WO2015098338A1 - フッ素ゴム組成物、並びに架橋ゴム成形体及びその製造方法 - Google Patents
フッ素ゴム組成物、並びに架橋ゴム成形体及びその製造方法 Download PDFInfo
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- WO2015098338A1 WO2015098338A1 PCT/JP2014/080027 JP2014080027W WO2015098338A1 WO 2015098338 A1 WO2015098338 A1 WO 2015098338A1 JP 2014080027 W JP2014080027 W JP 2014080027W WO 2015098338 A1 WO2015098338 A1 WO 2015098338A1
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- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09J127/12—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
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- 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
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- 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
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Definitions
- the present invention relates to a fluororubber composition.
- the present invention also relates to a crosslinked rubber molded body represented by a sealing material using the fluororubber composition and a method for producing the same.
- a sealing material gasket, packing, etc.
- a sealing material made of fluoro rubber is known, and fluoro rubber sealing material has relatively good heat resistance and plasma resistance (decomposition resistance by plasma). Therefore, it is also used as a sealing material for a plasma etching apparatus and a plasma CVD apparatus constituting a semiconductor manufacturing apparatus, for example, a sealing material for maintaining a vacuum in a process chamber in which a wafer is processed.
- Fluoro rubber sealant is also used in, for example, a gate part for partitioning a chamber and a transport part in a semiconductor manufacturing apparatus. In this case, compression and release are repeated, and thus an appropriate mechanical strength is required.
- the mechanical strength of the fluoro rubber sealant can be improved by adding an inorganic filler.
- an inorganic filler when a sealing material blended with an inorganic filler is used for semiconductor manufacturing equipment as described above, even when a fluororubber with good plasma resistance is used, the fluororubber used as a sealing material in a harsh plasma environment Ingredients may be etched by plasma, and in this case, the blended inorganic filler is scattered in the chamber (particles are generated), which may lead to problems such as chamber contamination and defective semiconductor products. .
- Patent Document 1 describes a fluorine-containing elastomer composition that does not contain a particulate filler that causes particle generation.
- Patent Document 2 discloses that the amount of the non-organic resin filler or the organic resin filler is suppressed as much as possible in order to suppress the generation of particles in the fluororubber seal material. Are listed.
- Patent Document 2 describes that polytetrafluoroethylene (PTFE) is blended as an organic resin filler in order to ensure mechanical strength and the like, but fluorine containing PTFE as a reinforcing agent is described.
- PTFE polytetrafluoroethylene
- the rubber sealing material is continuously used in a plasma environment, the above-mentioned particle problem does not occur, but it is clear from the examination by the present inventors that PTFE particles are precipitated on the etched sealing material surface and the surface is whitened. became. Such surface deposition (whitening) of the resin may drop in a lump larger than the particles, which may lead to problems such as chamber contamination and semiconductor product defects.
- the present invention provides the following fluororubber composition, cross-linked rubber molded product, and production method thereof.
- a fluororubber composition containing a hydrogen atom-containing fluororubber and a hydrogen atom-containing fluororesin containing a hydrogen atom-containing fluororubber and a hydrogen atom-containing fluororesin.
- the hydrogen atom-containing fluororesin is composed of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer.
- the fluororubber composition according to any one of [1] to [3], which is at least one selected from the group consisting of:
- a crosslinked rubber molded article comprising a crosslinked product of the fluororubber composition according to any one of [1] to [5].
- a method for producing a crosslinked rubber molded body comprising:
- a fluororubber composition capable of forming a crosslinked rubber molded article having no mechanical whitening problem when used in a plasma environment and having excellent mechanical strength.
- the obtained crosslinked rubber molded article does not cause a problem of surface whitening and has excellent mechanical strength, and can be suitably used as a sealing material such as a packing or gasket, particularly as a sealing material for use in semiconductor manufacturing equipment.
- the hydrogen atom-containing fluororubber used in the present invention is a crosslinkable rubber component capable of forming an elastomer having a crosslinked structure (crosslinked rubber) by a crosslinking reaction and contains a hydrogen atom or hydrogen. It is a polymer or copolymer comprising a monomer containing an atom and a fluorine atom as at least one constituent unit, or a fluorine-based thermoplastic elastomer containing a hydrogen atom.
