WO2022209753A1 - Procédé permettant de produire un polymère cristallin liquide poreux - Google Patents

Procédé permettant de produire un polymère cristallin liquide poreux Download PDF

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Publication number
WO2022209753A1
WO2022209753A1 PCT/JP2022/010869 JP2022010869W WO2022209753A1 WO 2022209753 A1 WO2022209753 A1 WO 2022209753A1 JP 2022010869 W JP2022010869 W JP 2022010869W WO 2022209753 A1 WO2022209753 A1 WO 2022209753A1
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Prior art keywords
liquid crystal
crystal polymer
porous liquid
sheet
porous
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PCT/JP2022/010869
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English (en)
Japanese (ja)
Inventor
吉紀 河野
秀典 大西
友浩 樽野
俊介 首藤
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日東電工株式会社
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Priority to KR1020237031939A priority Critical patent/KR20230164025A/ko
Priority to CN202280022822.2A priority patent/CN117062862A/zh
Priority to JP2023510828A priority patent/JPWO2022209753A1/ja
Publication of WO2022209753A1 publication Critical patent/WO2022209753A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing a porous liquid crystal polymer.
  • a foaming method using a supercritical fluid as a foaming material is known as a method for producing a porous liquid crystal polymer (see, for example, Patent Document 1 below).
  • a liquid crystal polymer is kneaded with a supercritical fluid to prepare a resin composition, then the prepared resin composition is injected into a mold, and the pressure and/or temperature of the supercritical fluid reaches a critical point.
  • the resin composition is foamed so that the
  • a thin porous liquid crystal polymer is required depending on the application and purpose of the porous liquid crystal polymer.
  • the foaming method described in Patent Document 1 has a problem that a thin porous liquid crystal polymer cannot be obtained because the resin composition is injected into a mold.
  • the present invention provides a method for producing a porous liquid crystal polymer that can produce a thin porous liquid crystal polymer.
  • the present invention (1) comprises a first step of preparing a liquid crystal polymer, a second step of impregnating the liquid crystal polymer with a supercritical fluid, and at least the pressure and temperature of the atmosphere of the liquid crystal polymer impregnated with the supercritical fluid.
  • a method for producing a porous liquid crystal polymer comprising a third step of producing a porous liquid crystal polymer by foaming the liquid crystal polymer by lowering one side below the critical point of the supercritical fluid. .
  • the liquid crystal polymer prepared in the first step is impregnated with a supercritical fluid in the second step, and the liquid crystal polymer impregnated with the supercritical fluid is foamed in the subsequent third step. Therefore, a thin porous liquid crystal polymer can be produced.
  • the liquid crystal polymer in the first step, is formed into a sheet to form a nonporous sheet, and in the third step, the nonporous sheet is foamed to form a porous liquid crystal polymer sheet.
  • the method for producing the porous liquid crystalline polymer according to (1) is included.
  • the present invention (3) includes the method for producing a porous liquid crystal polymer according to (1) or (2), further comprising a fourth step of pressing the porous liquid crystal polymer in the thickness direction after the third step. .
  • the present invention (3) includes the method for producing the porous liquid crystal polymer according to any one of (1) to (3), wherein the porous liquid crystal polymer has a thickness of 25 ⁇ m or more and 200 ⁇ m or less.
  • a thin porous liquid crystal polymer with a thickness of 200 ⁇ m or less can be manufactured.
  • the liquid crystal polymer is immersed in the supercritical fluid at a temperature higher than the melting point of the liquid crystal polymer minus 30° C. of (1) to (5).
  • a method for making a porous liquid crystalline polymer according to any one of claims 1 to 3 is included.
  • the liquid crystal polymer is immersed in a supercritical fluid having a temperature higher than the melting point of the liquid crystal polymer minus 30°C. It can be sufficiently impregnated with fluid. Therefore, a porous liquid crystal polymer having a high porosity P can be produced. As a result, a porous liquid crystal polymer with a low dielectric constant and a low dielectric loss tangent can be obtained.
  • a thin porous liquid crystal polymer can be produced.
  • FIG. 1A to 1D are process diagrams of one embodiment of the method for producing a porous liquid crystal polymer of the present invention.
  • FIG. 1A is the first step.
  • FIG. 1B is the second step.
  • FIG. 1C is the third step.
  • FIG. 1D is the fourth step.
