WO2019107746A1 - Procédé de production d'un film poreux de résine à base de fluor - Google Patents

Procédé de production d'un film poreux de résine à base de fluor Download PDF

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Publication number
WO2019107746A1
WO2019107746A1 PCT/KR2018/012659 KR2018012659W WO2019107746A1 WO 2019107746 A1 WO2019107746 A1 WO 2019107746A1 KR 2018012659 W KR2018012659 W KR 2018012659W WO 2019107746 A1 WO2019107746 A1 WO 2019107746A1
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Prior art keywords
film
fluororesin
porous
stretching
lubricant
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PCT/KR2018/012659
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English (en)
Korean (ko)
Inventor
서주연
한성재
안병인
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180126661A external-priority patent/KR20190062168A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/651,618 priority Critical patent/US11420162B2/en
Priority to JP2020512663A priority patent/JP7408902B2/ja
Priority to CN201880059016.6A priority patent/CN111093948B/zh
Publication of WO2019107746A1 publication Critical patent/WO2019107746A1/fr
Priority to JP2022028527A priority patent/JP2022078151A/ja

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    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment

Definitions

  • the present invention relates to a method for producing a fluororesin porous film having improved shrinkage while maintaining excellent filtration efficiency and air permeability.
  • Porous membranes used in a variety of applications are required to have both high filtration efficiency and gas and liquid permeability. Accordingly, it is known to increase the amount of the fluid passing through the pores under a specific pressure by uniformly controlling the pore diameter distribution of the inside of the porous membrane.
  • the porous film of the fluorine resin can have properties such as high heat resistance, chemical stability, weatherability, nonflammability, strength, non-stickiness, low friction coefficient and the like resulting from the fluorine resin itself, , It can have properties such as flexibility, liquid permeability, particle-trapping ability, and low dielectric constant.
  • the porous film using polytetrafluoroethylene has a high stability against various compounds, and in particular, has been used in the fields of semiconductors, liquid crystals, foods, It is widely used as a microfiltration filter (membrane filter) for liquid type mixture.
  • Such a PTFE membrane is produced by forming a preform by using a paste composed of a mixture of PTFE powder and a lubricant, forming the preform by a rolling or extrusion process, forming a sheet, removing the lubricant by heat treatment, Or in the longitudinal (MD) direction, or after stretching in the MD direction, 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the porous microporous body produced by extruding and stretching the microstructure preform has a fine structure composed of a plurality of fine fibrils and a plurality of nodes connected to each other by the fibrils.
  • this microstructure By this microstructure, Thereby forming a continuous porous porous structure.
  • the phenomenon that the pore shape and characteristics can not be maintained due to the high-temperature and high-pressure environment in the processes such as extrusion, drying, and drawing may occur, Defective air bubbles may be generated on the surface, and accordingly, The membrane is not provided with sufficient strength and filtration performance.
  • the membrane controls the porosity in the membrane by the stretching and sintering process. It is easy to secure the porosity of the separation membrane at the time of stretching, but the strength and pressure resistance in the transverse direction can be lowered, and shrinkage easily occurs due to different smell.
  • the grains have problems of increasing the air permeability (or flow rate) and improving the dimensional stability without decreasing the filter efficiency.
  • the present invention provides a method for producing a fluororesin porous film having an improved shrinkage ratio while maintaining excellent filtration efficiency and air permeability.
  • the porous fluororesin film is stretched in the longitudinal direction to obtain a stretched film having a stretching ratio of 330 or more and 340 ≪ / RTI > for 5 to 12 seconds; And
  • a fluorine resin porous membrane is a fluorine-based resin, specifically, ethylene (1) 0 1 61 as polytetrafluoroethylene; for £ 1 1101 061; 1 1 6116 ; ⁇ 3 ⁇ 4) .
  • the present invention refers to a filtration membrane used for removing foreign substances and the like.
  • the sintering process after stretching is performed or the sintering process is performed before stretching.