- the cross-linked rubber is one in which rubber elasticity is developed by causing a cross-linking reaction between molecular chains of a cross-linkable rubber component (hydrogen atom-containing fluoro rubber) using a cross-linking agent or the like to give a cross-linked structure.
- a cross-linkable rubber component hydrogen atom-containing fluoro rubber
- hydrogen atom-containing fluororubber examples include, for example, vinylidene fluoride (VDF) -hexafluoropropylene (HFP) copolymer; vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE).
- VDF vinylidene fluoride
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- the fluorine-based thermoplastic elastomer containing a hydrogen atom is not particularly limited.
- “DAIEL THERMO PLASTIC” manufactured by Daikin Industries, Ltd.
- “Cefalsoft” manufactured by Central Glass Co., Ltd.
- the hydrogen atom-containing fluororesin used in the present invention is a resin containing hydrogen atoms and fluorine atoms in the molecule.
- PVDF polyvinylidene fluoride
- VDF vinylidene fluoride
- HFP hexafluoropropylene copolymer Tetrafluoroethylene-ethylene copolymer
- ECTFE Chlorotrifluoroethylene-ethylene copolymer
- PVDF Polyvinyl fluoride
- PVDF Vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer
- PVDF polyvinylidene fluoride
- VDF vinylidene fluoride
- HFP hexafluoropropylene copolymer
- tetrafluoro is difficult to be precipitated on the surface of the crosslinked rubber molded body or has a higher reinforcing effect.
- One or more selected from the group consisting of ethylene-ethylene copolymer (ETFE) and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer (VDF-HFP-TFE copolymer) are preferably used. It is done.
- a fluororubber composition containing a VDF-HFP copolymer as a hydrogen atom-containing fluororesin provides a crosslinked rubber molded article that is excellent in rubber elasticity (smaller in hardness and modulus) while ensuring excellent tensile strength. It is advantageous in terms of obtaining. This advantage is obtained by partially crosslinking the fluororubber composition to obtain a moldable first crosslinked body, and crosslinking the first crosslinked body with ionizing radiation to obtain a second crosslinked body. This is particularly remarkable in the case of producing a crosslinked rubber molded article by the method described later including the second crosslinking step of obtaining
- VDF-HFP copolymer A commercially available product may be used as the VDF-HFP copolymer.
- Examples of commercial products of the VDF-HFP copolymer include “Kynar UltraFlex B” (manufactured by Arkema), “Kynar ADS2” (manufactured by Arkema) and the like under the trade name.
- the content of the fluorine atom-containing fluororesin in the fluororubber composition (the total amount when two or more hydrogen atom-containing fluororesins are used) is 1 to 50 parts by weight per 100 parts by weight of the hydrogen atom-containing fluororubber Is preferably 5 to 20 parts by weight, more preferably 10 to 20 parts by weight.
- Setting the content of the hydrogen atom-containing fluororesin to 1 part by weight or more is advantageous in increasing the mechanical strength (hardness and modulus) of the obtained crosslinked rubber molded product (sealing material or the like). Moreover, by making it 50 parts by weight or less, it is possible to achieve both good mechanical strength and good heat resistance (compression set characteristics).
- the content of the hydrogen atom-containing fluororesin exceeds 50 parts by weight, the content of the elastic hydrogen atom-containing fluororubber is relatively reduced, and heat resistance (compression set properties) is deteriorated.
- content of a hydrogen atom containing fluororesin exceeds 50 weight part, there exists a possibility that precipitation to the surface of the hydrogen atom containing fluororesin in a plasma environment cannot be suppressed effectively.
- the fluororubber composition of the present invention includes a hydrogen atom-containing fluororubber and a hydrogen atom-containing fluororesin, and thus occurs when the crosslinked rubber molded product is used in a plasma environment.
- the problem of surface precipitation (surface whitening) of the obtained fluororesin can be suppressed. This is because when a crosslinked rubber molding (seal material) is used in a plasma environment, the fluororubber component tends to be slightly etched by the plasma, but the structure is similar to that of a hydrogen atom-containing fluororubber.
- the plasma resistance becomes equivalent, and the fluororubber component is etched and decomposed into gas. This is probably because the hydrogen atom-containing fluororesin is also etched and decomposed into gas.
