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WO2019163693A1 - Article moulé en caoutchouc composite - Google Patents

Article moulé en caoutchouc composite Download PDF

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Publication number
WO2019163693A1
WO2019163693A1 PCT/JP2019/005764 JP2019005764W WO2019163693A1 WO 2019163693 A1 WO2019163693 A1 WO 2019163693A1 JP 2019005764 W JP2019005764 W JP 2019005764W WO 2019163693 A1 WO2019163693 A1 WO 2019163693A1
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WIPO (PCT)
Prior art keywords
ptfe
group
rubber
molded article
porous membrane
Prior art date
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PCT/JP2019/005764
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English (en)
Japanese (ja)
Inventor
茶圓　伸一
伊野　忠
田中　宏幸
伸樹 浦岡
柳口　富彦
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2020501741A priority Critical patent/JP7316995B2/ja
Publication of WO2019163693A1 publication Critical patent/WO2019163693A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material

Definitions

  • the present disclosure relates to a composite rubber molded article.
  • Patent Document 1 a polytetrafluoroethylene unfired body or semi-fired body was stretched on the surface of a sealing material body formed of an elastomer as a sealing material excellent in sealing properties, slidability and anti-sticking properties.
  • a sealing material in which a polytetrafluoroethylene porous film is laminated is described.
  • Patent Document 2 discloses a rubber molded product and a heat resistance laminated on at least one surface of the rubber molded product as a cushion for hot press having a rubber elasticity on the surface and good releasability.
  • a cushioning material for hot pressing is described that includes a surface layer material made of a porous resin membrane.
  • An object of the present disclosure is to provide a composite rubber molded article that has a small coefficient of friction over a long period of time and can maintain non-stickiness.
  • the present disclosure relates to a molded article including an elastomer, and a composite rubber molded article including a polytetrafluoroethylene porous film covering at least a part of the molded article, the longitudinal direction and the transverse direction of the polytetrafluoroethylene porous film. It is related with the composite rubber molded product characterized by the product of the matrix tensile strength of 30000 MPa ⁇ 2 > or more.
  • the rubber hardness of the coated surface by the polytetrafluoroethylene porous film is 1% or more higher than the hardness of the rubber not covering the porous film.
  • the film thickness of the polytetrafluoroethylene porous membrane is preferably 2 to 30 ⁇ m.
  • the molded article is preferably covered with a polytetrafluoroethylene porous membrane without using an adhesive.
  • a composite rubber molded article according to the present disclosure is a composite rubber molded article including a molded article including an elastomer and a polytetrafluoroethylene porous film (PTFE porous film) covering at least a part of the molded article.
  • the product of the matrix tensile strength in the longitudinal direction and the transverse direction of the membrane is 30000 MPa 2 or more.
  • covers the molded article containing an elastomer with a PTFE porous membrane can be freely designed according to the use of the composite rubber molded article of this indication.
  • the product of the longitudinal and transverse directions of the matrix tensile strength of the PTFE porous membrane is 30000 mPa 2 or more, preferably 35000MPa 2 or more, 40000 mPa 2 or more is more preferable.
  • the upper limit may be a 70000MPa 2. If it is less than 30000 MPa 2 , a thick porous film must be used, resulting in a decrease in wear resistance.
  • the longitudinal direction means the tensile strength in the longitudinal direction (paste extrusion direction)
  • the lateral direction means the width direction (paste extrusion direction).
  • the matrix tensile strength can be measured by the method described later.
  • a PTFE porous membrane having a product of the matrix tensile strength in the longitudinal direction and the transverse direction of 30000 MPa 2 or more has at least the film thickness of the PTFE porous membrane and the fibril / node area ratio (fibril area / node area) within the following predetermined range. It is obtained by adjusting to
  • the film thickness of the PTFE porous membrane is preferably 2 to 30 ⁇ m, more preferably 4 to 25 ⁇ m. If the film thickness is less than 2 ⁇ m, it is difficult to suppress the deformation of the rubber even with a high-strength film, and the friction coefficient increases. If it exceeds 30 ⁇ m, the friction coefficient decreases but the wear resistance tends to decrease.
  • the film thickness can be measured by the method described later.
  • the PTFE porous membrane preferably has a fine structure including nodes (nodules) and fibrils.
  • a PTFE porous membrane obtained by stretching PTFE is usually composed of fine fibrils called fibrils and granular nodes called nodes connecting these fibrils, and extremely fine between the fibrils and the nodes. It has a continuous porous structure in which various pores exist in a continuous state.
  • Nodes are usually granular or island-shaped parts (parts where primary particles are aggregated) made of PTFE folded crystals, and fibrils are PTFE drawn out from the nodes in a fiber form, and are interleaved between the nodes. Or it is connected to a spider web.
  • the node is usually a portion that remains unstretched after stretching, is located at the end of the fibril, and a mass to which the fibril is connected is a portion that is thicker than the fibril diameter.
  • a node is usually a primary particle or a collection of primary particles, and fibrils extend radially from the node. In the present specification, even if the fibril is branched, if the diameter of the branch portion is the same as that of the fibril, the branch is not regarded as a node.
  • the area ratio of fibril / node of the PTFE porous membrane is preferably 97/3 to 75/25, more preferably 95/5 to 75/25, and still more preferably 95/5 to 85/15.
  • the area ratio of the PTFE porous membrane is within the above range, the matrix strength of the membrane becomes strong, it is more difficult to peel off from the molded product, and the non-adhesiveness can be maintained for a longer period of time.
  • the area ratio of fibril / node can be measured by the following method. First, a photograph of the PTFE porous film is taken with a scanning electron microscope (SU8020, manufactured by HITACHI, vapor deposition is Hitachi E1030 type) (SEM photograph, magnification 1000 to 5000 times). This photograph is taken into an image processing apparatus (main body name: TV image processor TVIP-4100II manufactured by Nippon Avionics Co., Ltd., control software name: TV image processor image command 4198 manufactured by Ratok System Engineering Co., Ltd.), separated into nodes and fibrils, and only from the nodes And an image consisting only of fibrils. The area ratio of the fibril / node is obtained from the ratio of the total area of the fibril image and the total area of the node image.
  • main body name TV image processor TVIP-4100II manufactured by Nippon Avionics Co., Ltd.
  • control software name TV image processor image command 4198 manufactured by Ratok System Engineering Co., Ltd.
  • a node is one that satisfies one of the following: (1) A cluster of multiple fibrils connected together (Fig. 1: Part filled with dots) (2) The connected mass is thicker than the fibril diameter ( Figures 2 and 3: hatched area) (3) Primary particles are aggregated, and fibrils extend radially therefrom (FIGS. 4, 5, and 6: hatched portions)
  • FIG. 7 is an example that is not regarded as a node. That is, when the fibril is branched, the branch is not regarded as a node when the diameters of the fibril and the branch portion are the same.
  • a PTFE porous membrane having a fibril / node area ratio within the above range can be obtained by semi-baking PTFE or adjusting the draw ratio of uniaxial stretching or biaxial stretching.
  • the ratio of fibrils in the area ratio of fibrils / nodes of the PTFE porous membrane can be increased by semi-firing PTFE under predetermined conditions.
  • the fibril / node area ratio of the PTFE porous membrane can be adjusted by setting the draw ratio within a predetermined range for uniaxial stretching or biaxial stretching.
  • the area ratio of fibril / node of the PTFE porous film may be adjusted by semi-firing PTFE and adjusting the draw ratio. The conditions for the semi-firing and the range of the draw ratio will be described later.
  • the product of the tensile strength of the PTFE porous membrane may be improved by fusion of fibrils constituting the PTFE porous membrane.
  • the fusion point of the PTFE porous membrane is 1 point within the range of 5 ⁇ m ⁇ 5 ⁇ m observed in an electron micrograph taken at a magnification of 10,000 using a scanning electron microscope because a high-strength membrane can be obtained. It is preferable to have the above. More preferably, it is 5 points or more, and more preferably 10 points or more.
  • a PTFE porous membrane having a fusion point can be obtained by using a modified PTFE described later.
  • the fusion point a fibril connecting two nodes and a fibril connecting two other nodes are fused to each other.
  • the PTFE porous membrane has a fusion point, the PTFE porous membrane is more difficult to peel from the molded product, and the non-adhesiveness can be maintained for a longer period of time.
  • FIG. 8 shows a scanning electron micrograph when the PTFE porous membrane has a fusion point.
  • the PTFE porous membrane has a fusion point 100 where fibrils are fused.
  • the PTFE porous membrane shown in FIG. 9 has a fine structure including the node 200 and the fibril 300, but the fibrils only cross three-dimensionally.
  • the fibril connecting the two nodes and the fibril connecting the other two nodes are fused to each other.
  • the fusion point is formed by fusing each other at an intersecting portion where at least two fibrils intersect three-dimensionally.
  • the fusion point is formed by fusing two fibrils, and each of the two fibrils forming the fusion point is connected between two nodes, and one fibril is connected.
  • the set of nodes that are different from the set of nodes to which the other fibril connects.
  • Two or more fusion points can be formed by fusing one fibril with the other two fibrils.
  • the fusion point is formed by fusing fibrils during stretching.
  • the fusion point is formed by fusing each other at a crossing site where at least two fibrils cross three-dimensionally in the same porous body.
