Film for oscillation member, oscillation member and diaphragm pump

Abstract

To provide a film for oscillation members excellent in mechanical characteristics, drug resistance, heat resistance, adhesion and barrier property with a support based on an F polymer, an oscillation member using the same, and a diaphragm pump.SOLUTION: A film for an oscillation member that contains a thermoplastic tetrafluoroethylene-based polymer with a fluorine content of 60 mass% or more and 75 mass% or less, wherein at least a surface is composed of the tetrafluoroethylene-based polymer and a soft metal support is placed inside.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a film for an oscillating member, a oscillating member, and a diaphragm pump. [Background technology]

[0002] One of the areas requiring chemical resistance and heat resistance based on fluororesin is a diaphragm used in a valve or pump. Patent Document 1 discloses a diaphragm for a small metering pump for transporting liquid, which is made of a thin film substrate made of a polymer material with excellent mechanical strength such as polyimide, and a composite functional film in which a thin fluororesin film is laminated on one or both sides of the thin film substrate. Patent Document 2 discloses a composite diaphragm including a flexible composite material of a flexible polymer and an expanded polytetrafluoroethylene fabric, and a solid polytetrafluoroethylene layer bonded to one surface of the flexible composite material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2003-227467 A [Patent Document 2] Special Publication No. 7-504479 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, in the field of precision equipment such as semiconductor manufacturing equipment, there has been a demand for pumps that can discharge highly corrosive and penetrative chemical liquids stably for long periods of time, and there is a demand for further improvements in the chemical resistance, heat resistance, barrier properties, and mechanical properties of the diaphragm valves in diaphragm pumps, including resistance to repeated bending fatigue due to pulsating motion. The present inventors have discovered that a film containing a specific heat-fusible fluororesin and having a soft metal support disposed therein has excellent mechanical properties in addition to chemical resistance, heat resistance and barrier properties, and can be used as a film for various oscillating members, and is particularly useful as a film for oscillating members such as diaphragm valves. An object of the present invention is to provide a film for an oscillating member which is excellent in mechanical properties, chemical resistance, heat resistance, adhesion to a support, and barrier properties, and to provide an oscillating member and a diaphragm pump which use the same. [Means for solving the problem]

[0005] The present invention has the following aspects. <1> A film for an oscillating member comprising a heat-fusible tetrafluoroethylene-based polymer having a fluorine content of 60% by mass or more and 75% by mass or less, at least a surface of which is made of said tetrafluoroethylene-based polymer, and a soft metal support is disposed inside. <2> The MFR of the heat-meltable tetrafluoroethylene-based polymer is more than 10 g / 10 min and not more than 60 g / 10 min. <1> Film for oscillating components. <3> The heat-meltable tetrafluoroethylene-based polymer is one or more copolymers containing a tetrafluoroethylene unit and one or more units selected from the group consisting of a perfluoro(alkyl vinyl ether) unit, a hexafluoropropylene unit, a fluoroethylene unit, and an ethylene unit. <1> or <2> Film for oscillating components. <4> The heat-meltable tetrafluoroethylene-based polymer is a copolymer containing tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units. <1> ~ <3> A film for a rocking member according to any one of the above. <5> The heat-fusible tetrafluoroethylene polymer has a carbonyl group-containing group having 10 carbon atoms in the main chain. 6 Each piece has 50 or more pieces. <1> ~ <4> A film for a rocking member according to any one of the above. <6> After heat treatment at 180°C for 3 minutes, the oxygen element ratio is less than 1.5 atomic % when the surface condition of one or both sides is measured using a scanning X-ray photoelectron spectroscopy (XPS / ESCA). <1> ~ <5> A film for a rocking member according to any one of the above. <7> The soft metal support is a soft metal foil. <1> ~ <6> A film for a rocking member according to any one of the above. <8> The soft metal support is a woven or nonwoven soft metal fabric; <1> ~ <6> A film for a rocking member according to any one of the above. <9> The thickness of the soft metal support is in the range of more than 50% and not more than 200% of the total thickness of the film for swing member. <1> ~ <8> A film for a rocking member according to any one of the above. <10> The soft metal is aluminum. <1> ~ <9> A film for a rocking member according to any one of the above. <11> the adhesive strength between the soft metal support and the heat-fusible tetrafluoroethylene-based polymer is 100 N / m or more; <1> ~ <10> A film for a rocking member according to any one of the above. <12> For diaphragm valves, <1> ~ <11> A film for a rocking member according to any one of the above. <13> <1> ~ <12> A rocking member having any one of the films for a rocking member described above. <14> It is a diaphragm valve. <13> A swaying member. <15> <14> A diaphragm pump having a diaphragm valve. Effect of the Invention

