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WO2015098339A1 - Procédé de fabrication de moulage en caoutchouc réticulé - Google Patents

Procédé de fabrication de moulage en caoutchouc réticulé Download PDF

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Publication number
WO2015098339A1
WO2015098339A1 PCT/JP2014/080028 JP2014080028W WO2015098339A1 WO 2015098339 A1 WO2015098339 A1 WO 2015098339A1 JP 2014080028 W JP2014080028 W JP 2014080028W WO 2015098339 A1 WO2015098339 A1 WO 2015098339A1
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Prior art keywords
cross
rubber
crosslinking
molding
crosslinked
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Ceased
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PCT/JP2014/080028
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English (en)
Japanese (ja)
Inventor
直樹 大住
清華 戸田
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Nippon Valqua Industries Ltd
Nihon Valqua Kogyo KK
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Nippon Valqua Industries Ltd
Nihon Valqua Kogyo KK
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Publication of WO2015098339A1 publication Critical patent/WO2015098339A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1009—Fluorinated polymers, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/20—Homopolymers or copolymers of hexafluoropropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C09K2200/062—Polyethylene

Definitions

  • the present invention relates to a method for producing a crosslinked rubber molded body represented by a sealing material.
  • an elastomer having a crosslinked structure (hereinafter, also referred to as “crosslinked rubber”) is used as a sealing material such as a gasket and packing used in various applications.
  • a sealing material such as a gasket and packing used in various applications.
  • fluororubber and the like are excellent in heat resistance.
  • JP 2005-113035 A discloses a fluororubber seal material for semiconductor manufacturing equipment.
  • the cross-linked rubber is a rubber that expresses rubber elasticity by causing a cross-linking reaction between molecular chains of a rubber component (elastomer-forming component) using a cross-linking agent or the like to give a cross-linked structure.
  • thermoplastic elastomers there are elastomers called “thermoplastic elastomers” in addition to crosslinked rubber.
  • thermoplastic elastomers include blends of resin and rubber, dynamically cross-linked resin and rubber, block copolymers of resin component and rubber component, etc.
  • the resin component is below the melting point of the resin.
  • Working as a pseudo-crosslinking site the shape is fixed and rubber elasticity is developed.
  • a cross-linking reaction is essential for molding into a predetermined shape, it is not suitable for extrusion molding or injection molding, and it is difficult to continuously produce molded bodies by continuously molding.
  • the cross-linking reaction is irreversible, and even when heated, the shape is irreversible, so even if there is any defect in the shape after molding, The molding process cannot be performed again by reusing the molded material. It has been recognized that it is difficult to improve production efficiency.
  • thermoplastic elastomers are suitable for extrusion molding and injection molding because the resin part melts above the melting point of the resin that composes it, and the shape is fixed below the melting point. Therefore, the molded material can be reused and re-molded.
  • thermoplastic elastomer containing a resin component that is thermally melted is inferior in heat resistance as compared with a crosslinked rubber having a similar structure, and in particular, compression set characteristics showing distortion due to thermal deterioration are greatly inferior.
  • Patent Documents 2 and 3 describe that a radiation-based crosslinking is performed after molding on a fluorine-based thermoplastic elastomer, but it can also be used as a sealing material used in a high-temperature environment by using such radiation crosslinking. The compression set characteristics cannot be improved to a certain extent.
  • thermoplastic elastomer having a fluororesin described in Patent Document 2 as a continuous phase and a cross-linked fluororubber particle as a dispersed phase has a higher hardness and flexibility than a cross-linked rubber when subjected to radiation cross-linking after molding.
  • Patent Document 1 describes that after heat-pressure molding (one type of thermal crosslinking) of the fluororubber composition, a thermal crosslinking treatment and a radiation crosslinking treatment are performed. It does not provide a method for producing a crosslinked rubber molded product that allows reuse of the material after molding.
  • the object of the present invention is to produce a crosslinked rubber molded article that can be continuously molded by melt molding as in the case of using a thermoplastic elastomer, and that the material can be reused in the molding process, and exhibits excellent compression set characteristics. It is to provide a method that can do this.
  • the present invention provides a method for producing a crosslinked rubber molded body shown below.
  • a first crosslinking step in which a rubber composition containing a crosslinkable rubber component is partially crosslinked to obtain a moldable first crosslinked body;
  • a method for producing a crosslinked rubber molded body comprising:
  • crosslinkable rubber component is at least one selected from the group consisting of fluorine rubber and ethylene propylene rubber.
  • the method of the present invention it is possible to produce a crosslinked rubber molded body that can be continuously molded by melt molding and reuse of materials in the molding process, and exhibits excellent compression set characteristics.