  • FIG. 2 is a cross-sectional view of a wired circuit board comprising a porous liquid crystal polymer sheet.
  • a method for producing a porous liquid crystal polymer sheet which is one embodiment of the method for producing a porous liquid crystal polymer of the present invention, will be described with reference to FIGS. 1A to 1D.
  • the manufacturing method of the porous liquid crystal polymer sheet 1 includes a first step, a second step, and a third step as essential steps.
  • the method for manufacturing the porous liquid crystal polymer sheet 1 further includes a fourth step as an optional step. In the method for manufacturing the porous liquid crystal polymer sheet 1 of the present embodiment, the first to fourth steps are performed in order.
  • the first step is to sheet the liquid crystal polymer to form a non-porous sheet 3 .
  • Liquid crystal polymers are not limited.
  • a liquid crystal polymer is a liquid crystalline thermoplastic resin.
  • liquid crystalline polymers include liquid crystalline polyesters, preferably aromatic liquid crystalline polyesters.
  • Liquid crystal polymers are specifically described, for example, in JP-A-2020-147670 and JP-A-2004-189867.
  • a commercial item can be used for the liquid crystal polymer.
  • Commercially available products include, for example, UENO LCP (registered trademark, hereinafter the same) 8100 series (low melting point type, manufactured by Ueno Pharmaceutical Co., Ltd.) and UENO LCP 5000 series (high melting point type, manufactured by Ueno Pharmaceutical Co., Ltd.).
  • UENO LCP8100 series is mentioned.
  • the melting point of the liquid crystal polymer is not limited.
  • the melting point of the liquid crystal polymer is, for example, 200° C. or higher, preferably 220° C. or higher, and for example, 400° C. or lower, preferably 370° C. or lower.
  • the melting point of a liquid crystal polymer is determined by differential scanning calorimetry. In differential scanning calorimetry, the heating rate is 10° C./min, the range from 25° C. to 400° C. is scanned, and the liquid crystal polymer is heated in a nitrogen atmosphere. Moreover, if the liquid crystal polymer is a commercial product, the catalog value of the commercial product can be adopted as it is.
  • the porous liquid crystal polymer sheet 1 will be excellent in handleability and workability. If the melting point of the liquid crystal polymer is equal to or higher than the above lower limit, the porous liquid crystal polymer sheet 1 will be excellent in heat resistance.
  • additives can be added to the liquid crystal polymer.
  • additives include fillers.
  • Fillers include, for example, hollow spheres.
  • Hollow spheres include, for example, glass balloons. Hollow spheres are described, for example, in JP-A-2004-189867.
  • no additives are added to the liquid crystal polymer. If no additive is added to the liquid crystal polymer, it is possible to prevent the porous liquid crystal polymer sheet 1 from becoming brittle.
  • a liquid crystal polymer provided in bulk or particle form is kneaded, and then the kneaded product is made into a sheet. Kneading conditions are not limited.
  • the kneading temperature is, for example, 200° C. or higher, preferably 210° C. or higher, and is, for example, 300° C. or lower, preferably 270° C. or lower, more preferably 250° C. or lower.
  • a non-porous sheet 3 is produced by forming the kneaded material into a sheet.
  • Sheeting of the kneaded product includes, for example, pressing, extrusion, and injection. Pressing is preferred, and hot pressing is more preferred. Vacuum pressing is also preferred. Vacuum heat press is particularly preferred.
  • the temperature of the press is, for example, 200°C or higher and 300°C or lower.
  • the press pressure is, for example, 1 MPa or more, preferably 4 MPa or more, and for example, 20 MPa or less, preferably 10 MPa or less.
  • the pressure of the press atmosphere is, for example, 0.05 MPa or less, preferably 0.01 MPa or less.
  • the thickness of the nonporous sheet 3 is not limited. Specifically, the thickness of the nonporous sheet 3 is, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less. , 50 ⁇ m or more.
  • nonporous sheet 3 made of the liquid crystal polymer described above can be used as it is.
  • a commercially available nonporous sheet 3 can be used as it is.
  • the nonporous sheet 3 is impregnated with a supercritical fluid 15, as shown in FIG. 1B. Specifically, the nonporous sheet 3 is brought into contact with the supercritical fluid 15 .
  • a supercritical device 10 is used to impregnate the nonporous sheet 3 with the supercritical fluid 15 .