  • the fibril constituting the fusion point is generated by stretching a PTFE green body, a PTFE semi-fired body, or a paste extrudate using modified PTFE described later.
  • the diameter of the fibril can be adjusted depending on stretching conditions and the like. Generally, in the case of a uniaxially stretched film, the diameter of the fibril is about 5 ⁇ m at maximum, and in the case of a biaxially stretched film, it is about 1 ⁇ m at maximum.
  • the diameter of the fibril is preferably 0.7 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • a change in the fibril diameter or a change in direction is observed before and after the fusion point. There is nothing to do.
  • These structural features differ greatly from the structure of nodes having fibrils extending in multiple directions. Since a plurality of fibrils extend from a node in multiple directions, when the fibrils are observed around the node, variation in the diameter of each fibril is observed, and even if two fibrils having the same diameter are observed by chance, These fibrils rarely lie on a straight line. That is, at the fusion point, a node is easy in that one fibril with a diameter difference within 10% and a deviation from a straight line within ⁇ 10 degrees before and after the fusion point can be observed. Can be distinguished.
  • the film density of the PTFE porous film is not particularly limited, but is preferably 1.40 g / cm 3 or less, more preferably 1.00 g / cm 3, more preferably 0.80 g / cm 3 or less.
  • the film density is a value determined by the method described later.
  • the average pore diameter of the PTFE porous membrane is preferably 0.60 ⁇ m or less, and more preferably 0.40 ⁇ m or less in order to achieve high membrane strength.
  • the lower limit of the average pore diameter is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, and still more preferably 0.20 ⁇ m or more.
  • the average pore diameter can be measured by the method described later.
  • the PTFE porous film may be a uniaxially stretched film obtained by uniaxially stretching PTFE or a biaxially stretched film obtained by biaxially stretching PTFE. It is more preferable that the porous body be a biaxially stretched porous body obtained by biaxially stretching PTFE.
  • the PTFE porous membrane may be obtained by uniaxial stretching with a stretching ratio of 2 to 50 times, preferably 5 to 30 times, and a stretching ratio in the longitudinal and lateral directions of 2 to 100 times, preferably May be obtained by biaxial stretching of 5 to 39 times.
  • the PTFE porous membrane contains PTFE.
  • PTFE typically has stretchability, fibrillation properties, and non-melt secondary workability.
  • Non-melt secondary workability means the property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116, that is, the property that does not flow easily even in the melting temperature region. .
  • PTFE includes PTFE obtained by polymerizing TFE and a small amount of a comonomer, in addition to homopolymerized PTFE.
  • the trace comonomer is not particularly limited as long as it can be copolymerized with TFE.
  • perfluoroolefins such as hexafluoropropylene [HFP]; chlorofluoroethylenes such as chlorotrifluoroethylene [CTFE]
  • examples include olefins; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; perfluorovinyl ether; (perfluoroalkyl) ethylene and ethylene.
  • 1 type may be sufficient as the trace amount comonomer used, and multiple types may be sufficient as it.
  • perfluoro vinyl ether it does not specifically limit as perfluoro vinyl ether,
  • CF 2 CF-ORf (A) (Wherein Rf represents a perfluoro organic group), and the like.
  • Rf represents a perfluoro organic group
  • perfluoro organic group means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
  • the perfluoro organic group may have ether oxygen.
  • perfluorovinyl ether examples include perfluoro (alkyl vinyl ether) [PAVE] in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (A).
  • the perfluoroalkyl group preferably has 1 to 5 carbon atoms.
  • Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.
  • Rf is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is represented by the following formula:
  • Rf is the following formula:
  • n an integer of 1 to 4.
  • PFAE Perfluoroalkyl ethylene
  • PFBE perfluorobutyl ethylene
  • PFhexyl perfluorohexyl
  • a high-strength PTFE porous membrane can be obtained, so hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoro (alkyl vinyl ether), (perfluoroalkyl) ethylene, and ethylene
  • hexafluoropropylene chlorotrifluoroethylene
  • vinylidene fluoride fluoro (alkyl vinyl ether), (perfluoroalkyl) ethylene
  • ethylene Preferably, at least one selected from the group consisting of perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), (perfluorobutyl) ethylene, (perfluorohexyl) ethylene, and (perfluorooctyl) ethylene
  • More preferred is at least one selected from the group consisting of perfluoro (methyl vinyl ether).
  • the trace amount comonomer preferably contains at least perfluoro (methyl vinyl ether) (PMVE), more preferably only PMVE.
  • the modified PTFE preferably contains 0.011 mol% or more polymerized units derived from PMVE with respect to the total monomer units because a higher strength PTFE porous membrane can be obtained.
  • the content of the polymerization unit derived from PMVE is more preferably 0.015 mol% or more, and further preferably 0.025 mol% or more. From the viewpoint of the homogeneity of the PTFE porous membrane, the content of polymerized units derived from PMVE is preferably 0.250 mol% or less, more preferably 0.150 mol% or less, and even more preferably 0.100 mol% or less. . 0.050 mol% or less is most preferable.
  • PTFE may be obtained by polymerizing TFE, PMVE, and a small amount of a comonomer other than PMVE.
  • trace comonomer other than PMVE include fluorine-containing olefins such as hexafluoropropylene [HFP] and chlorotrifluoroethylene [CTFE]; alkyl having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. Fluoro (alkyl vinyl ether) having a group; Cyclic fluorinated monomer such as fluorodioxole; Perfluoroalkylethylene; ⁇ -hydroperfluoroolefin and the like.
  • the content of the polymer derived from a small amount of a comonomer other than PMVE is preferably 0.0001 to 0.300 mol%, and more preferably 0.010 to 0.100 mol%.
  • PTFE is preferably PTFE having no history of heating at a temperature equal to or higher than the primary melting point.
  • the PTFE may be unsintered PTFE or semi-sintered PTFE. Examples of unsintered PTFE include polymerized PTFE. Unsintered PTFE is PTFE that has no history of heating to a temperature above the secondary melting point, and semi-sintered PTFE is PTFE that has no history of heating at a temperature above the primary melting point and is below the primary melting point. And PTFE heated at a temperature equal to or higher than the secondary melting point.
  • the primary melting point means the maximum peak temperature of the endothermic curve that appears on the crystal melting curve when unsintered PTFE is measured with a differential scanning calorimeter.
  • the secondary melting point means the maximum peak temperature of the endothermic curve that appears on the crystal melting curve when PTFE heated to a temperature higher than the primary melting point (for example, 360 ° C.) is measured with a differential scanning calorimeter.
  • the endothermic curve is obtained by increasing the temperature using a differential scanning calorimeter at a temperature increase rate of 10 ° C./min.
  • PTFE preferably has an average primary particle diameter of 150 nm or more because a higher-strength PTFE porous membrane can be obtained. More preferably, it is 180 nm or more, More preferably, it is 210 nm or more, Especially preferably, it is 220 nm or more.
  • the upper limit is not particularly limited, but may be 500 nm. From the viewpoint of productivity in the polymerization step, 350 nm is preferable.
  • the average primary particle size was determined by using a PTFE aqueous dispersion obtained by polymerization, the transmittance of 550 nm projection light with respect to the unit length of the aqueous dispersion adjusted to a polymer concentration of 0.22% by mass, and transmission electron
  • a calibration curve with the average primary particle diameter determined by measuring the unidirectional diameter in the micrograph can be prepared, and the transmittance of the aqueous dispersion to be measured can be measured and determined based on the calibration curve.
  • PTFE may have a core-shell structure.
  • PTFE having a core-shell structure include modified PTFE including a high molecular weight PTFE core and a lower molecular weight PTFE shell or a modified PTFE shell in a particle.
  • modified PTFE include PTFE described in JP-T-2005-527652.
  • PTFE preferably has a standard specific gravity [SSG] of 2.160 or less because a higher-strength PTFE porous membrane can be obtained.
  • SSG standard specific gravity
  • PTFE having an SSG of 2.160 or less has a stretch ratio of the extruded product exceeding 3 times and is suitable for stretch molding.
  • SSG is more preferably 2.155 or less, even more preferably 2.150 or less, and particularly preferably 2.145 or less because more excellent stretchability can be obtained.
  • the standard specific gravity is preferably 2.130 or more from the viewpoint of suppressing an increase in paste extrusion pressure and being excellent in moldability.
  • SSG is SSG defined in ASTM D4895-89 as an index of the molecular weight of PTFE having no melt molding processability.
  • the extrusion pressure is preferably 22.0 MPa or less, more preferably 20.0 MPa or less, further preferably 19.0 MPa or less, and particularly preferably 18.0 MPa or less.
  • the extrusion pressure is too high, the extruded product becomes hard and is difficult to be crushed during rolling, which will be described later, and the homogeneity of the PTFE porous film tends to be lowered.
  • the strength of the PTFE porous membrane tends to be reduced.
  • the PTFE porous membrane has excellent strength even at an extrusion pressure in the above range.
  • the minimum of extrusion pressure is not specifically limited, For example, it is 12.0 MPa.
  • the extrusion pressure is a value obtained by a method described later.
  • PTFE preferably has a breaking strength of 20 N or more because a higher strength PTFE porous membrane can be obtained. More preferably, it is 28N or more. In particular, when the film is stretched at a high stretch ratio, the breaking strength is preferably in the above range. Although the upper limit of breaking strength is not specifically limited, For example, it is 70N.
