JP4845017B2 - High strength high crystalline tetrafluoroethylene resin compression molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article of a tetrafluoroethylene resin having high crystallinity, elongation and tear strength and remarkably improved gas permeability, compression creep, linear expansion coefficient, etc., while keeping practical strength by a versatile industrial technique comprising the irradiation of tetrafluoroethylene resin powder with ionizing radiation, compression molding of the irradiated powder at room temperature and baking of the molded product. <P>SOLUTION: The compression-molded article of tetrafluoroethylene resin has a crystal melting heat of 27-40 J/g and high elongation characterized by the tensile strength retention of &ge;1/2 of the article produced from resin powder free from irradiation with ionizing radiation. The article is produced by using tetrafluoroethylene resin powder for molding having an absorption dose of ionizing radiation of 0.5-3 kGy. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is a practical strength obtained by using a technique based on a free baking method in which a tetrafluoroethylene resin (PTFE) powder used for molding is preliminarily irradiated with ionizing radiation, compression-molded at room temperature, and then sintered. It is related with the compression molding body of the tetrafluoroethylene resin which hold | maintains and has a high crystallinity and a high drawability.

  Tetrafluoroethylene resin has a large bond energy between carbon and fluorine forming its molecular chain, and is extremely dense and stable, so it originally has a high degree of crystallinity, and even at a temperature higher than the melting point (327 ° C). Since it has almost no melt fluidity, it is known as a polymer excellent in heat resistance and chemical resistance that cannot be injection-molded or extruded as in ordinary plastics. In general, the crystallinity of the tetrafluoroethylene resin powder for molding is 93% to 98%, but the crystallinity of the fired product formed using this powder is usually 50 to 60%. On the other hand, the radiation resistance of the tetrafluoroethylene resin thus molded is extremely low, the molecular chain is cut by receiving ionizing radiation, and the mechanical properties of strength and elongation are drastically reduced. It is known to be a typical decay type resin. Therefore, after irradiating the molded tetrafluoroethylene resin with ionizing radiation, it is heated again to a temperature above the melting point, melted, and then slowly cooled, so that the broken molecular chains are rearranged and crystallization proceeds. Further, it is speculated that the degree of crystallinity further increases, and is already known. In this case, the increase in crystallinity leads to an increase in elongation in mechanical properties, but the strength is further reduced, so that the practical strength is impaired. For example, this high stretching is applied to the manufacturing and processing technology of a stretched tetrafluoroethylene resin porous membrane. If it is going to utilize the property, it is inevitable that technical difficulties are involved because the tensile strength at break is low. On the other hand, the tetrafluoroethylene resin obtained by irradiating a certain dose of ionizing radiation to the molding tetrafluoroethylene resin powder by the present inventors and surprisingly suppressing the deterioration of mechanical properties Rather, it has been found that rather excellent material properties such as an increase in tear strength and elongation have been developed, and it has been proposed as a modification means that radiation irradiation does not necessarily lead to collapse (Patent Documents 1 and 2 and 3).

However, these documents are basically molding under melt pressure and are limited to the case of quenched tetrafluoroethylene resin. In other words, room temperature compression molding of the tetrafluoroethylene resin powder compression molded at room temperature, which is the most widely used molding technology in the industry, was examined at room temperature and crystallinity by a slow heat treatment process. This has not been mentioned for material properties. Therefore, the actual situation is that the application range of the tetrafluoroethylene resin powder irradiated with ionizing radiation has been narrowed without any obvious support through the compression process and the heat treatment process so far.
Japanese Patent Laid-Open No. 2001-335643 JP 2002-256080 A JP 2004-149650 A

  The present invention is a general industrial technology for firing after compression molding the tetrafluoroethylene resin powder previously irradiated with ionizing radiation at room temperature, maintaining practical strength, high crystallinity, high stretchability and tear strength, Furthermore, it is an object of the present invention to widely spread as an industrial technique by providing a molded article of ethylene tetrafluoride resin that has remarkably improved gas permeability, compression creep, linear expansion coefficient, and the like.

