Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article

Abstract

The present invention aims to provide a modified fluorine-containing copolymer excellent in crack resistance, a fluororesin molded article, and a method of producing a fluororesin molded article. The present invention includes a modified fluorine-containing copolymer consisting only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units. The copolymer is modified by irradiation with radiation at an irradiation temperature not higher than the melting point of the copolymer but not lower than 200 C.

Claims

1. A modified fluorine-containing copolymer consisting only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units, the copolymer being modified by irradiation with radiation at an irradiation temperature that is 27 C. or more lower than the melting point of the copolymer but not lower than 230 C. and an irradiation dose of 20 kGy to 200 kGy, wherein the copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units contains the perfluoro(alkyl vinyl ether) units in an amount of 0.1 to 12% by mass based on all the monomer units, wherein the perfluoro(alkyl vinyl ether) is perfluoro(alkyl vinyl ether) represented by Formula (1):
CF.sub.2CFOR.sup.f(1) wherein R.sup.f represents a C1 to C5 perfluoroalkyl group.

2. A fluororesin molded article comprising: the modified fluorine-containing copolymer according to claim 1.

3. A fluororesin molded article obtained by a method of producing a molded article, the method comprising: molding a copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units; and irradiating the molded copolymer with radiation at an irradiation temperature that is 27 C. or more lower than the melting point of the copolymer but not lower than 230 C. and an irradiation dose of 20 kGy to 200 kGy, wherein the copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units contains the perfluoro(alkyl vinyl ether) units in an amount of 0.1 to 12% by mass based on all the monomer units, wherein the perfluoro(alkyl vinyl ether) is perfluoro(alkyl vinyl ether) represented by Formula (1):
CF.sub.2CFOR.sup.f(1) wherein R.sup.f represents a C1 to C5 perfluoroalkyl group, and wherein the fluororesin molded article has a thickness of 0.01 to 10 mm.

4. The fluororesin molded article according to claim 3, wherein the molding is performed by compression molding, injection molding, or extrusion molding.

5. The fluororesin molded article according to claim 2, wherein the fluororesin molded article is a sheet.

6. The fluororesin molded article according to claim 2, wherein the copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units has a melting point of 280 C. to 322 C.

7. The fluororesin molded article according to claim 2, wherein the perfluoro(alkyl vinyl ether) is perfluoro(propyl vinyl ether).

8. A method of producing a fluororesin molded article, the method comprising: molding a copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units; and irradiating the molded copolymer with radiation at an irradiation temperature that is 27 C. or more lower than the melting point of the copolymer but not lower than 230 C. and an irradiation dose of 20 kGy to 200 kGy, wherein the copolymer that consists only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units contains the perfluoro(alkyl vinyl ether) units in an amount of 0.1 to 12% by mass based on all the monomer units, wherein the perfluoro(alkyl vinyl ether) is perfluoro(alkyl vinyl ether) represented by Formula (1):
CF.sub.2CFOR.sup.f(1) wherein R.sup.f represents a C1 to C5 perfluoroalkyl group, and wherein the fluororesin molded article has a thickness of 0.01 to 10 mm.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention is described in detail below.

(2) One aspect of the present invention is a modified fluorine-containing copolymer consisting only of tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units. The copolymer is modified by irradiation with radiation at an irradiation temperature not higher than the melting point of the copolymer but not lower than 200 C. The modified fluorine-containing copolymer is thus excellent in crack resistance.

(3) The modified fluorine-containing copolymer of the present invention is obtainable by irradiating the copolymer that consists only of tetrafluoroethylene (TFE) units and perfluoro(alkyl vinyl ether) (PAVE) units (hereinafter, also referred to as a TFE/PAVE copolymer) with radiation at an irradiation temperature in a specific range.

(4) Examples of the PAVE constituting the TFE/PAVE copolymer include at least one selected from the group consisting of PAVE represented by Formula (1):
CF.sub.2CFO(CF.sub.2CFY.sup.1O).sub.p(CF.sub.2CF.sub.2CF.sub.2O).sub.qR.sup.f(1)
wherein Y.sup.1 represents F or CF.sub.3; R.sup.f represents a C1 to C5 perfluoroalkyl group; p represents an integer of 0 to 5; and q represents an integer of 0 to 5, and Formula (2):
CFXCXOCF.sub.2OR.sup.1(2)
wherein Xs are the same as or different from each other, each representing H, F, or CF.sub.3; R.sup.1 represents a C1 to C6 straight chain or branched fluoroalkyl group that may contain one or two atoms of at least one selected from the group consisting of H, Cl, Br, and I or a C1 to C5 or C6 cyclic fluoroalkyl group that may contain one or two atoms of at least one selected from the group consisting of H, Cl, Br, and I.