  • the breaking strength is a value obtained by the following method according to the description in JP-A-2002-201217.
  • the bead obtained by the above extrusion pressure measurement paste extrusion is heated at 230 ° C. for 30 minutes to remove the lubricant from the bead, and then the bead (extruded product) is cut to an appropriate length.
  • Each end is fixed to the clamp so that the clamp spacing is any 5.1 cm, heated to 300 ° C. in an air circulating oven, and then the clamp is separated corresponding to 2400% total stretch (total stretch)
  • Stretching beads (made by stretching the beads) are produced by separating at a stretching speed (stretching speed) of 100% / second until the distance is reached.
  • This stretch method essentially follows the method disclosed in US Pat. No.
  • the minimum tensile breaking load force is fixed by sandwiching a sample in a movable jaw having a gauge length of 5.0 cm (distance between chucks), driving the movable jaw at a speed of 300 mm / min, and using a tensile tester. A tensile test was performed at 25 ° C. at a speed of 300 mm / min, and the strength at the time of fracture was measured for each of the three samples.
  • the extrusion pressure is particularly preferably 20.0 MPa or less and the breaking strength is preferably 28 N or more, the extrusion pressure is 19.0 MPa or less, and the breaking strength is most preferably 29 N or more.
  • the PTFE porous membrane can be formed from PTFE fine powder made of PTFE.
  • the average particle size of PTFE fine powder is usually 100 to 1000 ⁇ m.
  • the average particle size is preferably 300 to 800 ⁇ m, more preferably 400 to 700 ⁇ m, because a PTFE porous membrane with better homogeneity can be obtained.
  • the average particle diameter of PTFE fine powder is a value measured according to JIS K6891.
  • the apparent density of the PTFE fine powder is usually 0.35 to 0.60 g / ml. In order to obtain a PTFE porous membrane having better homogeneity, 0.40 to 0.55 g / ml is preferable.
  • the apparent density is a value measured according to JIS K6892.
  • PTFE porous membrane used in the present disclosure described above is also excellent in homogeneity.
  • the molded product used in the composite rubber molded product of the present disclosure includes an elastomer.
  • the elastomer may be either fluororubber or non-fluororubber.
  • Elastomers include fluorine rubber, acrylonitrile-butadiene rubber (NBR) or its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), and isoprene rubber.
  • IR diene rubber
  • ethylene-propylene-termonomer copolymer rubber silicone rubber
  • butyl rubber epichlorohydrin rubber
  • acrylic rubber chlorinated polyethylene (CPE)
  • ethylene propylene diene rubber (EPDM) and the like.
  • at least one selected from the group consisting of fluoro rubber and silicone rubber is preferable. With fluoro rubber and silicone rubber, a composite rubber molded product having a smaller surface friction coefficient can be produced.
  • the fluororubber may be a partially fluorinated rubber or a perfluororubber.
  • Partially fluorinated rubbers include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber.
  • the vinylidene fluoride-based fluororubber is preferably a copolymer composed of 25 to 85 mol% of vinylidene fluoride and 75 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. More preferably, it is a copolymer comprising 45 to 80 mol% of vinylidene fluoride and 55 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.
  • the fluororubber may be a copolymer containing a monomer that provides a crosslinking site.
  • a monomer which gives a crosslinking site the formula (4):
  • CY 1 2 CY 2 R f 2 X 3 (4)
  • Y 1 and Y 2 are a fluorine atom, a hydrogen atom or —CH 3 ;
  • R f 2 may have one or more ether-bonded oxygen atoms, and may have an aromatic ring.
  • X 3 is an iodine atom or a bromine atom
  • Linear or branched fluorine-containing alkylene group that is, a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and part or all of the hydrogen atoms are fluorine a linear or branched fluorine-containing oxyalkylene group substituted with atoms or a fluorine-containing polyoxyalkylene group partially or entirely a linear or branched substituted with fluorine atoms of the hydrogen atom,;
  • R 1 is Hydrogen atom or methyl group
  • CY 4 2 CY 4 (CF 2 ) n -X 3 (6)
  • Y 4 is the same or different and is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8.
  • CF 2 CFCF 2 R f 4 -X 3 (7) (Where
  • CF 2 CFCF 2 (OCF (CF 3 ) CF 2 ) m (OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 —X 3 (8)
  • m is an integer of 0 to 5, and n is an integer of 0 to 5)
  • CF 2 CFCF 2 (OCH 2 CF 2 CF 2 ) m (OCF (CF 3 ) CF 2 ) n OCF (CF 3 ) -X 3 (9)
  • m is an integer of 0 to 5, and n is an integer of 0 to 5) CF 2 ⁇ CF (OCF 2 CF (CF 3 )) m O (CF 2 ) n —X 3 (10)
  • CF 2 CF (OCF 2 CF (CF 3 )) m -X 3 (11) (Where m is an integer is an integer from 0 to 8)
  • Preferred examples include iodine-containing fluorinated vinyl ethers represented by:
  • ICH 2 CF 2 CF 2 OCF ⁇ CF 2 is preferable among these. More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (6) include ICF 2 CF 2 CF ⁇ CH 2 and I (CF 2 CF 2 ) 2 CF ⁇ CH 2 . More specifically, the iodine-containing monomer or bromine-containing monomer represented by the formula (10) is preferably I (CF 2 CF 2 ) 2 OCF ⁇ CF 2 . More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (23) include CH 2 ⁇ CHCF 2 CF 2 I and I (CF 2 CF 2 ) 2 CH ⁇ CH 2 .
  • R 2 R 3 C ⁇ CR 4 —Z—CR 5 CR 6 R 7 (Wherein R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and all are H or an alkyl group having 1 to 5 carbon atoms; Z is linear (linear ) Or a branched, optionally containing oxygen atom, preferably an at least partially fluorinated alkylene or cycloalkylene group having 1 to 18 carbon atoms, or (per) fluoropolyoxyalkylene group) Bisolefin compounds are also preferred as monomers that provide a crosslinking site.
  • Z is preferably a (per) fluoroalkylene group having 4 to 12 carbon atoms, and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are preferably hydrogen atoms.
  • Z is a (per) fluoropolyoxyalkylene group, - (Q) p -CF 2 O- (CF 2 CF 2 O) m - (CF 2 O) n -CF 2 - (Q) p - (In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, and m and n have an m / n ratio of 0.2 to 5.
  • the (per) fluoropolyoxyalkylene group is preferably an integer such that the molecular weight of the (per) fluoropolyoxyalkylene group is in the range of 500 to 10,000, preferably 1000 to 4000.
  • Preferred bisolefin compounds are CH 2 ⁇ CH— (CF 2 ) 4 —CH ⁇ CH 2 , CH 2 ⁇ CH— (CF 2 ) 6 —CH ⁇ CH 2 , Formula: CH 2 ⁇ CH—Z 1 —CH ⁇ CH 2 (Wherein Z 1 is —CH 2 OCH 2 —CF 2 O— (CF 2 CF 2 O) m — (CF 2 O) n —CF 2 —CH 2 OCH 2 — (m / n is 0.5)) ) Etc.
  • VdF / HFP rubber VdF / HFP / TFE rubber
  • VdF / CTFE rubber VdF / CTFE / TFE rubber
  • VdF / general formula (1) Fluoromonomer rubber, VdF / fluoromonomer / TFE rubber represented by the general formula (1), VdF / perfluoro (methyl vinyl ether) (PMVE) rubber, VdF / PMVE / TFE rubber, VdF / PMVE / Examples include TFE / HFP rubber.
  • the tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site.
  • the fluoro rubber may be perfluoro rubber.
  • perfluoro rubber containing TFE for example, TFE / general formula (25):
  • CF 2 CF-ORf 31 (wherein Rf 31 represents a perfluoroalkyl group having 1 to 10 carbon atoms).
  • Rf 41 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, carbon
  • At least one selected from the group consisting of monomer copolymers is preferred.
  • the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
  • a monomer copolymer that provides a TFE / PMVE / cross-linking site it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), and more preferably 55 to 77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
  • the fluoromonomer copolymer represented by the general formula (25), (26) or (27) having 4 to 12 carbon atoms preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
  • the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
  • vinylidene fluoride (VdF) / hexafluoropropylene (HFP) fluorororubber VdF / HFP / tetrafluoroethylene (TFE) fluororubber
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkyl vinyl ether
  • Perfluoro rubbers include: TFE / fluoromonomer represented by the general formula (27) / fluoromonomer copolymer that gives a crosslinking site, TFE / perfluorovinyl ether copolymer represented by the general formula (27), TFE / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (25) and a fluoromonomer represented by TFE / general formula (25) / a monomer copolymer that gives a crosslinking site. Preferably there is.
  • perfluoro rubber examples include perfluoro rubbers described in International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. it can.
  • the monomer composition of the fluororubber can be measured by 19 F-NMR.
  • the glass transition temperature is preferably ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and further preferably ⁇ 50 ° C. or higher, from the viewpoint of excellent compression set at high temperatures. From the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably ⁇ 3 ° C. or lower.
  • the glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo Co., Ltd., DSC822e) to obtain a DSC curve by increasing the temperature of 10 mg of the sample at 10 ° C./min.