  • the obtained crosslinked rubber molded article can be suitably used as a sealing material such as packing or gasket.
  • the method for producing a crosslinked rubber molded body according to the present invention comprises: (1) a first crosslinking step in which a rubber composition containing a crosslinkable rubber component is partially crosslinked to obtain a moldable first crosslinked body; and (2) the first crosslinked body is crosslinked with ionizing radiation. , Including a second crosslinking step for obtaining a second crosslinked body, preferably between the first crosslinking step and the second crosslinking step, (3) It further includes a molding step of molding the first crosslinked body.
  • a first crosslinking step in which a rubber composition containing a crosslinkable rubber component is partially crosslinked to obtain a moldable first crosslinked body
  • the first crosslinked body is crosslinked with ionizing radiation.
  • the rubber composition provided to this process contains a crosslinkable rubber component.
  • the crosslinkable rubber component is not particularly limited as long as it can form an elastomer (crosslinked rubber) having the above-mentioned crosslinked structure by a crosslinking reaction.
  • Specific examples of the crosslinkable rubber component include, for example, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), nitrile rubber (NBR: acrylonitrile butadiene rubber), hydrogenated nitrile rubber (HNBR; hydrogenated acrylonitrile butadiene rubber).
  • fluoro rubber FKM
  • perfluoroelastomer FFKM
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • FKM fluoro rubber
  • FKM perfluoroelastomer
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • FKM fluorine rubber
  • EPM ethylene-propylene rubber
  • crosslinkable rubber component only one type may be used, or two or more types may be used in combination.
  • fluororubber examples include, for example, vinylidene fluoride (VDF) -hexafluoropropylene (HFP) polymer; vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE).
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • TFE tetrafluoroethylene
  • FFKM perfluoroelastomer
  • TFE tetrafluoroethylene
  • PMVE perfluoromethyl vinyl ether
  • the crosslinking system of the crosslinkable rubber component is not particularly limited.
  • a peroxide crosslinking system, a polyamine crosslinking system, and a polyol crosslinking system are ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) is a peroxide cross-linking system, sulfur cross-linking system, quinoid cross-linking system, and resin cross-linking system, and perfluoroelastomer (FFKM) is a peroxide cross-linking system, bisphenol cross-linking system, triazine cross-linking system, oxazole cross-linking system, imidazole. Examples thereof include a crosslinking system and a thiazole crosslinking system.
  • the crosslinkable rubber component may be cross-linked by any one cross-linking system, or may be cross-linked by two or more cross-linking systems.
  • the peroxide crosslinking agent (radical polymerization initiator) used in the peroxide crosslinking system is, for example, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (example of commercially available product: “Perhexa 25B manufactured by NOF Corporation”.
  • Dicumyl peroxide (example of commercial product: “Parkmill D” manufactured by NOF); 2,4-dichlorobenzoyl peroxide; di-t-butyl peroxide; t-butyl dicumyl peroxide; benzoyl peroxide (commercially available)
  • triallyl isocyanurate (example of commercially available product: “TAIC” manufactured by Nippon Kasei Co., Ltd.); triallyl cyanurate; triallyl formal; triallyl trimellitate; N, N ′
  • examples include compounds (polyfunctional monomers) capable of co-crosslinking with radicals such as -m-phenylenebismaleimide; dipropargyl terephthalate; diallyl phthalate; tetraallyl terephthalamide.
  • the co-crosslinking agent preferably contains triallyl isocyanurate from the viewpoint of reactivity and heat resistance of the obtained crosslinked rubber molded article.
  • the rubber composition used in this step is optionally filled with a filler (reinforcing agent), processing aid, anti-aging agent, antioxidant, vulcanization accelerator, stabilizer, silane coupling agent, flame retardant.
  • a filler forcing agent
  • processing aid include thermoplastic resin, liquid rubber, oil, plasticizer, softener, and tackifier.
  • crosslinkable rubber component when the crosslinkable rubber component is FKM or FFKM, a fluororesin or particles thereof may be contained as a filler, and liquid fluororubber may be contained as a processing aid.
  • crosslinkable rubber component is EPM or EPDM, for example, paraffinic oil can be contained as a processing aid. Only 1 type may be used for said additive and it may use 2 or more types together.
  • liquid fluororubber products are, for example, “DAIEL G-101” manufactured by Daikin Industries, Ltd. and “SIFEL series” (SIFEL 8000 series, etc.) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the rubber composition can also contain a thermoplastic resin or a thermoplastic elastomer.