[0006] According to the present invention, it is possible to provide a film for an oscillating member based on an F polymer, which has excellent mechanical properties, chemical resistance, heat resistance, adhesion to a support, and barrier properties, and an oscillating member and a diaphragm pump using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The following terms have the following meanings. The "melt flow rate (MFR) of a heat-meltable tetrafluoroethylene polymer" is a value measured at 372°C under a load of 5 kg in accordance with ASTM D3307. The "melting point of a polymer" is the temperature corresponding to the maximum of the melting peak of the polymer as measured by differential scanning calorimetry (DSC). "Glass transition temperature (Tg)" is a value measured by analyzing a polymer using the dynamic mechanical analysis (DMA) method. The thickness of the film and the metal support was the average value of measurements taken at any five points at 25° C. using a high-precision digital micrometer "MDH-25MB" manufactured by Mitutoyo Corporation. The term "unit" in a polymer means an atomic group based on a monomer formed by polymerization of the monomer. The unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a part of the unit is converted into a different structure by processing the polymer. Hereinafter, a unit based on monomer a is also referred to simply as a "monomer a unit."

[0008] The present invention relates to a film for an oscillating member (hereinafter also referred to as "the film for an oscillating member") which contains a heat-fusible tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer") having a fluorine content of 60% by mass or more and 75% by mass or less, at least a surface of which is made of the tetrafluoroethylene-based polymer, and a soft metal support is disposed inside. In this specification, "the soft metal support is disposed inside" means that it includes any of the following aspects: a soft metal support is disposed between film layers containing an F polymer; a soft metal support is present within a film layer containing an F polymer; and a soft metal support is embedded in an F polymer and its surface is composed of an F polymer. This film for oscillating members has excellent mechanical properties, chemical resistance, and heat resistance due to the fact that at least the surface is composed of F polymer. Furthermore, due to the soft metal support disposed inside, it has excellent barrier properties. And, since the fluorine content of the F polymer is within a specified range, the F polymer and the soft metal support tend to adhere firmly to each other, and the film has excellent mechanical properties such as resistance to repeated bending fatigue. Such properties are achieved because the F polymer is a copolymer composed of specific monomer constituent units, and the carbonyl group-containing group is contained in a main chain of 10 carbon atoms. 6 When the number of particles is 50 or more per particle, the adhesion to the soft metal support is improved, which becomes more remarkable.

[0009] The F polymer in the present invention is a heat-meltable polymer containing units (hereinafter also referred to as "TFE units") based on tetrafluoroethylene (hereinafter also referred to as "TFE"). Here, the heat-meltable polymer means a polymer having a temperature at which the melt flow rate is 1 to 1000 g / 10 min under a load of 49 N. The melting point of the F polymer is preferably more than 100° C., more preferably 180° C. or higher, and even more preferably 200° C. or higher. The melting point of the F polymer is preferably 325° C. or lower, and more preferably 320° C. or lower. In this case, the film for the oscillating member is likely to have excellent heat resistance.

[0010] The glass transition temperature of the F polymer is preferably 50° C. or higher, more preferably 75° C. or higher. The glass transition temperature of the F polymer is preferably 150° C. or lower, more preferably 125° C. or lower. The fluorine content of the F polymer is 60% by mass or more and 75% by mass or less, may be 67% by mass or more and 75% by mass or may be 60% by mass or more and 68% by mass or less, and is preferably 67% by mass or more and 75% by mass. In this case, the above-mentioned mechanism of action is more likely to be realized. The fluorine content of the F polymer is calculated as the ratio of fluorine atoms to all monomer units constituting the F polymer. The surface tension of the F polymer is preferably 16 to 26 mN / m. The surface tension of the F polymer can be measured by placing a droplet of a mixture for wetting tension testing (manufactured by Wako Pure Chemical Industries, Ltd.) specified in JIS K 6768 on a flat plate made of the F polymer.