  • the baseline before and after the second transition of the DSC curve And the temperature indicating the midpoint of the two intersections of the tangent line at the inflection point of the DSC curve.
  • the fluororubber may be obtained by using a chain transfer agent during polymerization.
  • a chain transfer agent a bromine compound or an iodine compound may be used.
  • the polymerization method using a bromine compound or iodine compound include a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of a bromine compound or iodine compound in a substantially oxygen-free state. (Iodine transfer polymerization method).
  • bromine compounds or iodine compounds to be used include, for example, the general formula: R 8 I x Br y (Wherein x and y are each an integer of 0 to 2 and satisfy 1 ⁇ x + y ⁇ 2, and R 8 is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
  • a bromine compound or an iodine compound iodine or bromine is introduced into the polymer and functions as a crosslinking point.
  • iodine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5- Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane , diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- propane, CF 2 Br 2, BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrCl
  • 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferable from the viewpoint of polymerization reactivity, crosslinking reactivity, availability, and the like.
  • the fluororubber examples include peroxide crosslinkable fluororubber, polyol crosslinkable fluororubber, polyamine crosslinkable fluororubber, and the like.
  • the fluororubber capable of peroxide crosslinking is not particularly limited as long as it is a fluororubber having a site capable of peroxide crosslinking.
  • the site capable of peroxide crosslinking is not particularly limited, and examples thereof include an iodine atom and a bromine atom.
  • the fluorine-crosslinkable fluororubber is not particularly limited as long as it is a fluororubber having a polyol-crosslinkable site.
  • the site capable of crosslinking with polyol is not particularly limited, and examples thereof include a site having a vinylidene fluoride (VdF) unit.
  • Examples of a method for introducing a crosslinking site include a method of copolymerizing a monomer that gives a crosslinking site during the polymerization of fluororubber.
  • the fluororubber is preferably a partially fluorinated rubber capable of polyol crosslinking. Moreover, as said fluororubber, when importance is attached to corrosion resistance, it is preferable that it is perfluoro rubber.
  • the fluorine content of the fluororubber is preferably 64% by mass or more, more preferably 68% by mass or more, and still more preferably 70% by mass or more.
  • the upper limit may be 85% by weight.
  • the iodine content of the fluororubber is preferably 0.001 to 10% by mass, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and more preferably 5% by mass or less.
  • silicone rubber polyorganosiloxane having a plurality of polymerizable unsaturated bonds in one molecule is preferable.
  • Polyorganosiloxane constitutes the main skeleton of silicone rubber.
  • the silicone rubber is preferably a polyorganosiloxane having a plurality of polymerizable unsaturated bonds in one molecule in order to be cured by a crosslinking reaction.
  • the group having a polymerizable unsaturated bond is preferably bonded to a silicon atom in the polyorganosiloxane.
  • the group other than the group having a polymerizable unsaturated bond that is bonded to the silicon atom may be either an organic group or a hydrogen atom.
  • known ones can be used as appropriate.
  • the number of the polymerizable unsaturated bonds in the polyorganosiloxane may be 2 or more, 2 or 3 or more.
  • the polyorganosiloxane preferably has an unsaturated bond between carbon atoms as the polymerizable unsaturated bond, preferably has a double bond, and preferably has an alkenyl group.
  • alkenyl group examples include ethenyl group (vinyl group), 2-propenyl group (allyl group), 1-propenyl group and the like.
  • the plurality of alkenyl groups in the polyorganosiloxane may all be the same, may all be different, or only some may be different.
  • the alkenyl group is preferably bonded to a silicon atom constituting the main skeleton of the polyorganosiloxane.
  • Examples of the organic group other than the alkenyl group constituting the polyorganosiloxane include an alkyl group and an aryl group which may have a substituent.
  • the alkyl group may be linear, branched or cyclic, but preferably has 1 to 10 carbon atoms.
  • linear or branched alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
  • the cyclic alkyl group may be monocyclic or polycyclic, and preferred examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a norbornyl group. And an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, and a tricyclodecyl group having 3 to 10 carbon atoms.
  • the aryl group may be monocyclic or polycyclic, and preferred examples include a phenyl group, an o-tolyl group (2-methylphenyl group), an m-tolyl group (3-methylphenyl group), and a p-tolyl group. Examples include those having 6 to 15 carbon atoms such as (4-methylphenyl group), 1-naphthyl group and 2-naphthyl group.
  • the alkyl group and aryl group may have a substituent.
  • “the alkyl group (aryl group) has a substituent” means that one or more hydrogen atoms constituting the alkyl group (aryl group) are substituted with a group other than a hydrogen atom, or an alkyl group It means that one or more carbon atoms constituting (aryl group) are substituted with a group other than carbon atoms. And both the hydrogen atom and the carbon atom may be substituted with a substituent.
  • the alkyl group and aryl group having a substituent preferably have a carbon number within the above range including the substituent.
  • Examples of the substituent for substituting the hydrogen atom of the alkyl group and the aryl group include an alkyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an alkoxy group, an alkylcarbonyl group, an alkenyl group, an alkenyloxy group, an aryl group, an alkylaryl group, Examples thereof include an arylalkyl group, an aryloxy group, an arylalkyloxy group, an alkylaryloxy group, a hydroxyl group (—OH), a cyano group (—CN), and a halogen atom.
  • Examples of the alkyl group substituting a hydrogen atom include the same alkyl groups as those in the organic group.
  • Examples of the alkyloxycarbonyl group that substitutes a hydrogen atom include monovalent groups in which the alkyl group in the organic group is bonded to the oxycarbonyl group.
  • Examples of the alkylcarbonyloxy group for substituting a hydrogen atom include monovalent groups in which the alkyl group in the organic group is bonded to the carbonyloxy group.
  • Examples of the alkoxy group that substitutes a hydrogen atom include a monovalent group in which an alkyl group in an organic group is bonded to an oxygen atom.
  • Examples of the alkylcarbonyl group replacing a hydrogen atom include a monovalent group in which an alkyl group in an organic group is bonded to a carbonyl group.
  • An alkenyl group that replaces a hydrogen atom is an alkyl group in an organic group in which one single bond (C—C) between carbon atoms is replaced by a double bond (C ⁇ C), and is polymerizable. The thing which does not correspond to the alkenyl group which has an unsaturated bond can be illustrated.
  • the position of the double bond between the carbon atoms in the alkenyl group replacing the hydrogen atom is not particularly limited.
  • Examples of the alkenyloxy group that substitutes a hydrogen atom include a monovalent group in which an alkenyl group as a substituent is bonded to an oxygen atom.
  • Examples of the aryl group that substitutes a hydrogen atom include the same aryl groups as those in an organic group.
  • Examples of the alkylaryl group that substitutes a hydrogen atom include a group in which one hydrogen atom bonded to a carbon atom constituting the aromatic ring of an aryl group in an organic group is substituted with an alkyl group in the organic group.
  • Examples of the arylalkyl group that substitutes a hydrogen atom include a group in which one hydrogen atom of an alkyl group in an organic group is substituted with an aryl group in the organic group.
  • Examples of the aryloxy group that substitutes a hydrogen atom include a monovalent group in which an aryl group in an organic group is bonded to an oxygen atom.
  • Examples of the arylalkyloxy group for substituting a hydrogen atom include a monovalent group in which an aryl group in an organic group and an oxygen atom are bonded to an alkylene group obtained by removing one hydrogen atom from an alkyl group in the organic group.
  • an alkylaryloxy group for substituting a hydrogen atom an arylene group in an organic group, which is an arylene group in which one hydrogen atom bonded to a carbon atom constituting an aromatic ring is removed, an alkyl group and an oxygen in the organic group are substituted.
  • An example is a monovalent group having atoms bonded thereto.
  • halogen atom that replaces the hydrogen atom
  • examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of substituents replacing the hydrogen atom is not particularly limited, and may be one or plural, and all the hydrogen atoms may be substituted with substituents. Moreover, the position of the hydrogen atom substituted with a substituent is not particularly limited.
  • Carbon atoms of the alkyl group and aryl group may be substituted with the following substituents.
  • substituents include a carbonyl group (—C ( ⁇ O) —), an ester bond (—C ( ⁇ O) —O—), an amide bond (—NH—C ( ⁇ O) —), and a hetero atom.
  • the hetero atom that substitutes a carbon atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a boron atom.
  • the number of substituents replacing the carbon atom is not particularly limited, and may be one or more. Further, the position of the carbon atom substituted with the substituent is not particularly limited.
  • polyorganosiloxane a commercially available product may be used, or a polyorganosiloxane synthesized according to a known method may be used.
  • a polyorganosiloxane may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.
  • Examples of a commercially available product (trade name) of polyorganosiloxane and a product (trade name) containing the above polyorganosiloxane are as follows. Asahi Kasei Wacker Silicone ELASTOSIL EL 1000 Series, ELASTOSIL EL 4000 Series, ELASTOSIL EL 3000 Series, ELASTOSIL EL 7000 Series, ELASTOSIL R401 Series, etc. Toray Dow Corning SH800 Series, SH50 Series, SH70 Series, SH700 Series, SE4000 Series SE1000 series, SH500 series, SE6000 series, SH80 series, SRX400 series, DY32-400 series, DY32-500 series, DY32-1000 series, DY32-7000 series, DY32-4000 series, etc.
