thickness 1mm from each formation of lots body, use the surface of each sheet of microscopic examination of magnification 20, whether investigation has the space.
Evaluation about sliding properties (wear resistant), be to use ring to dish (ring on disk) wear test device, according to JIS K7218, go up applying test film (external diameter 25.6mm, internal diameter 20.6mm, thickness 1mm) at cylinder ring (external diameter 25.6mm, internal diameter 20.6mm), respective material is used SUS304 plate (vertical 30mm, horizontal 30mm, thick 5mm, surface roughness Ra 0.2 μ m), carries out under the condition of pressure 4MPa, speed 60m/min.The test atmosphere is in air, 20 ℃ of temperature.After 24 hours on-tests, measure the loss of weight amount, obtain relative wear loss V by following formula
SA, measure frictional coefficient simultaneously.
V
SA＝V/(P·L)
V: wear loss, P: test is born a heavy burden, L: average sliding distance
Table 2
| Characteristic | Embodiment | Comparative example | |||||
| 1 | 2 | 3 | 4 | 1 | 2 | 3 | |
| The relative wear loss (* 10 of tight sliding properties is arranged -8mm 3/ Nm) frictional coefficient | Do not have 50 0.18 | Do not have 35 0.20 | Do not have 72 0.18 | Do not have 95 0.17 | Have 1,500 0.17 | Do not have 280 0.21 | Do not have 2,300 0.24 |
As shown in table 2, each test film of embodiment 1～4 all be can't see the space.In addition, the relative wear loss of each test film is all little, 35～95 (* 10
-8Mm
3/ Nm) between, simultaneously frictional coefficient is also low, about 0.18, the wear resistant excellence.
With respect to this, the test film of comparative example 1, its formed body can be seen the space, and then relative wear loss height, is 1500 (* 10
-8Mm
3/ Nm), wear resistant is poor.
In addition, do not contain polyamidoimide comparative example 2, do not contain each test film of the comparative example 3 of modified fluorin resin, wear loss is all high relatively, compares with each test film of embodiment 1～4, wear resistant descends significantly.
Claims (10)
1. modified fluorin resin composition is at organic polymer and carry out with the ionization radioactive rays that mixed polyamide imide and organic fibre form in the fluoro-resin of modification.
2. according to the modified fluorin resin composition of claim 1 record, described modified fluorin resin, polyamidoimide, and the total weight of organic fibre be 10 weight parts～50 weight parts of gross weight, wherein, modified fluorin resin accounts for 5 weight parts～30 weight parts of gross weight, 2 weight parts～15 weight parts that polyamidoimide accounts for gross weight, 3 weight parts～10 weight parts that organic fibre accounts for gross weight.
3. according to the modified fluorin resin composition of claim 1 or 2 records, described organic fibre is a carbon fiber.
4. according to the modified fluorin resin composition of each record in the claim 1～3, described organic fibre is length 1～300 μ m, slenderness ratio 1～500.
5. according to the modified fluorin resin composition of each record in the claim 1～4, described organic polymer is more than select from tetrafluoroethylene based polymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) based polymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) based polymer at least a.
6. according to the modified fluorin resin composition of claim 5 record, described polytetrafluoroethyl-ne alkene copolymer contains 1 mole of % with the second interior composition or a plurality of ternary heterogeneous fluorine monomer.
7. according to the modified fluorin resin composition of each record in the claim 1～6, the crystallization heat of described modified fluorin resin is below the 40J/g, and fusing point is below 325 ℃.
8. according to the modified fluorin resin composition of each record in the claim 1～7, the fluoro-resin of described modified fluorin resin is more than select from tetrafluoroethylene based polymer, tetrafluoroethylene-perfluor (alkyl vinyl ether) based polymer, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) based polymer at least a.
9. according to the modified fluorin resin composition of each record in the claim 1～8, described modified fluorin resin is with in the atmosphere of inert gases of fluoro-resin below oxygen concn 10torr and be heated under its state more than fusing point with the scope irradiation ionization radioactive rays of illuminated line amount 1kGy～10MGy and obtain.
10. use the modified fluorin resin composition of each record in the claim 1～9 and the formed body of moulding.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005363772 | 2005-12-16 | ||
| JP2005363772 | 2005-12-16 |
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|---|---|
| CN1982366A true CN1982366A (en) | 2007-06-20 |
| CN100489026C CN100489026C (en) | 2009-05-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102625A (en) * | 2012-12-27 | 2013-05-15 | 上海长园电子材料有限公司 | Fluorine plastic and fluorine plastic sleeve |
| CN104662084A (en) * | 2012-08-10 | 2015-05-27 | Nok株式会社 | Fluororubber composition |
| CN104411752B (en) * | 2012-07-05 | 2017-06-23 | 大金工业株式会社 | The manufacture method of modified fluoride-containing copolymer, fluororesin products formed and fluororesin products formed |
| CN114933771A (en) * | 2022-05-25 | 2022-08-23 | 济南赛诺富隆新材料有限公司 | High-temperature wear-resistant material and preparation method and application thereof |
-
2006
- 2006-11-27 CN CNB2006101468866A patent/CN100489026C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411752B (en) * | 2012-07-05 | 2017-06-23 | 大金工业株式会社 | The manufacture method of modified fluoride-containing copolymer, fluororesin products formed and fluororesin products formed |
| CN104662084A (en) * | 2012-08-10 | 2015-05-27 | Nok株式会社 | Fluororubber composition |
| CN104662084B (en) * | 2012-08-10 | 2016-10-05 | Nok株式会社 | Fluoro-rubber composite |
| US9505905B2 (en) | 2012-08-10 | 2016-11-29 | Nok Corporation | Fluororubber composition |
| CN103102625A (en) * | 2012-12-27 | 2013-05-15 | 上海长园电子材料有限公司 | Fluorine plastic and fluorine plastic sleeve |
| CN114933771A (en) * | 2022-05-25 | 2022-08-23 | 济南赛诺富隆新材料有限公司 | High-temperature wear-resistant material and preparation method and application thereof |
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| CN100489026C (en) | 2009-05-20 |
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