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WO2025249337A1 - Film poreux, élément perméable à l'air et feuille pour alimentation d'élément - Google Patents

Film poreux, élément perméable à l'air et feuille pour alimentation d'élément

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Publication number
WO2025249337A1
WO2025249337A1 PCT/JP2025/018827 JP2025018827W WO2025249337A1 WO 2025249337 A1 WO2025249337 A1 WO 2025249337A1 JP 2025018827 W JP2025018827 W JP 2025018827W WO 2025249337 A1 WO2025249337 A1 WO 2025249337A1
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WO
WIPO (PCT)
Prior art keywords
porous film
heat resistance
liquid
resistance test
main surface
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/JP2025/018827
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English (en)
Japanese (ja)
Inventor
栄作 田中
航大 上田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
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 Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2025249337A1 publication Critical patent/WO2025249337A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Definitions

  • the present invention relates to a porous film, a ventilation member, and a member supply sheet.
  • Fluororesin porous films are used in a variety of applications, including filters, sound-permeable membranes, air-permeable membranes, and diaphragms. Fluorine-free porous films have also been proposed for use in these applications.
  • Patent Document 1 discloses a porous polyethylene film used in acoustic devices. Patent Document 1 also describes that the porous polyethylene film is oil-repellent treated with a fluorine-based oil-repellent agent (Examples 3 and 7).
  • Attaching a porous film to a device such as a smartphone may involve a heat treatment. Furthermore, the porous film may reach high temperatures (e.g., 60°C or higher) due to heat generated by the attached device itself or due to a rise in temperature in the location where the attached device is placed. It is desirable to minimize changes in the properties of the porous film, such as breathability, sound permeability, and liquid repellency, caused by temperature rise.
  • the present invention therefore aims to provide a fluorine-free porous film, ventilation member, and member supply sheet that are suitable for suppressing changes in properties due to temperature increases.
  • the present invention provides A porous film containing a fluorine-free thermoplastic resin as a main component, a main surface that has been treated with a liquid-repellent agent; the liquid repellent agent includes at least one selected from the group consisting of a silicone resin having an alkoxy group directly bonded to a silicon atom and a polymethylpentene resin; porous film, to provide.
  • the present invention provides a method for manufacturing a semiconductor device comprising: A porous film containing a fluorine-free thermoplastic resin as a main component, a main surface that has been treated with a liquid-repellent agent; the ratio (A 2 /A 1 ⁇ 100) of the air permeability A 2 expressed in Gurley number after heat resistance test A to the air permeability A 1 expressed in Gurley number is in the range of 50 to 150%, the ratio (B 2 /B 1 ⁇ 100) of the insertion loss B 2 of the sound after the heat resistance test A to the insertion loss B 1 of the sound having a frequency of 1 kHz is in the range of 70 to 130%,
  • the heat resistance test A is a test in which the sample is heated at 160°C for 3 minutes. porous film, to provide.
  • the present invention provides The porous film of the present invention; An adhesive layer bonded to the porous film, Ventilation member, to provide.
  • the present invention provides a method for manufacturing a semiconductor device comprising: A member supply sheet including: a ventilation member to be placed on a surface of an object having an opening; and a base sheet having the ventilation member placed on a surface thereof,
  • the ventilation member is a porous film having a shape that covers the opening when placed on the surface; an adhesive layer bonded to the porous film,
  • the porous film is the porous film of the present invention.
  • Material supply sheet to provide.
  • the present invention provides a fluorine-free porous film, ventilation member, and member supply sheet that are suitable for suppressing changes in properties due to temperature increases.
  • FIG. 1 is a cross-sectional view schematically showing an example of the porous film of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of the film member of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a first modification of the film member of FIG.
  • FIG. 4 is a cross-sectional view schematically showing a second modified example (rolled body) of the film member of FIG.
  • FIG. 5 is a cross-sectional view that schematically shows an example of the ventilation member of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing a first modification of the ventilation member of FIG.
  • FIG. 7 is a cross-sectional view schematically showing a second modification of the ventilation member of FIG. FIG.
  • FIG. 8 is a cross-sectional view schematically showing a third modification of the ventilation member of FIG.
  • FIG. 9 is a cross-sectional view schematically showing a fourth modification of the ventilation member of FIG.
  • FIG. 10 is a cross-sectional view schematically showing a fifth modification of the ventilation member of FIG.
  • FIG. 11 is a cross-sectional view schematically showing an example of the member supplying sheet of the present invention.
  • FIG. 12 is a cross-sectional view schematically showing a first modification of the member supplying sheet of FIG.
  • FIG. 13 is a cross-sectional view schematically showing a second modification of the member supplying sheet of FIG. FIG.
  • FIG. 14 is a diagram illustrating the state of the liquid-repellent layer after heating a porous film that has been treated with a liquid-repellent agent.
  • FIG. 15 is a cross-sectional view schematically showing a sample body for evaluating the air resistance (Gurley air permeability) of a porous film.
  • FIG. 16A is a cross-sectional view schematically showing a sample body for evaluating the insertion loss of a porous film.
  • FIG. 16B is a cross-sectional view showing the sample body of FIG. 16A attached to a mock housing that imitates the housing of a mobile phone.
  • FIG. 17 is a schematic diagram for explaining a method for evaluating the insertion loss of a porous film.
  • FIG. 18 is a diagram illustrating an example of a method for applying a liquid-repellent treatment to the main surface of a porous film.
  • the porous film according to the first aspect of the present invention is A porous film containing a fluorine-free thermoplastic resin as a main component, a main surface that has been treated with a liquid-repellent agent;
  • the liquid repellent agent includes at least one selected from the group consisting of a silicone resin having an alkoxy group directly bonded to a silicon atom and a polymethylpentene resin.
  • the ratio (A2/A1 x 100) of the air permeability A2 expressed in Gurley number after heat resistance test A to the air permeability A1 expressed in Gurley number is in the range of 50 to 150%
  • the ratio ( B2 / B1 x 100) of the sound insertion loss B2 after heat resistance test A to the sound insertion loss B1 of a frequency of 1 kHz is in the range of 70 to 130%
  • the heat resistance test A is a test in which the film is heated at 160°C for 3 minutes.
  • the ratio (B 2 /B 1 ⁇ 100) is in the range of 75 to 125%.
  • the ratio ( C2 / C1 x 100) of the contact angle C2 of liquid paraffin on the main surface after heat resistance test B to the contact angle C1 of liquid paraffin on the main surface is 80% or more, and the heat resistance test B is a test in which the film is heated at 160°C for 10 minutes.
  • the contact angle C2 is 45° or more.
  • the porous film according to the sixth aspect of the present invention is A porous film containing a fluorine-free thermoplastic resin as a main component, a main surface that has been treated with a liquid-repellent agent; the ratio (A 2 /A 1 ⁇ 100) of the air permeability A 2 expressed in Gurley number after heat resistance test A to the air permeability A 1 expressed in Gurley number is in the range of 50 to 150%, the ratio (B 2 /B 1 ⁇ 100) of the insertion loss B 2 of the sound after the heat resistance test A to the insertion loss B 1 of the sound having a frequency of 1 kHz is in the range of 70 to 130%,
  • the heat resistance test A is a test in which the sample is heated at 160° C. for 3 minutes.
  • the ratio ( C2 / C1 x 100) of the contact angle C2 of liquid paraffin on the main surface after heat resistance test B to the contact angle C1 of liquid paraffin on the main surface is 80% or more, and the heat resistance test B is a test in which the film is heated at 160°C for 10 minutes.
  • the contact angle C2 is 45° or more.
  • thermoplastic resin includes at least one selected from the group consisting of polyolefin resins and polyimide resins.
  • the porous film according to any one of the first to ninth aspects is a stretched film.
  • a ventilation member according to an eleventh aspect of the present invention comprises: For example, a porous film according to any one of the first to tenth aspects; and an adhesive layer bonded to the porous film.
  • a member supply sheet comprises: A member supply sheet including: a ventilation member to be placed on a surface of an object having an opening; and a base sheet having the ventilation member placed on a surface thereof,
  • the ventilation member is a porous film having a shape that covers the opening when placed on the surface; an adhesive layer bonded to the porous film,
  • the porous film is, for example, the porous film according to any one of the first to tenth aspects.
  • FIG. 1 An example of the porous film of the present invention is shown in Figure 1.
  • the porous film 1 in Figure 1 contains a fluorine-free thermoplastic resin as a main component.
  • the term "main component” refers to the component that is contained in the porous film 1 in the largest amount by weight.
  • the porous film 1 can be adhered to the housing of a smart watch or the like by heat fusion without using an adhesive or pressure-sensitive adhesive, for example.
  • Porous film 1 has a main surface that has been treated with a liquid-repellent agent.
  • a liquid-repellent agent In other words, at least one main surface of porous film 1 has been treated with a liquid-repellent agent.