  • the composite rubber molded article of the present disclosure includes, for example, a step of producing a PTFE green body or a PTFE semi-fired body, a step of obtaining a PTFE porous film by stretching the PTFE green body or a PTFE semi-fired body, and a PTFE porous material It can manufacture suitably by the manufacturing method including the process of closely_contact
  • the PTFE porous film having a product of the matrix tensile strength in the vertical direction and the horizontal direction of 30000 MPa 2 or more is overlapped with the molded article containing the elastomer, the molded article and the PTFE porous film are firmly adhered to each other. Even if it is not used, a composite rubber molded article in which the PTFE porous membrane is difficult to peel can be produced.
  • the surface of the PTFE porous membrane or the molded product can be chemically or physically treated, or an adhesive can be applied to the surface of the PTFE porous membrane or the molded product.
  • the PTFE green body is, for example, Introducing a surfactant, an aqueous medium, and TFE into the polymerization tank; Introducing a polymerization initiator into the polymerization tank and starting the emulsion copolymerization of TFE; A step of aggregating PTFE in an aqueous PTFE dispersion obtained by emulsion copolymerization; Recovering PTFE obtained by agglomeration, A drying process for obtaining PTFE fine powder by drying the recovered PTFE; Paste extruding step to obtain a paste extrudate by paste extruding the PTFE fine powder, A rolling step of rolling the paste extrudate to obtain a PTFE green body, and
  • the PTFE green body can be suitably produced by a production method including a drying step of drying the PTFE green body and removing the extrusion aid.
  • the PTFE semi-fired body can be produced, for example, by semi-firing the dried PTFE green body. That is, the said manufacturing method can include the process of semi-baking the PTFE green body after drying as needed, and obtaining a PTFE semi-fired body.
  • the above-mentioned small amount of comonomer is charged into the polymerization layer, a polymerization initiator is charged into the polymerization tank, and emulsion copolymerization of TFE and the above-mentioned small amount of monomer is started. Good.
  • the supply of a small amount of comonomer may be added all at once before the start of polymerization, or may be added continuously or intermittently.
  • Emulsion copolymerization will be described with a more specific example.
  • an aqueous medium and the above surfactant are charged into a pressure-resistant reaction vessel equipped with a stirrer, and after deoxidation, TFE is charged, brought to a predetermined temperature, and a polymerization initiator is added to start emulsion copolymerization. Since the pressure decreases with progress, additional TFE and a small amount of comonomer are added continuously or intermittently as necessary to maintain the initial pressure.
  • the supply is stopped, the TFE in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated.
  • a PTFE porous membrane having higher strength, a small pore size and excellent homogeneity can be obtained, and therefore a fluorinated surfactant is preferable, and a fluorinated surfactant having a Log POW of 3.4 or less is more preferable.
  • a compound with a large Log POW is concerned about the burden on the environment, and considering this, it is preferable to use a compound with a Log POW of 3.4 or less. So far, in the production of fluorine-containing polymers by emulsion polymerization, ammonium perfluorooctanoate [PFOA] has been mainly used as a surfactant.
  • PFOA has a Log POW of 3.5
  • the Log POW is 3.4 or less. It is preferable to switch to the fluorine-containing surfactant.
  • a fluorine-containing surfactant having a Log POW of 3.4 or less has a problem of poor emulsifying ability.
  • the stability of the aqueous dispersion during polymerization is important.
  • a fluorine-containing surfactant that is actually inferior in emulsifying ability is used, sufficient breaking strength is obtained. I can't. Therefore, International Publication No.
  • 2009/001894 describes a method of using a large amount of a fluorine-containing surfactant having a small Log POW in order to improve the stability of an aqueous dispersion.
  • the PTFE obtained by this method is not sufficient in breaking strength.
  • PTFE obtained by emulsion copolymerization of tetrafluoroethylene and perfluoromethyl vinyl ether (PMVE) in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less, it has the above-mentioned microstructure, high strength, A PTFE porous membrane having a small pore diameter and excellent uniformity can be formed.
  • PTFE is preferably obtained by emulsion copolymerization of tetrafluoroethylene and at least perfluoromethyl vinyl ether in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less.
  • the surfactant may be a fluorine-containing surfactant having a Log POW of 2.5 or more, or may be a fluorine-containing surfactant having a Log POW of 3.0 or more.
  • Log POW is the partition coefficient between 1-octanol and water, and Log P [where P is the octanol / water (1: 1) mixture containing the fluorinated surfactant in the octanol when phase separation occurs. This represents the ratio of fluorine-containing surfactant concentration / fluorine-containing surfactant concentration in water].
  • the octanol / water partition coefficient represented by Log POW is as follows.
  • a fluorine-containing anionic surfactant is preferable, and US Patent Application Publication No. 2007/0015864, US Patent Application Publication No. 2007/0015865, US Patent Application Publication No. 2007/0015866. Specification, US Patent Application Publication No. 2007/0276103, US Patent Application Publication No. 2007/0117914, US Patent Application Publication No. 2007/0142541, US Patent Application Publication No. 2008/0015319 , U.S. Pat.No. 3,250,808, U.S. Pat.No. 3,271,341, JP-A No. 2003-119204, International Publication No. 2005/042593, International Publication No. 2008/060461, International Publication No. 2007/046377, International Publication No. 2007/11 526 No., WO 2007/046482, and such as those described in WO 2007/046345 can be used.
  • fluorine-containing surfactant a general formula: CF 3- (CF 2 ) 4 -COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal), general formula: CF 3 CF 2 CF 2 OCF (CF 3 ) COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), general formula: CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), and a general formula: CF 3 CF 2 OCF 2 CF 2 OCF 2 COOX (In the formula, X represents a hydrogen atom, NH 4 or an alkali metal atom.) It is preferably at least one fluorine-containing surfactant selected from the group consisting of
  • fluorine-containing surfactant a general formula: CF 3 OCF 2 CF 2 OCF 2 CF 2 COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), general formula: CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COOX (In the formula, X represents a hydrogen atom, NH 4 or an alkali metal atom.) Etc. can also be mentioned.
  • examples of the counter ion forming the salt include an alkali metal ion or NH 4+ , and examples of the alkali metal ion include Na + and K + .
  • fluorine-containing surfactant examples include CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOH, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , CF 3 CF 2 OCF 2 CF 2 OCF 2 COOH, CF 3 CF 2 OCF 2 CF 2 OCF 2 COONH 4, CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COOH, CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COONH 4, CF 3 - (CF 2) 4 - COOH, CF 3- (CF 2 ) 4 -COONH 4 , CF 3 CF 2 CF 2 OCF (CF 3 ) COONH 4 , CF 3 CF 2 CF 2 OCF (CF 3 ) COOH, and the like.
  • the surfactant is preferably added in a total addition amount of 0.0001 to 10% by mass with respect to the aqueous medium.
  • a more preferred lower limit is 0.1% by mass
  • a more preferred upper limit is 2% by mass
  • a still more preferred upper limit is 1% by mass. If the amount is too small, the stability of the emulsified particles is not good, and the yield may not be increased, and the system becomes unstable, such as agglomerates during the reaction and after the reaction, and a large amount of deposits on the reaction vessel. The phenomenon may occur. If the amount is too large, the effect of stability corresponding to the amount added cannot be obtained, and there is a possibility that the system becomes unstable, and the polymerization rate may be lowered or the reaction may be stopped.
  • the surfactant may be added into the tank all at once before the polymerization reaction is started, or may be added continuously or intermittently after the polymerization reaction is started.
  • the addition amount of the surfactant is appropriately determined depending on the stability of the emulsified particles, the primary particle diameter of the target PTFE, and the like.
  • the polymerization initiator in the emulsion copolymerization those conventionally used in the polymerization of TFE can be used.
  • a polymerization initiator in emulsion copolymerization a radical polymerization initiator, a redox polymerization initiator, or the like can be used.
  • the smaller the amount of the polymerization initiator the more preferable in that PTFE having a low SSG can be obtained.
  • the amount is too small, the polymerization rate tends to be too small, and when the amount is too large, PTFE having a high SSG tends to be produced. is there.
  • radical polymerization initiator examples include water-soluble peroxides, and persulfates such as ammonium persulfate and potassium persulfate, and water-soluble organic peroxides such as disuccinic acid peroxide are preferable. Ammonium persulfate or disuccinate Acid peroxide is more preferable. These may be used alone or in combination of two or more.
  • the amount of the radical polymerization initiator used can be appropriately selected according to the polymerization temperature and the target SSG, but is preferably an amount corresponding to 1 to 100 ppm of the mass of the aqueous medium generally used. An amount corresponding to 20 ppm is more preferable, and an amount corresponding to 1 to 6 ppm is still more preferable.
  • the radical concentration in the system can be adjusted by adding a peroxide decomposing agent such as ammonium sulfite during the polymerization.
  • PTFE having a low SSG can be easily obtained by adding a radical scavenger during the polymerization.
  • the radical scavenger include unsubstituted phenols, polyhydric phenols, aromatic hydroxy compounds, aromatic amines, quinone compounds, etc. Among them, hydroquinone is preferable.
  • the radical scavenger is preferably added before 50% by mass of the total TFE consumed in the polymerization reaction is polymerized in that PTFE having a low SSG is obtained. More preferably, it is added before 40% by mass of TFE, more preferably 30% by mass, is polymerized.
