WO1999038670A1 - Article moule en resine thermoplastique et techniques de fabrication et d'utilisation - Google Patents

Article moule en resine thermoplastique et techniques de fabrication et d'utilisation Download PDF

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Publication number
WO1999038670A1
WO1999038670A1 PCT/JP1999/000371 JP9900371W WO9938670A1 WO 1999038670 A1 WO1999038670 A1 WO 1999038670A1 JP 9900371 W JP9900371 W JP 9900371W WO 9938670 A1 WO9938670 A1 WO 9938670A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
molding
resin molded
molded product
reduced pressure
Prior art date
Application number
PCT/JP1999/000371
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English (en)
Japanese (ja)
Inventor
Sadaatsu Yamaguchi
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO1999038670A1 publication Critical patent/WO1999038670A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/02—Moulding by agglomerating
    • B29C67/04—Sintering

Definitions

  • the present invention relates to a thermoplastic resin molded article having excellent mechanical strength, particularly excellent tensile strength and surface smoothness, and a method for producing and using the same.
  • Molded articles made of thermoplastic resins such as polyethylene and polypropylene are widely used in extremely diverse fields due to their ease of molding. Molded articles made of fluororesin have excellent properties such as heat resistance, chemical resistance, and friction resistance, and are widely used in the daily necessities field, office automation equipment fields, and high-tech fields such as space. In recent years, such molded products, especially those made of polyethylene and fluororesin, have been developed with the advancement of semiconductor manufacturing technology, making use of these excellent chemical resistances to make high-purity chemical containers for semiconductor manufacturing, piping for transferring ultrapure water, etc. It is used for
  • these molded products have high mechanical properties, for example, high tensile strength.
  • molding under reduced pressure has been conventionally performed in the molding industry, but it is for removing moisture, residual monomers, bubbles, etc., which are absorbed by the molding material. there were. They have been applied to resins that may contain moisture, residual monomers, etc., for example, polystyrene, polyacrylates, polyamides, polyethylene terephthalate, polyimides, polyarylates, and the like.
  • Japanese Unexamined Patent Publication No. 60-171110 discloses tetrafluoroethylene / hexaflu Disclosed in the extrusion finishing method of a polypropylene copolymer molding material is a technique for removing the source of volatile substances that cause bubbles and voids in the copolymer by limiting the temperature and the shear rate under reduced pressure. Have been. However, this technology is not concerned with the conditions under which the final part is formed.
  • Japanese Patent Application Laid-Open No. 7-73097 discloses that in order to smooth the surface of a melt-molded product of tetrafluoroethylene nofluoroalkoxy trifluoroethylene copolymer (PFA), There is disclosed a technique in which a small amount of specific polytetrafluoroethylene (PTFE) is added and contained to refine the spherulites of PFA to obtain the surface smoothness of a molded product.
  • PTFE polytetrafluoroethylene
  • an object of the present invention is to provide a molded article having improved tensile strength compared to the case of the same molding material and exhibiting superior surface smoothness, and a method for producing and using the same. It is.
  • the present invention relates to a thermoplastic resin molded product obtained by subjecting a molding material containing a thermoplastic resin to molding under high pressure, wherein the molding material is the same as the molding material containing the thermoplastic resin.
  • This is a thermoplastic resin molded product characterized in that its tensile strength is increased by at least 5% with respect to other molded products obtained by molding under the same conditions except that it is not performed under reduced pressure.
  • the present invention provides the method for producing a thermoplastic resin molded article, wherein the molded article obtained by molding a molding material containing the thermoplastic resin is processed under a high vacuum. This is a method for producing a thermoplastic resin molded product.
  • the present invention is a method of using the thermoplastic resin molded product described above as a high-purity chemical container, an insulator, and an inflation film.
  • Figure 1 shows the crystal of polyvinylidene fluoride (PVdF) obtained in Example 1. It is an electron micrograph (400000 magnification) which shows a structure.
  • FIG. 2 is an electron micrograph ( ⁇ 3000) showing the crystal structure of PV dF obtained in Comparative Example 2.
  • FIG. 3 is a scanning electron micrograph ( ⁇ 30) showing the crystal structure of PVd F obtained in Comparative Example 1.
  • FIG. 4 is a schematic perspective view showing a method for creating a closed molding space in a compression molding machine.
  • FIG. 5 is a schematic sectional view showing a method for creating a closed molding space in a compression molding machine.
  • FIG. 6 is a schematic cross-sectional view showing a method for creating a closed molding space in a melt extrusion molding machine.
  • the tensile strength is increased by at least 5%.
  • “tensile strength” is defined as follows according to the method described in ASTM D 638-94b and ASTM D 882-91 in accordance with the thickness of the sample. A sample punched out with a dumbbell was measured at a speed of 500 mm / min.
  • ASTM D 8 8 2 9 1 Micro dumbbell
  • the above-mentioned increase in tensile strength of at least 5% means that a molded material containing the same thermoplastic resin is used as a raw material and is not subjected to reduced pressure, and other molded products are molded under the same conditions. 5% or more, and the tensile strength at break also increased by 5% or more.
  • the cause of the increase in the tensile strength is not necessarily clear, but for example, a molding method close to vacuum can be used.
