WO2023042510A1 - Fluorine-containing elastomer composition - Google Patents

Fluorine-containing elastomer composition Download PDF

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Publication number
WO2023042510A1
WO2023042510A1 PCT/JP2022/024835 JP2022024835W WO2023042510A1 WO 2023042510 A1 WO2023042510 A1 WO 2023042510A1 JP 2022024835 W JP2022024835 W JP 2022024835W WO 2023042510 A1 WO2023042510 A1 WO 2023042510A1
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fluorine
mol
containing elastomer
perfluoro
weight
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PCT/JP2022/024835
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French (fr)
Japanese (ja)
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佑介 村上
洋之 佐野
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ユニマテック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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
    • 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
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/16—Sealings between relatively-moving surfaces

Definitions

  • the present invention relates to a fluorine-containing elastomer composition. More particularly, it relates to a fluorine-containing elastomer composition suitably used as a molding material for plasma irradiation applications such as seals for semiconductor manufacturing equipment.
  • Seals for semiconductor manufacturing equipment are applied as face seals used in processing chambers for processing such as etching or forming thin films on the surface of semiconductor substrates such as silicon wafers. , low gas permeability, low dust emission (low dust generation from seals), etc. are required.
  • plasma is irradiated in an atmosphere of oxygen or CF4 , so gases such as oxygen and halogen are excited, and as a result, seals for semiconductor manufacturing equipment are likely to deteriorate and Problems such as the surface becoming brittle and degraded and brittle materials scattering and adhering to the silicon wafer are observed.
  • cyano group-containing perfluoroelastomers and the like which have excellent heat resistance, are used at high temperatures such as 300°C.
  • inorganic fillers such as silica, barium sulfate, alumina, and aluminum silicate have been added. Although the suppression effect is recognized, the presence of elements such as titanium, barium, and aluminum themselves is disliked in the semiconductor industry.
  • fluorine-containing elastomers such as vinylidene fluoride [VdF]/hexafluoropropylene [HFP] copolymer, VdF/HFP/tetrafluoroethylene [TFE] terpolymer, and other fluorinated fluoroelastomers , TFE/perfluoromethyl vinyl ether [PMVE] copolymer and other perfluorinated perfluoroelastomers have superior performance compared to other rubbers in terms of heat resistance, chemical resistance, etc. Therefore, it is widely used as a molding material for sealing materials such as O-rings, gaskets and packings in various industrial fields including automobiles.
  • perfluoroelastomers which are polymers of perfluoromonomers such as TFE, HFP, and PMVE, have superior heat resistance and chemical resistance compared to fluorine-containing elastomers other than perfluoroelastomers. It is suitable for O-rings used in semiconductor manufacturing equipment.
  • a filler that captures radicals such as carbon black is added.
  • such fillers are contaminants as foreign matter, they are limited in that they can only be applied to areas that are not directly exposed to plasma.
  • plasma resistance is ensured by increasing the TFE content to 72.8 to 74.0 mol%, but the rubber hardness becomes very hard, and there is a high possibility that problems will occur during assembly. I have a problem.
  • the recommended hardness for assembly is 75 or less.
  • the service life of an O-ring is set at 70% or less, preferably 50% or less after 500 hours at a target temperature of 300°C. Or at 315° C., the value (Shore A hardness) for 70 hours is only given.
  • Patent Document 2 describes (a) a peroxide-crosslinkable tetrafluoroethylene-perfluoro(alkyl vinyl ether) obtained by copolymerizing a fluorine-containing olefin in the presence of a bromine- and/or iodine-containing crosslink-point-forming compound.
  • fluororubber compositions are said to give vulcanizates exhibiting good vulcanizate physical properties.
  • Patent Document 3 0.5 to 20 parts by weight of at least one of isoindolinone-based pigments, quinacridone-based pigments, diketopyrrolopyrrole-based pigments and anthraquinone-based pigments is contained in 100 parts by weight of the fluorine-containing elastomer.
  • a fluorine-containing elastomer composition that improves the plasma resistance of vulcanized products has been disclosed. It is difficult to say that it has sufficient heat resistance even at around 250°C.
  • An object of the present invention is to provide a fluorine-containing elastomer having a cyano group as a crosslinkable group, the vulcanizate of which is used under plasma irradiation conditions and exhibits excellent heat resistance even under high temperature conditions of 300°C or higher. To provide an elastomer.