  • main surface refers to the surface of a film-like or sheet-like member that has the largest area.
  • the liquid-repellent agent may contain at least one selected from the group consisting of a silicone resin having an alkoxy group directly bonded to a silicon atom and a polymethylpentene resin. A porous film 1 having this configuration is suppressed from changing in properties due to temperature increases.
  • Figure 14 illustrates the state of the liquid repellent layer after heating a porous film treated with a fluorine-containing liquid repellent agent.
  • a porous film 9 treated with a fluorine-containing liquid repellent agent is heated, the liquid repellent layer 91 tends to flow and penetrate into the porous film 9, or the surface 9s of the porous film 9 becomes exposed (see Figure 14 (A)).
  • Such structural changes can cause changes in the properties of the porous film 9, such as breathability, sound permeability, and liquid repellency.
  • the flow of the liquid repellent layer 91 with increasing temperature is thought to be related to the intermolecular interactions in the fluorine-containing liquid repellent agent.
  • fluorine-containing organic compounds have low intermolecular interactions. Therefore, it is thought that the side chains contained in the fluorine-containing liquid repellent agent tend to tilt with increasing temperature, causing the liquid repellent layer 91 to flow.
  • the liquid repellent layer 11 is less likely to flow even with increasing temperature. This is thought to suppress changes in the properties of the porous film 1 (see Figure 14 (B)).
  • the porous film 1 has a first main surface 1a and a second main surface 1b. At least one of the first main surface 1a and the second main surface 1b is treated with a liquid-repellent agent.
  • the first main surface 1a is treated with a liquid-repellent agent.
  • both the first main surface 1a and the second main surface 1b may also be treated with a liquid-repellent agent. With this configuration, for example, there is no need to be careful about confusing the main surface with higher liquid repellency, improving ease of handling.
  • the porous film 1 contains a fluorine-free thermoplastic resin as a main component.
  • fluorine-free thermoplastic resins include polyolefin resins and polyimide resins.
  • the fluorine-free thermoplastic resin may contain at least one selected from the group consisting of polyolefin resins and polyimide resins.
  • the fluorine-free thermoplastic resin may be one selected from the group consisting of polyolefin resins and polyimide resins.
  • the fluorine-free thermoplastic resin may contain a polyolefin resin.
  • the fluorine-free thermoplastic resin may be a polyolefin resin.
  • Polyolefin resins include polyethylene (PE) resin, polypropylene (PP) resin, and polymethylpentene (PMP) resin.
  • the polyolefin resin may be polyethylene resin or polypropylene resin.
  • the porous film 1 contains polyethylene resin or polypropylene resin as its main component, it is preferable that the liquid repellent agent contains polymethylpentene resin.
  • the polyolefin resin may be polymethylpentene resin.
  • Polymethylpentene resin is a homopolymer or copolymer such as poly(4-methylpentene-1) resin or poly(3-methylpentene-1) resin. Copolymers include random copolymers and block copolymers. From the standpoints of heat resistance and moldability, a homopolymer of poly(4-methylpentene-1) resin is preferred.
  • the liquid repellent agent preferably contains a silicone resin having an alkoxy group directly bonded to a silicon atom.
  • the polyolefin resin may be poly(4-methylpentene-1) resin.
  • Poly(4-methylpentene-1) resin refers to a homopolymer of 4-methylpentene-1 or a copolymer of 4-methylpentene-1 and at least one type of ⁇ -olefin.
  • the composition ratio of 4-methylpentene-1 to ⁇ -olefin contained in the copolymer can be adjusted so long as the melting point is in the range of 180°C or higher.
  • the fluorine-free thermoplastic resin may include a polyimide resin.
  • the fluorine-free thermoplastic resin may be a polyimide resin.
  • the fluorine-free thermoplastic resin may be a thermoplastic resin with a melting point of 180°C or higher and 300°C or lower. If the melting point of the thermoplastic resin is 180°C or higher, sufficient heat resistance can be ensured in the porous film 1. If the melting point of the thermoplastic resin is 300°C or lower, the porous film 1 can be produced, for example, by melt molding.
  • the melting point of the thermoplastic resin may be 200°C or higher and 280°C or lower, or even 220°C or higher and 260°C or lower.
  • the porous film 1 may also contain additives such as plasticizers and antioxidants.
  • the liquid repellent agent may contain at least one selected from the group consisting of a silicone resin having an alkoxy group directly bonded to a silicon atom and a polymethylpentene resin. Such a liquid repellent agent can impart excellent liquid repellency to the porous film 1.
  • silicone resins having alkoxy groups directly bonded to silicon atoms include polydimethylsiloxane, polydimethyldiphenylsiloxane, polymethylphenylsiloxane, and oligomers thereof.
  • the silicone resins may also be polymers containing the above structural units, such as copolymers.
  • the polymethylpentene resin can be the same as the polymethylpentene resin described above for the thermoplastic resin.
  • Porous film 1 can suppress changes in air permeability and sound permeability due to temperature rise.
  • the ratio (A2/A1 x 100) of the air permeability A2 (sec/100 mL) expressed as a Gurley number after heat resistance test A to the air permeability A1 (sec/100 mL) expressed as a Gurley number is in the range of 50 to 150%
  • the ratio ( B2 / B1 x 100) of the sound insertion loss B2 after heat resistance test A to the sound insertion loss B1 of a frequency of 1 kHz is in the range of 70 to 130%.
  • Heat resistance test A is a test in which the film is heated at 160°C for 3 minutes.
  • Gurley number refers to the air resistance (Gurley air permeability) measured in accordance with the Oken Tester Method defined in JIS P8117: 2009.
  • the air resistance can be evaluated in accordance with the Oken Tester Method by using a measuring jig, as described below.
  • the measuring jig has a shape and size that can be placed in the air permeability measuring section of the Oken testing machine, and is made of a thickness and material that will not deform due to the differential pressure applied to the test piece when measuring air permeability resistance.
  • An example of a measuring jig is a 2 mm thick, 47 mm diameter SUS circular plate.
  • Figure 15 is a schematic cross-sectional view of a sample 1A for evaluating the air permeability resistance (Gurley air permeability) of a porous film 1.
  • a through hole with an opening 51a smaller than the porous film 1 to be evaluated is provided in the center of the surface of the SUS circular plate 51 serving as the measuring jig.
  • the cross section of the through hole is typically circular, and the diameter is set so that the opening 51a of the through hole is completely covered by the porous film 1 to be evaluated.
  • the diameter of the through hole is 3 mm.
  • the porous film 1 to be evaluated is fixed to one side of the circular plate 51 so as to cover the opening 51a.
  • the second main surface 1b is fixed so that it faces the opening 51a.
  • the porous film 1 can be fixed using double-sided adhesive tape 55 with a vent hole 55a (4 mm diameter) punched in the center.
  • the double-sided adhesive tape 55 is simply placed between the disk 51 and the porous film 1 so that the central axis of the vent hole 55a coincides with the central axis of the opening 51a. In this manner, sample 1A is obtained.
  • sample body 1A has a bonded region R1 where porous film 1 and double-sided adhesive tape 55 are bonded, and a non-bonded region R2 surrounded by bonded region R1 when viewed from a direction perpendicular to the main surface of porous film 1.
  • the air resistance measured without using a measuring jig for a porous film 1 that meets the recommended dimensions (50 mm x 50 mm) of the test piece for the Oken testing machine method is in good agreement with the air resistance measured using a measuring jig after cutting the porous film 1 into small pieces, i.e., the use of a measuring jig does not substantially affect the measured value of air resistance.
  • the air permeability A1 (sec/100 mL) expressed in Gurley number of porous film 1 is measured, and then the air permeability A2 (sec/100 mL) expressed in Gurley number after heat resistance test A is measured.
  • the ratio ( A2 / A1 x 100) can be calculated from air permeability A1 and air permeability A2 .
  • Method for measuring insertion loss 16A to 17 a method for measuring the insertion loss of the porous film 1 for a sound of a specific frequency will be described.
  • the insertion loss can be measured by the following method using a simulated housing that imitates the housing of a mobile phone.
  • Figure 16A is a cross-sectional view schematically showing a sample body 1B for evaluating the insertion loss of a porous film 1.
  • the sample body 1B comprises a measuring jig and a porous film 1.
  • An example of the measuring jig is a SUS circular plate with a thickness of 2 mm and a diameter of 47 mm.
  • a through hole having an opening 52a smaller than the porous film 1 to be evaluated is provided in the center of the surface of the SUS circular plate 52 serving as the measuring jig.
  • the cross section of the through hole is typically circular, and the diameter is set so that the opening 52a of the through hole is completely covered by the porous film 1 to be evaluated. In this embodiment, the diameter of the through hole is 0.7 mm.
  • the porous film 1 to be evaluated is fixed to one side of the circular plate 52 so as to cover the opening 52a. If only the first main surface 1a of the porous film 1 has been treated with a liquid-repellent agent, the porous film 1 is fixed so that the second main surface 1b faces the opening 52a.