  • a method for producing a fluororesin porous film according to an embodiment of the present invention includes :
  • the porous fluororesin film is stretched in the longitudinal direction (stretching), and 330 More than 340 ≪ / RTI > for 5 to 12 seconds (step 1); And
  • Step 2 of sintering the heat-treated porous fluororesin film at a temperature equal to or higher than the melting point of the fluororesin film after the transverse stretching, and the fluororesin porous film produced according to the production method has a lateral 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the orienting ratio is 30% or less.
  • Step 1 is a step of subjecting the porous fluororesin film to longitudinal heat treatment (first heat treatment after stretching).
  • the porous fluororesin film can be used without particular limitation as long as it is generally used for producing a porous film of a fluororesin.
  • the porous fluororesin film may be produced by: extruding and rolling a fluororesin-containing composition containing a fluororesin and a lubricant to produce a fluororesin film; And a step of heat treating the fluororesin film to remove the lubricant.
  • the fluororesin porous film according to an embodiment of the present invention may further include a step of manufacturing the porous fluororesin film.
  • the fluororesin-containing composition can be produced by mixing a fluororesin with a lubricant.
  • the fluorine-based resin can be used without limitation as long as it is usually used in a fluorine resin film.
  • Specific examples thereof include polytetrafluoroethylene (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene- Nuclear fluoropropylene copolymer, Ethylene tetrafluoroethylene copolymer resin (hepatic phthalocyanine, tetrafluoroethylene-chlorotrifluoroethylene copolymer 0 inhibitor: / 013 ⁇ 4) or ethylene chlorotrifluoroethylene resin Suppression, etc., and any one or a mixture of two or more of them may be used.
  • Resins can be used.
  • the above-mentioned resin can be produced by a usual method such as fouling polymerization and can be used in powder form.
  • the resin may be an agglomerated secondary particle of several primary particles with an average particle size of 0.2 to 0.3 g, wherein the average particle size of the secondary particles may range from 400 to 700.
  • the lubricant serves to facilitate the extrusion while spraying the surface of the fluororesin powder.
  • the lubricant can be used without any particular limitation as far as it can be removed by a method such as evaporation extraction by heat after forming into a sheet form.
  • Specific examples include hydrocarbon oils such as liquid paraffin, naphtha, white oil, toluene and xylene, various alcohols, ketones, and esters.
  • the lubricant may be used in an amount of 10 to 30 parts by weight, more specifically 15 to 30 parts by weight, based on 100 parts by weight of the fluororesin. 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • a process of aging for a certain period of time may be selectively performed for uniform mixing of the components in the mixture.
  • the aging can be carried out specifically by holding at a temperature of 15 to 50 V, more specifically at a temperature of 23 ⁇ 5 ° 0 for 12 to 24 hours.
  • the mixture is pressurized
  • a process for producing a fluororesin film is carried out by extruding and rolling the mixture obtained through the above process.
  • the thickness of the fluorine resin film is made after the extrusion is about 3000 _, thickness after rolling, since the fluorine resin film may be 80 to 600 / fail. It is possible to exhibit the effect of the fluororesin porous film superior in the thickness range.
  • the extrusion and rolling process may be carried out according to a conventional method, except that the thickness of the fluororesin film to be produced has the above-mentioned range. Specifically, the extrusion process may be carried out at a temperature of from 25 to 50 x: 1 and under a pressure of from 1 to 10 kg, and the rolling process may be carried out at a temperature of from 30 to 100 and a pressure of from 10 to 30 ⁇ 3 ⁇ 4.
  • the rolling process may be performed once in consideration of the thickness of the fluorine resin film, or may be performed in two or more steps.
  • the second mixture may be first extruded to a thickness of 1 to 3 in the mixture, and then extruded into a sheet of 80 to 600 in thickness.
  • a process of removing the lubricant by heat-treating the fluororesin film prepared above is performed. 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the temperature during the heat treatment is not particularly limited as long as it is a temperature at which the lubricant can be removed. Specifically, it can be performed for a time period at which the lubricant can be completely removed at 120 to 200 ° C, more specifically, 150 to 200 ° C. Next, a longitudinal stretching process is performed on the porous fluororesin film prepared above.