- a perfluoro resin such as PTFE is used, it is less likely to be decomposed by etching than the hydrogen atom-containing fluororubber. It is done.
- a crosslinked rubber molded article having excellent mechanical strength can be provided. This is thought to be because the structure of the hydrogen atom-containing fluororesin is close to that of the hydrogen atom-containing fluororubber and the compatibility with the hydrogen atom-containing fluororubber is high. It is done. Furthermore, according to the fluororubber composition of the present invention, it is possible to provide a crosslinked rubber molded article having good elongation characteristics. This is because the crosslinked rubber molded article has a highly compatible hydrogen atom-containing fluororubber and hydrogen atom-containing fluororesin. This is considered to be because it is composed of a co-continuous phase consisting of
- the hydrogen atom-containing fluororubber crosslinking system may be a peroxide crosslinking system, a polyamine crosslinking system, a polyol crosslinking system, etc., but has a higher heat resistance and plasma resistance and can be suitably applied to semiconductor manufacturing equipment applications. Since a body (sealant etc.) is given, it is preferable that it is a peroxide bridge system.
- the organic peroxide (peroxide crosslinking agent) 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)
- the content of the organic peroxide in the fluororubber composition (the total amount when two or more organic peroxides are used) is, for example, 0.01 to 20 parts by weight per 100 parts by weight of the hydrogen atom-containing fluororubber. It is preferably 0.1 to 10 parts by weight.
- 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 (unsaturated polyfunctional compounds) capable of co-crosslinking with radicals such as -m-phenylene bismaleimide; 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 content of the co-crosslinking agent in the fluororubber composition (the total amount when two or more co-crosslinking agents are used) is, for example, 0.1 to 40 parts by weight per 100 parts by weight of the hydrogen atom-containing fluororubber, The amount is preferably 0.2 to 10 parts by weight.
- the fluororubber composition of the present invention is an anti-aging agent, an antioxidant, a vulcanization accelerator, a processing aid (liquid rubber, oil, plasticizer, Softeners, tackifiers, etc.), stabilizers, silane coupling agents, flame retardants, mold release agents, waxes, lubricants and the like. Only 1 type may be used for an additive and it may use 2 or more types together.
- a crosslinked rubber molded body (sealant) is used for semiconductor manufacturing equipment, volatilization, elution, or precipitation may cause contamination of the manufacturing process or decrease in semiconductor manufacturing efficiency.
- Is preferably as small as possible for example, 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1 part by weight or less per 100 parts by weight of the hydrogen atom-containing fluororubber). It is desirable not to contain.
- the fluororubber composition of the present invention may contain carbon black, silica, alumina, zinc oxide, titanium oxide, clay, talc, diatomaceous earth, barium sulfate, calcium carbonate, magnesium carbonate, calcium oxide, mica, graphite, as necessary.
- Fillers such as aluminum hydroxide, aluminum silicate, hydrotalcite, metal powder, glass powder, ceramic powder can also be included.
- the amount of inorganic filler is It is preferably as small as possible (for example, 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1 part by weight or less per 100 parts by weight of the hydrogen atom-containing fluororubber). It is desirable not to mix.
- the inorganic filler refers to a filler containing a metal element (Ba, Ti, Zn, Al, Mg, Ca, Si, etc.).
- the fluororubber composition of the present invention uniformly contains a hydrogen atom-containing fluororubber, a hydrogen atom-containing fluororesin, a crosslinking agent (such as an organic peroxide and a co-crosslinking agent), and other compounding agents that are added as necessary. It can be prepared by kneading.
- a kneader for example, a conventionally known one such as a mixing roll such as an open roll; a mixer such as a kneader or a Banbury mixer can be used.
- compounding agents may be mixed and kneaded at one time, or after kneading a part of the compounding agents, kneading all the compounding agents in multiple stages such as kneading the remaining compounding agents. You may do it.
- kneading of hydrogen atom-containing fluorororubber and hydrogen atom-containing fluororesin for example, 1) a method of kneading hydrogen atom-containing fluororubber powder and hydrogen atom-containing fluororesin powder using a mixing roll, 2) hydrogen atom A method of melt-kneading the fluorine-containing rubber powder or pellets and the hydrogen atom-containing fluorine resin powder or pellets using a mixer can be used.