  • double-sided adhesive tape 56 with a vent hole 56a (1.6 mm diameter) punched in the center can be used. The double-sided adhesive tape 56 is placed between the disk 52 and the porous film 1 so that the central axis of the vent hole 56a coincides with the central axis of the opening 52a.
  • double-sided adhesive tape 57 for securing the microphone is placed on the other main surface of the porous film 1 (the second main surface 1b in Figure 15A).
  • the double-sided adhesive tape 57 has the same shape as the double-sided adhesive tape 56 and has a vent hole 57a (1.6 mm diameter) punched in the center.
  • sample 1B is obtained.
  • sample 1B has a bonded region r1 where the porous film 1 and the double-sided adhesive tape 56 are bonded, and a non-bonded region r2 surrounded by the bonded region r1 when viewed perpendicular to the main surface of the porous film 1.
  • FIG 17 is a schematic diagram illustrating a method for evaluating the insertion loss of porous film 1.
  • a speaker unit 135 to be housed in the simulated housing is prepared. Specifically, the process is as follows: a speaker 140 (Star Micronics, SCC-16A), which serves as the sound source, and fillers 130a, 130b, and 130c made of urethane sponge are prepared. These fillers house speaker 140 and prevent unnecessary diffusion of sound from the speaker (reducing as much sound as possible that is input to the evaluation microphone without passing through the porous film 1 to be evaluated).
  • a sound-passing hole 132 with a circular cross-section and a diameter of 2 mm is provided in filler 130a in the thickness direction.
  • Filler 130b has a cutout corresponding to the shape of speaker 140, as well as a cutout for accommodating speaker cable 142 and leading speaker cable 142 out of speaker unit 135.
  • fillers 130c and 130b are placed on top of each other, and speaker 140 and speaker cable 142 are placed in the cutout of filler 130b ( Figure 17(A)).
  • filler 130a is placed on top of it so that sound is transmitted from speaker 140 to the outside of speaker unit 135 through sound hole 132, completing speaker unit 135 ( Figure 17(B)).
  • the speaker unit 135 prepared above is placed inside a simulated housing 160 (made of polystyrene, outer dimensions 60 mm x 50 mm x 28 mm) that resembles the housing of a mobile phone.
  • the prepared simulated housing 160 consists of two parts 160a and 160b, and parts 160a and 160b can be fitted together.
  • Part 160a is provided with a sound vent 162 (having a circular cross section with a diameter of 2 mm) that transmits sound emitted from the speaker unit 135 housed inside to the outside of the simulated housing 160, and a conduction hole 164 that leads the speaker cable 142 to the outside of the simulated housing 160.
  • parts 160a and 160b By fitting parts 160a and 160b together, a space with no openings other than the sound vent 162 and the conduction hole 164 is formed inside the simulated housing 160.
  • parts 160a and 160b After placing the manufactured speaker unit 135 on part 160b, parts 160a and 160b are fitted together to house the speaker unit 135 inside the simulated housing 160.
  • the sound passage 132 of the speaker unit 135 and the sound passage 162 of part 160a are aligned so that sound is transmitted from the speaker 140 to the outside of the simulated housing 160 through both sound passages 132, 162.
  • the speaker cable 142 is pulled out to the outside of the simulated housing 160 through the conduction hole 164, which is then sealed with putty.
  • sample body 1B is fixed to the sound vent 162 of the simulated housing 160.
  • Figure 16B is a cross-sectional view showing the sample body of Figure 16A attached to the simulated housing 160.
  • sample body 1B can be fixed using double-sided adhesive tape 58 with a vent hole (diameter 2.5 mm) punched in the center.
  • sample body 1B is fixed so that the entire non-bonded region r2 is located within the opening of the sound vent 162.
  • a microphone 150 (Knowles Acoustics, SPU0410LR5H) is fixed to the second main surface 1b of sample body 1B so as to cover the non-bonded region r2 of sample body 1B.
  • microphone 150 is fixed using an adhesive layer 57 on the second main surface 1b of sample body 1B.
  • the distance between speaker 140 and microphone 150 when fixed varies by up to about 2 mm depending on the thickness of sample body 1B to be evaluated, but is generally in the range of 22 to 24 mm.
  • a weight 151 (344 g) is placed on microphone 150 (not shown in Figure 17(E)).
  • the speaker 140 and microphone 150 are connected to an acoustic evaluation device (B&K Multi-analyzer System 3560-B-030), and the SSR (Solid State Response) mode (test signal 20 Hz to 20 kHz, sweep up) is selected and executed as the evaluation method to evaluate the insertion loss of the porous film 1 for sound of a specific frequency (e.g., 1 kHz).
  • the insertion loss is automatically determined from the test signal input from the acoustic evaluation device to the speaker 140 and the signal received by the microphone 150.
  • the insertion loss value (blank value) when sample body 1B is removed is determined in advance.
  • the blank value is -22 dB at a frequency of 1 kHz.
  • the insertion loss of the porous film 1 for sound of a specific frequency is the value obtained by subtracting this blank value from the measurement value obtained by the acoustic evaluation device.
  • the insertion loss B1 (dB) of the porous film 1 for a sound with a frequency of 1 kHz is measured, and then the insertion loss B2 (dB) for a sound with a frequency of 1 kHz is measured after the heat resistance test A.
  • the ratio ( B2 / B1 x 100) can be calculated from the insertion loss B1 and the insertion loss B2 .
  • heat resistance test A can be performed, for example, by placing sample 1A or sample 1B inside a drying oven (e.g., Yamato Scientific Co., Ltd., DKM300) whose internal temperature has been raised to a predetermined temperature for a predetermined period of time.
  • a drying oven e.g., Yamato Scientific Co., Ltd., DKM300
  • the air permeability ratio (A 2 / A 1 ⁇ 100) may be in the range of 60 to 120%, 70 to 130%, 80 to 120%, or even 90 to 110%.
  • the air permeability A2 expressed as a Gurley number after heat resistance test A is, for example, 500 seconds/100 mL or less.
  • the upper limit of the air permeability A2 may be 250 seconds/100 mL, 100 seconds/100 mL, or even 65 seconds/100 mL.
  • the lower limit of the air permeability A2 is, for example, 0.1 seconds/100 mL.
  • the lower limit of the air permeability A2 may be 1 second/100 mL or 5 seconds/100 mL.
  • the air permeability A 1 expressed by the Gurley number in the initial state before the heat resistance test A is, for example, 0.1 sec/100 mL or more and 500 sec/100 mL or less.
  • the insertion loss ratio (B 2 /B 1 ⁇ 100) for a sound with a frequency of 1 kHz may be in the range of 75 to 125%.
  • the insertion loss ratio (B 2 /B 1 ⁇ 100) may be in the range of 77 to 120%.
  • the insertion loss B2 for a sound having a frequency of 1 kHz after the heat resistance test A is, for example, 20 dB.
  • the upper limit of the insertion loss B2 may be 15 dB, 13 dB, or even 11 dB.
  • the lower limit of the insertion loss B2 is, for example, 0 dB.
  • the insertion loss B1 for a sound with a frequency of 1 kHz in the initial state before the heat resistance test A is, for example, 0 dB or more and 20 dB or less.
  • Heat resistance test A may be a test in which the film is heated at 160°C for 3 minutes, or a test in which the film is heated at 60°C for 7 days.
  • the porous film 1 not only has excellent heat resistance to short-term, high-temperature heating, such as when attached to a device using a thermosetting adhesive, but also has excellent heat resistance to long-term, high-temperature heating, such as when the attached device generates heat or when the temperature rises in the location where the attached device is located.
  • Heat resistance test A may be a test of heating at 160°C for 1 minute, a test of heating at 160°C for 3 minutes, or a test of heating at 60°C for 7 days.
  • the ratio ( B2 / B1 x 100) of the insertion loss B2 (dB) of the sound after heat resistance test A to the insertion loss B1 (dB) of a sound with a frequency of 100 Hz may be in the range of 70 to 130%.
  • the blank value for the 100 Hz frequency when calculating the insertion loss for the 100 Hz frequency sound is -31 dB.
  • the ratio ( B2 / B1 x 100) of the insertion loss B2 (dB) of the sound after heat resistance test A to the insertion loss B1 (dB) of a sound with a frequency of 5 kHz may be in the range of 70 to 130%.
  • the blank value for the frequency of 5 kHz when calculating the insertion loss for the sound with a frequency of 5 kHz is -34 dB.
  • the ratio ( B2 / B1 x 100) of the insertion loss B2 (dB) of the sound after heat resistance test A to the insertion loss B1 (dB) of a sound with a frequency of 8 kHz may be in the range of 70 to 130%.
  • the blank value for the 8 kHz frequency when calculating the insertion loss for the 8 kHz frequency sound is -35 dB.
  • the porous film 1 can suppress changes in liquid repellency due to temperature rise.