  • the stretching process may be performed between rolls rotating at different speeds or may be performed using a tenter in an oven.
  • the stretching process may be performed by longitudinal stretching the fluororesin film at a stretching magnification of 2 to 20 times, more specifically 3 to 15 times.
  • the stretching process may be performed at a temperature not higher than the melting point of the fluorine resin film, and more specifically, at a temperature of 100 to 320 V, more specifically 200 to 300 I :. Porous structure formation is advantageous when the stretching process is performed in the temperature range described above.
  • the fluorine-containing resin film is heated at a temperature higher than the melting point of the stretched fluorine resin film and less than the sintering temperature at which the fluorine- And a heat treatment for 5 to 12 seconds at a temperature of less than 340 X: is performed.
  • the fluorine resin film subjected to the heat treatment after stretching in the above direction is subjected to differential thermal analysis (1) And the degree of firing of the fluororesin film can be determined.
  • the melting point of the fluorine-based resin film measured with (: was about 327 to 333 X: and the temperature not affecting the degree of baking of the fluorine-containing film was 340 Respectively.
  • the heat treatment may be performed for 5 to 12 seconds at a temperature of 330 X: or more and 3401: or less of the fluororesin film. 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the fluororesin film made porous by stretching in the longitudinal direction has poor dimensional stability and may shrink even at room temperature. By doing so, it is possible to prevent such shrinkage by heat-setting through the first heat treatment under the above-
  • the temperature during the heat treatment is 3401: or more, or when the heat treatment time exceeds 12 seconds, the fibril strands in the fluororesin film are aggregated and thickened, and at the same time, the pore size is increased to change the physical properties of the fluororesin film , It is easy to break at the time of 10 stretching. More specifically, the heat treatment may be performed for 33 to 339 minutes for 5 to 10 seconds. In this case, the fluororesin film exhibiting a more improved moldability while maintaining excellent physical properties due to optimization of temperature and time conditions during heat treatment It is possible to manufacture.
  • Step 2 is a step of stretching the fluorine resin film heat-treated in step 1 in the transverse direction and sintering the resin at a temperature not lower than the melting point of the fluorine resin film to produce a fluorine-containing porous resin film.
  • the transverse stretching step may be carried out by transversely stretching the fluororesin film at an elongation ratio of 2 to 50 times, more specifically 10 to 30 times.
  • the transverse direction drawing step In the transverse direction drawing step,
  • the transverse stretching resistance can be improved by increasing the porosity while reducing the average pore size during the transverse stretching process under the above conditions.
  • the transverse stretching process may be performed between rolls rotating at different speeds or may be performed using a tenter in an oven. Subsequently, sintering treatment is performed on the transversely stretched fluororesin film at a temperature not lower than the melting point. 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the sintering process is performed to prevent heat shrinkage of the fluorine-containing film porous film which is finally produced by thermally fixing the drawn fluorine resin film.
  • the temperature is preferably from 350 to 450 X, more specifically from 360 to 380 I: 100 seconds, more specifically 10 to 30 seconds.
  • the pore distribution in the fluororesin porous film finally produced by the sintering treatment under such conditions can be further narrowed.
  • the sintering process may be performed according to a conventional method, specifically, a tenter in an oven.
  • the porous film of the fluororesin produced by the above-described production method is a film obtained by stretching a fluororesin film stretched through a heat treatment performed for each stretching process
  • the porous film of the fluorine resin produced by the above-described production method can be prevented from changing in size and porosity of the pores in the fluorine resin film by performing under the control condition that the firing does not occur during the heat treatment. Accordingly, it is possible to maintain a high porosity while maintaining a fine pore size, and the amount of the fluid passing through the porous membrane per unit time under a predetermined pressure is also relatively high. As a result, the filtration efficiency and permeability can be improved well.
  • the conventional fine thickness and the porous membrane may vary in shape due to application pressure during filtration, the diameter of the pores distributed in the inside, etc., and the filtration characteristics may be greatly lowered due to rupture of the membrane itself.