  • Such an object of the present invention is (A) 60.0 to 80.0 mol% of tetrafluoroethylene, (B) 19.8 to 35.0 mol% of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) and (C) perfluoro 0.2-0.9 parts by weight of quinacridone and bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexa per 100 parts by weight of fluorine-containing elastomer having a copolymer composition of 0.2-5.0 mol% of unsaturated nitrile compound This is achieved by a fluorine-containing elastomer composition containing 0.2 to 5 parts by weight of fluoropropane.
  • the fluorine-containing elastomer composition according to the present invention is vulcanized using a bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a vulcanizing agent after blending a specific amount of quinacridone.
  • a sealing material for a semiconductor manufacturing apparatus which is effective even when used at a high temperature of 300° C., which is an excellent effect.
  • the resulting sealing material exhibits excellent heat resistance even if it does not contain fillers other than quinacridone, such as inorganic fillers such as carbon black and silica.
  • fillers other than quinacridone such as inorganic fillers such as carbon black and silica.
  • 168 hours, 300 hours and 500 hours of compression set values show good high temperature heat resistance.
  • the fluorine-containing elastomer used in the present invention comprises (A) 60.0 to 80.0 mol %, preferably 60 to 68.8 mol % of tetrafluoroethylene, and (B) perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether). It has a copolymer composition of 19.8 to 35.0 mol%, preferably 31 to 35 mol%, and (C) a perfluorounsaturated nitrile compound of 0.2 to 5.0 mol%, preferably 0.5 to 3.0 mol%.
  • the copolymerization ratio of tetrafluoroethylene of the component (A) is lower than this, the heat resistance will be inferior and the adhesiveness to silicon, metal, silica glass, etc. will be strong. However, since it behaves more like a resin than an elastomer, the sealing performance deteriorates and the workability deteriorates.
  • the copolymerization ratio of component (B) perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether) is lower than this, the copolymerization ratio of tetrafluoroethylene may relatively increase. As a result, the copolymer is in a state close to that of a resin, resulting in a significant decrease in sealing performance. On the other hand, if the copolymerization ratio is higher than this, the tackiness in particular will be remarkably deteriorated.
  • perfluoro (lower alkyl vinyl ether) as the component (B) comonomer, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether) and the like are generally used. Further, as the perfluoro (lower alkoxy lower alkyl vinyl ether), for example, the following are used, Among these, those in which the C n F 2n+1 group is a CF 3 group are particularly preferred.
  • the perfluorounsaturated nitrile compound of the (C) component comonomer as the cross-linking site monomer, the following compounds are used.
  • the copolymerization amount of the perfluorounsaturated nitrile compound as component (C) is 0.2 to 5.0 mol%, preferably 0.5 to 3.0 mol%, which is necessary for the crosslinkable group.
  • the copolymerization reaction using each of these monomers is generally carried out by charging water, a fluorine-containing emulsifier such as ammonium perfluorooctanoate, and a buffering agent such as potassium dihydrogen phosphate into a stainless steel autoclave.
  • Fluoroethylene, perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether) and perfluoro unsaturated nitrile compound are sequentially charged, heated to about 50-80°C, and then a radical generator such as ammonium persulfate is added. and a redox initiator formed from a reducing agent such as sodium sulfite.
  • the reaction pressure is preferably maintained at about 0.75 to 0.85 MPa. Therefore, in order to increase the internal pressure of the reaction vessel, which decreases with the progress of the reaction, the reaction is continued while additionally adding these three monomer mixtures. preferably.
  • fluorinated olefins examples include vinylidene fluoride, monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, chlorotrifluoroethylene, and dichlorodifluoroethylene.
  • vinyl compounds include ethylene, propylene, 1-butene, isobutylene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, and trifluorostyrene.
  • quinacridone (melting point: 390°C) is added in an amount of 0.2 to 0.9 parts by weight, preferably 0.2 to 0.8 parts by weight, more preferably 0.2 to 0.4 parts by weight, per 100 parts by weight of the fluoroelastomer. used at a rate of If the quinacridone is used in a smaller proportion, the heat resistance at high temperatures of 300°C or higher becomes poor, while if the quinacridone is used in a larger proportion, the dispersibility becomes poor, resulting in visible agglomeration. Lumps are formed, which in turn can become fracture initiation points.
  • Patent Document 4 100 parts by weight of a perfluoroelastomer having a cyano group as a crosslinkable group, 0.2 to 5 parts by weight of a bisamidoxime compound vulcanizing agent, which is also used as a vulcanizing agent in the present invention, and a melting point of 300°C or higher are added.