  • the porous film 1 has a main surface that has been treated with a liquid repellent agent, and the ratio (C2/C1 x 100) of the contact angle C2 of liquid paraffin on the main surface after heat resistance test B to the contact angle C1 of liquid paraffin on the main surface that has been treated with the liquid repellent agent (first main surface 1a in the example of Figure 1 ) can be 80 % or more.
  • Heat resistance test B is a test in which the film is heated at 160°C for 10 minutes.
  • Heat resistance test B can be performed, for example, by placing the porous film 1 in a drying oven (e.g., DKM300, manufactured by Yamato Scientific Co., Ltd.) for a predetermined time, with the temperature inside the oven increased to a predetermined temperature.
  • a drying oven e.g., DKM300, manufactured by Yamato Scientific Co., Ltd.
  • the liquid paraffin used for measuring the contact angle has a kinematic viscosity at 40°C in the range of 64.5 to 69.7 mm /sec.
  • An example of a liquid paraffin having a kinematic viscosity at 40°C in the range of 64.5 to 69.7 mm /sec is Kaydol (manufactured by Sonneborn), which is used in oil repellency grade 0.1 according to the AATCC (American Association of Textile Chemists and Colorists) TM118 method (1997).
  • the contact angle C1 (°) of liquid paraffin on the liquid-repellent treated main surface of the porous film 1 is measured, and then the contact angle C2 (°) of liquid paraffin on the main surface after heat resistance test B is measured.
  • the ratio ( C2 / C1 x 100) can be calculated from the contact angle C1 and the contact angle C2 .
  • the amount of liquid paraffin dropped is 3 ⁇ L. The measurement is carried out three times by changing the dropping point, and the average of the three measured values is taken as the contact angle.
  • the contact angle ratio (C 2 /C 1 ⁇ 100) may be in the range of 80 to 130%.
  • the contact angle ratio (C 2 /C 1 ⁇ 100) may be in the range of 80 to 125%.
  • the contact angle C2 after the heat resistance test B may be 45° or more.
  • the lower limit of the contact angle C2 may be 46°, 47°, 48°, 49°, or even 50°.
  • the upper limit of the contact angle C2 is, for example, 75°.
  • the contact angle C 1 in the initial state before the heat resistance test B is, for example, 40° or more and 75° or less.
  • Heat resistance test B may be a test in which the film is heated at 160°C for 10 minutes, or a test in which the film is heated at 60°C for 7 days.
  • the porous film 1 not only has excellent heat resistance to short-term, high-temperature heating, such as when attached to a device using a thermosetting adhesive, but also has excellent heat resistance to long-term, high-temperature heating, such as when the attached device generates heat or when the temperature rises in the location where the attached device is located.
  • the porous film 1 is in the form of a film or sheet.
  • the thickness of the porous film 1 is preferably 200 ⁇ m or less.
  • the thickness of porous film 1 can be determined by measuring the thickness at any five points on porous film 1 using, for example, a dial gauge, and taking the average of these measurements.
  • the thickness of porous film 1 can also be determined by measuring the thickness at any five points on an SEM image of the cross section of porous film 1 and taking the average of these measurements.
  • the upper limit of the thickness of the porous film 1 may be 200 ⁇ m, 150 ⁇ m, 125 ⁇ m, or even 100 ⁇ m.
  • the lower limit of the thickness of the porous film 1 is, for example, 1 ⁇ m.
  • the porous film 1 may be a stretched film.
  • the stretched film may be a biaxially stretched film or a uniaxially stretched film.
  • At least one of the main surfaces of the porous film 1 may be subjected to a surface modification treatment other than liquid-repellent treatment.
  • surface modification treatments include chemical treatment, sputter etching treatment, and plasma treatment.
  • the bonding strength of the porous film 1 is improved in the area where the surface modification treatment has been applied.
  • the porous film 1 can be produced, for example, by the following method.
  • the method for manufacturing porous film 1 includes, for example, kneading a composition containing a fluorine-free thermoplastic resin and a plasticizer to obtain a kneaded mixture (step S1), heat-pressing the kneaded mixture to obtain a pressed body (step S2), cooling the pressed body to obtain a molded body (step S3), stretching the molded body to obtain a porous sheet body (step S4), removing the plasticizer from the porous sheet body to obtain a porous film body (step S5), applying a liquid-repellent treatment to at least one main surface of the porous film body with a liquid-repellent agent (step S6), and drying the liquid-repellent treated porous film body (step S7).
  • Steps S1 to S3 correspond to the process of producing a precursor for porous film 1.
  • Steps S4 to S5 correspond to the process of growing a porous structure.
  • Step S6 corresponds to the process of imparting liquid repellency to porous film 1.
  • Step S1 is carried out, for example, at a temperature of 130°C to 260°C for 5 to 30 minutes.
  • composition containing the thermoplastic resin and plasticizer may be mixed with resins such as polyethylene, polypropylene, poly-1-butene, and cyclic polyolefins, as long as the properties of the porous film 1 are not affected.
  • the plasticizer is a non-volatile solvent that, when mixed with a thermoplastic resin such as a polyolefin resin (e.g., polyethylene resin, polymethylpentene resin), forms a mixture at or above the melting point of the resin, and exhibits thermally induced phase separation when the mixture is cooled.
  • a thermoplastic resin such as a polyolefin resin (e.g., polyethylene resin, polymethylpentene resin)
  • the plasticizer may be in the form of a liquid or a solid at room temperature.
  • a single plasticizer may be used, or two or more types of plasticizers may be mixed and used.
  • a plasticizer having a kinematic viscosity at 40°C of 5 to 1000 mm2 /s may be used.
  • the mixing ratio of the thermoplastic resin and plasticizer is set so that a uniform mixture can be obtained in step S1 and a molded body can be formed in step S3.
  • the weight ratio of the thermoplastic resin in a composition containing a thermoplastic resin and a plasticizer is, for example, 20% by weight or more and 80% by weight or less, and preferably 30% by weight or more and 70% by weight.
  • a weight ratio of the thermoplastic resin of 20% by weight or more prevents the viscosity of the composition from decreasing too much.
  • a weight ratio of the thermoplastic resin of 80% by weight or less makes it easier to obtain a good porous structure.
  • compositions containing thermoplastic resins and plasticizers may further contain additives such as antioxidants, nucleating agents, antistatic agents, flame retardants, lubricants, UV absorbers, colorants, and inorganic fillers to improve strength, depending on the purpose.
  • additives such as antioxidants, nucleating agents, antistatic agents, flame retardants, lubricants, UV absorbers, colorants, and inorganic fillers to improve strength, depending on the purpose.
  • Step S2 is carried out, for example, at a temperature of 130°C to 260°C for 2 to 30 minutes.
  • the thickness of the pressed body obtained by step S2 is, for example, 0.1 mm.
  • step S3 the pressed body obtained in step S2 may be cooled to a temperature sufficiently lower than the crystallization temperature of the thermoplastic resin and solidified, for example, by contacting it with a thermal conductor.
  • thermal conductors used for cooling include metal, water, air, and plasticizers.
  • step S4 the molded body is stretched at least once in at least one axial direction. Stretching in at least one axial direction includes uniaxial stretching in the longitudinal direction, uniaxial stretching in the transverse direction, simultaneous biaxial stretching, and sequential biaxial stretching. The molded body may be biaxially stretched sequentially, or simultaneously. Step S4 generates voids in the molded body.
  • the stretching temperature may be 20°C to 130°C, 50°C to 120°C, or even 70°C to 100°C for both longitudinal and transverse stretching.
  • the stretching ratio in the longitudinal and/or transverse uniaxial directions may be 1.1 to 50.0 times, 2.0 to 30.0 times, or even 4.0 to 20.0 times.
  • step S5 the plasticizer is removed from the porous sheet, for example, using an extraction solvent.
  • the extraction solvent used is preferably one that is a poor solvent for thermoplastic resins such as polyethylene resins and polymethylpentene resins, but is a good solvent for plasticizers and has a boiling point lower than the melting point of the porous sheet.
  • extraction solvents include hydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride and 1,1,1-trichloroethane; alcohols such as ethanol and isopropanol; ethers such as diethyl ether and tetrahydrofuran; and ketones such as acetone and 2-butanone. Considering safety, alcohols and ketones are preferred. Methyl ethyl ketone (MEK) may also be used as the extraction solvent.
  • MEK Methyl ethyl ketone
  • the porous sheet may be heat-set.
  • Heat-set can be performed, for example, using a hot air circulating oven. Heat-set can reduce the thermal shrinkage of the porous sheet after stretching.
  • the heat-set temperature is, for example, 50°C to 130°C.
  • the heat-set temperature may also be 70°C to 120°C, or even 80°C to 110°C.
  • Heat setting may be performed after step S4, between steps S4 and S5, or both after steps S4 and S5.