  • the fluororesin porous film produced according to the method has not only excellent mechanical properties but also has characteristics such that the shape and shape of the inner pores do not change much during the manufacturing process and the filtration operation process. Accordingly, according to another embodiment of the present invention, there is provided a fluororesin porous film produced by the above-described production method and having an excellent shrinkage ratio.
  • the transverse shrinkage ratio of the porous film of the fluorine resin is measured by measuring the dimension of the porous film of the fluorine resin when the porous film is cut to a predetermined length and then left at a predetermined heat treatment temperature for a certain time in the free standing state, Value can be calculated according to the following formula 1.
  • the transverse length before heat treatment is 5 cm.
  • the length in the transverse direction after the heat treatment is set to a transverse length of the measured fluorinated resin porous film after leaving the fluorinated resin porous film in the Free Standing state for a certain time at a specific temperature, specifically, for 30 minutes, for example, And then put in a free standing state for 30 minutes, the transverse length after the heat treatment is the transverse length of the fluororesin porous film after being maintained at 100 ° C for 30 minutes.
  • the fluororesin porous film has a shrinkage ratio of 50% or less at 120 to 200 I: and is also excellent in shape stability at a high temperature. Accordingly, when the product of the fluororesin porous film is applied, the shape stability can be maintained even under the condition of contact with the high-temperature sulfuric acid or the like.
  • the porous film of the fluorine resin produced by the above-described production method has a high linearity of the fibrils constituting the film, and the diameter distribution of the pores distributed inside is precise and uniform, and passes through the porous film per unit time under a predetermined pressure The amount of fluid is also relatively high.
  • the porous membrane having a fine thickness may change its shape or the diameter of the pores distributed therein due to application pressure at the time of filtration, and the filtration property may be greatly deteriorated due to rupture of the membrane itself.
  • the fluorinated resin porous film produced according to the present invention has not only excellent mechanical properties, The shape and the shape of the internal pores and the like do not change significantly during the manufacturing process and the filtration operation process. Especially superior dimensional stability compared to a porous membrane having the same porosity and pore size distribution.
  • the average pore size (pore Si ze) of the pores contained in the fluororesin porous film may be 50 to 2000 nm, more specifically 100 to 450 nm.
  • the fluororesin porous film may have a bubble point of 1 to 49 psi, more specifically 10 to 35 psi.
  • the bubble point refers to the pressure at the starting point at which the wetting curve is drawn in the capillary flow porosimeter, and reflects the maximum pore size in the fluororesin porous film.
  • the bubble point is obtained by wetting the sample with the solution, filling the pore with the solution, and injecting air while increasing the pressure, the solution filled in the large pore is first pushed to the pressure, and the pressure at this point is called the bubble point pressure .
  • the fluoropolymer porous film according to an embodiment of the present invention exhibits a bubble point pressure (psi) within the above-described range in the wetting and drying curve of a capillary flow pore measuring instrument, pore size is variously distributed and the air permeability is good, I can go ahead.
  • psi bubble point pressure
  • the average pore size and bubble point in the fluororesin porous film can be measured using a measuring device such as a Capillary Flow Porometer of PMI, according to a conventional measuring method. Specifically, Can be measured in the same manner as described above.
  • the fluororesin porous film has a porosity of 70 to 90%, more specifically, a porosity of 80 to 90%. As the average pore size is small and the porosity is increased as described above, the permeability can be remarkably improved. 2019/107746 1 »(: 1 ⁇ ⁇ 2018/012659
  • the porosity of the fluororesin porous film can be determined according to the following equation (2) after the density is determined from the volume and weight of the porous membrane.
  • the weight, thickness, It can be measured in the manner described:
  • the fluorine-based resin porous film preferably has a thickness of 5 to 100 IM, more specifically,
  • the porous film of the fluororesin is not more than 10% when it is left in a free standing state for 67 hours under the conditions of room temperature and normal pressure (23 ⁇ 5 ° C, 1 ⁇ 0.2 atm) More specifically 5% or less, and more particularly 2 to 4%.
  • the fluororesin porous membrane can be widely used as a filter media for corrosive gases and liquids, a permeable membrane for electrolysis, and a battery separator, and can also be used for precision filtration of various gases and liquids used in the semiconductor industry.