(5) The PAVE preferably contains a bulky side chain. In particular, the PAVE is preferably perfluoro(propyl vinyl ether).

(6) The TFE/PAVE copolymer preferably contains polymer units based on PAVE in an amount of 0.1 to 12% by mass, more preferably 1.0 to 8.0% by mass, still more preferably 2.0 to 6.5% by mass, and particularly preferably 3.5 to 6.0% by mass based on all the polymer units.

(7) The amount of the polymer units based on PAVE may be measured by .sup.19F-NMR.

(8) The TFE/PAVE copolymer preferably has a melting point of 280 to 322 C. The melting point is more preferably not lower than 285 C., and also more preferably not higher than 315 C.

(9) The melting point herein is a temperature corresponding to a local maximum value on a heat of fusion curve that is determined by increasing the temperature of the copolymer at a rate of 10 C./min using a differential scanning calorimeter [DSC].

(10) The TFE/PAVE copolymer preferably has a glass transition temperature (Tg) of 70 C. to 110 C.

(11) The glass transition temperature is more preferably not lower than 80 C., and also more preferably not higher than 100 C.

(12) The glass transition temperature herein is measured by dynamic viscoelasticity measurement.

(13) The TFE/PAVE copolymer can be produced by a conventionally known method. For example, the copolymer can be produced by appropriately mixing monomers as the constitutional units with additives such as a polymerization initiator and performing emulsion polymerization, solution polymerization, suspension polymerization, or the like.

(14) The TFE/PAVE copolymer preferably has a melt flow rate (MFR) of 1 to 50 g/10 min at 372 C. If the MFR is within this range, a remarkable crosslinking effect can be obtained.

(15) The MFR is more preferably not lower than 10 g/10 min, and also more preferably not higher than 40 g/10 min. The MFR herein is determined in accordance with ASTM D1238. Specifically, it is determined as the mass of the polymer exiting from a nozzle (inner diameter: 2 mm, length: 8 mm) per 10 minutes measured with a melt indexer (from Yasuda Seiki seisakusho Ltd.) at 372 C. under a load of 5 kg.

(16) In the present invention, the TFE/PAVE copolymer is irradiated with radiation at an irradiation temperature not higher than the melting point of the copolymer but not lower than 200 C. Therefore, even if the irradiation is performed after molding the TFE/PAVE copolymer into the desired shape, the molded article does not lose its shape.

(17) The reason why the crack resistance of the TFE/PAVE copolymer is improved by such heating of the TFE/PAVE copolymer to a temperature in the above-described specific range and irradiation is presumably as follows. The TFE/PAVE copolymer contains a large amount of large side chains that comprise alkoxy groups, and molecular motion of these side chains is large even at lower temperatures. This allows the effects of the irradiation to be sufficiently produced even at low temperatures.

(18) The irradiation temperature is not higher than the melting point of the TFE/PAVE copolymer but not lower than 200 C. When the irradiation temperature is not lower than 200 C., a fluorine-containing copolymer and a fluororesin molded article each excellent in crack resistance can be obtained. The irradiation temperature is more preferably not lower than 210 C., and still more preferably not lower than 230 C., and also preferably not higher than 300 C., more preferably not higher than 270 C., and still more preferably not higher than 265 C. If the irradiation temperature is within the above range, the copolymer has even better crack resistance.

(19) The irradiation temperature is preferably more than 20 C. lower than the melting point of the TFE/PAVE copolymer, and more preferably 25 C. or more lower than the melting point.

(20) The way of adjustment of the irradiation temperature is not particularly limited, and the temperature may be adjusted by a conventionally known method. Specifically, the irradiation temperature may be adjusted by, for example, holding the TFE/PAVE copolymer in a heating furnace maintained at a predetermined temperature. Alternatively, it may be adjusted by placing the copolymer on a hot plate and heating the hot plate by powering a heater built therein or by using an external heating means.