  • Examples of heat setting methods include fixing the film in the width direction with a tenter and continuously passing it through a heat treatment furnace, applying appropriate tension and continuously passing it through a heat treatment furnace without fixing it in the width direction, or winding the film around a roll and feeding it into a heat treatment furnace in batches.
  • Figure 18 is a diagram illustrating an example of a method for applying a liquid-repellent treatment to the main surface of a porous film.
  • step S6 at least one main surface of the porous film body 1p from which the plasticizer was removed in step S5 is treated with a liquid-repellent agent.
  • methods for liquid-repellent treatment include slot die coating, gravure coating, spin coating, and bar coating.
  • the porous film body 1p may be fixed using adhesive tape 63 on a glass plate 61 fixed on a flat table using adhesive tape 62, and a liquid-repellent treatment liquid containing a liquid-repellent agent may be applied from above the porous film body 1p using a wireless bar coater 65 (for example, KCN-OSP-04S manufactured by Cortec).
  • a wireless bar coater 65 for example, KCN-OSP-04S manufactured by Cortec.
  • step S7 the porous film body 1p that has been subjected to the liquid-repellent treatment is dried, for example, by air drying for 24 hours. In this way, the porous film 1 is obtained.
  • the porous film 1 can be produced, for example, by the following method.
  • the porous film 1 can be manufactured, for example, by a phase separation method.
  • phase separation methods are the non-solvent induced phase separation method (NIPS method) and the drying induced phase separation method (DIPS method).
  • NIPS method non-solvent induced phase separation method
  • DIPS method drying induced phase separation method
  • a porous film is obtained by inducing phase separation in a coating of a polymer solution or polymer precursor solution when a non-solvent such as water is incorporated.
  • a porous film is obtained by inducing phase separation in a coating of a polymer solution or polymer precursor solution as the solvent evaporates.
  • the method for manufacturing porous film 1 includes, for example, applying a soluble polyimide solution containing a soluble polyimide and a solvent onto a substrate to form a coating film (step ST1), immersing the coating film in water (step ST2), and drying the coating film (step ST3), in this order.
  • the solvent includes at least one selected from the group consisting of lactone-based solvents, sulfone-based solvents, ketone-based solvents, and cyclic ether-based solvents.
  • the polyethylene glycol content in the soluble polyimide solution is less than 0.1 wt%.
  • a soluble polyimide solution is applied to a predetermined substrate to form a coating film.
  • soluble polyimide is a soluble polyimide varnish (Neoprim S100 (solid content: 20 wt%), manufactured by Mitsubishi Gas Chemical Company, Inc.).
  • the solvent are lactone-based solvents, sulfone-based solvents, or ketone-based solvents.
  • the solvent may also be a lactone-based solvent.
  • An example of the substrate is a porous material containing a fluororesin.
  • the substrate is preferably a predetermined polytetrafluoroethylene (PTFE) porous membrane (TEMISH (registered trademark), manufactured by Nitto Denko Corporation).
  • the air permeability of the PTFE porous membrane measured according to the Air Permeability Measurement Method B (Gurley method) specified in JIS L1096:2010, is 30 sec/100 cm 3 to 50 sec/100 cm 3 .
  • the PTFE porous membrane has a thickness of, for example, 50 to 100 ⁇ m.
  • the average pore size on the surface of the PTFE porous film is, for example, 100 to 200 nm.
  • a first microporous layer can be formed in contact with the contact surface of the coating film of the soluble polyimide solution with the substrate.
  • the solvent includes at least one selected from the group consisting of lactone solvents, sulfone solvents, ketone solvents, and cyclic ether solvents.
  • lactone solvents include gamma-butyl lactone.
  • the lactone solvent may be gamma-butyl lactone.
  • sulfone solvents include sulfolane.
  • ketone solvents include cyclopentanone.
  • cyclic ether solvents include 1,3-dioxolane.
  • the soluble polyimide solution is substantially free of polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • substantially free of polyethylene glycol means that the polyethylene glycol content in the soluble polyimide solution is less than 0.1 wt%.
  • PEG has traditionally been used as a porosifying agent when producing porous films. Therefore, the common idea in this field is to use PEG to adjust the size of the pores in the porous film and improve breathability. However, contrary to expectations, PEG is not used in this embodiment. This tends to result in the formation of characteristic rod-shaped pores in step ST2.
  • step ST2 the coating of the soluble polyimide solution is immersed in water. This promotes phase separation in the coating, promoting porosity, and extracting the solvent from the coating.
  • the coating of the soluble polyimide solution is immersed, for example, in a water bath at 20°C to 40°C.
  • the water used in the water bath is typically pure water.
  • the immersion time is, for example, 1 to 30 minutes.
  • step ST2 the closer to the outermost layer of the coating, the faster the phase separation rate becomes, and the more rapidly the solvent is extracted.
  • a second microporous layer with a denser structure is formed on the surface of the coating, and a first microporous layer is formed in contact with the surface of the coating that comes into contact with the substrate.
  • the formation of the first and second microporous layers makes it difficult for the solvent to be extracted from the inside of the coating, resulting in the formation of a porous layer with rod-shaped voids on the inside of the coating.
  • step ST3 the porous coating film is dried.
  • the resulting film is peeled off from the substrate after drying to obtain porous film 1.
  • the drying time is, for example, 1 to 30 minutes.
  • FIG. 2 An example of the film member of the present invention is shown in Figure 2.
  • the film member 2 (2A) in Figure 2 includes a porous film 1.
  • a first modified example of the film member of Figure 2 is shown in Figure 3.
  • the film member 2 (2B) in Figure 3 further includes an air-permeable support material 3.
  • the air-permeable support material 3 is laminated on the porous film 1.
  • the air-permeable support material 3 can improve the strength and handleability of the film member 2.
  • the breathable support material 3 typically has higher breathability in the thickness direction than the porous film 1.
  • Examples of the breathable support material 3 include woven fabric, nonwoven fabric, net, and mesh.
  • Examples of materials that make up the breathable support material 3 include polyesters such as polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), and aramid resin.
  • PET polyethylene terephthalate
  • PE polyolefins
  • PP polypropylene
  • aramid resin aramid resin.
  • the shape of the breathable support material 3, when viewed perpendicular to the main surface of the film member 2, may be the same as or different from the shape of the porous film 1.
  • the breathable support material 3 may have a peripheral edge that corresponds to the peripheral edge of the porous film 1, when viewed perpendicular to the main surface of the film member 2.
  • the film member 2B in Figure 3 includes one breathable support material 3 arranged on one main surface of the porous film 1.
  • the breathable support material 3 is arranged on the main surface (second main surface 1b) of the porous film 1 that has not been treated with a liquid repellent.
  • the breathable support material 3 may also be arranged on the main surface (first main surface 1a) of the porous film 1 that has been treated with a liquid repellent.
  • the film member 2 may include two or more breathable support materials 3.
  • the breathable support materials 3 may be arranged on both surfaces of the porous film 1.
  • the porous film 1 and the breathable support material 3 may be joined by welding, such as thermal welding or ultrasonic welding, or by an adhesive or pressure-sensitive adhesive.
  • the film member 2 may include any layers and/or members other than those described above.
  • the thickness of the film member 2 is, for example, 1 to 300 ⁇ m.
  • the thickness of the film member 2 may also be 50 to 200 ⁇ m.
  • the basis weight of the film member 2 is, for example, 1.0 to 200.0 g/m 2.
  • the basis weight of the film member 2 may be 10.0 to 100.0 g/m 2 .
  • the film member 2 can have the same properties as the porous film 1, such as breathability and sound permeability.
  • the film member 2 may be treated to be liquid-repellent and/or colored.
  • the film member 2 can be used, for example, as a filter member. However, the uses of the film member 2 are not limited to the above example.
  • the shape of the film member 2 may be, for example, a polygon including a square or rectangle, a circle, an ellipse, or a strip. The corners of the polygon may be rounded.
  • the shape of the film member 2 is not limited to the above examples.
  • a strip-shaped film member 2 may be wound to form a wound body. Furthermore, if necessary, it may be wound while laminated with a release liner.
  • FIG 4 shows a second modified example (roll) of the film member of Figure 2.
  • the roll 10 shown in Figure 4 includes the film member 2A and release liner 11 of Figure 2.
  • the film member 2A and release liner 11 are bonded to each other by an adhesive layer 12.
  • the release surface 13 formed when the release liner 11 is peeled from the film member 2A is located between the film member 2A and the adhesive layer 12. That is, in the roll 10, when the release liner 11 is peeled off, the adhesive layer 12 is also peeled off from the film member 2A, resulting in a film member 2A without the adhesive layer 12 formed on its surface.
  • the release liner 11 may be disposed on the main surface of the porous film 1 that has not been treated with a liquid repellent coating (second main surface 1b), or on the main surface of the porous film 1 that has been treated with a liquid repellent coating (first main surface 1a).
  • adheresive means “sticking” or “adhesion.”