  • the increase in the tensile strength is 5% or more, and more preferably 10% or more.
  • thermoplastic resin means polyethylene, ultra-high molecular weight polyethylene, polypropylene, and fluororesin. The thermoplastic resin in the present specification has not been molded under reduced pressure to obtain a final molded product.
  • fluororesin examples include those that cannot be melt-processed include polytetrafluoroethylene and modified polytetrafluoroethylene, and those that can be melt-processed include tetrafluoroethylene.
  • thermoplastic resins general-purpose resins are preferably polyethylene, ultra-high molecular weight polyethylene and polypropylene, and fluorine resins are preferably polytetrafluoroethylene, modified polytetrafluoroethylene, and tetrafluoroethylene hexafluoro.
  • fluorine resins are preferably polytetrafluoroethylene, modified polytetrafluoroethylene, and tetrafluoroethylene hexafluoro.
  • Preferred are a polypropylene copolymer, a vinylidene fluoride z-tetrafluoroethylene copolymer, and a vinylidene fluoride trifluoroethylene copolymer.
  • the molding material containing a thermoplastic resin used in the present invention may have a filler added thereto.
  • the above-mentioned filler is not particularly restricted but includes, for example, rubbers such as titanium oxide, zircon, fibrous glass short fibers, asbestos, flaky graphite, mica, talc: ethylene-propylene rubber, fluorine rubber and the like. it can. These can be used alone or in combination of two or more.
  • the size of the filler and the amount of the filler are not particularly limited, and a commonly used size and the amount of the filler can be applied.
  • the shape of the molding material containing a thermoplastic resin used in the present invention is not particularly limited.
  • any shape can be used as a usual molding material such as a powder or a pellet. Good.
  • the shape may be a block shape, a plate shape, a sheet shape, a film shape, a hollow shape, or another shape.
  • the method for molding the molding material containing the thermoplastic resin of the present invention is not particularly limited, but it is important that this is performed at least at the time of heating and melting or firing the thermoplastic resin under a specific high vacuum.
  • under reduced pressure used in the present specification for a molding process refers to a thermoplastic resin molding machine having a closed molding space connected to at least one operating vacuum line and having a vacuum gauge disposed on the vacuum line.
  • the degree of pressure reduction in one of the vacuum lines in the closed molding space where the thermoplastic resin to be molded is present in a molten state, and the portion closest to the obtained molded product is obtained by reading the above vacuum gauge. 1 OT orr, preferably less than 5 Torr.
  • the degree of decompression of the part closest to the obtained molded product means the reduced pressure state of the vacuum line when there are only one vacuum line, and the obtained molded product when there are two or more vacuum lines. Is the decompression state of the vacuum line that is closest to the space that is connected in a sealed state, and the interval between them is not specified.
  • the degree of pressure reduction in the vacuum line on the right side of the two vacuum lines is the degree of pressure reduction in the portion closest to the molded product that can be obtained.
  • such a reduced pressure condition is necessary when molding a thermoplastic resin molded product, but it is more preferable to employ it also in the steps of pelletization and transfer thereof.
  • the molded article referred to in the present invention means only a molded article giving a final shape, and does not include a pellet used as a raw material of a molded article giving a final shape, and a molded article for producing the pellet.
  • the closed molding space can be formed, for example, as follows in a typical molding method.
  • thermoplastic resin that cannot be melt-processed
  • Compression molding The same compression molding is the same as powder metallurgy pre-molding, in which a molding material is poured into a mold of a desired shape or a similar shape, and is pressed at room temperature and pressed from a certain direction. The molding material inside the machine is compressed to obtain a preform.
  • the above-mentioned closed molding space is obtained by mounting a 0 ring in a mold, drawing a vacuum, and placing these compression molding machine molding spaces under high pressure reduction. Can be made.
  • the firing means that the raw material is present inside a furnace having a heating device for raising the temperature to a constant temperature of, for example, about 360 to 380 ° C. The heating is continued for a certain time and then cooled. It is not always necessary to reduce the pressure during cooling.
  • the sealed molding space can be created by placing a sealed container in a furnace for performing the above-described firing, placing the preformed product therein, and evacuating the container.
  • Ram extrusion The extrusion is the simultaneous compression molding and baking.
  • ram extrusion a type of extrusion molding, a ram extruder consisting of a feeding section, a baking section, and a cooling section is used, and the molding powder is intermittently injected with a ram from the top of a single cylinder and heated in the baking section. Then, after cooling in the lower cooling section, molding era is obtained.
  • the entire cylinder and ram should be sealed by installing a 0 ring at the connection part, sealing with a copper seal or other methods as necessary, and further molding powder.
  • a nozzle is provided by sealing the upper part of the hopper without opening, and the nozzle is opened to supply molding powder, and the nozzle is closed to shut off the outside.
  • the evacuation can be performed in the nozzle portion above the hopper or in the closed portion of the cylinder.
  • (2-1) Melt extrusion molding examples include extrusion molding and injection molding. Extrusion molding is performed using an ordinary molding machine composed of a barrel, a screw, a die and the like. Injection molding is performed using an ordinary molding machine composed of a cylinder, a screw, a plunger, a nozzle and the like.