  • a thermoplastic resin or a thermoplastic elastomer for example, when the crosslinkable rubber component is FKM or FFKM, blending a fluororesin or a fluoroplastic elastomer may be advantageous for moldability. Further, when the crosslinkable rubber component is EPM or EPDM, blending polyethylene or polypropylene may be advantageous for moldability. Only one type of thermoplastic resin or thermoplastic elastomer may be used, or two or more types may be used in combination.
  • the total amount is 300 weights with respect to 100 parts by weight of the crosslinkable rubber component. Part or less, preferably 200 parts by weight or less.
  • fluororesin examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • tetrafluoroethylene-ethylene copolymer examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer.
  • EFE Polymer
  • PCTFE polychlorotrifluoroethylene
  • ECTFE chlorotrifluoroethylene-ethylene copolymer
  • PVDF polyvinylidene fluoride
  • PVDF polyvinyl fluoride
  • VDF-HFP copolymer a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer
  • VDF-HFP-TFE copolymer a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer
  • a fluororesin may be used individually by 1 type and may use 2 or more types together.
  • the rubber composition is partially cross-linked by any one or more of the cross-linking systems to obtain a moldable first cross-linked body.
  • Partially crosslinked means that the degree of crosslinking is higher than that in an uncrosslinked state, but the crosslinking agent (including a crosslinking aid such as a co-crosslinking agent) is insufficient, and the crosslinking agent (cross-linking such as a co-crosslinking agent).
  • a vulcanization curve of a rubber composition having a horizontal axis as a time and a vertical axis as a torque value is obtained by a curast meter (rheometer, vulcanization / curing characteristic tester).
  • the rubber composition is preferably partially crosslinked so that the maximum torque value MH is 2 to 70% of the maximum torque value MH 0 in the reference system.
  • the maximum torque value MH is more preferably 3 to 40% of MH 0 .
  • the reference system includes a crosslinking agent (including a crosslinking aid such as a co-crosslinking agent) in a sufficient amount, and when a sufficient amount of heat is applied, the maximum degree of crosslinking that can be developed. It refers to a rubber composition that can form a crosslinked product. More specifically, the cross-linked body refers to a cross-linked body in which the degree of cross-linking has progressed to a state where it does not melt even when the cross-linked body is heated to the decomposition temperature of the cross-linked portion in an air atmosphere.
  • a crosslinking agent including a crosslinking aid such as a co-crosslinking agent
  • a sufficient amount of the crosslinking agent in various crosslinking systems and a crosslinking temperature and a crosslinking time for achieving the maximum degree of crosslinking that can be expressed can be selected based on common technical knowledge in the field.
  • the decomposition temperature of the crosslinked portion is, for example, about 200 ° C. in the case of fluorine rubber crosslinked by a peroxide crosslinking system, and about 230 ° C. in the case of fluorine rubber crosslinked by a polyol crosslinking system.
  • the uncrosslinked rubber composition is crosslinked until it can be molded.
  • “Moldable” means that the molding process itself can be performed and the shape after molding can be maintained. If the rubber composition remains uncrosslinked, the fluidity is too high to be molded. On the other hand, if the degree of crosslinking is too high, shaping becomes difficult due to excessive progress of shape fixing by crosslinking, and melting by heat becomes impossible.
  • the cross-linking method in this step may be cross-linking by heat, cross-linking by ionizing radiation, or a combination thereof.
  • cross-linking by heat partial cross-linking is performed by reducing the amount of the cross-linking agent and / or cross-linking auxiliary agent from the above reference system, or by adding an additive that inhibits cross-linking to the rubber composition. Can do.
  • the degree of crosslinking can be controlled by adjusting the blending amount of the crosslinking agent and / or crosslinking aid and the blending amount of the crosslinking inhibitor.
  • crosslinking is performed by irradiation with ionizing radiation, there is a tendency that partial crosslinking occurs even if the irradiation amount is sufficiently large.
  • the degree of crosslinking can be controlled by adjusting the irradiation amount.
  • additives that inhibit crosslinking include 2,2-bis (4-hydroxyphenyl) hexafluoropropane; o-phenylphenol; hydroquinone; 2,4-diphenyl-4-methyl-1-pentene; -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane; amine-ketone antioxidants (eg poly 2,2,4-trimethyl-1,2-dihydroquinoline); aromatic secondary amines Anti-aging agent (for example, 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine); Monophenol type anti-aging agent (for example, 2,6-di-t-butyl-4-methylphenol); Bisphenol type Anti-aging agent (for example, 4,4′-thiobis (3-methyl-6-tert-butylphenol); benzimidazole anti-aging agent (eg, If, and 2-mercaptobenzimidazole).