  The inventors of the present invention have long been irradiated with ionizing radiation to a powder for forming a tetrafluoroethylene resin, and variously produced by compression molding in a molten state at a temperature of 327 ° C. or higher, which is the melting point of the tetrafluoroethylene resin. We have studied the irradiation effect. However, the effect of irradiation obtained by compression-molding this at room temperature, then releasing the pressure, and subsequent firing is unknown because the resin is crystalline, so the relationship with the firing conditions cannot be determined. Therefore, the inventors have intensively studied to find out the mutual relationship between compression and firing of tetrafluoroethylene resin and the irradiation conditions of ionizing radiation, and found that there are many obvious added values for the molded product. The present invention has been reached.

That is, the present invention
(1) By using a powder for molding tetrafluoroethylene resin that has been pre-irradiated with ionizing radiation, the heat of crystal melting of the molded resin is in the range of 27 J / g to 40 J / g, and the tensile rupture strength retention rate A tetrafluoroethylene resin compression-molded body by a free baking method, which has a high stretchability that is 1/2 or more when using a molding powder that does not irradiate ionizing radiation,
(2) A tetrafluoroethylene resin compression molded article by the free baking method of (1) above, wherein the absorbed dose of ionizing radiation applied to the powder of tetrafluoroethylene resin molding is 0.5 kGy to 3 kGy,
(3) Tetrafluoroethylene resin produced by the free baking method of (1) above, which is a powder for molding tetrafluoroethylene resin mixed with fibrous materials such as carbon, carbon graphite, glass, and econol or powder as filler. Compression molded body,
(4) The tetrafluoroethylene resin compression-molded body by the free baking method of the above (1), in which the gas permeability, linear expansion coefficient, compression creep, etc. of the molded resin are kept low and the physical properties are improved,
(5) A machined product obtained by machining using the tetrafluoroethylene resin compression molded article according to (1) above,
(6) A porous body of tetrafluoroethylene resin stretched using a tape or sheet cut by machining from the tetrafluoroethylene resin compression-molded body described in (1) above,
Is to provide.

  In the present invention, the irradiation absorbed dose of ionizing radiation to the tetrafluoroethylene resin molding powder is limited to 0.5 kGy to 3 kGy, which is fired after compression molding, and the crystal has a high heat of crystal melting of the resin after firing. By adjusting it to the range of 27 J / g to 40 J / g, which shows the properties, it maintains the practical strength of the molded product, high crystallinity, high stretchability and tear strength, gas permeability, compression creep, wire It is possible to obtain a molded product of a tetrafluoroethylene resin with significantly improved expansion coefficient and the like.

  In the compression molding of the tetrafluoroethylene resin (PTFE) in the present invention, a molding powder having an excellent compression aggregation property is usually used. In addition, the molding powder may be a mixture of a fibrous substance such as carbon, carbon graphite, glass, and econol, or powder as a filler in order to improve the wear resistance of the molded product. This molding powder is preliminarily irradiated with ionizing radiation at room temperature and in the atmosphere, and the absorbed dose is in the range of 0.5 kGy to 3 kGy (kilo gray). Here, ionizing radiation refers to γ-rays, electron beams, X-rays, neutron beams, and high-energy ions, and these may be used alone or in combination of two or more.

  In the present invention, the holding pressure and holding time at the time of compression molding do not need to modify the prior art in particular, and there is no effect on the physical properties after firing in the preforming at 30 MPa to 40 MPa for 10 minutes to 15 minutes, It is recommended that the time required to increase to a predetermined holding pressure is about 1/3 of the holding time referred to here and that the pressure is increased as linearly as possible.

  The temperature when free-baking the preform is preferably low, and the time is preferably short. In other words, if fired for a long time at a high temperature, the tensile strength at break tends to decrease. Therefore, if firing for a long time is necessary, a firing temperature as low as possible is selected and at 350 ° C. for at least 4 hours or more. It is preferable that For example, the firing conditions for compression molded rods with a diameter of 50 mm and a height of 70 mm are selected from 350 ° C. to 380 ° C., and the firing time is 350 ° C. for 4 hours or longer, 360 ° C. for 2 hours or longer, and 380 ° C. for 1 hour. More than needed. Moreover, crystallinity can be further improved by taking a long baking time. At this time, the time required for the temperature to rise to a predetermined firing temperature, and the rate at which the temperature is lowered from the predetermined firing temperature to room temperature is preferably 70 ° C. to 80 ° C. per hour. Inconveniences such as internal cracks are likely to occur.