[0011] Examples of F polymers include copolymers containing TFE units and units based on ethylene (ethylene units) (ETFE), copolymers containing TFE units and units based on propylene (propylene units), copolymers containing TFE units and units based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE units) (PFA), copolymers containing TFE units and units based on hexafluoropropylene (HFP) (HFP units) (FEP), TFE / ethylene / HFP copolymers, copolymers containing ethylene units and units based on chlorotrifluoroethylene (CTFE) (CTFE units) (ECTFE), copolymers containing CTFE units and TFE units, copolymers containing TFE units and units based on vinylidene fluoride (VdF) (VdF units) (VT), copolymers containing TFE units, VdF units, and CTFE units (VTC), and copolymers containing TFE units, HFP units, and VdF units.

[0012] Among them, the F polymer is preferably one or more copolymers containing a TFE unit and one or more units selected from the group consisting of a PAVE unit, an HFP unit, a fluoroethylene unit and an ethylene unit. More specifically, copolymers containing TFE units and ethylene units (ETFE), copolymers containing TFE units and HFP units (FEP), and copolymers containing TFE units and PAVE units (PFA) are preferred, with PFA being more preferred. These copolymers may further contain units based on other comonomers. PAVE is preferably CF2=CFOCF3, CF2=CFOCF2CF3 or CF2=CFOCF2CF2CF3 (hereinafter also referred to as "PPVE"), and more preferably PPVE.

[0013] The PFA preferably contains TFE units and PAVE units in an amount of 96 to 98.5 mol % and 1.5 to 4 mol % in this order based on all units. The PAVE units in the PFA are preferably PPVE units. Such PFA is prone to forming tiny spherulites, which promote the formation of fine irregularities on the F polymer surface that comes into contact with the soft metal support within the film for the oscillating member, improving the adhesion between the F polymer and the soft metal support and making it easier to realize the above-mentioned mechanism of action.

[0014] The F polymer preferably has a carbonyl group-containing group. In this case, the adhesion between the F polymer and the soft metal support is excellent in the film for the swing member. In addition, the film for the swing member is excellent in mechanical properties, heat resistance, and surface properties, and has a small dimensional change rate. The carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH2), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.), a formyl group, a halogenoformyl group, a urethane group (-NHC(O)O-), a carbamoyl group (-C(O)-NH2), a ureido group (-NH-C(O)-NH2), an oxamoyl group (-NH-C(O)-C(O)-NH2) or a carbonate group (-OC(O)O-), and more preferably an acid anhydride residue. F polymer is a polymer having a carbonyl group-containing group with 10 carbon atoms in the main chain. 6 Preferably, the number of carbonyl-containing groups in the F polymer is 50 or more, more preferably 100 or more, and even more preferably 200 or more. 6 The number of carbonyl-containing groups per unit is preferably 3000 or less, more preferably 1200 or less. The number of carbonyl-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in WO 2020 / 145133.

[0015] The carbonyl group-containing group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer. The latter embodiment includes an F polymer having a carbonyl group-containing group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc. The monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, or 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), and more preferably NAH.

[0016] The F polymer is more preferably a copolymer having a carbonyl group-containing group containing TFE units and PAVE units, and more preferably a polymer containing units based on a monomer having a TFE unit, a PAVE unit, and a carbonyl group-containing group, and containing these units in this order, with respect to all units, in an amount of 96 to 98.5 mol%, 1.5 to 4 mol%, and 0.01 to 0.5 mol%. Specific examples of such F polymers include the polymers described in International Publication No. 2018 / 16644. Such PFA is prone to form minute spherulites, which promote the formation of fine irregularities on the F polymer surface in contact with the soft metal support in the present rocking member film, improving the adhesion between the F polymer and the soft metal support, and making it easier to express the above-mentioned mechanism of action.

[0017] The MFR of the F polymer contained in the film for rocking members is preferably more than 10 g / 10 min and not more than 60 g / 10 min. When the MFR is within the above range, the film for rocking members can easily exhibit properties such as chemical resistance and heat resistance based on the F polymer while ensuring flexibility. In the present film for oscillating members, the F polymer may be used alone or in combination of two or more kinds. The F polymer in the present film for oscillating members may have a single layer structure of one type of F polymer, or a multi-layer structure of two or more types of F polymer. Specifically, the latter may be an F polymer layer (1) and a multi-layer structure of a polymer layer (2) having a carbonyl group-containing group and a carbonyl group-containing group having 10 carbon atoms in the main chain. 6An example of such a film for a rocking member is an F polymer layer (2) having 50 or more per unit and an F polymer layer (3) laminated in this order, with a soft metal support disposed in the F polymer layer (2). The F polymer constituting the F polymer layer (1) and the F polymer layer (3) is preferably an F polymer having less carbonyl group-containing groups than the F polymer constituting the F polymer layer (2).