  • the radical scavenger is preferably in an amount corresponding to 0.1 to 20 ppm of the mass of the aqueous medium used, and more preferably in an amount corresponding to 3 to 10 ppm.
  • Redox polymerization initiators include permanganates such as potassium permanganate, persulfates, bromates, chlorates, hydrogen peroxide and other oxidizing agents, sulfites, bisulfites, oxalic acid or succinate.
  • permanganates such as potassium permanganate, persulfates, bromates, chlorates, hydrogen peroxide and other oxidizing agents, sulfites, bisulfites, oxalic acid or succinate.
  • a combination with an organic acid such as an acid, a reducing agent such as thiosulfate, ferrous chloride, and diimine can be used. Any of the above oxidizing agents and reducing agents may be used alone or in combination of two or more. Among these, a combination of potassium permanganate and oxalic acid is preferable.
  • the amount of redox polymerization initiator used can be appropriately selected according to the type of redox polymerization initiator to be used, the polymerization temperature, and the target SSG, and corresponds to 1 to 100 ppm of the mass of the aqueous medium used. An amount is preferred.
  • the redox polymerization initiator may start the polymerization reaction by simultaneously adding the oxidizing agent or the reducing agent, or either one of the oxidizing agent or the reducing agent is previously added to the tank and the remaining one is left. The polymerization reaction may be started by adding.
  • redox polymerization initiator either one of the oxidizing agent or reducing agent is added to the tank in advance, and when the remaining one is added to start the polymerization, the remaining one is added continuously or intermittently. Is preferred.
  • the remaining redox initiator is continuously or intermittently added, it is preferable to gradually reduce the rate of addition in order to obtain PTFE with low SSG, and it is preferable to stop the polymerization in the middle.
  • the addition stop timing is preferably before 80% by mass of the total TFE consumed in the polymerization reaction is polymerized. More preferably, 65% by mass of TFE is polymerized, more preferably before 50% by mass of TFE is polymerized, and particularly preferably before 30% by mass of polymerized.
  • a pH buffering agent When using a redox polymerization initiator, it is desirable to use a pH buffering agent in order to adjust the pH in the aqueous medium to a range that does not impair the redox reactivity.
  • a pH buffering agent inorganic salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium carbonate can be used, and disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate include preferable.
  • various metals having a plurality of ionic valences can be used as metal ions that undergo redox reaction.
  • transition metals such as iron, copper, manganese, and chromium are preferable, and iron is particularly preferable.
  • the aqueous medium is a medium for performing polymerization and means a liquid containing water.
  • the aqueous medium is not particularly limited as long as it contains only water or contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and ketone, and / or a boiling point of 40 ° C.
  • a fluorine-free organic solvent such as alcohol, ether, and ketone, and / or a boiling point of 40 ° C.
  • the following fluorine-containing organic solvent may be included.
  • the polymerization can be performed under a pressure of 0.05 to 5.0 MPa.
  • a preferable pressure range is 0.5 to 3.0 MPa.
  • the polymerization can be carried out at a temperature of 10 to 100 ° C.
  • a preferred temperature range is 50-90 ° C.
  • a known stabilizer, chain transfer agent and the like may be further added depending on the purpose.
  • the stabilizer examples include saturated hydrocarbons having 12 or more carbon atoms that are substantially inert to the reaction and become liquid under the above reaction conditions.
  • paraffin wax is preferable.
  • the paraffin wax may be liquid, semi-solid or solid at room temperature, but is preferably a saturated hydrocarbon having 12 or more carbon atoms.
  • the melting point of paraffin wax is usually preferably 40 to 65 ° C, more preferably 50 to 65 ° C.
  • dispersion stabilizers other than saturated hydrocarbons include fluorinated oils, fluorinated solvents, and silicone oils. You may use these individually or in combination of 2 or more types.
  • the stabilizer can be used at 1 to 10 parts by mass with respect to 100 parts by mass of the aqueous medium.
  • chain transfer agent known ones can be used, for example, saturated hydrocarbons such as methane, ethane, propane and butane, halogenated hydrocarbons such as chloromethane, dichloromethane and difluoroethane, alcohols such as methanol and ethanol, Hydrogen etc. are mentioned.
  • the amount of the chain transfer agent used is usually 1 to 1000 ppm, preferably 1 to 500 ppm, based on the total amount of TFE supplied.
  • a pH buffer inorganic salts such as disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium carbonate can be used, and disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate include preferable.
  • various metals having a plurality of ionic valences can be used as metal ions that undergo redox reaction.
  • transition metals such as iron, copper, manganese, and chromium are preferable, and iron is particularly preferable.
  • the polymerization may be carried out in the presence of 5 to 500 ppm dicarboxylic acid relative to the aqueous medium in order to reduce the amount of coagulum produced during the polymerization, in which case it is carried out in the presence of 10 to 200 ppm dicarboxylic acid. It is preferable. If the amount of the dicarboxylic acid is too small relative to the aqueous medium, a sufficient effect may not be obtained. If the amount is too large, a chain transfer reaction may occur and the resulting polymer may have a low molecular weight.
  • the dicarboxylic acid is preferably 150 ppm or less. The dicarboxylic acid may be added before the start of the polymerization reaction or may be added during the polymerization.
  • dicarboxylic acid for example, those represented by the general formula: HOOCRCOOH (wherein R represents an alkylene group having 1 to 5 carbon atoms) are preferred.
  • Succinic acid, malonic acid, glutaric acid, adipic acid, pimelin Acid is more preferred, and succinic acid is even more preferred.
  • an aqueous dispersion having a solid content of 10 to 50% by mass can be obtained.
  • the aqueous dispersion contains a fluorine-containing surfactant and PTFE.
  • the average primary particle diameter of PTFE is 150 to 500 nm.
  • the production method preferably includes a step of aggregating PTFE in the obtained PTFE aqueous dispersion, a step of recovering PTFE obtained by agglomeration, and a drying step of drying the recovered PTFE.
  • a PTFE fine powder can be obtained by aggregating PTFE contained in the aqueous dispersion.
  • An aqueous dispersion of PTFE is recovered as a fine powder through aggregation, washing, and drying, and can be used for the production of a PTFE porous membrane.
  • the aqueous dispersion obtained by polymerization of a polymer latex or the like is usually diluted with water to a polymer concentration of 10 to 20% by mass, and 5 to 50
  • the pH is adjusted to neutral or alkaline, and then the mixture is stirred more vigorously than stirring during the reaction in a vessel equipped with a stirrer.
  • the agglomeration temperature can be appropriately selected according to the shape and size of the stirring blade used, the polymer concentration, and the average particle diameter of the target fine powder.
  • the agglomeration may be carried out while adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant. Aggregation may also be carried out continuously using an in-line mixer or the like.
  • Drying of the wet powder obtained by aggregating PTFE is usually carried out using means such as vacuum, high frequency, hot air, etc. while keeping the wet powder not flowing so much, preferably in a stationary state. Friction between powders, particularly at high temperatures, generally has an undesirable effect on PTFE fine powder. This is because particles of this type of PTFE have the property of easily fibrillating even with a small shearing force and losing the original stable particle structure.
  • the drying can be performed at a drying temperature of 10 to 250 ° C., preferably 120 to 230 ° C.
  • the production method preferably includes a step of obtaining a PTFE fine powder mixed with a liquid lubricant by adding a liquid lubricant such as solvent naphtha or white oil to the PTFE fine powder before the paste extrusion step.
  • a liquid lubricant such as solvent naphtha or white oil
  • the amount of the liquid lubricant added is preferably 17 to 34 parts by mass with respect to 100 parts by mass of the PTFE fine powder, although it depends on the paste extrusion conditions described later.
  • the paste extrusion step it is preferable to obtain a rod-like or sheet-like paste extrudate using an extruder equipped with a die having a specific diameter or a die capable of obtaining a sheet-like extrudate.
  • the extrusion pressure may be appropriately set according to the extruder used, the extrusion speed, and the like.
  • the extrusion temperature is 5 to 100 ° C. because a porous material having high strength is obtained. More preferably, it is 30 to 80 ° C.
  • a PTFE fine powder is preformed to obtain a preform, and the preform is placed in an extruder and extruded to obtain a rod-like paste extrudate.
  • the rolling temperature is preferably 5 to 100 ° C, more preferably 30 to 80 ° C.
  • the thickness of the unsintered PTFE after rolling is usually 20 to 500 ⁇ m, preferably 50 to 400 ⁇ m.
  • the drying step may be performed at room temperature or may be performed by heating.
  • the liquid lubricant can be removed by drying.
  • the drying temperature is preferably from 70 to 280 ° C., more preferably from 100 to 250 ° C., depending on the type of liquid lubricant.
  • Rolling can be performed by a method using a rolling roll or the like, a belt press or the like.
  • the manufacturing method includes a step of obtaining a PTFE semi-fired body by semi-firing the PTFE green body as necessary.
  • Semi-firing is heating at a temperature below the primary melting point of PTFE and above the secondary melting point.
  • the primary melting point means the maximum peak temperature of the endothermic curve that appears on the crystal melting curve when unsintered PTFE is measured with a differential scanning calorimeter.
  • the secondary melting point means the maximum peak temperature of the endothermic curve that appears on the crystal melting curve when PTFE heated to a temperature higher than the primary melting point (for example, 360 ° C.) is measured with a differential scanning calorimeter.