  • the supercritical apparatus 10 includes a pressure vessel 11, a circulation device (not shown), and a temperature control device (not shown).
  • the pressure vessel 11 accommodates the supercritical fluid 15 and is capable of circulating inside.
  • the circulation device circulates the supercritical fluid 15 in the pressure vessel 11 .
  • a temperature control device can control the temperature of the pressure vessel 11 .
  • Supercritical Fluid 15 The type of supercritical fluid 15 is not limited. Examples of the supercritical fluid 15 include supercritical carbon dioxide and supercritical nitrogen. Supercritical carbon dioxide (critical temperature: 31° C., critical pressure: 7.4 MPa) is preferably used as the supercritical fluid 15 from the viewpoint of manufacturing costs.
  • the nonporous sheet 3 is installed in the pressure vessel 11. Subsequently, the supercritical fluid 15 is caused to flow into the pressure vessel 11 in the supercritical apparatus 10 . Subsequently, the supercritical fluid 15 is circulated by a circulation device (not shown). These allow the supercritical fluid 15 to contact the nonporous sheet 3 .
  • the nonporous sheet 3 is impregnated with the supercritical fluid 15 outside the nonporous sheet 3 . That is, the supercritical fluid 15 penetrates into the nonporous sheet 3 . This impregnates the nonporous sheet 3 with the supercritical fluid 15 .
  • the conditions for the second step are not limited. Specifically, the temperature of the supercritical fluid 15 is higher than, for example, the melting point of the liquid crystal polymer minus 30°C. If the temperature of the supercritical fluid 15 is higher than the melting point of the liquid crystal polymer minus 30° C., the nonporous sheet 3 can be sufficiently impregnated with the supercritical fluid 15 in the second step. Therefore, a porous liquid crystal polymer sheet 1 having a high porosity P can be produced. As a result, a porous liquid crystal polymer sheet 1 having a low dielectric constant and a low dielectric loss tangent can be obtained. Specifically, the temperature of the supercritical fluid 15 is, for example, 150° C. or higher, preferably 175° C.
  • the pressure of the supercritical fluid 15 is, for example, 5 MPa or higher, preferably 10 MPa or higher, and is, for example, 50 MPa or lower, preferably 30 MPa or lower.
  • the impregnation time is not limited. The impregnation time is, for example, 20 minutes or longer, preferably 1 hour or longer, and is, for example, 100 hours or shorter, preferably 24 hours or shorter.
  • ⁇ Third step> In the third step, as shown in FIG. 1C, at least one of the pressure and temperature of the atmosphere of the nonporous sheet 3 impregnated with the supercritical fluid is lowered to below the critical point of the supercritical fluid.
  • the pressure of the atmosphere of the non-porous sheet 3 impregnated with the supercritical fluid is lowered to below the critical pressure of the supercritical fluid.
  • the critical point is a point corresponding to the lower limit of pressure and the lower limit of temperature at which the fluid can be maintained as a supercritical fluid.
  • the pressure inside the pressure vessel 11 is reduced so that the pressure of the atmosphere of the nonporous sheet 3 becomes the atmospheric pressure (0.1 MPa). While removing the supercritical fluid 15 inside the pressure vessel 11, the pressure of the pressure vessel 11 is lowered. The pressure reduction inside the pressure vessel 11 is adjusted so as to promote foaming by the supercritical fluid 15 impregnated in the nonporous sheet 3 .
  • the time taken to drop from the pressure when the supercritical fluid 15 exists inside the pressure vessel 11 to the atmospheric pressure (0.1 MPa) is, for example, 5 minutes or less, preferably 1 minute. Thereafter, it is more preferably set to 10 seconds or less, still more preferably 3 seconds or less.
  • the lower limit of time is not limited. The lower limit of time is, for example, 0.1 seconds.
  • the average pressure drop rate is, for example, 1 MPa/second or more, preferably 10 MPa/second or more, more preferably 15 MPa/second or more, and still more preferably 20 MPa/second or more.
  • the upper limit of the average pressure drop rate is not limited.
  • the average upper limit of the pressure drop rate is, for example, 100 MPa/sec.
  • the nonporous sheet 3 is foamed to obtain a porous liquid crystal polymer sheet 1 containing a plurality of pores 2.