[0018] The F polymer may contain other components other than the F polymer, as long as the effects of the present invention are not impaired. Examples of other components include known resin additives and other heat-melting heat-resistant resins other than the F polymer, such as polyimide and polyether ether ketone.

[0019] The soft metal support disposed inside the present film for an oscillating member may be a soft metal foil or plate, more preferably a soft metal foil, or may be a woven or nonwoven fabric of a soft metal, which may be microporous or mesh-like. The soft metal constituting the soft metal support may be at least one selected from the group consisting of aluminum, stainless steel, and copper. From the viewpoint of further improving the mechanical properties, barrier properties, and chemical resistance (corrosion resistance) of the present film for oscillating members, aluminum is preferred as the soft metal. Aluminum may be a simple metal or an alloy. In the latter case, an aluminum alloy having an aluminum content of 80 mass% or more is preferred.

[0020] The thickness of the soft metal support is preferably 10 μm to 60 μm, more preferably 15 μm to 50 μm, from the viewpoint of enhancing the mechanical properties of the film for oscillating members and further improving the barrier properties and chemical resistance (corrosion resistance). In other words, the soft metal support is preferably a metal foil, more preferably an aluminum foil. Furthermore, from the viewpoint of facilitating pulsating motion when the present film for oscillating members is used for a diaphragm valve described below, while also providing resistance to repeated bending fatigue due to such pulsating motion, the thickness of the soft metal support is preferably more than 50% and not more than 200% of the total thickness of the present film for oscillating members, and more preferably is 75% or more and not more than 150%.

[0021] In the present film for oscillating members, the adhesive strength between the soft metal support and the F polymer is preferably 100 N / m or more. The upper limit of the adhesive strength is 1000 N / m. When the adhesive strength of the present film for oscillating members is within the above range, the mechanical properties of the film for oscillating members when used for a diaphragm valve described later are more likely to be improved. The adhesive strength between the soft metal support and the F polymer is a value obtained by measuring the peel strength, which will be explained in the Examples section below.

[0022] The water vapor transmission rate of the soft metal support is 1 g / m 2 ·day or less is preferable, 0.1g / m 2 ·day or less is preferable, 0.01g / m 2 The water vapor transmission rate is measured by a differential pressure gas / water vapor transmission tester (GC method) at 40°C and RH90% based on JIS K7129-1:2019. The oxygen permeability of the soft metal support is 1 g·ml / m 2 ·day·atm or less is preferable, and 0.1g·ml / m 2 ·day·atm or less is preferable, and 0.01g·ml / m 2 The oxygen permeability is measured at 23° C. using a differential pressure gas / water vapor permeability tester (GC method) in accordance with JIS K7126-2:2006. The surface of the soft metal support may be subjected to a surface treatment.

[0023] The present film for oscillating members has an oxygen element ratio of preferably less than 1.5 atomic %, more preferably 1.0 atomic % or less, when the surface condition of one or both sides of the film is measured by a scanning X-ray photoelectron spectroscopy analyzer (XPS / ESCA) after heat treatment at 180° C. for 3 minutes. The oxygen element ratio is preferably 0.1 atomic % or more. In this case, the chemical resistance and gas barrier property of the film for oscillating members are likely to be improved. Even if the oxygen element ratio is within the above range, the F polymer contained in the film for oscillating members is likely to have excellent surface properties and excellent adhesion to the soft metal support. The oxygen atomic ratio was determined by placing a test piece for XPS / ESCA measurement made from this oscillating member film on a metal tray, heat-treating it in an electric furnace at 180°C for 3 minutes in an air atmosphere, and then measuring the surface condition of one or both sides by XPS / ESCA.