  • amine-ketone antioxidants eg poly 2,2,4-trimethyl-1
  • cross-linking by heat is preferably used from the viewpoint of preventing an increase in manufacturing cost.
  • an electron beam or ⁇ -ray can be used as the ionizing radiation as in the second crosslinking step described later.
  • the manufacturing method of the present invention preferably includes a molding process for molding the first crosslinked body. Since the first crosslinked body is partially crosslinked to the extent that it can be molded, it can be melted by heat, for example, continuous molding using melt molding such as extrusion molding or injection molding is possible. is there. This makes it possible to continuously produce a crosslinked rubber molded body, and thus to reduce manufacturing costs.
  • the first cross-linked body can be melted by heat, there is some problem in the shape after molding, especially when it is not cross-linked by heat due to factors such as lack of cross-linking agent or cross-linking aid.
  • the molded material can be reused by re-melting the molded body and performing the molding process again. Reuse of such materials is also advantageous for reducing manufacturing costs.
  • the melt molding (extrusion molding or injection molding) of the first crosslinked body can be performed in the same manner as a general thermoplastic resin or thermoplastic elastomer.
  • the molding temperature can be, for example, 150 to 320 ° C.
  • Second cross-linking step In this step, the first cross-linked body or the molded body thereof is cross-linked by ionizing radiation to give a degree of cross-linking required as a final product, thereby obtaining a second cross-linked body.
  • ionizing radiation is not particularly limited, electron beams and ⁇ rays can be preferably used.
  • the dose of ionizing radiation is preferably 10 to 500 kGy, more preferably 30 to 200 kGy. When the irradiation dose is less than 10 kGy, a sufficient degree of crosslinking cannot be obtained, and the desired mechanical strength tends to be not obtained. Moreover, when the irradiation amount exceeds 500 kGy, the second crosslinked body may be deteriorated by ionizing radiation.
  • heat treatment may be applied to the second cross-linked body using an oven (electric furnace, vacuum electric furnace) or the like, if necessary.
  • the heat treatment conditions can usually be 100 to 320 ° C. (for example, about 170 to 230 ° C. or about 170 to 200 ° C.).
  • the crosslinked rubber molded body (second crosslinked body) obtained by the production method of the present invention exhibits excellent heat resistance (compression set properties) and has a rubber component as a continuous phase (thermoplastic to the rubber composition). When a resin is blended, a co-continuous phase can be taken.), Having a suitable hardness and excellent flexibility.
  • Example 1 According to the compounding composition shown in Table 1 (the unit of the compounding amount in Table 1 is parts by weight), after kneading predetermined amounts of the crosslinkable rubber component, the crosslinking agent and the co-crosslinking agent with an open roll, the obtained kneading The product was thermally crosslinked at 200 ° C. for 15 minutes to obtain a first crosslinked product (first crosslinking step). Next, the first crosslinked body was extrusion molded at 230 ° C. to obtain a molded body having a sealing material (O-ring) shape (molding process). Extrusion molding (melt molding) into a sealing material shape was easy.
  • Table 1 the unit of the compounding amount in Table 1 is parts by weight
  • a sealing material which is a second crosslinked body (crosslinked rubber molded body) (second crosslinking step).
  • the first cross-linked body exhibited heat melting property, and it was easy to heat melt the molded body and perform molding again.
  • the obtained sealing material exhibited excellent compression set characteristics.
  • Examples 2 to 8> According to the composition shown in Table 1, after kneading a predetermined amount of the crosslinkable rubber component, the thermoplastic elastomer and the fluororesin at 230 ° C. with a kneader, the predetermined amount of the crosslinking agent and the co-crosslinking agent is kneaded into the kneaded product. Got. Using the obtained kneaded material, the 1st bridge
  • thermoplastic elastomer predetermined amounts of thermoplastic elastomer, crosslinking agent and co-crosslinking agent were kneaded.
  • the obtained kneaded product is subjected to press molding at 230 ° C. for 15 minutes to obtain a sealing material (O-ring) shaped molded body, and then irradiated with radiation at an irradiation dose of 80 kGy to obtain a sealing material. Obtained. Since the thermoplastic elastomer is used, the kneaded product can be melt-molded. Also, the molded product can be melted by heat after press molding, and molding can be performed again. It was inferior to the permanent set characteristics.
  • thermoplastic elastomer is extruded at 230 ° C. to obtain a molded material having a sealing material (O-ring) shape, and then irradiated with radiation at a dose of 80 kGy to obtain a sealing material. It was.
  • the thermoplastic elastomer can be melt-molded, and it was possible to heat-mold and re-mold the molded body after extrusion molding, but the obtained sealing material was inferior in compression set characteristics. It was.