  • adhesive layer means “sticking layer” or “adhesive layer.”
  • pressure-sensitive adhesive refers to a type of adhesion that is temporary and can bond with just the application of slight pressure. It also refers to a property that, while it adheres strongly due to its cohesive strength and elasticity, it can also be peeled off from hard, smooth surfaces. Pressure-sensitive adhesives are soft solids that do not change state like glue. Pressure-sensitive adhesives wet to the adherend in their original state and resist peeling, so when two adherends are bonded together, they instantly demonstrate practical adhesive strength. In other words, pressure-sensitive adhesives possess both the properties of a liquid (fluidity) that allows them to wet to the adherend, and the properties of a solid (cohesive strength) that resist peeling. Because pressure-sensitive adhesives are soft solids, the contact area with the adherend gradually increases as pressure is applied or over time. Furthermore, because they can maintain this softness for long periods of time, they have the property of being removable when desired.
  • adhesive refers to the property of bonding solid surfaces of the same or different types together to form a single unit, as defined by JIS.
  • An adhesive is a fluid substance that wets and blends with the adherends when bonding them together. It then transforms into a solid through heating or chemical reaction, firmly bonding the adherends at their interfaces and exerting resistance to peeling.
  • an adhesive is a fluid substance that wets and adheres as a solid.
  • the film member 2A supplied by the roll 10, which does not have the adhesive layer 12 formed on its surface, can be bonded to the opening of the housing using any bonding method.
  • Bonding methods include, for example, bonding using an adhesive layer newly placed on the surface of the film member 2A, bonding by heat welding, and bonding by ultrasonic welding.
  • the film member 2A supplied by the roll 10 can be processed into any shape as needed.
  • the film member 2A has a high degree of freedom in terms of shape.
  • shape also includes “size.” The above means that the roll 10 allows the film member 2A, which functions as a waterproof membrane, to be supplied with a high degree of freedom in terms of the joining method to the opening of the housing and/or the shape.
  • the adhesive layer 12 prevents misalignment between the film member 2A and the release liner 11 during winding.
  • the wound body 10 can prevent malfunctions (abnormal shape of the wound body) caused by tightness during winding, etc.
  • FIG. 5 An example of a ventilation member of the present invention is shown in FIG. 5.
  • the ventilation member 4 (4A) in FIG. 5 has breathability in the thickness direction and includes the porous film 1 or film member 2 described above as a member that prevents the penetration of foreign matter in that direction.
  • the ventilation member 4 is, for example, a member that is placed on the surface of an object having an opening, and ensures ventilation through the opening while preventing the penetration of foreign matter through the opening. In this case, the ventilation member 4 is typically placed so that the porous film 1 or film member 2 covers the opening of the object.
  • the ventilation member 4A in FIG. 5 includes a porous film 1. Below, an example will be described in which the ventilation member 4 has breathability in the thickness direction and includes a porous film 1 as a member that prevents the penetration of foreign matter in that direction.
  • the ventilation member 4 (4A) has an adhesive layer 5 arranged on one main surface of the porous film 1.
  • the porous film 1 and the adhesive layer 5 are directly bonded to each other.
  • the ventilation member 4A can be placed on the surface of the object via the adhesive layer 5.
  • the adhesive layer 5 is arranged on the main surface of the porous film 1 that has not been treated with a liquid repellent treatment (second main surface 1b).
  • the adhesive layer 5 may also be arranged on the main surface of the porous film 1 that has been treated with a liquid repellent treatment (first main surface 1a).
  • Examples of adhesives that may form the adhesive layer 5 include acrylic adhesives, silicone adhesives, urethane adhesives, epoxy adhesives, and rubber adhesives. When consideration must be given to using the ventilation member 4 at high temperatures, it is preferable to select an acrylic adhesive or silicone adhesive, particularly a silicone adhesive, which have excellent heat resistance.
  • the adhesive layer 5 may be a substrate-less double-sided adhesive tape.
  • the adhesive may be a curable adhesive such as a phenolic resin, epoxy resin, urea resin, polyurethane resin, melamine resin, or polyester resin.
  • the outer periphery of the porous film 1 and the outer periphery of the adhesive layer 5 are coincident when viewed perpendicularly to the main surface of the porous film 1. Furthermore, the shape of the adhesive layer 5 corresponds to the peripheral edge of the porous film 1 when viewed perpendicularly to the main surface of the porous film 1.
  • the area of the porous film 1 to which the adhesive layer 5 is not bonded can be used as the ventilation area of the ventilation member 4A.
  • the shape of the adhesive layer 5 is not limited to the above example.
  • the area of the ventilation region is, for example, 40 mm2 or less.
  • a ventilation member 4 with a ventilation region area within this range is suitable for placement in an object with a small diameter opening, for example.
  • the lower limit of the ventilation region area is, for example, 0.008 mm2 .
  • the area of the ventilation region may be in a larger range depending on the type of object in which the ventilation member 4 is placed.
  • Fig. 6 shows a first variation of the ventilation member of Fig. 5.
  • the ventilation member 4 (4B) of Fig. 6 has the same configuration as the ventilation member 4A of Fig. 5, except that it further includes an adhesive layer 5 (5B) arranged on the other main surface of the porous film 1.
  • the porous film 1 is sandwiched between a pair of adhesive layers 5 (5A, 5B).
  • the adhesive layer 5 may include a first adhesive layer 5A bonded to one main surface (first main surface 1a) of the porous film 1 and a second adhesive layer 5B bonded to the other main surface (second main surface 1b) of the porous film 1.
  • FIG. 7 A second variation of the ventilation member of FIG. 5 is shown in FIG. 7.
  • the ventilation member 4 (4C) of FIG. 7 further includes a base material layer 6 disposed on one main surface of the porous film 1, and has the same configuration as the ventilation member 4A of FIG. 5, except that the porous film 1 and the adhesive layer 5 are bonded via the base material layer 6.
  • the base material layer 6 improves the strength and handleability of the ventilation member 4, and can prevent damage to the porous film 1 during handling or placement on an object.
  • Examples of materials that can be used to form the substrate layer 6 include polyolefins such as PE and PP, polyesters such as PET, silicone resins, polycarbonate, polyimide, polyamideimide, polyphenylene sulfide, polyether ether ketone (PEEK), polyvinyl chloride, fluororesins, and metals such as aluminum and stainless steel.
  • Examples of fluororesins include PTFE, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE).
  • the materials that can be used to form the substrate layer 6 are not limited to the above examples.
  • the outer periphery of the porous film 1 and the outer periphery of the base layer 6 are coincident when viewed perpendicular to the main surface of the porous film 1. Furthermore, the shape of the base layer 6 corresponds to the peripheral edge of the porous film 1 when viewed perpendicular to the main surface of the porous film 1.
  • the area of the porous film 1 to which the base layer 6 is not bonded can be used as the ventilation area of the ventilation member 4C.
  • the shape of the base layer 6 is not limited to the above example.
  • the porous film 1 and the base layer 6 may be joined using an adhesive or glue, or may be joined by welding such as thermal welding or ultrasonic welding.
  • the porous film 1 and the base layer 6 may be joined by an adhesive layer.
  • This adhesive layer may have the same structure as the adhesive layer 5.
  • the base layer 6 may be a single-sided adhesive tape or a double-sided adhesive tape.
  • FIG 8 shows a third variation of the ventilation member of Figure 5.
  • the ventilation member 4 (4D) of Figure 8 has the same configuration as the ventilation member 4C of Figure 5, except that it further includes a base material layer 6 (6B) arranged on the other main surface of the porous film 1.
  • the porous film 1 is sandwiched between a pair of base material layers 6 (6A, 6B). This sandwiching structure further improves the strength and handleability of the ventilation member 4.
  • the substrate layer 6 may include a first substrate layer 6A bonded to one main surface (first main surface 1a) of the porous film 1 and a second substrate layer 6B bonded to the other main surface (second main surface 1b) of the porous film 1.
  • FIG 9 shows a fourth variation of the ventilation member in Figure 5.
  • the ventilation member 4 (4E) in Figure 9 has the same configuration as the ventilation member 4B in Figure 6, except that it further includes a release liner 7 and the porous film 1 and the release liner 7 are bonded via an adhesive layer 5 (5B).
  • the ventilation member 4 (4E) may further include a release liner 7, with a second adhesive layer 5B disposed between the release liner 7 and the porous film 1, and the second adhesive layer 5B bonded to the release liner 7.
  • the release liner 7 has a tab that protrudes outward beyond the outer periphery of the porous film 1 when viewed perpendicular to the main surface of the porous film 1.
  • the ventilation member 4E can be handled or placed on the surface of an object by grasping the tab.
  • the release liner 7 is typically removed when the ventilation member 4E is used.
  • the release liner 7 can be made of, for example, the same material as the material that makes up the base layer 6.
  • FIG 10 shows a fifth variation of the ventilation member of Figure 5.