  • Figure 6 shows a typical device. In Figure 6, where no pressure is applied Vacuum with. In an extruder, since a vent hole exists in the molding machine itself, it is desirable to evacuate the vent hole.
  • the molding apparatus of the present invention is appropriately employed in a molding apparatus such as a T-die method or an inflation method for forming a film, and a blow molding method for forming a hollow product in the same manner as in (2-1).
  • a molding apparatus such as a T-die method or an inflation method for forming a film
  • a blow molding method for forming a hollow product in the same manner as in (2-1).
  • articles including pipes, tubes, films, irregularly shaped articles, hollow molded articles, monofilaments, wire coatings, laminate molded articles, etc.
  • the molded article of the present invention Eliminates ultra-fine voids that have not been known to improve mechanical strength and smoothness, and greatly improves stress crack resistance.
  • voids micropores formed by air
  • the chemical penetrates into it, and then expands and contracts repeatedly, causing distortion and cracks. Since the molded article of the present invention has almost no voids, there is no concern about occurrence of such distortion and cracks.
  • Thermoplastic resin molded articles suitable for these uses include those made of polyethylene, ultra-high molecular weight polyethylene, fluororesin, and the like.
  • thermoplastic resin molded article of the present invention has a very low dielectric breakdown voltage due to a small amount of voids in the molded article, and is suitable for application to products requiring this.
  • examples of such a product include an insulator, and specific examples include an insulating film and an insulating sheet.
  • thermoplastic resin molded article of the present invention suitable for these uses a molded article made of polyethylene, ultrahigh molecular weight polyethylene, PTFE, or the like is preferable.
  • the molded article of the present invention has an improved tensile strength of 5% or more, it can be made thinner and requires less molding material. Therefore, it is also suitable as an inflation film.
  • Polyethylene, melt-processable fluororesin, etc. are suitable for this application.
  • the PvdF film was injection molded at a temperature of 230 ° C and atmospheric pressure to create a sheet with a thickness of 2 mm.
  • the surface was observed with a scanning electron microscope (30 ⁇ ).
  • Figure 3 shows the results. It was found that there were irregularities on the surface that seemed to indicate that bubbles had escaped.
  • Example 1 In addition, a portion where no bubble was present was partially selected, and further observed with an electron microscope (40000 magnification). Clear spherulites were formed, indicating no surface smoothness.
  • Comparative Example 2 The sheet obtained in Comparative Example 1 was placed in a sealed glass container, and the whole container was immersed in a thermostat kept at 230 ° C. for 10 minutes while drawing a vacuum of 2 Torr from one location. Then, after air-cooling at room temperature under the same reduced pressure, it is taken out of the container and the surface is Observation was performed with a microscope (400,000 times). The results are shown in FIG. No spherulites could be observed, indicating that the surface smoothness was clear. Comparative Example 2
  • Example 2 The sheet obtained in Comparative Example 1 was melted in the air, and cooled in the air at room temperature. . The results are shown in FIG. Plane smoothness is not sufficient.
  • Example 2 The sheet obtained in Comparative Example 1 was melted in the air, and cooled in the air at room temperature. . The results are shown in FIG. Plane smoothness is not sufficient.
  • the PVdF powder was put into a mold and kept at a temperature of 237 ° C. for 30 minutes. At least the last 10 minutes of the 30 minutes was kept at a reduced pressure of 2 T 0 rr. After applying a pressure of 30 kg / cm 2 for 90 seconds with a compression press, the mold was cooled with circulating cooling water to produce a compression molded sheet. The resulting create five specimens from the sheet, by Shimadzu Sakushosha made Otogurafu DC S 5 0 0, was measured each tensile strength, an average 6 3 0 kgf / cm 2. Comparative Example 3
  • a PV dF sheet was prepared in the same manner as in Example 2 except that the operation was performed under the atmospheric pressure, and five test pieces were prepared from the obtained sheets, and the tensile strength at break was measured. As a result, the average was 570 kgf / cm 2 .
  • Example 3 Comparative Example 4
  • test piece B (example).
  • test piece C (Example).
  • the decompression conditions were maintained at 2 Torr for at least the last 10 minutes of the 40-minute aging process.
  • the molded article of the present invention increases mechanical strength and achieves excellent surface smoothness, it can be favorably applied to, for example, applications requiring extremely high purity containers such as semiconductor-related applications. it can.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Cette invention a trait à un article moulé en résine thermoplastique dont les caractéristiques de résistance à la traction et de poli de la surface sont supérieures en comparaison de celles d'un autre produit utilisant la même matière à mouler ainsi que des techniques identiques de fabrication. Cet article moulé en résine thermoplastique, que l'on obtient en constituant une matière à mouler contenant de la résine thermoplastique sous des pression fortement réduites, fait montre d'une résistance à la traction supérieure d'au moins 5 % à celle d'un autre article moulé fait de la même matière à mouler et selon des conditions de production identiques, sinon que ce dernier n'est pas façonné sous des pressions réduites.
PCT/JP1999/000371 1998-01-29 1999-01-29 Article moule en resine thermoplastique et techniques de fabrication et d'utilisation WO1999038670A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/34130 1998-01-29
JP3413098 1998-01-29