- the crosslinked rubber molded article of the present invention is composed of a crosslinked product of the above-described fluororubber composition, surface precipitation (surface whitening) of the fluororesin hardly occurs even when used in a plasma environment, and the mechanical strength is also improved. Are better. Also, good elongation characteristics and heat resistance (compression set characteristics) can be exhibited.
- the crosslinked rubber molded body can typically be a sealing material such as a packing or a gasket.
- the shape of the sealing material is appropriately selected according to the application, and a typical example is an O-ring having a cross-sectional shape of O-type. Since the sealing material which concerns on this invention has the above favorable physical properties, it can be used suitably especially as a sealing material for a semiconductor manufacturing apparatus use.
- the crosslinked rubber molded body can be produced by crosslinking (vulcanizing) the fluororubber composition.
- Crosslinking molding can be performed, for example, by preforming a fluororubber composition as necessary and then press molding using a mold.
- the molding temperature is, for example, about 150 to 220 ° C.
- molding can be performed by feed press molding, injection molding, extrusion molding, or the like.
- secondary crosslinking may be performed at a temperature of about 150 to 280 ° C. as necessary.
- compression set characteristics can be improved even when a hydrogen atom-containing fluororesin having a relatively low melting point is used.
- first cross-linking step in which the fluororubber composition is partially cross-linked to obtain a moldable first cross-linked body, and (2) the first cross-linked body is cross-linked with ionizing radiation to form a second cross-linked cross section.
- Second cross-linking step to obtain a body.
- This production method is preferably performed between the first crosslinking step and the second crosslinking step. (3) It further includes a molding step of molding the first crosslinked body.
- a cross-linking reaction is indispensable for molding into a predetermined shape, it is not suitable for continuous molding such as extrusion molding or injection molding, and it is possible to continuously produce molded bodies by continuously molding. Have difficulty, b) Once the cross-linked structure is formed and the shape is fixed, 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.
- the fluororubber composition is partially cross-linked by any one or more of the above cross-linking systems (preferably a peroxide cross-linking system) and can be molded. Get the 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 fluororubber composition is crosslinked to a formable state.
- “Moldable” means that the molding process itself can be performed and the shape after molding can be maintained. If the fluororubber 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.
- crosslinking by heat partial crosslinking is performed by reducing the amount of the crosslinking agent and / or crosslinking assistant in the fluororubber composition by reducing the amount of the crosslinking agent and / or crosslinking auxiliary agent compared to the above reference system or by adding an additive that inhibits crosslinking. be able to.
- 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.
- 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.
- Molding step It is preferable to include a molding step for molding the first crosslinked body after the first crosslinking step. 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 crosslinked body when the first crosslinked body is not further crosslinked by heat due to factors such as lack of crosslinking agent or crosslinking aid, it differs from the conventional method for producing a crosslinked rubber molded body by heat. Scorch where cross-linking proceeds is difficult to occur. This is also advantageous for continuous molding using melt molding such as extrusion molding or injection molding.
- 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.
- the irradiation amount 500 kGy or less, it is possible to prevent the hydrogen atom-containing fluororesin from melting and to obtain a second crosslinked body (crosslinked rubber molded body) having excellent elongation characteristics. Further, when the main crosslinking step using ionizing radiation is performed, the compression set characteristics can be sufficiently improved even when a hydrogen atom-containing fluororesin having a relatively low melting point is used.
- 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 be about 150 to 280 ° C.
- Examples 1 to 4 Comparative Examples 1 to 5> According to the composition shown in Table 1 (the unit of the blending amount in Table 1 is parts by weight), a predetermined amount of each compounding agent was kneaded with an open roll. Next, the obtained fluororubber composition was press molded at 170 ° C. for 20 minutes, and then heat treated at 200 ° C. for 4 hours to obtain a sealing material (O-ring).
- a sealing material O-ring
- the sealing material of Example 1 does not melt even when heated to 200 ° C. in an air atmosphere, and the kneaded product (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 curve (200 ° C., 15 minutes) in the first crosslinking step of Example 5 were measured using a curast meter (Orientec Co., Ltd.).
- the maximum torque value MH 0 in the reference system and the maximum torque value MH of Example 5 were determined.
- the maximum torque value MH was 10.1% when the maximum torque value MH 0 was 100%.
- FKM 1 Vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE) polymer [“Daiel G902” manufactured by Daikin Industries, Ltd.].