  • a filter including the above-mentioned fluororesin porous film, and a filter device.
  • the filter may further include a filter element such as a nonwoven fabric, a fabric, a mesh, or a screen in addition to the fluororesin porous film, and may have various shapes such as a flat plate, a corrugated, a spiral or a hollow cylinder.
  • a filter element such as a nonwoven fabric, a fabric, a mesh, or a screen in addition to the fluororesin porous film, and may have various shapes such as a flat plate, a corrugated, a spiral or a hollow cylinder.
  • the fluororesin porous film according to the present invention can exhibit an improved shrinkage ratio while maintaining excellent filtration efficiency and air permeability.
  • Fig. 1 shows the results of evaluating the heat shrinkage ratio of the porous film of the fluorine resin prepared in Examples 1 and 2 and Comparative Example 1.
  • Example 1
  • the prepared film was heat treated in a heating oven of 200 I: in a roll-to-roll process to completely remove the lubricant, and then subjected to 6-fold stretching in the longitudinal direction using a roll speed difference of 300 I: 335 for 9 seconds.
  • the heat-treated stretched film was stretched 15 times in the transverse direction at 300 X: Tenter 61 61. ), and stretched at 380 ° (for 13 seconds using a tenter)
  • the block was prepared, extruded into a sheet form using a paste extrusion equipment, and then rolled to a thickness of 500 _ using a rolling roll to prepare a seedling film.
  • the prepared film was heat-treated in a heating oven at 200 ° C. in a roll-to-roll process to completely remove the lubricant, and then subjected to three-fold stretching in the longitudinal direction using a roll speed difference at 300 ° C., Heat treatment for 2 seconds.
  • Containing composition was prepared and then aged at room temperature for 24 hours. Next, the pressure block was prepared by applying a pressure of 4 kPa,
  • the prepared hepatocyte film was subjected to a roll-to-roll process in a 200-well heating oven
  • the block was prepared, extruded into a sheet form using a paste extrusion equipment, and then rolled to a thickness of 500 / L using a rolling roll to prepare a liver seedling film.
  • Preparation A ⁇ 200 (film after completely removing the lubricant by heating the roll-to-roll process in the heating oven, 300 I of: carried out by a roll speed difference in a six-fold stretched in the longitudinal direction, and 340 I : Heat treatment for 9 seconds. Heat treated one direction stretching 1 3 ⁇ 4 film 300 The stretching was performed in the transverse direction using a tenter.
  • a lubricant As a lubricant, To prepare a fluorocarbon resin-containing composition, and then aged at room temperature for 24 hours. Following, A preform block was produced by applying pressure, extruded into a sheet form using a paste extruding machine, and then rolled to a thickness of 500 11 using a rolling roll to prepare a roll-to-roll film.
  • the film was heat-treated in a 200 oven in a roll-to-roll process to completely remove the lubricant, and then subjected to a 6-fold stretching in the longitudinal direction using a difference in roll speed at 300 rpm and heat-treated at 300 I: for 9 seconds.
  • the film was stretched 15 times in the transverse direction using a tenter at 300 X: heat treatment, and the film was sintered at 380 (: for 13 seconds using a tenter to prepare a seeded porous film (thickness: 30 - ).
  • Example 5 The procedure of Example 1 was repeated except that longitudinal stretching of the porous fluororesin film was followed by heat treatment for 4 seconds Membranes were prepared. Comparative Example 5
  • Example 1 The procedure of Example 1 was repeated, except that the porous fluororesin After stretching the film longitudinally, the heat treatment process was carried out at a temperature of 335 I, which is the melting point or higher, for 10 minutes. After heat treatment The transverse stretching process was performed on the film, but the 1 & cir & Test Example 1
  • Example 1 was measured and compared to two "heat shrinkage and shrinkage variation of the membrane temperature of the fluorine-containing resin prepared in Example 1. The results are shown in Fig.