  The practical strength of the tetrafluoroethylene resin in the present invention thus molded and baked is that when the tensile fracture strength measured with respect to the cutting tape is molded using non-irradiated molding powder (when the dose is 0). Say that you hold over 50%. That is, the absorbed dose of the molding powder with which practical strength can be obtained in the present invention is 3 kGy or less. A cutting sheet formed by using an unirradiated molding powder by a conventional method is irradiated with ionizing radiation, and its tensile breaking strength is 50 It is one of the features of the present invention that the absorbed dose is about three times higher than the common-sense absorbed dose (0.8 to 0.9 kGy) that is less than or equal to%.

  High stretchability is recovered at a dose of 1.5 kGy or less, usually by compressing the non-irradiated molding powder and then subjecting the fired rod cutting tape to ionizing radiation and then annealing again. 1 is based on the elongation at room temperature as shown in FIG. 1 and is in the range of 150 to 175% when not irradiated. In this case, recovery of the tensile rupture strength due to annealing is not recognized, and it is common knowledge that the strength retention rate is reduced to 50% or less when not irradiated at a dose of 0.5 kGy or more. In the present invention, the high stretchability obtained by irradiating the molding powder in advance can achieve this at a dose of 3 kGy or less, which gives practical strength, but it is particularly recommended that the strength retention is in the range of 1 kGy to 2 kGy. Is done.

  According to the present invention, as a means for obtaining high stretchability as shown in FIG. 1, it is not necessary to perform annealing after irradiation, and the tetrafluoroethylene resin having high stretchability while maintaining practical strength. A molded body can be made. The high stretchability of the present invention is due to the high crystallinity, that is, according to the analysis by the differential scanning calorimeter of the crystal melting heat amount of the tetrafluoroethylene resin, when the absorbed dose of the molding powder is 2 kGy, when not irradiated This is because it is 37 J / g, which is equivalent to about 1.85 times the above. This value is obtained by irradiating the sheet formed by the above-mentioned conventional method, and then annealing the sheet, further increasing the absorbed dose to increase to about 700%, in other words, annealing after 0.5 kGy irradiation. It is because it is equal to 37 J / g which is the heat of fusion at the time.

  The tetrafluoroethylene resin thus produced has not only high breaking stress, yield strength and high stretchability, but also features such as low gas permeability, linear expansion coefficient, and compressive creep. is there. Furthermore, since there is no heat shrinkage, even when manufacturing a stretched porous membrane with a small pore size using a thin cutting tape, it is possible to immediately lead to the stretching step by omitting complicated steps such as irradiation and annealing. It has high added value and practicality that cannot be obtained from unirradiated powders for molding tetrafluoroethylene resin.

    EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

Example 1
Asahi Glass Fluoropolymers Co., Ltd. molding powder (G350) is irradiated with 1 kGy / h γ-rays at room temperature in the atmosphere for 0.5 hours, 1 hour, 1.5 hours, and 2 hours. Each sample was prepared. A compression molded rod having a diameter of 50 mm and a height of 70 mm was prepared from each sample including those not irradiated. At this time, the compression molding was linearly pressurized to 30 MPa over 5 minutes and then held at 30 MPa for 10 minutes. Further, the compression-molded rod taken out from the mold was transferred to an oven for firing, the temperature was increased at a rate of 80 ° C./h, held at 360 ° C. for 4 hours, and then cooled to room temperature at −100 ° C./h. The compression molded rod thus prepared was free from defects such as cracks. The compression molded rods were applied to a cutting machine, and each was prepared as a cutting sheet having a thickness of 0.5 mm. Further, a dumbbell-shaped tensile test piece with the cutting direction and the compression direction aligned is punched from this cutting sheet, and the respective breaking strength and breaking elongation are measured at a tensile speed of 200 mm / min with an Instron 4302 type tensile testing machine. did. The elongation at break was determined by tracking the distance between the marked lines and determining the true value. The results are shown in Table 1-1 (Tensile strength characteristics in the cutting direction) and Table 1-2 (Tensile strength characteristics in the compression direction). The elongation at break increased significantly with increasing dose.