Publications (1)

Publication Number Publication Date
WO1999038670A1 true WO1999038670A1 (fr) 1999-08-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017082315A1 (fr) * 2015-11-13 2017-05-18 旭硝子株式会社 Film de résine et son procédé de production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5277181A (en) * 1975-12-24 1977-06-29 Sumitomo Electric Industries Method and apparatus for sintering tubes made of ethylene tetrafluoride resin
JPS55100145A (en) * 1979-01-25 1980-07-30 Nippon Valqua Ind Ltd Compression molding of emulsion polymer powder of tetrafluoruethylene resin
JPS6079933A (ja) * 1983-10-07 1985-05-07 Nec Corp 樹脂シ−トの調質方法
JPS61188428A (ja) * 1985-02-15 1986-08-22 Kanebo Ltd 熱可塑性樹脂成形品の製造方法
JPH08505094A (ja) * 1992-08-19 1996-06-04 ダブリュ．エル．ゴア アンド アソシエーツ，インコーポレイティド 緻密なポリテトラフルオロエチレン製品及びそれらの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5277181A (en) * 1975-12-24 1977-06-29 Sumitomo Electric Industries Method and apparatus for sintering tubes made of ethylene tetrafluoride resin
JPS55100145A (en) * 1979-01-25 1980-07-30 Nippon Valqua Ind Ltd Compression molding of emulsion polymer powder of tetrafluoruethylene resin
JPS6079933A (ja) * 1983-10-07 1985-05-07 Nec Corp 樹脂シ−トの調質方法
JPS61188428A (ja) * 1985-02-15 1986-08-22 Kanebo Ltd 熱可塑性樹脂成形品の製造方法
JPH08505094A (ja) * 1992-08-19 1996-06-04 ダブリュ．エル．ゴア アンド アソシエーツ，インコーポレイティド 緻密なポリテトラフルオロエチレン製品及びそれらの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017082315A1 (fr) * 2015-11-13 2017-05-18 旭硝子株式会社 Film de résine et son procédé de production
US10807776B2 (en) 2015-11-13 2020-10-20 AGC Inc. Resin film and process for its production

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