(21) Examples of the radiation include electron beam, ultraviolet rays, gamma rays, X-rays, neutron rays, and high energy ions. Among these, electron beam is preferred in view of excellent penetrating power, high dose rates, and suitable for industrial production.

(22) The way of irradiation with radiation is not particularly limited. For example, the irradiation may be performed with a conventionally known radiation irradiation device.

(23) The irradiation dose is preferably 10 kGy to 250 kGy. If the irradiation dose is less than 10 kGy, production of radicals that are involved in crosslinking reaction may be insufficient, which may lead to insufficient crosslinking effect. If the irradiation dose is more than 250 kGy, the copolymer may be degraded to lower molecular weight products due to main-chain break, which may significantly reduce mechanical strength.

(24) The irradiation dose is more preferably not less than 20 kGy, and still more preferably not less than 30 kGy, and also preferably not higher than 100 kGy, still more preferably not higher than 90 kGy, and particularly preferably not higher than 80 kGy.

(25) The irradiation environment is not particularly limited. The irradiation is preferably performed at an oxagen concentration of not higher than 1000 ppm, more preferably in the absence of oxygen, and still more preferably in vacuum or in an inert gas atmosphere such as nitrogen, helium, or argon atmosphere.

(26) Thus, the irradiation of the TFE/PAVE copolymer with radiation at an irradiation temperature within a specific range can provide a modified fluorine-containing copolymer having excellent crack resistance.

(27) A fluororesin molded article produced from the modified fluorine-containing copolymer of the present invention is another aspect of the present invention.

(28) The fluororesin molded article of the present invention is preferably produced by a method including: molding a copolymer (a TFE/PAVE copolymer) that consists only of TFE units and PAVE units; and irradiating the molded copolymer with radiation at an irradiation temperature not higher than the melting point of the copolymer but not lower than 200 C.

(29) A fluororesin molded article produced by such a specific production method is another aspect of the present invention.

(30) In the present invention, the TFE/PAVE copolymer is molded into the desired shape and then irradiated with radiation at the above-mentioned irradiation temperature, so that the resulting molded article can have excellent crack resistance.

(31) Examples of the TFE/PAVE copolymer include those described above.

(32) The way of molding the TFE/PAVE copolymer is not particularly limited. The TFE/PAVE copolymer may be molded by, for example, a conventionally known method such as extrusion molding, injection molding, transfer molding, inflation method, or compression molding. These molding methods can be appropriately selected depending on the shape of the molded article to be obtained.

(33) Among these, compression molding, injection molding, and extrusion molding are preferred, with injection molding and extrusion molding being more preferred from the viewpoint of easy formation of very small or complex shapes.

(34) Particularly preferred examples of the extrusion molding include wire coating extrusion molding, tube extrusion molding, profile extrusion molding, film extrusion molding, and fiber extrusion molding and the like, are especially the most suitable.

(35) The fluororesin molded article of the present invention is produced through irradiation with radiation after the step of molding of the copolymer mentioned above.

(36) The same way as described above may be employed for irradiating the TFE/PAVE copolymer molded into the desired shape with radiation at an irradiation temperature not higher than the melting point of the TFE/PAVE copolymer but not lower than 200 C.

(37) The fluororesin molded articles of the present invention may further contain other components depending on the needs. Examples of other components include additives, such as cross-linking agents, antistatic agents, heat stabilizer, foaming agents, foam nucleating agents, antioxidants, surfactants, photopolymerization initiators, antiwear agents, and surface modifiers.

(38) The form of the fluororesin molded articles of the present invention is not particularly limited. Examples thereof include films, sheets, plates, rods, blocks, cylinders, containers, wires, and tubes. Among these, sheets and wires are preferred because they are demanding with respect to crack resistance. More preferred are sheets.

(39) The sheets preferably have a thickness of 0.01 to 10 mm.

(40) Examples of applications of the fluororesin molded articles of the present invention include, but not limited to, the following applications:

(41) a diaphragm of diaphragm pumps, bellows molded articles, wire-coated products, semiconductor components, packings and seals, thin wall tubes for rollers in copy machines, monofilaments, gaskets, optical lens parts, tubes for oil drilling, wires for satellites, wires for nuclear power generation, and solar battery panel films.