[0024] The present film for oscillating members is preferably heat-treated at 180° C. for 10 minutes, and then cooled to 25° C., and the absolute value of the dimensional change rate before and after the heat treatment is preferably 2% or less, and more preferably 1.8% or less. The dimensional change rate is calculated from the amount of change in the gauge intervals before and after the heat treatment by cutting a 300 mm square test piece from the present film for oscillating members, marking marks at 180 mm intervals, heat-treating the test piece at 180° C. for 10 minutes in an electric furnace in an air atmosphere without applying a load, and then measuring the gauge intervals in the longitudinal and transverse directions of the test piece that has been cooled to 25° C.

[0025] The film for the oscillating member, at least the surface of which is made of an F polymer and the soft metal support is disposed inside, can be obtained, for example, by a method of thermocompression bonding a film containing an F polymer to both sides of a soft metal support (thermal lamination method). The film containing an F polymer may be a film containing the same type of F polymer or a film containing different types of F polymers. The film containing the F polymer can be formed by melt extruding the F polymer using, for example, an extruder having a T-die. The melt extrusion of the F polymer may be performed continuously after melt kneading the F polymer, or may be performed while melt kneading in the extruder. In addition, after melt extrusion, the F polymer may be uniaxially or biaxially stretched, or may not be stretched. The conditions for melt extrusion are usually preferably set to a temperature 20°C or higher than the melting point of the F polymer. The thickness of the film containing the F polymer can be controlled by appropriately adjusting the clearance of the T-die, the take-up speed, the amount of the F polymer applied, and the like. The film containing the F polymer can also be obtained by preparing a solution or dispersion containing the F polymer, applying it to a substrate, heating it, and then separating it from the substrate.

[0026] The thickness of the film containing the F polymer is preferably 20 to 200 μm, more preferably 25 to 125 μm, and the total thickness of the film containing the F polymer used on both sides of the soft metal support is preferably 50 μm to 500 μm, more preferably 70 μm to 250 μm. When the thickness of the film containing the F polymer is within the above range, the film for the oscillating member is more excellent in chemical resistance and heat resistance, and is synergistic with the soft metal support to be more excellent in mechanical properties such as resistance to repeated bending fatigue. The present film for oscillating members can also be obtained by a method of extruding an F polymer onto a soft metal support, which is a soft metal foil, or by impregnating a soft metal support, which may be in the form of a mesh made of a woven or nonwoven soft metal fabric, with a solution or dispersion containing an F polymer.

[0027] The present film for oscillating members may, if necessary, contain a resin layer containing a heat-resistant resin other than F polymer, such as a fluorine-based resin, polyimide, polyether ether ketone, etc., between the surface composed of F polymer and the soft metal support, as long as the effect of the present invention is not impaired.

[0028] The film for oscillating members of the present invention has excellent mechanical properties, chemical resistance, heat resistance, adhesion to metal supports, and barrier properties based on the F polymer, and can be used for oscillating members such as bellows, diaphragms, hoses, piston rings, butterfly valves, ball valve seats, packings, gaskets, and piston rings. Among them, the film for an oscillating member of the present invention is preferably used for a diaphragm valve. In particular, the film for an oscillating member of the present invention can be suitably used as a valve membrane of a diaphragm valve having a liquid-contacting membrane portion, a sealing portion (valve seat pressing portion) and an attachment portion. Also, the film can be suitably used as a sheet-like valve membrane in a diaphragm pump. When the film for oscillating members of the present invention is used as a valve membrane of a diaphragm valve or a valve membrane of a diaphragm pump, the surface having the F layer is preferably the liquid-contacting side. When the surface having the F layer of the film for oscillating members of the present invention is the liquid-contacting side, the film has excellent chemical resistance and barrier properties. In addition, the amount of dust generated is small, and the adhesion and retention of particles in the fluid is easily suppressed.

[0029] The present invention also includes an oscillating member having the film for oscillating members of the present invention, and particularly includes the film for oscillating members of the present invention which is a diaphragm valve. More specifically, in a diaphragm valve having a valve seat formed in a valve body and a diaphragm to which a diaphragm valve membrane is attached which is in pressure contact with or spaced from the valve seat, the diaphragm valve membrane is the film for oscillating members of the present invention. The shape of the diaphragm valve is not particularly limited, and the center portion may be curved in an arc shape. Such a diaphragm valve has particularly excellent chemical resistance and barrier properties because the surface having the F layer of the film for oscillating members of the present invention is used on the liquid-contacting side, and can be suitably used as a valve installed in piping for supplying strong acid or in CMP slurry supply piping in a semiconductor manufacturing plant.