Comparative Example 1
In order to clarify the merits of the present invention in which molding powder is preliminarily irradiated with ionizing radiation, the dose and machine when the same ionizing radiation is irradiated to a sheet of tetrafluoroethylene resin molded by a conventional method The change of characteristics was compared. That is, using the unirradiated molding powder shown in Table 1, a cutting sheet sample prepared in the same manner as in Example 1 was irradiated with γ rays under the same conditions as in Example 1. For these irradiated samples, the tensile breaking strength and breaking elongation in the cutting direction were measured in the same manner as in Example 1 at each dose. As a result, as shown in Table 2, the breaking strength was drastically decreased by irradiation, and was halved at a dose of 1 kGy or less. On the other hand, the elongation at break increased slightly to 0.5 kGy, but it simply decreased when it exceeded 0.5 kGy. These results show that the deterioration of tetrafluoroethylene resin (PTFE) due to radiation is extremely fast, and denies measures for improving the material properties by irradiation. It is clear that it appears as a measure to improve the characteristics.

Comparative Example 2
In the compression molding by the free baking method according to the present invention, since the irradiated powder is compression molded at room temperature and fired over time, this thermal history promotes recrystallization. Therefore, as a condition after irradiation when ionizing radiation was irradiated to a tetrafluoroethylene resin sheet formed by a conventional method, mechanical characteristics after giving a thermal history were measured. As in Comparative Example 1, each dose of γ-rays was irradiated onto a cutting sheet prepared using unirradiated molding powder. Each irradiated sheet was placed in an oven to check the change in elongation at break due to annealing, heated to 360 ° C at 80 ° C / h, held at 360 ° C for 2 hours, and then cooled to room temperature at a rate of -100 ° C / h. did. For these samples, the breaking strength and breaking elongation were measured at each dose in the same manner as in Example 1. The breaking elongation increased as shown in FIG. 1, but the breaking strength did not increase at each dose and was equal or further decreased. Was.

  In FIG. 1, curve 1 shows the relationship between the dose and elongation at break when ionizing radiation is applied to a sheet of tetrafluoroethylene resin compression-molded by a conventional method, and curve 2 shows a further 360 ° C. after irradiation. The relationship between the dose after annealing for 2 hours and the elongation at break is shown.

Example 2
The cutting sheet prepared in the same manner as in Example 1 was measured with a differential scanning calorimeter (DSC) at a rate of temperature increase of 10 ° C./min. When the molded powder is used, as shown in Table 3, the amount of heat of fusion of the crystal is greater at each dose than the cutting sheet sample prepared using unirradiated molding powder, and the crystallinity is clearly higher. showed that.

Example 3
As in Example 1, the tear strength of a cutting sheet compression molded using a molding powder irradiated with 2 kGy was measured, and the tearing stress toward the cutting direction per 1 mm thickness was 90.4 N, and the compression direction The tearing stress toward 94.4N was 94.4N. Similarly, the tear stresses of the cutting sheets compression-molded using the unirradiated molding powder were 27.6 N and 25.3 N, respectively. From this result, it is clear that the tear strength is increased by about 3.3 times in the cutting direction and about 3.7 times in the compression direction by irradiation with molding powder in advance, and it has the feature that it does not tear easily even if a tear is opened. It was.

Example 4
Using a molding powder (New Polyflon PTFE, M-139) manufactured by Daikin Industries, Ltd., in the same manner as in Example 1, a cutting sheet (thickness 0.5) that was compression-molded by irradiation with 1 kGy ionizing radiation in advance. mm) and the mechanical characteristics of a cutting sheet prepared using unirradiated molding powder were measured and compared. As a result, as shown in Table 4, even with a new type of tetrafluoroethylene resin (PTFE) that has been subjected to a small amount of modification treatment, although the tensile strength is slightly reduced by irradiation with ionizing radiation, the yield point strength is practical. In addition, the tensile modulus, elongation at break, and tear strength increased significantly, and an excellent irradiation effect was exhibited.