  • the porous film of the fluororesin prepared in Examples 1 and 2 and Comparative Example 1 was cut to a length of 5 cm in the longitudinal direction and 5 cm in the transverse direction, followed by drying at 30 ° C, 40 ° C and 50 ° C , 60 ° C, 70 ° C, 100 ° C, 120 ° C, 150 ° C and 200 ° C, respectively, and the free standing state was measured for 30 minutes. Using the measured results, the TD shrinkage ratio was calculated according to the following equation (1).
  • the length in the transverse direction in the heat treatment is 5011.
  • the seedlings of Comparative Example 1 in which the heat treatment was not performed between the longitudinal and transverse stretching processes had a transverse shrinkage ratio of more than 50% at 10 or less, The membrane is 100 Or less, and a transverse shrinkage ratio of 30% or less, specifically, 25% or less.
  • the transverse shrinkage ratio was greatly increased.
  • Examples 1 and 2 still exhibited a low transverse shrinkage ratio, specifically, the transverse shrinkage ratio was less than 50% at 120 to 200 I :. From this, according to the production method of the present invention, It can be confirmed that the heat shrinkage ratio of the film can be greatly improved.
  • the shrinkage rate change was calculated according to the following equation (3): "
  • a sujuk rate (Comparative sujuk rate of Example 1) n _ (Example 1 or 2 sujuk rate) n a result, as shown in Figure 1, Examples 1 and 2 of the PTFE porous film in Comparative Example 1, the shrinkage gradient The shrinkage rate was increased at a relatively constant slope up to 100 ° C. The slopes of the shrinkage ratios of the PTFE porous films of Examples 1 and 2 were found to increase in the 100-120 ° C range. However, in Examples 1 and 2
  • the PTFE porous membrane showed a larger shrinkage gradient.
  • Average pore size (nm) and bubble point (psi) The average pore size and bubble point were measured using a Capillary flow porometer instrument manufactured by PMI.
  • a PTFE porous membrane was mounted on the above measuring equipment, thoroughly wetted with a surface tension test solution (GALWICK (TM)), and air or nitrogen was injected vertically into the porous membrane. When the pressure increases to a certain pressure, a drop of the test solution filling the largest hole of the pores is blown out. The pressure at this point is determined as a bubble point.
  • GALWICK surface tension test solution
  • the pore size was calculated by recording the Fl ow RateCWet Curve according to the pressure.
  • the flow rate increases steadily as the pressure increases (Dry Curve).
  • the graph shows that the dry curve is 1/2 and the pressure at the point where the wet curve intersects
  • the pore size is defined as the average pore size.
  • Porosity The weight, thickness, and area of the PTFE porous membrane were measured, and porosity was measured according to the following formula (2). At this time, the thickness of the PTFE porous membrane was instantaneously measured using a mi tsutoyo dial thickness gauge. &Quot; (2) "
  • Porosity (%) ⁇ 1 - (weight of thickness [011] X area [a 2] X true density [/ 0 11 3 for [for])) ⁇ > ⁇ 100
  • Equation (4 ) the length in the transverse direction of the test is 50 1) .

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne un procédé de production d'un film poreux de résine à base de fluor ayant un taux de retrait amélioré tout en conservant une excellente efficacité de filtration et une excellente perméabilité à l'air.
PCT/KR2018/012659 2017-11-28 2018-10-24 Procédé de production d'un film poreux de résine à base de fluor WO2019107746A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/651,618 US11420162B2 (en) 2017-11-28 2018-10-24 Method for preparing porous membrane of fluorine-based resin
JP2020512663A JP7408902B2 (ja) 2017-11-28 2018-10-24 フッ素系樹脂多孔性膜の製造方法
CN201880059016.6A CN111093948B (zh) 2017-11-28 2018-10-24 用于制备基于氟的树脂的多孔膜的方法
JP2022028527A JP2022078151A (ja) 2017-11-28 2022-02-25 フッ素系樹脂多孔性膜の製造方法

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KR20170160642 2017-11-28
KR10-2017-0160642 2017-11-28
KR10-2018-0126661 2018-10-23
KR1020180126661A KR20190062168A (ko) 2017-11-28 2018-10-23 불소계 수지 다공성 막의 제조방법

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