(42) The fluororesin molded products are especially preferably used in members which require resistance to cracks caused by repeated movement, such as a diaphragm of diaphragm pumps, bellows molded articles, and wire coating materials.

(43) Yet another aspect of the present invention is a method of producing a fluororesin molded article. The method includes molding a TFE/PAVE copolymer; and irradiating the molded copolymer with radiation at an irradiation temperature not higher than the melting point of the copolymer but not lower than 200 C.

(44) The step of molding the TFE/PAVE copolymer may be performed by the above-described method for molding the TFE/PAVE copolymer.

(45) The step of irradiation with radiation may be performed by the above-described method for irradiating TFE/PAVE copolymer with radiation.

(46) As described above, according to the present invention, a modified fluorine-containing copolymer and a fluororesin molded article each having an improved crack resistance can be provided.

EXAMPLES

(47) The present invention is described in more detail below based on, but not limited to, examples.

(48) The amount of the monomer units, the melt flow rate, (MFR), the melting point, and the glass transition temperature were determined by the following methods.

(49) (Amount of Monomer Units)

(50) The amount of each monomer unit was determined by .sup.19F-NMR.

(51) (MFR)

(52) The MFR was determined in accordance with ASTM D1238. Specifically, the mass (g) of the polymer exiting from a nozzle (inner diameter: 2 mm, length: 8 mm) per 10 minutes was measured using a melt indexer (from Yasuda Seiki seisakusho Ltd.) at 372 C. under a load of 5 kg.

(53) (Glass Transition Temperature)

(54) The glass transition temperature was determined by a dynamic viscoelasticity measurement using DVA-220 (IT Keisoku Seigyo K.K.). The measurement was performed at a temperature-increasing rate of 2 C./min at a frequency of 10 Hz. The temperature at which the tan reached the peak was employed as the glass transition temperature.

(55) (Melting Point)

(56) The melting point is a temperature corresponding to a local maximum value on a heat of fusion curve measured at a temperature rise of 10 C./min using a differential scanning calorimeter [DSC].

Example 1

(57) A tetrafluoroethylene (TFE)/perfluoro(propyl vinyl ether)(PAVE) copolymer [TFE/PAVE=94.5/5.5 (% by mass), MFR: 30 g/10 min, melting point: 302 C., glass transition temperature: 93 C.] was processed into a sheet having a thickness of 0.215 mm with a heat-press molding machine. A strip-shaped specimen (width: 12.5 mm, length: 130 mm) was cut out of the sheet.

(58) The specimen was housed in an electron beam irradiation vessel of an electron beam irradiation device (from NHV Corporation). Thereafter, nitrogen gas was injected to place the vessel under a nitrogen atmosphere. The vessel was heated to have an inner temperature of 245 C., and after the temperature was stabilized, the specimen was irradiated with electron beam at an electron beam accelerating voltage of 3000 kV at an intensity of the irradiation dose of 20 kGy/5 min.

(59) The irradiated specimen was subjected to the following MIT repetitive folding test. The result is shown in Table 1.

(60) (MIT Repetitive Folding Test)

(61) The test was performed in accordance with ASTM D2176. Specifically, the obtained specimen (width: 12.7 mm, length: 130 mm) irradiated with electron beam was mounted on a MIT measuring device (model 12176, from Yasuda Seiki seisakusho Ltd.) and was folded under the following conditions: load: 1.25 kg, folding angle: 135 degrees on each of the right and the left sides, and the folding frequency: 175 times/min. The number of folds before the specimen broke (the number of MIT repetition times) was determined.

Examples 2 to 9, Comparative Example 2

(62) Specimens were obtained and subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the electron beam irradiation was performed at the irradiation temperatures and the irradiation doses shown in Table 1. The results are shown in Table 1.

Comparative Example 1

(63) A specimen was obtained and subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the specimen was not irradiated with electron beam. The result is shown in Table 1.

Examples 10 to 14, Comparative Examples 3 and 4

(64) Specimens were obtained in the same manner as in Example 1 except that a tetrafluoroethylene(TFE)/perfluoro(propyl vinyl ether)(PAVE) copolymer [TFE/PAVE=99.9/0.1 (% by mass), MFR: 0.1 g/10 min, melting point: 320 C., glass transition temperature: 105 C.] was used as the material.