  • the ventilation member 4 (4F) of Figure 10 further includes a release liner 7, and has the same configuration as the ventilation member 4D of Figure 8, except that the base material layer 6 (6B) and the release liner 7 are bonded via an adhesive layer 5 (5B).
  • the ventilation member 4 can be supplied, for example, by a component supply sheet.
  • An example of a component supply sheet, which is a supply mode of the ventilation member 4, is shown in FIG. 11 .
  • the component supply sheet 20 (20A) in FIG. 11 includes a ventilation member 4 (4A) to be placed on the surface of an object having an opening, and a base sheet 9 on whose surface the ventilation member 4 (4A) is placed.
  • the component supply sheet 20A includes the ventilation member 4A as the ventilation member 4.
  • the ventilation member 4A includes a porous film 1 having a shape that covers the opening when placed on the surface of the object, and an adhesive layer 5 bonded to the porous film 1. In the example shown in FIG.
  • the base sheet 9 is arranged to face the main surface (second main surface 1b) of the porous film 1 that has not been treated with a liquid repellent coating.
  • the base sheet 9 may also be arranged to face the main surface (first main surface 1a) of the porous film 1 that has been treated with a liquid repellent coating.
  • the ventilation member 4 (4A) is placed on the base sheet 9 via the adhesive layer 5.
  • the member supply sheet 20 (20A) allows the ventilation member 4 to be efficiently supplied, for example, during the process of placing it on the surface of an object.
  • the ventilation member 4 may be placed on the base sheet 9 via an adhesive layer provided on the placement surface of the base sheet 9 on which the ventilation member 4 is placed.
  • the adhesive layer on the placement surface preferably has weak adhesive properties.
  • multiple ventilation members 4 may be arranged on the surface of the base sheet 9.
  • Examples of materials that make up the base sheet 9 include paper, metal, resin, and composite materials of these.
  • Examples of metal include stainless steel and aluminum.
  • Examples of resin include polyester such as PET, and polyolefins such as PE and PP.
  • the base sheet 9 may be in the form of a sheet or a strip. If the base sheet 9 is in the form of a strip, the member supply sheet 20 may be rolled up to form a roll.
  • Examples of objects on which the ventilation member 4 can be placed include the housing of an electronic device and the housing of an electrical component for a vehicle.
  • the ventilation member 4 can be placed on the outer surface and/or inner surface of the housing.
  • the openings may be air vents and/or sound vents provided in the housing.
  • Examples of electronic devices include wearable devices such as smartwatches and wristbands; various cameras including action cameras and security cameras; information and communication devices such as mobile phones, smartphones and tablets; virtual reality (VR) devices; augmented reality (AR) devices; and sensor devices.
  • Examples of electrical components for a vehicle include lamps and ECUs.
  • the objects are not limited to the above examples.
  • Foreign matter that is prevented from passing through by the placement of the ventilation member 4 includes, for example, particles such as dust, and liquid water such as water droplets.
  • Figure 12 shows a first variation of the member supply sheet of Figure 11.
  • the member supply sheet 20 (20B) of Figure 12 has the same configuration as the member supply sheet 20A of Figure 11, except that it is equipped with the ventilation member 4E of Figure 9 as the ventilation member 4.
  • Figure 13 shows a second variation of the member supply sheet of Figure 11.
  • the member supply sheet 20 (20C) of Figure 13 has the same configuration as the member supply sheet 20A of Figure 11, except that it is equipped with the ventilation member 4F of Figure 10 as the ventilation member 4.
  • Example 1 A porous film containing polyethylene resin as a main component was prepared as a substrate.
  • the porous film had a thickness of 30 ⁇ m, a pore size of 0.1 ⁇ m, a porosity of 80%, a ratio of the tensile elongation in the machine direction (MD) T MD to the tensile elongation in the transverse direction (TD) T TD (T TD ) of 15/30, a water flow rate of 17 mL/min/cm 2 at a differential pressure of 100 kPa in the flat membrane state, and an ethanol flow rate of 12 mL/min/cm 2 at a differential pressure of 100 kPa in the flat membrane state.
  • a liquid repellent agent containing a silicone resin having alkoxy groups directly bonded to silicon atoms (X-48-2316, manufactured by Shin-Etsu Chemical Co., Ltd.: viscosity 100 mm 2 /sec (25°C), specific gravity 1.07 (25°C)) was prepared as the liquid repellent agent.
  • Isopropanol (IPA) was prepared as the diluent. 0.1 g of the liquid repellent agent and 9 g of the diluent were mixed to prepare a 1.0 wt % liquid repellent treatment liquid.
  • a liquid repellent treatment was applied to one main surface of a porous film body cut into a size of 50 mm x 50 mm using a wireless bar coater (KCN-OSP-04S, manufactured by Cortec Co., Ltd.). Specifically, a 1 mL dropper was used to drop approximately 0.5 mL of liquid repellent treatment liquid in front of the wireless bar coater, and the wireless bar coater was moved in the direction of the arrow in Figure 18 to scrape off the liquid repellent treatment liquid, thereby applying the liquid repellent treatment liquid to one main surface of the porous film body at a wet thickness of 54 ⁇ m. Nitto Denko No. 318 (thickness: 50 ⁇ m) was used as adhesive tapes 62 and 63.
  • the porous film After applying the liquid-repellent treatment liquid, the porous film was left to stand for 30 minutes and then air-dried for 24 hours. In this way, the porous film of Example 1 was obtained.
  • Example 2 The liquid repellent agent used was a liquid repellent agent containing a silicone resin having alkoxy groups directly bonded to silicon atoms (KP611, manufactured by Shin-Etsu Chemical Co., Ltd.: viscosity 550 mm2 /sec (25°C), specific gravity 0.98 (25°C)). 0.19 g of the liquid repellent agent was mixed with 9 g of diluent (IPA) to prepare a 1.0 wt% liquid repellent treatment liquid. After coating with the liquid repellent treatment liquid, the porous film was air-dried for 24 hours. Except for these, the porous film of Example 2 was obtained by the same method as Example 1.
  • the liquid repellent agent used was a liquid repellent agent containing polymethylpentene resin (manufactured by Mitsui Chemicals, Inc., RT18: high rigidity grade, density 0.833, MFR 26 g/10 min).
  • the diluent used was a solvent obtained by mixing cyclohexane and tetrahydrofuran (THF) at a weight ratio of 1:1.
  • 0.1 g of the liquid repellent agent and 9.9 g of the diluent were stirred at 60°C and 800 rpm for 6 hours to prepare a 1.0 wt% liquid repellent treatment liquid.
  • the porous film body after coating with the liquid repellent treatment liquid was air-dried for 24 hours. Except for these factors, the porous film of Example 3 was obtained by the same method as Example 1.
  • Example 4 As the liquid repellent agent, a liquid repellent agent containing polymethylpentene resin (manufactured by Mitsui Chemicals, Inc., MX002: low rigidity grade, density 0.834, MFR 21 g/10 min) was used. Except for this, a porous film of Example 4 was obtained by the same method as in Example 3.
  • Example 1 The porous film of Example 1 was used as the porous film of Comparative Example 1. That is, the porous film of Comparative Example 1 was not subjected to a liquid-repellent treatment with a liquid-repellent agent.
  • liquid repellent agent a fluorine-based liquid repellent agent containing a polymer having a compound represented by the following chemical formula (a) as a monomer was used.
  • CH2 CHCOOCH2CH2C6F13 ... ( a )
  • Example 3 AE3000 manufactured by AGC (viscosity: 0.65 mPa ⁇ s (25°C), specific gravity: 1.474) was used as the diluent. 0.65 g of the liquid repellent agent was mixed with 9 g of the diluent to prepare a 1.0 wt % liquid repellent treatment liquid. After coating with the liquid repellent treatment liquid, the porous sheet was air-dried for 24 hours. With these exceptions, the porous film of Comparative Example 3 was obtained using the same method as in Example 1.
  • liquid repellent agent a fluorine-based liquid repellent agent containing a polymer having a compound represented by the following chemical formula (b) as a monomer was used.
  • CH2 C ( CH3 ) COOCH2CH2C5F10CH2C4F9 ... ( b )
  • Poly(4-methylpentene-1) resin (RT18, manufactured by Mitsui Chemicals, Inc.) was prepared as a fluorine-free thermoplastic resin.
  • Liquid paraffin (manufactured by MORESCO) with a kinematic viscosity of 110 mm 2 /s at 40°C was prepared as a plasticizer.
  • Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl))propionate (manufactured by BASF Japan Ltd.) was prepared as an antioxidant.
  • thermoplastic resin 50.000 wt% of the thermoplastic resin, 49.865 wt% of the plasticizer, and 0.135 wt% of the antioxidant were kneaded to obtain a kneaded mixture.
  • the kneaded mixture was then pelletized at 240°C to obtain pellets.
  • the pellets were then sheeted at 270°C using an injection molding machine to obtain a sheet-like molded product.