Example 5
A cutting sheet (thickness 0.5 mm) formed in the same manner as in Example 1 except that the molding powder (G350) previously irradiated with 1 kGy was used and the firing time was 2 hours, and the molding powder (M-139) previously irradiated with 1 kGy ), The gas permeability to dry nitrogen and oxygen at 23 ° C. of a cutting sheet (thickness 0.5 mm) formed in the same manner as in Example 1 was measured by the differential pressure method (JIS K7126 compliant, differential pressure 1 atm.) Table 5 compares the cases of non-irradiation and irradiation modification. As a result, it was proved that gas permeability was obviously improved by irradiation modification.

Example 6
The same gas permeability test as in Example 5 was performed on each cutting sheet formed using molding powder containing carbon graphite and short glass fibers. In the case of carbon graphite, the molding pressure was 40 MPa, the firing time was 2 hours, and in the case of short glass fibers, the firing time was 2 hours, and the molding conditions were the same as in Example 1. The dose of the molding powder required for irradiation modification was 0.8 kGy for carbon graphite and 0.5 kGy for short glass fibers. As shown in Table 6, these filler-containing molding powders, which have high gas permeability, have a particularly large effect of suppressing gas permeability by irradiation modification. In the case of, the effect on nitrogen gas was large, and it decreased to a little over 1/4.

Example 7
Using a molding powder (G350) irradiated with 1.6 kGy in advance, a specimen with a diameter of 20φ and a height of 50 mm was made by machining from a compression-molded rod molded in the same way as in Example 1, and the compression creep at 100 ° C was measured at a test stress of 7 MPa. As a result, the molded body using the same unirradiated molding powder was 2.4%, whereas the molded body using the molding powder irradiated with 1.6 kGy was 1.8%. That is, it has been found that the tetrafluoroethylene resin using the molding powder modified by irradiation has a feature that it is difficult to be deformed and has excellent creep resistance.

Industrial application fields

  In the present invention, by compressing and molding the tetrafluoroethylene resin powder irradiated with ionizing radiation, practical strength is maintained, high crystallinity, high stretchability and tear strength, gas permeability, compression creep The present invention provides a molded product of a tetrafluoroethylene resin with significantly improved linear expansion coefficient.

It is a figure which shows the relationship between fracture | rupture elongation when a sheet | seat of a tetrafluoroethylene resin is irradiated with ionizing radiation, and a dose.

Claims (5)

A tetrafluoroethylene resin compression molded product obtained by a free baking method in which a powder for molding tetrafluoroethylene resin mixed with carbon graphite or short glass fiber is irradiated with ionizing radiation and then molded . with a heat of crystal fusion is from 27 J / g in the range of 40 J / g, the tensile lifting Chi high stretchability is 1/2 or more when using the molding powder retention of the breaking strength is not irradiated with ionizing radiation A tetrafluoroethylene resin compression molded product having a gas permeability coefficient of oxygen and nitrogen of the resin of 1/2 or less when a molding powder not irradiated with ionizing radiation is used .   2. The tetrafluoroethylene resin compression-molded body by the free baking method according to claim 1, wherein the absorbed dose of ionizing radiation applied to the molding powder of the tetrafluoroethylene resin is 0.5 kGy to 3 kGy.   A machined product obtained by machining using the tetrafluoroethylene resin compression-molded body according to claim 1.   A porous body of tetrafluoroethylene resin obtained by stretching using a tape or sheet cut from the tetrafluoroethylene resin compression-molded body according to claim 1 by machining. The powder for tetrafluoroethylene resin molding formed by mixing with carbon graphite or short glass fiber is irradiated with ionizing radiation, and the resulting tetrafluoroethylene resin molding powder having an absorbed dose of 0.5 kGy to 3 kGy is compression molded. The method for producing a tetrafluoroethylene resin compression-molded body according to claim 1 or 2, wherein the compression-molded body is fired at 350 to 380 ° C and annealed.

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