  • the endothermic curve is obtained by using a differential scanning calorimeter and raising the temperature at a rate of temperature rise of 10 ° C./min.
  • the specific temperature and the half firing time of the half firing can be determined with reference to the conditions described in JP-A-59-152825.
  • the stretching includes a uniaxial stretching step of stretching a PTFE green body or a PTFE semi-fired body in the machine direction (MD) to obtain a uniaxially stretched film, and a biaxial stretching process of stretching the uniaxially stretched film in the transverse direction (TD). It is preferable because the PTFE porous membrane having the above-described membrane thickness and the above-described tensile strength can be easily obtained.
  • the PTFE is easily fibrillated, and a biaxially stretched film composed of a nodule and a fiber is obtained.
  • the said longitudinal direction (MD) is the same direction as the direction which paste-extruded at the paste extrusion process.
  • the horizontal direction (TD) is a direction perpendicular to the vertical direction.
  • the film may be stretched in the transverse direction to obtain a uniaxially stretched film, and then stretched in the longitudinal direction to obtain a biaxially stretched film.
  • both the stretching in the longitudinal direction (uniaxial stretching step) and the stretching in the lateral direction (biaxial stretching step) may be performed multiple times ( So-called multistage stretching).
  • the stretching ratio is preferably 2 to 50 times, and more preferably 5 to 30 times.
  • the stretching temperature is preferably from room temperature to less than the primary melting point, more preferably from 200 to 330 ° C, and more preferably from 250 to 300 ° C. Further preferred.
  • a high-strength PTFE porous membrane is obtained, so that the stretching speed is preferably 5 to 2000% / second, more preferably 7 to 1000% / second, and 10 to 700% / second. More preferably, it is seconds.
  • the method for performing uniaxial stretching is not particularly limited. Industrially, roll stretching, hot plate stretching and the like can be mentioned.
  • a high-strength PTFE porous membrane can be obtained, so that the stretching ratio is preferably 2 to 100 times, and more preferably 10 to 50 times.
  • a high-strength PTFE porous membrane is obtained, so that the stretching temperature is preferably from room temperature to 400 ° C., more preferably from 150 to 390 ° C., and preferably from 200 to 380 ° C. Further preferred.
  • the stretching speed is preferably 5 to 2000% / second, more preferably 7 to 2000% / second, and 10 to 2000%. More preferably, it is / sec.
  • the production method preferably includes a heat setting step after the biaxial stretching step because a high-strength PTFE porous membrane is obtained.
  • the temperature for heat setting is preferably 300 to 420 ° C, more preferably 350 to 400 ° C.
  • the manufacturing method further includes a step of closely contacting the PTFE porous membrane and the molded product.
  • the adhesion can be carried out by superimposing the PTFE porous membrane and the molded article made of the composition containing the uncrosslinked elastomer and heating them to a temperature equal to or higher than the crosslinking temperature of the elastomer.
  • the close contact is a method in which a PTFE porous membrane is placed in a mold, a composition containing an uncrosslinked elastomer is filled in the mold and pressed, and a preform is formed from the uncrosslinked elastomer. After obtaining, it can be carried out by a method of hot pressing the preform and the PTFE porous membrane.
  • the composition may contain a crosslinking agent, a crosslinking aid and the like in addition to the elastomer described above.
  • the crosslinking agent include a polyol crosslinking agent and a peroxide crosslinking agent.
  • the composition can be prepared by mixing the uncrosslinked elastomer and the like using a normal elastomer processing machine, for example, an open roll, a Banbury mixer, a kneader and the like. In addition, it can be prepared by a method using a closed mixer.
  • a normal elastomer processing machine for example, an open roll, a Banbury mixer, a kneader and the like.
  • it can be prepared by a method using a closed mixer.
  • the preform includes a method in which a composition containing the uncrosslinked elastomer is heated and compressed in a mold, a method in which a composition containing the uncrosslinked elastomer is pressed into a heated mold, and a composition containing the uncrosslinked elastomer. It can be manufactured by a known method such as a method of extruding a product with an extruder.
  • the rubber hardness of the coating surface with the PTFE porous film is preferably 1% or more higher than the rubber hardness of the rubber not covering the porous film, and more preferably 1.5% or more.
  • the hardness can be measured by a type E durometer (JIS-K-6253 spring load value 550-8379 mN, probe radius 2.5 mm, height 2.5 mm hemisphere).
  • the composite rubber molded article of the present disclosure can be suitably used in the following fields.
  • semiconductor-related fields such as semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma addressed liquid crystal panels, field emission display panels, solar cell substrates, O (square) rings, packing, sealing materials, gaskets, diaphragms, etc.
  • CVD apparatus dry etching apparatus, wet etching apparatus, oxidation diffusion apparatus, sputtering apparatus, ashing apparatus, cleaning apparatus, ion implantation apparatus, and exhaust apparatus.
  • seal material As a gate valve O-ring, seal material, quartz window O-ring, seal material, chamber O-ring, seal material, gate O-ring, seal material, bell jar O-ring, seal material
  • a sealing material As an O-ring for a coupling, as a sealing material, as an O-ring for a pump, as a sealing material, as a diaphragm, as an O-ring for a semiconductor gas control device, as a sealing material, as an O-ring for a resist developer, as a stripping solution, as a sealing material Can be used.
  • gaskets, shaft seals, valve stem seals, seal materials can be used for engines and peripheral devices, seal materials can be used for AT devices, O (square) rings, packing, seal materials and diaphragms It can be used for fuel systems as well as peripheral devices.
  • engine head gasket metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, manifold packing, oxygen sensor seal, injector O-ring, injector packing, fuel pump O-ring, diaphragm, Crankshaft seal, gear box seal, power piston seal, cylinder liner seal, valve stem seal, automatic transmission front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston Diaphragm for cup, torque transmission O-ring, oil seal, exhaust gas reburner seal, bearing seal, carburetor sensor It can be used as a beam or the like.
  • valves In the field of chemical products such as plants, there are valves, packings, diaphragms, O (square) rings, sealing materials, and the like, which can be used in the manufacturing process of chemical products such as pharmaceuticals, agricultural chemicals, paints, and resins.
  • Seals packing for high-temperature vacuum dryers, roller seals for papermaking belts, fuel cell seals, wind tunnel joint seals, gas chromatography, packing for pH meter tube connections, analytical instruments, physics and chemistry instrument seals, diaphragms, valve parts Etc. can be used.
  • the field of photography such as a developing machine
  • the field of printing such as a printing machine
  • the field of painting such as a painting facility
  • it can be used as a seal or valve part of a dry copying machine.
  • valves, packings, diaphragms, O (square) rings, sealing materials and the like can be mentioned and used in food production processes. Specifically, it can be used as a seal for a plate heat exchanger, a solenoid valve seal for a vending machine, or the like.
  • packing In the general industrial field, packing, O-rings, sealing materials, diaphragms, valves and the like can be mentioned.
  • hydraulic, lubrication machinery seals bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seals (vacuum) valves, automatic packaging machine seals, air Used for diaphragms (pollution measuring devices) of sulfur dioxide and chlorine gas analysis pumps.
  • the fuel cell field specifically, it is used as a sealing material between electrodes and separators, a seal for hydrogen / oxygen / product water piping, and the like.
  • the electronic component field specifically, it is used as a heat radiating material, an electromagnetic shielding material, a hard disk drive gasket of a computer, and the like. Further, it can be suitably used as a cushion molded product and a release molded product for presses such as PCB (printed circuit board) using non-adhesiveness.
  • PCB printed circuit board
  • sealing material for clean equipment such as a gasket for a magnetic recording device (hard disk drive), a sealing material for a device storage such as a semiconductor manufacturing device or a wafer.
  • fuel cell sealing materials such as packing used between fuel cell electrodes and surrounding piping.
  • fuel cell sealing materials such as packing used between fuel cell electrodes and surrounding piping.
  • fuel cell sealing materials such as packing used between fuel cell electrodes and surrounding piping.
  • fuel cell sealing materials such as packing used between fuel cell electrodes and surrounding piping.
  • fuel cell sealing materials such as packing used between fuel cell electrodes and surrounding piping.
  • It can also be applied to the medical field, and is particularly suitably used for an inner lid (including a septum) of a chemical solution transport container, a gasket of a medical instrument, and the like.
  • PTFE-A Modified PTFE fine powder A
  • PTFE-B Homo PTFE fine powder B was obtained by the method described in Comparative Example 3 of International Publication No. 2005/061567 except that the drying temperature was changed to 160 ° C.
  • the obtained PTFE-B was evaluated in the same manner as PTFE-A. The results are shown in Table 1.
  • ⁇ Average primary particle size> The polytetrafluoroethylene aqueous dispersion was diluted with water until the solid content concentration became 0.15% by mass, and the transmittance of 550 nm projection light with respect to the unit length of the obtained diluted latex was determined by a transmission electron micrograph.
  • a calibration curve is created by measuring the number-basis length average particle diameter determined by measuring the constant direction diameter. Using this calibration curve, the number average particle diameter is determined from the measured transmittance of projection light of 550 nm of each sample.
  • Non-melt-processable PTFE fine powder was melted at high temperature, F 19 -NMR measurement was performed, and calculation was performed from signals derived from functional groups in the obtained trace comonomer.