  • This porous liquid crystal polymer sheet 1 is larger in the thickness direction and surface direction than the nonporous sheet 3 before foaming. That is, the nonporous sheet 3 expands to become the porous liquid crystal polymer sheet 1 .
  • the porous liquid crystal polymer sheet 1 obtained in the third step is thinned.
  • Methods for thinning the porous liquid crystal polymer sheet 1 include, for example, pressing, drawing, and rolling. From the viewpoint of precision in adjusting the thickness of the porous liquid crystal polymer sheet 1 obtained as a product, pressing is preferred.
  • the porous liquid crystal polymer sheet 1 is pressed in the thickness direction. More specifically, the porous liquid crystal polymer sheet 1 is hot-pressed.
  • hot pressing for example, a pressing device having two pressing plate members 30 is used.
  • a spacer member 35 can be arranged around the porous liquid crystal polymer sheet 1 between the two press plate members 30 .
  • the thickness of the manufactured porous liquid crystal polymer sheet 1 is adjusted by adjusting the thickness of the spacer member 35 .
  • the conditions for hot pressing are not limited.
  • the porous liquid crystal polymer sheet 1 is manufactured by performing the first to fourth steps described above.
  • the porous liquid crystal polymer sheet 1 has a thickness and a sheet shape.
  • a sheet shape includes a film shape.
  • the porous liquid crystal polymer sheet 1 extends in the plane direction.
  • the plane direction is perpendicular to the thickness direction.
  • the porous liquid crystal polymer sheet 1 has a large number of fine pores (voids) 2 .
  • the cell structure of the porous liquid crystal polymer sheet 1 includes, for example, a closed cell structure, an open cell structure, and a semi-closed and semi-open cell structure. A closed cell structure is preferred.
  • the thickness of the porous liquid crystal polymer sheet 1 is, for example, preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, and is, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less, more preferably 250 ⁇ m or less, further preferably 250 ⁇ m or less. , 200 ⁇ m or less. If the thickness of the porous liquid crystal polymer sheet 1 is at least the lower limit described above, the porous liquid crystal polymer sheet 1 is excellent in workability and handleability. If the thickness of the porous liquid crystal polymer sheet 1 is equal to or less than the upper limit described above, the thickness of the porous liquid crystal polymer sheet 1 can be reduced.
  • the porosity P of the porous liquid crystal polymer sheet 1 is, for example, 1% or more, preferably 1.5% or more, more preferably 10% or more, still more preferably 20% or more, or 22% or more. % or more, 30% or more, further 35% or more, further 40% or more, further 50% or more, furthermore 55% or more is preferable.
  • the upper limit of the porosity P of the porous liquid crystal polymer sheet 1 is not limited.
  • the upper limit of the porosity P of the porous liquid crystal polymer sheet 1 is, for example, 95%, and from the viewpoint of ensuring the mechanical strength of the porous liquid crystal polymer sheet 1, preferably 90%.
  • the porosity P of the porous liquid crystal polymer sheet 1 can be obtained by using a non-porous liquid crystal polymer film corresponding to the porous liquid crystal polymer sheet 1 . Specifically, the specific gravity G1 of the porous liquid crystal polymer sheet 1 and the specific gravity G0 of the nonporous liquid crystal polymer sheet are respectively measured, and the porosity P of the porous liquid crystal polymer sheet 1 is obtained by the following equation.
  • the dielectric constant of the porous liquid crystal polymer sheet 1 at 10 GHz is, for example, less than 3.10, preferably 2.60 or less, more preferably 2.50 or less, even more preferably 2.20 or less, or even 2. 0.10 or less, 2.00 or less, or 1.90 or less are preferred. If the dielectric constant of the porous liquid crystal polymer sheet 1 is equal to or less than the above upper limit, the porous liquid crystal polymer sheet 1 has a low dielectric.
  • the lower limit of the dielectric constant of the porous liquid crystal polymer sheet 1 at 10 GHz is not limited. For example, the dielectric constant of the porous liquid crystal polymer sheet 1 at 10 GHz is 1.00. A method for measuring the dielectric constant of the porous liquid crystal polymer sheet 1 will be described later in Examples.
  • the dielectric loss tangent of the porous liquid crystal polymer sheet 1 at 10 GHz is, for example, 0.00129 or less, preferably 0.00100 or less, more preferably 0.00080 or less, still more preferably 0.00070 or less, and particularly preferably 0.00060 or less. If the dielectric loss tangent of the porous liquid crystal polymer sheet 1 is equal to or less than the above upper limit, the porous liquid crystal polymer sheet has a low dielectric.