  • ⁇ Comparative Example 3> According to the composition shown in Table 1, predetermined amounts of the crosslinkable rubber component, the crosslinking agent, and the co-crosslinking agent were kneaded with an open roll. The obtained kneaded product was subjected to press molding at 170 ° C. for 15 minutes, and then heat treated at 200 ° C. for 4 hours to obtain a sealing material (O-ring). The kneaded product can be melt-molded itself such as extrusion, but the melt-molding conditions are extremely limited due to the occurrence of scorch (a phenomenon in which crosslinking proceeds by heat). When scorching occurs during molding, 1) molding defects such as surface roughness occur during extrusion.
  • scorch a phenomenon in which crosslinking proceeds by heat
  • cross-linked rubber molded body (seal material) after press molding in this comparative example did not melt even when reheated, and it was impossible to re-mold by reusing it.
  • FKM 1 Vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE) polymer [“Daiel G912” manufactured by Daikin Industries, Ltd.].
  • FKM 2 Tetrafluoroethylene (TFE) -propylene (Pr) polymer [Aflas 150P manufactured by Asahi Glass Co., Ltd.
  • Thermoplastic Elastomer A fluorinated thermoplastic elastomer that is a block polymer in which a fluororubber part and a fluororesin part are bonded (“Dai-L Thermoplastic T-530” manufactured by Daikin Industries, Ltd.).
  • PVDF polyvinylidene fluoride [“Kureha KF Polymer # 850” manufactured by Kureha Corporation].
  • ETFE Tetrafluoroethylene-ethylene copolymer
  • Neofluon EP610 Tetrafluoroethylene-ethylene copolymer
  • Crosslinker Perhexa 25B (2,5-dimethyl-2,5-di (t-butylperoxy) hexane) [“Perhexa 25B” manufactured by NOF Corporation].
  • Co-crosslinking agent triallyl isocyanurate [“TAIC” manufactured by Nippon Kasei Co., Ltd.].
  • the sealing material of Comparative Example 3 does not melt even when heated to 200 ° C. in an air atmosphere, and the kneaded material (material before press molding) contains a sufficient amount of a crosslinking agent and a co-crosslinking agent. Since sufficient heat is applied for crosslinking, the kneaded product can be regarded as the above-mentioned reference system.
  • the vulcanization curve (200 ° C., 15 minutes) of this reference system and the vulcanization curves (200 ° C., 15 minutes) in the first crosslinking step of Examples 1 to 8 were used with a curast meter (Orientec).
  • the maximum torque value MH 0 in the reference system and the maximum torque value MH of each example were determined. Table 1 shows the maximum torque value MH (%) when the maximum torque value MH 0 is set to 100%.
  • Table 1 shows measured values of compression set of the sealing materials obtained in each of Examples and Comparative Examples.
  • the compression set is the most important evaluation item for evaluating the life (heat resistance) of the rubber seal material.
  • the compression set was measured as follows.
  • Compression set (%) ⁇ (T0 ⁇ T1) / (T0 ⁇ T2) ⁇ ⁇ 100% Calculated based on T0 is the height of the sample before the test, T1 is the height of the sample after being allowed to cool for 30 minutes, and T2 is the thickness (height) of the spacer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Sealing Material Composition (AREA)
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Abstract

La présente invention concerne un procédé de fabrication de moulages en caoutchouc réticulé, le procédé comprenant : une première étape de réticulation permettant de réticuler en partie une composition de caoutchouc contenant des constituants caoutchouc réticulable afin d'obtenir un premier produit réticulé pouvant être moulé ; et une seconde étape de réticulation permettant de réticuler le premier produit réticulé à l'aide d'un rayonnement ionisant afin d'obtenir un second produit réticulé. L'invention concerne également une étape de moulage permettant de mouler le premier produit réticulé qui est de préférence intercalée entre la première étape de réticulation et la seconde étape de réticulation. Ledit moulage peut être un moulage par extrusion, un moulage par injection, etc. Le moulage en caoutchouc réticulé obtenu peut par exemple être utilisé de manière avantageuse comme matériau d'étanchéité.
PCT/JP2014/080028 2013-12-27 2014-11-13 Procédé de fabrication de moulage en caoutchouc réticulé Ceased WO2015098339A1 (fr)

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JP6942218B2 (ja) * 2017-11-06 2021-09-29 三菱電線工業株式会社 シール材
KR102591386B1 (ko) * 2019-05-20 2023-10-19 다이킨 고교 가부시키가이샤 불소 함유 엘라스토머 조성물 및 물품
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JP2020128544A (ja) * 2020-04-27 2020-08-27 三菱電線工業株式会社 シール材
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