  • a perfluoroelastomer composition comprising 0.005 to 0.3 parts by weight of a colorant is disclosed, and the colorant is quinacridone.
  • the addition of quinacridone is only for the purpose of coloring, and the examples show an aspect in which 0.1 part by weight, which is less than the amount specified in the present invention, is used. However, it does not disclose the technical idea of the present invention for the purpose of improving heat resistance.
  • a perfluoroelastomer having a copolymer composition of 30 to 24 mol % of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) as component (B) is used. It is stated that if the copolymerization ratio is higher than this, the tackiness will be significantly deteriorated. In contrast, in the present invention, the preferred range of component (B) is set to 31 to 35 mol% without particularly deteriorating the adhesiveness, which means that the preferred range of component (A) is 60 to 68.8 mol%. It is also related to setting
  • the fluorine - containing elastomer includes a n: 1 to 10
  • a bisamidoxime compound represented by or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a vulcanizing agent is 0.2 to 5 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. It is used by adding in the proportion of parts by weight.
  • composition shown in the examples of Patent Document 5 contains carbon black as a reinforcing material, so it is difficult to apply it in some applications such as applications that require a high degree of cleanliness. Further improvement in heat resistance is required from the values of compression set at 275°C or 300°C for 70 hours in the examples. Moreover, in Patent Document 6, silica is essential, and the problem still remains in terms of plasma resistance.
  • Preparation of the fluorine-containing elastomer composition comprising the above essential components is carried out, for example, by kneading using a twin roll or the like at about 30 to 100°C, and cross-linking is carried out at about 100 to 250°C for about 10 to 10°C. It is carried out by heating for 120 minutes. If secondary vulcanization is carried out, it is carried out at about 90°-300° C., and oven vulcanization is preferably carried out with a stepwise temperature increase as described in the examples below.
  • TFE was added at 92-100g/hr, PMVE at 92-100g/hr, and CPeVE at 3.9-4.3g/hr, respectively, while the autoclave pressure was maintained at 0.78-0.87MPa. .
  • the partial addition was stopped, and the state was maintained for an additional hour.
  • the autoclave was cooled and purged of residual gas to obtain 7.7 kg of aqueous latex having a solids concentration of 25% by weight.
  • the resulting aqueous latex was added to a mixture of 0.5 L of a 26% by weight magnesium chloride aqueous solution and 6 L of ethanol to coagulate, washed with water, and dried at 110°C for 10 hours to give a white rubbery ternary 2 kg of copolymer was obtained (yield 99%).
  • This rubber-like terpolymer had a Mooney viscosity ML 1+10 (121° C.) of 88, and was confirmed to have the following composition from infrared absorption spectrum and NMR analysis. TFE 65.4 mol% FMVE 33.3 mol% CPeVE 1.3 mol%
  • Example 2 In Example 1, 3.0 parts by weight of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was used instead of the bisamidoxime compound, and the amount of quinacridone was changed to 0.40 parts by weight. .
  • Comparative example 1 In Example 1, the amount of quinacridone was changed to 0.05 parts by weight.
  • Comparative example 2 In Example 1, the amount of quinacridone was changed to 0.1 parts by weight.
  • a composition obtained by blending a specific amount of quinacridone and a bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with the fluorine-containing elastomer used in the present invention is vulcanized and molded.
  • the resulting sealing material such as an O-ring does not discolor or bloom even under high temperature conditions of 300° C. or higher, has excellent heat resistance, and can maintain good sealing performance.

Abstract

This fluorine-containing elastomer composition is obtained by blending 0.2-0.9 parts by weight of quinacridone and 0.2-5 parts by weight of a bis-amidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro propane, with respect to 100 parts by weight of a fluorine-containing elastomer having a copolymerization compositional makeup comprising (A) 60.0-80.0 mol% of tetrafluoroethylene, (B) 19.8-35.0 mol% of perfluoro(lower alkyl vinyl ether) or perfluoro(lower alkoxy lower alkyl vinyl ether), and (C) 0.2-5.0 mol% of a perfluoro unsaturated nitrile compound. In a case where a cyano group is used as a crosslinkable group in the fluorine-containing elastomer, a vulcanizate of the fluorine-containing elastomer composition exhibits excellent heat resistance even when being placed in a high temperature condition of at least 300℃ and used in a plasma irradiation condition.