  • the lower limit of the dielectric loss tangent of the porous liquid crystal polymer sheet 1 at 10 GHz is not limited.
  • the dielectric loss tangent of the porous liquid crystal polymer sheet 1 at 10 GHz is 0.00000. A method for measuring the dielectric loss tangent of the porous liquid crystal polymer sheet 1 will be described later in Examples.
  • porous liquid crystal polymer sheet 1 Applications of the porous liquid crystal polymer sheet 1 are not limited. Applications of the porous liquid crystal polymer sheet 1 include, for example, insulating layers for printed circuit boards and antenna substrates for wireless communication.
  • FIG. 2 shows an example of a wired circuit board having the porous liquid crystal polymer sheet 1 as an insulating layer.
  • the printed circuit board 21 extends in the planar direction.
  • the wired circuit board 21 has a sheet shape.
  • the printed circuit board 21 includes an insulating layer 12 and a conductor layer 13 in order toward one side in the thickness direction.
  • the insulating layer 12 is made of the porous liquid crystal polymer sheet 1 described above.
  • the conductor layer 13 contacts one surface of the insulating layer 12 in the thickness direction.
  • the conductor layer 13 has a predetermined wiring pattern 14 .
  • a laminated plate 16 including an insulating layer 12 and a conductor sheet 25 is prepared.
  • the conductor sheet 25 is drawn in phantom lines in FIG.
  • a nonporous laminate (phantom line in FIG. 1A) including the above nonporous sheet 3 and a conductor sheet 25 is prepared, and the nonporous sheet 3 in the nonporous laminate is manufactured by the above manufacturing method.
  • the laminated plate 16 described above is obtained by making it porous using (first step to fourth step).
  • the conductor sheet 25 in the laminated plate 16 is patterned to form the conductor layer 13 .
  • etching is used in the patterning.
  • the nonporous sheet 3 formed into a sheet in the first step is impregnated with a supercritical fluid 15 in the second step, and the supercritical fluid 15 is impregnated in the subsequent third step. Since the non-porous sheet 3 impregnated with the critical fluid 15 is foamed, a thin porous liquid crystal polymer sheet 1 can be produced.
  • the porous liquid crystal polymer sheet 1 in the fourth step after the third step, is pressed in the thickness direction, so that a thinner porous liquid crystal polymer sheet 1 can be produced. can be done.
  • a thin porous liquid crystal polymer sheet 1 with a thickness of 200 ⁇ m or less can be manufactured.
  • the porous liquid crystal polymer sheet 1 having a thickness of 25 ⁇ m or more is manufactured, the porous liquid crystal polymer sheet 1 having excellent workability and handleability can be manufactured.
  • the nonporous sheet 3 is immersed in the supercritical fluid 15 at a temperature higher than the melting point of the liquid crystal polymer minus 30°C. 3 can be sufficiently impregnated with the supercritical fluid 15 . Therefore, a porous liquid crystal polymer sheet 1 having a high porosity P can be produced. As a result, a porous liquid crystal polymer sheet 1 having a low dielectric constant and a low dielectric loss tangent can be obtained.
  • the pressure inside the pressure vessel 11 is lowered in the third step, but in a modification, the temperature inside the pressure vessel 11 is lowered to below the critical temperature. Furthermore, both the pressure and temperature inside the pressure vessel 11 can be lowered below the critical point (critical pressure and critical temperature, respectively).
  • the modified manufacturing method does not include the fourth step.
  • the method for manufacturing the porous liquid crystal polymer sheet 1 preferably includes a fourth step. If the manufacturing method includes the fourth step, a thinner porous liquid crystal polymer sheet 1 can be manufactured.
  • the method for producing the porous liquid crystal polymer sheet 1 preferably does not include the fourth step. That is, when the manufacturing method does not include the fourth step, narrowing of the pores 2 caused by thinning the porous liquid crystal polymer sheet 1 in the fourth step can be suppressed. Therefore, a porous liquid crystal polymer sheet 1 having a low dielectric constant and a low dielectric loss tangent can be obtained.
  • the printed circuit board of the modification includes a conductor layer, an insulating layer, and a conductor layer in order toward one side in the thickness direction.