[0030] The present invention also relates to a diaphragm pump having a diaphragm valve which is the film for oscillating members of the present invention. That is, the diaphragm pump is a diaphragm pump which pumps out a fluid by the reciprocating motion of a diaphragm valve membrane, and the diaphragm valve is the film for oscillating members of the present invention. The diaphragm pump of the present invention uses the film for oscillating members of the present invention as the diaphragm valve membrane, and the surface having the F layer is used as the liquid-contacting side, and therefore has excellent chemical resistance and barrier properties, and can be suitably used for piping which supplies strong acid, CMP slurry supply piping of semiconductor manufacturing equipment, etc. EXAMPLES

[0031] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. 1. Preparation of Each Component [Film of heat-meltable tetrafluoroethylene polymer (F polymer)] F film 1: containing 58.0 mol %, 38.6 mol %, 3.1 mol %, and 0.3 mol % of TFE units, ethylene units, units based on CH2=CH(CF2)2F, and NAH units, in that order, and having a carbonyl group-containing group at 10 carbon atoms in the main chain 6 ETFE film (thickness: 25 μm, oxygen atom ratio: 0.8 atomic%) with 3,000 particles per particle (fluorine content: 64 mass%, MFR: 27.0 g / 10 min, melting point 237°C) F film 2: TFE units, PPVE units, and NAH units are contained in the order of 97.9 mol%, 2.0 mol%, and 0.1 mol%, respectively, and the carbonyl group-containing group has a main chain carbon number of 1×10 6 PFA film (thickness: 25 μm, oxygen atom ratio: 0.5 atomic%) with 1,000 particles per unit (fluorine content: 75 mass%, MFR: 11.0 g / 10 min, melting temperature: 300°C) F film 3: TFE unit, PPVE unit, 98.7 mol% and 1.3 mol% in that order, carbonyl group-containing group with a main chain carbon number of 1 × 10 6 PFA film (thickness: 25 μm, oxygen atom ratio: 0.4 atomic%) with 400 particles per unit (fluorine content: 75 mass%, melting temperature: 305°C) F film 4: Contains TFE units and PPVE units, and has a main chain carbon number of 1×10 6 PFA film (thickness: 25 μm, oxygen atom ratio: less than 0.1 atomic %) with less than 10 per particle (fluorine content: 75 mass %, melting temperature: 305 °C) F film 5: Nitrogen gas containing 0.50% by volume of vinyl acetate was passed around the roll-shaped ground electrode of the corona discharge device, and the F film 4 was passed continuously along the roll-shaped ground electrode, achieving a discharge rate of 1000 W min / m. 2 The above corona discharge treatment was performed on the F film (thickness: 25 μm, oxygen atomic ratio: 10 atomic%).

[0032] [Soft metal support] Metal support 1: Aluminum alloy foil (aluminum alloy foil based on JIS H 4160:1994, alloy part number 8079, thickness 40 μm)

[0033] 2. Preparation of film for rocking member Example 1 Film 1 was laminated on both sides of metal support 1, and release films (polyimide film "Kapton (registered trademark) 200H / V" manufactured by DuPont-Toray Co., Ltd., thickness 50 μm) were laminated on the outer sides of both sides. This laminate was pressed at 240°C, 15 minutes, and 10 MPa using a vacuum press device, and then removed and allowed to stand in an atmosphere of 25°C for 5 minutes to cool. After cooling, the release films on both sides were peeled off to obtain film 1 for an oscillating member.

[0034] Example 2 Film 2 was laminated on both sides of metal support 1, and release films similar to those in Example 1 were laminated on the outer sides of both sides. This laminate was pressed using a vacuum press under conditions of 305°C, 15 minutes, and 1 MPa, and then removed and allowed to stand for 5 minutes in an atmosphere of 25°C to cool. After cooling, the release films on both sides were peeled off to obtain film 2 for an oscillating member.

[0035] Examples 3-5 Film 3 for oscillating members (Example 3) was obtained in the same manner as in Example 2 except that film 2 was changed to film 3, film 4 for oscillating members (Example 4) was obtained in the same manner as in Example 2 except that film 2 was changed to film 4, and film 5 for oscillating members (Example 5) was obtained in the same manner as in Example 2 except that film 2 was changed to film 5.