- FKM 2 Vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE) polymer (“Technoflon P959” manufactured by Solvay Specialty Polymers).
- FKM 3 Fluorine-based block polymer of vinylidene fluoride (VDF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE) polymer and tetrafluoroethylene-ethylene polymer (ETFE) Thermoplastic elastomer [Daikin Thermoplastic T-530, manufactured by Daikin Industries, Ltd.].
- VDF vinylidene fluoride
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- ETFE tetrafluoroethylene-ethylene polymer
- Thermoplastic elastomer Thermoplastic elastomer [Daikin 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" manufactured by Daikin Industries, Ltd.]
- VDF-HFP Vinylidene fluoride-hexafluoropropylene copolymer (“Kynar UltraFlex B” manufactured by Arkema).
- PTFE polytetrafluoroethylene [Mitsui / DuPont "Zonyl MP1500” manufactured by Fluorochemical Co., Ltd.].
- FEP Tetrafluoroethylene-hexafluoropropylene copolymer [“Neofluon NC1500” manufactured by Daikin Industries, Ltd.]
- Cross-linking agent 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.].
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- Polymers & Plastics (AREA)
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Abstract
Description
[8] [1]~[5]のいずれかに記載のフッ素ゴム組成物を架橋成形する工程を含む、架橋ゴム成形体の製造方法。
前記第1架橋体を電離性放射線により架橋させて、第2架橋体を得る第2架橋工程と、
を含む、架橋ゴム成形体の製造方法。
〔a〕水素原子含有フッ素ゴム
本発明で用いる水素原子含有フッ素ゴムとは、架橋反応によって架橋構造を有するエラストマー(架橋ゴム)を形成可能な架橋性ゴム成分であり、水素原子を含むか又は水素原子とフッ素原子を含むモノマーを構成単位の少なくとも1つとする重合体又は共重合体からなるもの、又は水素原子を含むフッ素系熱可塑性エラストマーである。架橋ゴムとは、架橋剤等を用いて架橋性ゴム成分(水素原子含有フッ素ゴム)の分子鎖間に架橋反応を起こさせ、架橋構造を持たせることによってゴム弾性を発現させたものである。
本発明の架橋ゴム成形体は、上記フッ素ゴム組成物の架橋物からなるものであるため、プラズマ環境下で使用してもフッ素樹脂の表面析出(表面白化)が生じにくく、機械的強度にも優れている。また、良好な伸び特性及び耐熱性(圧縮永久歪特性)を示し得る。
(2)第1架橋体を電離性放射線により架橋させて、第2架橋体を得る第2架橋工程。
(3)第1架橋体を成形する成形工程
をさらに含む。
a)所定の形状に成形するためには架橋反応が必須であるため、押出成形や射出成形のような連続成形に適しておらず、連続的に成形を行って成形体を連続生産することが困難である、
b)一度架橋構造を形成して形状を固定すると、架橋反応は不可逆的であり、加熱しても溶融せず形状も不可逆的であるため、成形後の形状に何らかの不具合があった場合でも、成形後の材料を再利用して再度成形工程を実施することができない、
といった課題があり、生産効率の向上は困難であると認識されてきた。