Description

含フッ素エラストマー組成物Fluorinated elastomer composition
　本発明は、含フッ素エラストマー組成物に関する。さらに詳しくは、半導体製造装置用シール等のプラズマ照射用途の成形材料として好適に用いられる含フッ素エラストマー組成物に関する。 The present invention relates to a fluorine-containing elastomer composition. More particularly, it relates to a fluorine-containing elastomer composition suitably used as a molding material for plasma irradiation applications such as seals for semiconductor manufacturing equipment.
　半導体製造装置用シールは、半導体の基板であるシリコンウェハー等の表面にエッチング加工あるいは薄膜を形成させるなどの処理をするための加工室等に用いられる面シールとして適用されるものであり、耐熱性、低ガス透過性、低発塵性(シールからの塵の発生が少ないこと)などが要求される。シリコンウェハーエッチング処理時などには、酸素あるいはCF4雰囲気下などでプラズマ照射されるため、酸素あるいはハロゲン等のガスが励起された状態となり、その結果半導体製造装置用シールは劣化し易く、またその表面が脆くなり、劣化物や脆化物が飛散して、シリコンウェハー上に付着するなどの不具合がみられる。 Seals for semiconductor manufacturing equipment are applied as face seals used in processing chambers for processing such as etching or forming thin films on the surface of semiconductor substrates such as silicon wafers. , low gas permeability, low dust emission (low dust generation from seals), etc. are required. During etching of silicon wafers, etc., plasma is irradiated in an atmosphere of oxygen or CF4 , so gases such as oxygen and halogen are excited, and as a result, seals for semiconductor manufacturing equipment are likely to deteriorate and Problems such as the surface becoming brittle and degraded and brittle materials scattering and adhering to the silicon wafer are observed.
　ところで、半導体製造装置においては、300℃といった高温での使用要求に対して耐熱性にすぐれたシアノ基含有パーフルオロエラストマー等が使用されている。一方、耐プラズマ性向上のために、シリカ、硫酸バリウム、アルミナ、珪酸アルミニウム等の無機充填剤を添加することが行われており、これら無機充填剤の添加はプラズマ照射環境下での重量減少の抑制に効果が認められるものの、チタン、バリウム、アルミニウムといった元素自体の存在が半導体業界では嫌われていることもあり、無機充填剤の使用を最低限とする材料であることが好ましい。 By the way, in semiconductor manufacturing equipment, cyano group-containing perfluoroelastomers and the like, which have excellent heat resistance, are used at high temperatures such as 300°C. On the other hand, in order to improve plasma resistance, inorganic fillers such as silica, barium sulfate, alumina, and aluminum silicate have been added. Although the suppression effect is recognized, the presence of elements such as titanium, barium, and aluminum themselves is disliked in the semiconductor industry.
　ここで、含フッ素エラストマーである、フッ化ビニリデン[VdF]/ヘキサフルオロプロピレン[HFP]共重合体、VdF/HFP/テトラフルオロエチレン[TFE]3元共重合体等のフッ素化されたフルオロエラストマーや、TFE/パーフルオロメチルビニルエーテル[PMVE]共重合体などの過フッ素化されたパーフルオロエラストマーは、耐熱性、耐薬品性などの点で他のゴムと比べて優れた性能を有していることから、自動車をはじめ各種工業分野でＯリング、ガスケット、パッキン等のシール材の成形材料として広く使用されている。 Here, fluorine-containing elastomers such as vinylidene fluoride [VdF]/hexafluoropropylene [HFP] copolymer, VdF/HFP/tetrafluoroethylene [TFE] terpolymer, and other fluorinated fluoroelastomers , TFE/perfluoromethyl vinyl ether [PMVE] copolymer and other perfluorinated perfluoroelastomers have superior performance compared to other rubbers in terms of heat resistance, chemical resistance, etc. Therefore, it is widely used as a molding material for sealing materials such as O-rings, gaskets and packings in various industrial fields including automobiles.
　なかでも、パーフルオロモノマーであるTFE、HFP、PMVE等の重合体であるパーフルオロエラストマーは、パーフルオロエラストマー以外の含フッ素エラストマーと比較して、より優れた耐熱性と耐薬品性とを有しており、半導体製造装置に用いられるＯリングとして適している。ただし、単純にパーフルオロポリマーを架橋しただけでは、十分な耐熱性を確保できないことから、カーボンブラック等のラジカルを補足する充填剤がそこに配合されるが、一方で耐プラズマ性を考慮した場合、こういった充填剤は異物としてコンタミ源となることから、プラズマが直接当たらない部位しか適用できないなどの制限がある。 Among them, perfluoroelastomers, which are polymers of perfluoromonomers such as TFE, HFP, and PMVE, have superior heat resistance and chemical resistance compared to fluorine-containing elastomers other than perfluoroelastomers. It is suitable for O-rings used in semiconductor manufacturing equipment. However, since sufficient heat resistance cannot be ensured simply by cross-linking the perfluoropolymer, a filler that captures radicals such as carbon black is added. However, since such fillers are contaminants as foreign matter, they are limited in that they can only be applied to areas that are not directly exposed to plasma.