(65) The specimens were each subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the electron beam irradiation was performed at the irradiation temperature and the irradiation dose shown in Table 2. The results are shown in Table 2.

Examples 15 to 19, Comparative Examples 5 and 6

(66) Specimens were obtained in the same manner as in Example 1 except that a tetrafluoroethylene (TFE)/perfluoro(propyl vinyl ether)(PAVE) copolymer [TFE/PAVE=88/12 (% by mass), MFR: 40 g/10 min, melting point: 260 C., glass transition temperature: 80 C.] was used as the material.

(67) The specimens were each subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the electron beam irradiation was performed at the irradiation temperature and the irradiation dose shown in Table 3. The results are shown in Table 3.

Examples 20 to 24, Comparative Examples 7 and 8

(68) A tetrafluoroethylene (TFE)/perfluoro(propyl vinyl ether)(PAVE) copolymer [TFE/PAVE=94.5/5.5 (% by mass), MFR 12 g/10 min, melting point: 302 C., glass transition temperature: 93 C.] was processed into a sheet having a thickness of 0.215 mm with an injection molding machine. A strip-shaped specimen (width: 12.5 mm, length: 130 mm) was cut out of the sheet.

(69) The specimen was subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the electron beam irradiation was performed at the irradiation temperature and the irradiation dose shown in Table 4. The results are shown in Table 4.

Examples 25 to 29, Comparative Examples 9 and 10

(70) A tetrafluoroethylene (TFE)/perfluoro(propyl vinyl ether)(PAVE) copolymer [TFE/PAVE=94.5/5.5 (% by mass), MFR: 3 g/10 min, melting point: 302 C., glass transition temperature: 93 C.] was processed into a sheet that had a thickness of 0.215 mm with an extrusion molding machine. A strip-shaped specimen (width: 12.5 mm, length: 130 mm) was cut out of the sheet.

(71) The specimen was subjected to the MIT repetitive folding test in the same manner as in Example 1 except that the electron beam irradiation was performed at the irradiation temperature and the irradiation dose shown in Table 5. The results are shown in Table 5.

(72) TABLE-US-00001 TABLE 1 Examples Comparative Examples 1 2 3 4 5 6 7 8 9 1 2 Electron beam irradiation not irradiated Irradiation temperature ( C.) 245 260 260 260 275 215 290 245 245 60 Irradiation dose (kGy) 60 20 40 60 40 40 40 150 200 60 MIT repetitive folding test 63 103 376 70 218 57 85 89 61 53 47 (one thousand times)

(73) TABLE-US-00002 TABLE 2 Comparative Examples Examples 10 11 12 13 14 3 4 Electron beam irradiation not irradiated Irradiation 245 260 260 260 275 60 temperature ( C.) Irradiation dose (kGy) 60 20 40 60 40 60 MIT repetitive folding test 18 53 107 38 78 17 9 (one thousand times)

(74) TABLE-US-00003 TABLE 3 Comparative Examples Examples 15 16 17 18 19 5 6 Electron beam irradiation not irradiated Irradiation temperature 245 260 260 260 275 60 ( C.) Irradiation dose (kGy) 60 20 40 60 40 60 MIT repetitive folding test 12 20 65 25 34 10 3 (one thousand times)

(75) TABLE-US-00004 TABLE 4 Comparative Examples Examples 20 21 22 23 24 7 8 Electron beam irradiation not irradiated Irradiation temperature ( C.) 245 260 260 260 275 60 Irradiation dose (kGy) 60 20 40 60 40 60 MIT repetitive folding test 138 264 732 324 240 120 54 (one thousand times)

(76) TABLE-US-00005 TABLE 5 Comparative Examples Examples 25 26 27 28 29 9 10 Electron beam irradiation not irradiated Irradiation temperature 245 260 260 260 275 60 ( C.) Irradiation dose (kGy) 60 20 40 60 40 60 MIT repetitive 183 255 1020 180 600 150 61.5 folding test (one thousand times)

INDUSTRIAL APPLICABILITY

(77) The molded article produced from the modified fluorine-containing copolymer of the present invention can be used in various applications requiring crack resistance, such as a diaphragm of diaphragm pumps or bellows molded articles.