  • the sheet-like molded product was then extruded through a chill roll at 107°C to obtain a sheet.
  • the sheet was longitudinally stretched under the conditions of a front roll temperature of 60°C, a rear roll temperature of 120°C, and a stretch ratio of 1.2 times (i.e., a line speed of the front roll feed side of 5 m/min, and a line speed of the rear roll of 6 m/min). This resulted in a longitudinally stretched film.
  • the longitudinally stretched film was transversely stretched under conditions of a stretching temperature of 100°C and a stretch ratio of 2.5 times, and then annealed at 150°C. This resulted in a porous sheet.
  • porous sheet was immersed in room temperature methyl ethyl ketone (MEK) as an extraction solvent for 140 seconds to remove the plasticizer from the porous sheet. In this way, a porous film containing polymethylpentene resin as the main component was produced.
  • MEK room temperature methyl ethyl ketone
  • the produced porous film was treated with a liquid-repellent treatment in the same manner as in Example 1, using the liquid-repellent treatment liquid produced in Example 1. In this way, the porous film of Example 5 was obtained.
  • Example 6 The substrate used was a porous film containing polymethylpentene resin as a main component, which was prepared in Example 5.
  • the porous film was subjected to a liquid-repellent treatment using the liquid-repellent treatment solution prepared in Example 2 in the same manner as in Example 2. In this way, the porous film of Example 6 was obtained.
  • Comparative Example 5 The porous film of Comparative Example 5 was a porous film containing polymethylpentene resin as a main component, which was produced in Example 5. That is, the porous film of Comparative Example 5 was not subjected to a liquid-repellent treatment with a liquid-repellent agent.
  • Example 7 A soluble polyimide varnish (Neoprim S100 (solid content: 20 wt%) manufactured by Mitsubishi Gas Chemical Company, Inc.) was prepared as a fluorine-free thermoplastic resin. ⁇ -Butyllactone (manufactured by Tokyo Chemical Industry Co., Ltd.), a lactone solvent, was prepared as a dilution solvent. 6.5 g of ⁇ -butyllactone was added to 3.5 g of the soluble polyimide varnish and mixed uniformly. This resulted in a soluble polyimide (PI) solution. The polyimide concentration of the soluble PI solution was 7.0 wt%.
  • a PTFE porous membrane (TEMISH (registered trademark), manufactured by Nitto Denko Corporation) was prepared as the substrate.
  • the soluble PI solution was applied to the PTFE porous membrane using an applicator to a wet thickness of 125 ⁇ m to form a coating.
  • the coating was then immersed in a 20°C water bath for 10 minutes to allow for phase separation to create pores and for the solvent to be extracted.
  • the coating was then fixed to a square SUS member with a side length of 10 cm in plan view, and dried at 80°C for 10 minutes. This resulted in a porous film body on the PTFE porous membrane. Finally, the porous film body was peeled off from the PTFE porous membrane. In this way, a porous film body containing polyimide resin as the main component was produced.
  • Example 2 The liquid-repellent treatment liquid prepared in Example 2 was applied to one main surface of the prepared porous film body to a wet thickness of 16 ⁇ m. Except for this, the liquid-repellent treatment was carried out in the same manner as in Example 2. In this way, the porous film of Example 7 was obtained.
  • Example 8 The porous film body containing polyimide resin as the main component prepared in Example 7 was used as the substrate.
  • the liquid-repellent treatment liquid prepared in Example 2 was applied to one main surface of the prepared porous film body with a wet thickness of 20 ⁇ m. Except for this, the liquid-repellent treatment was performed in the same manner as in Example 2. In this way, the porous film of Example 8 was obtained.
  • the porous films of Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated for the air permeability ratio ( A2 / A1 x 100), insertion loss ratio ( B2 / B1 x 100), and contact angle ratio ( C2 / C1 x 100).
  • the air permeability ratio ( A2/A1 x 100) was evaluated when heat resistance test A was performed at 160°C for 1 minute and at 160°C for 3 minutes.
  • the insertion loss ratio (B2 / B1 x 100) of a sound with a frequency of 1 kHz was evaluated when heat resistance test A was performed at 160°C for 1 minute and at 160 °C for 3 minutes.
  • heat resistance test B involved heating at 160°C for 10 minutes, and evaluation was performed on the contact angle ratio ( C2 / C1 x 100).
  • a fully automatic contact angle meter (Dmo-702, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle.
  • Heat resistance tests A and B were performed using a drying oven (DKM300, manufactured by Yamato Scientific Co., Ltd.). The evaluation results are shown in Tables 1 to 4.
  • the air permeability ratio ( A2 / A1 x 100) was evaluated using Sample 1A shown in Figure 15 when Heat Resistance Test A was performed at 60°C for 7 days.
  • the insertion loss ratio ( B2 / B1 x 100) was evaluated using Sample 1B shown in Figure 16A when Heat Resistance Test A was performed at 60°C for 7 days.
  • Kaydol manufactured by Sonneborn
  • the contact angle ratio ( C2 / C1 x 100) and other properties were evaluated when Heat Resistance Test B was performed at 60°C for 7 days.
  • the evaluation results are shown in Tables 5 to 7.
  • the ratios of insertion loss (B2/ B1 x 100) in Heat Resistance Test A which involved heating at 160°C for 3 minutes and at 60 °C for 7 days, were in the range of 70 to 130%, and changes in sound permeability due to short-term and long-term temperature rise were suppressed.
  • heat resistance test B was a test in which the sample was heated at 160°C for 10 minutes and a test in which the sample was heated at 60°C for 7 days
  • the contact angle ratio ( C2 / C1 x 100) was 80% or more, and changes in liquid repellency due to temperature increases over short and long periods were suppressed.
  • the ratios of insertion loss ( B2 /B1 x 100) in Heat Resistance Test A which involved heating at 160°C for 3 minutes and at 60°C for 7 days, were in the range of 70 to 130%, and changes in sound permeability due to short-term and long-term temperature increases were suppressed.
  • the contact angle ratio ( C2 / C1 x 100) was 80% or more, and changes in liquid repellency due to temperature increases over short and long periods were suppressed.
  • the ratios of insertion loss ( B2 / B1 x 100) in Heat Resistance Test A which involved heating at 160°C for 3 minutes and at 60°C for 7 days, were in the range of 70 to 130%, indicating that changes in sound permeability due to short-term and long-term temperature increases were suppressed.
  • heat resistance test B was a test in which the sample was heated at 160°C for 10 minutes and a test in which the sample was heated at 60°C for 7 days
  • the contact angle ratio ( C2 / C1 x 100) was 80% or more, and changes in liquid repellency due to temperature increases over short and long periods were suppressed.
  • the porous films of Examples 1 to 8 had their main surfaces treated with a liquid-repellent agent containing at least one selected from the group consisting of a silicone resin having an alkoxy group directly bonded to a silicon atom and a polymethylpentene resin.
  • the porous films of Comparative Examples 2 to 4 had their main surfaces treated with a fluorine-based liquid-repellent agent.
  • the main surfaces of the porous films of Comparative Examples 1 and 5 were not treated with a liquid-repellent agent.
  • the properties of the porous films of Comparative Examples 2 to 4 changed with increasing temperature.
  • the porous film of Comparative Example 1 had low contact angles C1 and C2 of 30° or less, and did not have sufficient liquid repellency.
  • the porous film of Comparative Example 5 had an insertion loss ratio ( B2 / B1 x 100) of more than 130%, and its sound permeability changed with both short-term and long-term temperature increases.
  • porous films of Examples 1 to 8 are suitable for suppressing changes in properties due to temperature increases.
  • the technology of the present invention can be applied to, for example, waterproof breathable membranes, waterproof sound-permeable membranes, and separators for electricity storage devices.

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Le film poreux selon l'invention contient une résine thermoplastique exempte de fluor en tant que composant principal et a une surface principale qui a été soumise à un traitement hydrofuge par un agent hydrofuge. L'agent hydrofuge comprend au moins un élément choisi dans le groupe constitué par des résines de silicone ayant un groupe alcoxy directement lié à un atome de silicium et des résines de polyméthylpentène. Le film poreux a, par exemple, un rapport (A2/A1×100) entre la perméabilité à l'air A2 exprimée par le nombre de Gurley après un test de résistance à la chaleur A et la perméabilité à l'air A1 exprimée par le nombre de Gurley dans la plage de 50 à 150 % et un rapport (B2/B1×100) entre la perte d'insertion B2 après un test de résistance à la chaleur A et la perte d'insertion B1 d'un son de 1 kHz dans la plage de 70 à 130 %. Le test de résistance à la chaleur A implique un chauffage pendant 3 minutes à 160 °C.
PCT/JP2025/018827 2024-05-31 2025-05-23 Film poreux, élément perméable à l'air et feuille pour alimentation d'élément Pending WO2025249337A1 (fr)

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