  • a porous liquid crystal polymer for example, a bulk porous liquid crystal polymer can be produced.
  • a liquid crystal polymer in bulk form is prepared.
  • the supercritical fluid is immersed in the liquid crystal polymer in bulk form.
  • the bulk-shaped liquid crystal polymer is foamed to produce a bulk-shaped porous liquid crystal polymer.
  • a thin porous liquid crystal polymer sheet 1 can be produced.
  • First step UENO LCP A5000 manufactured by Ueno Pharmaceutical Co., Ltd. as a liquid crystal polymer is kneaded with Laboplastomill manufactured by Toyo Seiki Co., Ltd. (model number: 100C100), followed by manual hydraulic vacuum press manufactured by Imoto Seisakusho Co., Ltd. (model number: 11FD ) to prepare a nonporous sheet 3 having a thickness of 100 ⁇ m (FIG. 1A).
  • the temperature during kneading was 300° C. and the rotation speed was 30 min ⁇ 1 .
  • the temperature in the press was 300° C., the press pressure was 4-10 MPa, and the atmospheric pressure was 0.1 MPa.
  • the non-porous sheet 3 was impregnated with supercritical carbon dioxide as a supercritical fluid using "CO2 Supercritical Fluid Experimental Apparatus” manufactured by AKICO (Fig. 1B).
  • the temperature of supercritical carbon dioxide in the fifth step was 263° C.
  • the pressure of supercritical carbon dioxide was 25.0 MPa
  • the impregnation time was 60 minutes.
  • Example 2 to Example 5> Using the same manufacturing method as in Example 1, a porous liquid crystal polymer sheet 1 was manufactured. However, the conditions of the foaming method were changed as shown in Table 1.
  • Example 6 Using the same manufacturing method as in Example 1, a porous liquid crystal polymer sheet 1 was manufactured. After the third step, the fourth step (vacuum heat press) was performed.
  • the porous liquid crystal polymer sheet 1 obtained in the third step was further thinned by vacuum heat pressing (Fig. 1D).
  • the temperature was 245° C.
  • the pressing pressure was 2.0 MPa
  • the atmospheric pressure was 0.1 MPa.
  • a spacer member 35 having a thickness of 0.1 mm was used in the vacuum heat press.
  • a porous liquid crystal polymer sheet 1 having a thickness of 100 ⁇ m was obtained.
  • ⁇ Porosity P> The specific gravity G1 of the porous liquid crystal polymer sheet 1 and the specific gravity G0 of the non-porous sheet 3 made of a liquid crystal polymer corresponding to the porous liquid crystal polymer sheet 1 were measured using an electronic hydrometer (model number: EW300SG) manufactured by Alpha Mirage. measured by After that, the porosity P of the porous liquid crystal polymer sheet 1 was determined using the following formula.
  • the porous liquid crystal polymer sheet of the present invention is used for an insulating layer of a wiring circuit board and an antenna substrate for wireless communication.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé de production qui comprend une première étape, une deuxième étape et une troisième étape. Dans la première étape, un polymère à cristaux liquides est formé en feuille pour former une feuille non poreuse (3). Dans la deuxième étape, la feuille non poreuse (3) est imprégnée d'un fluide supercritique (15). Dans la troisième étape, la pression ou la température de l'atmosphère de la feuille non poreuse (3) imprégnée du fluide supercritique (15) est abaissée pour être inférieure au point critique du fluide supercritique (3), ce qui permet de faire mousser la feuille non poreuse (3) pour produire une feuille de polymère à cristaux liquides poreux (1).
PCT/JP2022/010869 2021-03-31 2022-03-11 Procédé permettant de produire un polymère cristallin liquide poreux WO2022209753A1 (fr)

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KR1020237031939A KR20230164025A (ko) 2021-03-31 2022-03-11 다공질 액정 폴리머의 제조 방법
CN202280022822.2A CN117062862A (zh) 2021-03-31 2022-03-11 多孔质液晶聚合物的制造方法
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04318039A (ja) * 1991-01-17 1992-11-09 Hoechst Celanese Corp たわみ性およびセルの均一性にすぐれた発泡液晶ポリマーフィルム／シート
WO2018092845A1 (fr) * 2016-11-18 2018-05-24 住友化学株式会社 Composition polymère à cristaux liquides pour moulage de mousse, et corps moulé en mousse ainsi que procédé de fabrication de celui-ci

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