本工程では、上記フッ素ゴム組成物を上記いずれか1以上の架橋系(好ましくはパーオキサイド架橋系である。)によって部分的に架橋させて、成形可能な第1架橋体を得る。「部分的に架橋させる」とは、未架橋の状態より架橋度は高いが、架橋剤(共架橋剤のような架橋助剤を含む。)の不足、架橋剤(共架橋剤のような架橋助剤を含む。)の失活、架橋阻害、電離性放射線の線量不足等により、最終製品として必要とされる架橋度には至っていない状態、又は架橋剤(共架橋剤のような架橋助剤を含む。)がゴム組成物中に残存しているにもかかわらず、それ以上熱を加えたり、電離性放射線を照射しても最終製品として必要とされる架橋度には至らない状態をいう。
第1架橋工程の後に、第1架橋体を成形する成形工程を含むことが好ましい。第1架橋体は、成形可能な程度に部分的に架橋されたものであるので、熱溶融させることが可能であり、例えば押出成形や射出成形のような溶融成形を用いた連続成形が可能である。これにより、架橋ゴム成形体の連続生産、ひいては製造コストの削減が可能となる。
本工程にて第1架橋体又はその成形体は、電離性放射線により架橋され、最終製品として必要とされる架橋度が付与され、第2架橋体が得られる。電離性放射線は特に制限されないが、電子線やγ線を好ましく用いることができる。電離性放射線の照射量は、好ましくは10~500kGyであり、より好ましくは30~200kGyである。照射量が10kGy未満であると、十分な架橋度が得られず、所望する機械的強度が得られない傾向にある。一方、照射量を500kGy以下とすることにより、水素原子含有フッ素樹脂の溶融を防止することができるとともに、伸び特性に優れる第2架橋体(架橋ゴム成形体)を得ることができる。また、電離性放射線による本架橋工程を行うと、比較的融点の低い水素原子含有フッ素樹脂を用いる場合であっても、圧縮永久歪特性を十分に高めることができる。
表1に示される配合組成に従って(表1における配合量の単位は重量部である。)、各配合剤の所定量をオープンロールにより混練した。次に、得られたフッ素ゴム組成物を、170℃、20分の条件でプレス成形した後、200℃、4時間の条件で熱処理を施して、シール材(Oリング)を得た。
表2に示される配合組成に従って(表2における配合量の単位は重量部である。)、ニーダーにより水素原子含有フッ素ゴム及び水素原子含有フッ素樹脂の所定量を230℃で混練した後、これに架橋剤及び共架橋剤の所定量を混練して混練物を得た。得られた混練物に対し、200℃、15分の条件で熱架橋を施して第1架橋体を得た(第1架橋工程)。次いで、第1架橋体を、230℃で押出成形して、シール材(Oリング)形状の成形体を得た(成形工程)。シール材形状への押出成形(溶融成形)は容易であった。その後、80kGyの照射量で放射線(γ線)を照射して第2架橋体(架橋ゴム成形体)であるシール材(Oリング)を得た(第2架橋工程)。第1架橋体は、熱溶融性を示し、その成形体を熱溶融させ、再度成形を行うことも容易であった。
〔1〕FKM 1:ビニリデンフルオライド(VDF)-ヘキサフルオロプロピレン(HFP)-テトラフルオロエチレン(TFE)系重合体〔ダイキン工業(株)製「ダイエルG902」〕。
〔2〕FKM 2:ビニリデンフルオライド(VDF)-ヘキサフルオロプロピレン(HFP)-テトラフルオロエチレン(TFE)系重合体〔ソルベイスペシャリティポリマーズ社製「テクノフロンP959」〕。
〔3〕FKM 3:ビニリデンフルオライド(VDF)-ヘキサフルオロプロピレン(HFP)-テトラフルオロエチレン(TFE)系重合体とテトラフルオロエチレン-エチレン系重合体(ETFE)とのブロック重合体であるフッ素系熱可塑性エラストマー〔ダイキン工業(株)製「ダイエルサーモプラスチックT-530」〕。
〔4〕PVDF:ポリフッ化ビニリデン〔株式会社クレハ製「クレハKFポリマー #850」〕。
〔5〕ETFE:テトラフルオロエチレン-エチレン共重合体〔ダイキン工業(株)製「ネオフロンEP610」〕。
〔6〕VDF-HFP:ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体〔アルケマ社製「Kynar UltraFlex B」〕。
〔7〕PTFE:ポリテトラフルオロエチレン〔三井・デュポン フロロケミカル社製「ゾニールMP1500」〕。
〔8〕FEP:テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体〔ダイキン工業(株)製「ネオフロン NC1500」〕。
〔9〕架橋剤:パーヘキサ25B(2,5-ジメチル-2,5-ジ(t-ブチルペルオキシ)ヘキサン)〔日油製「パーヘキサ25B」〕。
〔10〕共架橋剤:トリアリルイソシアヌレート〔日本化成社製「TAIC」〕。
得られたシール材について、下記の項目を測定、評価した。結果を表1及び表2に示す。
JIS K6250に従い、2mmの厚さに作製したシートから、JIS K6251に従い、ダンベル状3号型試験片を型抜きした。この試験片を、500mm/分で引張し、引張強度、破断伸び、100%モジュラスを測定した。また、JIS K6253に従い、タイプAデューロメータ硬さ試験機にてシートの硬度を測定した。これらの試験はすべて25℃の温度下で行った。