  • the content of PMVE used in Examples of the present application is calculated based on the following formula by performing F 19 -NMR measurement at 360 ° C.
  • the extrusion pressure is a value obtained by measuring the load when the extrusion load is in an equilibrium state in paste extrusion and dividing by the cross-sectional area of the cylinder used for paste extrusion.
  • an extrusion bead stretching test is first performed by the following method to prepare a sample for measuring the breaking strength.
  • the bead obtained by paste extrusion is dried at 230 ° C. for 30 minutes to remove the lubricant.
  • the dried bead is cut to an appropriate length, each end is fixed so that the distance between the clamps is 5.1 cm, and heated to 300 ° C. in an air circulation furnace.
  • the clamp is then released at a stretch rate of 100% / sec until the total stretch is a separation distance corresponding to 2400% and a stretch test is performed.
  • Total stretch is an increase in length due to stretching relative to the bead length (100%) before the stretching test.
  • the drawn bead created under the drawing conditions is cut to an appropriate length and fixed by being sandwiched by a movable jaw having a gauge length of 5.0 cm, and the movable jaw is driven at a speed of 300 mm / min. Measured at room temperature using Shimadzu Corporation), three samples obtained from stretched beads, one from each end of the stretched bead (excluding any neckdown in the clamp range), and One minimum tensile breaking load (force) from the center is defined as the breaking strength.
  • Production Examples 1-8 Per 100 parts by mass of the fine powder of PTFE obtained in Production Example 1 or 2, hydrocarbon oil (“IP Solvent 2028” manufactured by Idemitsu Kosan Co., Ltd.) as an extrusion aid is added and mixed, Allowed to stand for 12 hours. Next, a mixture of fine powder and extrusion aid was put into a 100 ⁇ mm preforming machine and compressed at a pressure of 3 MPa to obtain a preform. Subsequently, the preform was put in a die having an inner diameter of 16 mm ⁇ in an extruder having an inner diameter of 100 mm and paste was extruded to obtain a PTFE molded body.
  • IP Solvent 2028 manufactured by Idemitsu Kosan Co., Ltd.
  • the obtained PTFE molded body was molded (rolled) into a film shape by a calendar roll to obtain an unsintered PTFE film.
  • the hydrocarbon oil was removed by evaporation through a hot-air drying furnace to obtain a strip-shaped unsintered PTFE film having an average thickness of about 300 ⁇ m.
  • semi-firing was further performed under the conditions described in Table 2.
  • the obtained unsintered PTFE film and semi-sintered PTFE film were stretched at the temperatures and stretch ratios shown in Table 2.
  • the physical properties of the obtained porous film (biaxially stretched film) were measured by the following methods. Table 2 shows the results.
  • ⁇ Film density> The mass of the sample cut into a 4.0 cm ⁇ 12.0 cm rectangle is measured with a precision balance, and the film density is calculated from the measured mass and the film thickness by the following formula.
  • ⁇ M / (4.0 ⁇ 12.0 ⁇ t)
  • ⁇ density (g / cm 3 )
  • M mass (g)
  • t film thickness (cm)
  • the film thickness is measured by using a film thickness meter, measuring the total film thickness by stacking five biaxially stretched porous films, and dividing the value by 5 is one film thickness.
  • Vertical matrix tensile strength First, five samples were cut out from the biaxially stretched porous membrane. Each sample has a dimension of 15.0 cm in the longitudinal direction (longitudinal direction, that is, the paste extrusion direction) and 2.0 cm in the lateral direction (width direction, that is, a direction perpendicular to the paste extrusion direction). About five samples, the tensile strength measurement of a vertical direction is performed and the maximum load which each of five samples shows is calculated
  • the vertical matrix tensile strength is determined from the vertical average maximum load, the sample width (2.0 cm), the film thickness (unit: cm), and the porosity using the following formula.
  • Longitudinal matrix tensile strength ⁇ longitudinal average maximum load / (2.0 ⁇ membrane thickness) ⁇ / (1 ⁇ porosity) (Horizontal matrix tensile strength) Five samples were cut from the biaxially stretched porous membrane.
  • Each sample has a dimension of 2.0 cm in the longitudinal direction (longitudinal direction, that is, the paste extrusion direction) and 15.0 cm in the lateral direction (width direction, that is, a direction perpendicular to the paste extrusion direction).
  • the tensile strength of the horizontal direction was measured and the maximum load which each of five samples showed was calculated
  • the transverse average maximum load is obtained in the same manner as in the longitudinal direction, and the transverse matrix tensile strength is obtained using the following formula.
  • Horizontal matrix tensile strength ⁇ horizontal average maximum load / (2.0 ⁇ membrane thickness) ⁇ / (1 ⁇ porosity)
  • the tensile strength is measured using a tensile tester equipped with a 50N load cell, a chuck length of 5.0 cm, and a crosshead speed of 300 mm / min.
  • the porosity is calculated
  • Porosity 1- (Membrane density / PTFE true density)
  • the PTFE true density is 2.2 g / cm 3 .
  • MFP mean flow pore size
  • ⁇ Area ratio of fibril / node> a picture of the PTFE porous film is taken with a scanning electron microscope (SU8020, Hitachi E1030, vapor deposition manufactured by HITACHI) (SEM photograph, magnification 1000 to 5000 times). This photograph is taken into an image processing apparatus (main body name: TV image processor TVIP-4100II manufactured by Nippon Avionics Co., Ltd., control software name: TV image processor image command 4198 manufactured by Ratok System Engineering Co., Ltd.), separated into nodes and fibrils, and only from the nodes And an image consisting only of fibrils.
  • the area ratio of the fibril / node is obtained from the ratio of the total area of the fibril image and the total area of the node image.
  • the PTFE porous membrane and silicone rubber are overlapped and primary vulcanized at 160 ° C for 10 minutes, followed by secondary vulcanization at 180 ° C for 4 hours, 25mm x 50mm x 2mm A thick vulcanized rubber molded composite rubber molded product was produced.
  • the films obtained in the examples and comparative examples were subjected to S45C (outer shape 20.) under the conditions of a load of 500 N / cm 2 , a rotational speed of 0.5 m / second, and a time of 60 minutes using a ring-on-disk type frictional wear tester.
  • a friction and wear test was performed using a ring having a diameter of 5 mm and an inner diameter of 16.5 mm, and the average friction coefficient, the friction coefficient amplitude, and the wear resistance were evaluated.
  • Abrasion resistance was evaluated by visual observation with a stereomicroscope in the wear test section and the following criteria.

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  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un article moulé en caoutchouc composite dans lequel le coefficient de frottement est faible sur une longue période de temps et une non-adhésivité peut être maintenue. L'invention concerne un article moulé contenant un élastomère, et un article moulé en caoutchouc composite qui comprend un film poreux de polytétrafluoroéthylène qui recouvre au moins une partie de l'article moulé, l'article moulé en caoutchouc composite étant caractérisé en ce que le produit de la résistance à la traction de la matrice dans la direction longitudinale et la direction latérale du film poreux de polytétrafluoroéthylène est supérieur ou égal à 30 000 MPa2.
PCT/JP2019/005764 2018-02-20 2019-02-18 Article moulé en caoutchouc composite Ceased WO2019163693A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS521480A (en) * 1975-06-24 1977-01-07 Hitachi Ltd Thermostat
JPS56144954A (en) * 1980-04-15 1981-11-11 Sumitomo Electric Industries Elastic structure
JPH05202217A (ja) * 1991-07-23 1993-08-10 Daikin Ind Ltd ポリテトラフルオロエチレン多孔膜
US20030012905A1 (en) * 1998-02-13 2003-01-16 Zumbrum Michael Allen Flexure endurant composite elastomer compositions
JP2008273199A (ja) * 2007-04-02 2008-11-13 Daikin Ind Ltd シール材
WO2009031610A1 (fr) * 2007-09-05 2009-03-12 Daikin Industries, Ltd. Composite
JP2011183814A (ja) * 2004-04-23 2011-09-22 Gore Enterprise Holdings Inc フッ素ポリマーのバリア材料
JP2015127413A (ja) * 2013-11-29 2015-07-09 ダイキン工業株式会社 多孔質体、高分子電解質膜、フィルター用濾材及びフィルターユニット

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS521480A (en) * 1975-06-24 1977-01-07 Hitachi Ltd Thermostat
JPS56144954A (en) * 1980-04-15 1981-11-11 Sumitomo Electric Industries Elastic structure
JPH05202217A (ja) * 1991-07-23 1993-08-10 Daikin Ind Ltd ポリテトラフルオロエチレン多孔膜
US20030012905A1 (en) * 1998-02-13 2003-01-16 Zumbrum Michael Allen Flexure endurant composite elastomer compositions
JP2011183814A (ja) * 2004-04-23 2011-09-22 Gore Enterprise Holdings Inc フッ素ポリマーのバリア材料
JP2008273199A (ja) * 2007-04-02 2008-11-13 Daikin Ind Ltd シール材
WO2009031610A1 (fr) * 2007-09-05 2009-03-12 Daikin Industries, Ltd. Composite
JP2015127413A (ja) * 2013-11-29 2015-07-09 ダイキン工業株式会社 多孔質体、高分子電解質膜、フィルター用濾材及びフィルターユニット

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