[0036] 3. Evaluation of films for oscillating components (1) The films for oscillating members obtained in each example were cut to a width of 1 cm, and the film layer made of F polymer and the aluminum layer were peeled off from one end in the longitudinal direction to a position 50 mm from the end, and then the peeling was performed at 90° with a tensile tester at 25°C and a pulling speed of 100 mm / min, and the average load was measured over a measurement distance of 20 mm to 80 mm to determine the peel strength (N / cm). As a result, the peel strength was 100 N / m or more for films for oscillating members 1, 2, 3, and 5, and the initial oscillating properties were also good. Note that the peel strength of film 4 for oscillating members was less than 100 N / m, so further evaluation was not performed.

[0037] (2) Diaphragm valves each having the film for oscillating member 1, 2, 3 or 5 as a valve membrane of a liquid-contacting portion were prepared.

[0038] (3) In the clean booth, a needle valve, a tube, the diaphragm valve prepared in (2) above, and a tube were connected in this order to create a strong acid supply line. A strong acid was flowed into this strong acid supply line at a flow rate of 1 L / min, and the diaphragm valve was opened for 2 seconds, and then closed for 2 seconds, which constituted one cycle. The valve was opened and closed 1000 times. Thereafter, the film for oscillating member was taken out from the diaphragm valve, and the peel strength was measured in the same manner as above. The rate of change in the peel strength after the test in which the strong acid was flowed, relative to the peel strength of the film for oscillating member before the strong acid was flowed, was measured, and evaluated according to the following evaluation criteria.

[0039] [Evaluation Criteria] A: The change in peel strength is less than 1%. B: The rate of change in peel strength is 1% or more and less than 5%. C: The rate of change in peel strength is 5% or more. The results are shown in Table 1.

[0040] [Table 1]

[0041] The disclosures of Japanese Patent Applications Nos. 2023-120103, 2023-194606, and 2024-34259 are incorporated by reference in their entireties into this disclosure. All publications, patent applications, and standards in this disclosure are incorporated by reference into this disclosure to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A film for an oscillating member comprising a heat-fusible tetrafluoroethylene-based polymer having a fluorine content of 60% by mass or more and 75% by mass or less, at least a surface of which is made of said tetrafluoroethylene-based polymer, and a soft metal support is disposed inside.

2. 2. The film for an oscillating member according to claim 1, wherein the MFR of the heat-fusible tetrafluoroethylene polymer is more than 10 g / 10 min and not more than 60 g / 10 min.

3. 2. The film for an oscillating member according to claim 1, wherein the heat-meltable tetrafluoroethylene-based polymer is one or more copolymers containing tetrafluoroethylene units and one or more units selected from the group consisting of perfluoro(alkyl vinyl ether) units, hexafluoropropylene units, fluoroethylene units and ethylene units.

4. 2. The film for an oscillating member according to claim 1, wherein the heat-fusible tetrafluoroethylene polymer is a copolymer containing tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units.

5. The heat-fusible tetrafluoroethylene polymer has a carbonyl group-containing group having 10 carbon atoms in the main chain. ６ The film for a swing member according to claim 1 , wherein each film has 50 or more particles.

6. 2. The film for an oscillating member according to claim 1, wherein the oxygen element ratio is less than 1.5 atomic % when the surface condition of one or both sides of the film is measured by a scanning X-ray photoelectron spectroscopy / chemical analysis (XPS / ESCA) after heat treatment at 180° C. for 3 minutes.

7. 2. The film for an oscillating member according to claim 1, wherein the soft metal support is a soft metal foil.

8. 2. The film for an oscillating member according to claim 1, wherein the soft metal support is a woven or nonwoven fabric of a soft metal.

9. 2. The film for an oscillating member according to claim 1, wherein the thickness of the soft metal support is in the range of more than 50% and not more than 200% of the total thickness of the film for an oscillating member.

10. 2. The film for an oscillating member according to claim 1, wherein the soft metal is aluminum.

11. 2. The film for an oscillating member according to claim 1, wherein the adhesive strength between said soft metal support and said heat-fusible tetrafluoroethylene-based polymer is 100 N / m or more.

12. 2. The film for a swing member according to claim 1, which is for a diaphragm valve.

13. A rocking member comprising the film for a rocking member according to any one of claims 1 to 12.

14. 14. The oscillating member of claim 13, which is a diaphragm valve.

15. A diaphragm pump comprising the diaphragm valve of claim 14.

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