出力1000W、照射時間6時間、真空度1torr、ガス比O2:CF4=190:10の条件でプラズマを照射した後、シール材表面を目視で観察して、樹脂析出(表面白化)の有無を確認した。
上記条件でのプラズマ照射を行う前のシール材の重量W0と、プラズマ照射後のシール材の重量W1を測定し、下記式:
重量減少率(%)={(W0-W1)/W0}×100%
に基づき、重量減少率を算出した。比較例2~5及び7~8において重量減少率が高いのは、表面に析出したパーフルオロ樹脂の脱落に起因するものと推察される。
JIS K 6262に準拠して、試料(AS214 Oリング)を圧縮率25%で鉄板に挟み込み、200℃×72時間の条件で電気炉で加温後、圧縮解放し、30分間放冷後の試料の圧縮永久歪を下記式:
圧縮永久歪(%)={(T0-T1)/(T0-T2)}×100%
に基づいて算出した。T0は試験前の試料の高さ、T1は30分間放冷後の試料の高さ、T2はスペーサ-の厚み(高さ)である。
Claims (12)
- 水素原子含有フッ素ゴムと、水素原子含有フッ素樹脂とを含むフッ素ゴム組成物。
- 前記水素原子含有フッ素樹脂の含有量が、前記水素原子含有フッ素ゴム100重量部あたり1~50重量部である、請求項1に記載のフッ素ゴム組成物。
- 有機過酸化物と、共架橋剤とをさらに含む、請求項1に記載のフッ素ゴム組成物。
- 前記水素原子含有フッ素樹脂は、ポリフッ化ビニリデン、ビニリデンフルオライド-ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン-エチレン共重合体及びフッ化ビニリデン-ヘキサフルオロプロピレン-テトラフルオロエチレン共重合体からなる群から選択される少なくとも1種である、請求項1に記載のフッ素ゴム組成物。
- 無機充填剤を含まない、請求項1に記載のフッ素ゴム組成物。
- 請求項1に記載のフッ素ゴム組成物の架橋物からなる架橋ゴム成形体。
- 半導体製造装置用シール材である、請求項6に記載の架橋ゴム成形体。
- 請求項1に記載のフッ素ゴム組成物を架橋成形する工程を含む、架橋ゴム成形体の製造方法。
- 請求項1に記載のフッ素ゴム組成物を部分的に架橋させて、成形可能な第1架橋体を得る第1架橋工程と、
前記第1架橋体を電離性放射線により架橋させて、第2架橋体を得る第2架橋工程と、
を含む、架橋ゴム成形体の製造方法。 - 前記第1架橋工程と前記第2架橋工程との間に、前記第1架橋体を成形する成形工程をさらに含む、請求項9に記載の製造方法。
- 前記第1架橋体を押出成形又は射出成形により成形する、請求項10に記載の製造方法。
- 前記第1架橋工程において前記フッ素ゴム組成物を熱によって架橋させる、請求項9に記載の製造方法。
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JP2015127358A (ja) * | 2013-12-27 | 2015-07-09 | 日本バルカー工業株式会社 | 架橋ゴム成形体の製造方法 |
JP2017538023A (ja) * | 2014-12-19 | 2017-12-21 | スリーエム イノベイティブ プロパティズ カンパニー | 硬化性部分フッ素化ポリマー組成物 |
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JP2019172897A (ja) * | 2018-03-29 | 2019-10-10 | 三菱電線工業株式会社 | 未架橋ゴム組成物並びにそれを用いて製造されるゴム製品及びその製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
TWI617608B (zh) | 2018-03-11 |
KR20160105778A (ko) | 2016-09-07 |
EP3088461A1 (en) | 2016-11-02 |
SG11201605258XA (en) | 2016-08-30 |
JPWO2015098338A1 (ja) | 2017-03-23 |
CN105849180B (zh) | 2018-09-21 |
US20170002153A1 (en) | 2017-01-05 |
JP6134391B2 (ja) | 2017-05-24 |
CN105849180A (zh) | 2016-08-10 |
US9908980B2 (en) | 2018-03-06 |
EP3088461A4 (en) | 2017-08-16 |
TW201533118A (zh) | 2015-09-01 |
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