　かかる制限に対し本出願人は先に、半導体製造装置の高温使用環境において使用される、すぐれた耐熱性を示すシアノ基含有パーフルオロエラストマー(含フッ素エラストマー)およびその加硫剤として、(A)テトラフルオロエチレン72.8～74.0モル％、(B)パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)26.8～24.0モル％および(C)パーフルオロ不飽和ニトリル化合物0.2～3.0モル％の共重合組成を有する含フッ素エラストマー100重量部当り、0.2～5重量部のビスアミドキシム化合物を加硫剤として配合せしめた含フッ素エラストマー組成物を提案している(特許文献１)。 In response to such restrictions, the present applicant has previously proposed (A) Tetrafluoroethylene 72.8 to 74.0 mol%, (B) perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) 26.8 to 24.0 mol% and (C) perfluorounsaturated nitrile compound 0.2 to 3.0 mol% A fluorine-containing elastomer composition has been proposed in which 0.2 to 5 parts by weight of a bisamidoxime compound is compounded as a vulcanizing agent per 100 parts by weight of a fluorine-containing elastomer having a copolymer composition (Patent Document 1).
　ここで開示されている発明では、TFE含量を72.8～74.0モル％と増加させることで耐プラズマ性を確保する一方で、ゴム硬度が大変硬くなり、組付け時に問題が発生する可能性が高いといった課題がある。一般に、組付けに望ましい硬さ(Duro A, PEAK)は75以下が目安とされている。 In the invention disclosed here, plasma resistance is ensured by increasing the TFE content to 72.8 to 74.0 mol%, but the rubber hardness becomes very hard, and there is a high possibility that problems will occur during assembly. I have a problem. In general, the recommended hardness for assembly (Duro A, PEAK) is 75 or less.
　また一般的に、Ｏリングの使用寿命は、対象温度300℃で500時間後に圧縮永久歪70％以下、好ましくは50％以下が目安とされているが、そこに開示されているのは300℃または315℃で、70時間の値(ショアーＡ硬さ)が示されているにすぎない。 In general, the service life of an O-ring is set at 70% or less, preferably 50% or less after 500 hours at a target temperature of 300°C. Or at 315° C., the value (Shore A hardness) for 70 hours is only given.
　特許文献２には、(a)臭素および/またはヨウ素含有架橋点形成化合物の存在下で含フッ素オレフィンを共重合反応させて得られたパーオキサイド架橋可能なテトラフルオロエチレン-パーフルオロ(アルキルビニルエーテル)共重合体エラストマーまたはフッ化ビニリデン-ヘキサフルオロプロペン系共重合体エラストマー、(b)有機過酸化物架橋剤、(c)多官能性不飽和化合物共架橋剤および(d)トリアリルイソシアヌレート重合体を含有してなり、カーボンブラックおよび金属含有充填剤を含有しないフッ素ゴム組成物が開示されており、このフッ素組成物は良好な加硫物性を示す加硫物を与えるとされている。しかしながら、その実施例に示される加硫物の200℃、70時間における圧縮永久歪値あるいは250℃、70時間での空気老化試験の結果からみて、半導体用途などで要求される300℃における十分な耐熱性能を有しているとはいい難いものとなっている。 Patent Document 2 describes (a) a peroxide-crosslinkable tetrafluoroethylene-perfluoro(alkyl vinyl ether) obtained by copolymerizing a fluorine-containing olefin in the presence of a bromine- and/or iodine-containing crosslink-point-forming compound. Copolymer elastomer or vinylidene fluoride-hexafluoropropene copolymer elastomer, (b) organic peroxide cross-linking agent, (c) polyfunctional unsaturated compound co-cross-linking agent and (d) triallyl isocyanurate polymer and is free of carbon black and metal-containing fillers, which fluororubber compositions are said to give vulcanizates exhibiting good vulcanizate physical properties. However, judging from the compression set value at 200°C for 70 hours or the air aging test at 250°C for 70 hours of the vulcanizates shown in the examples, it was found that sufficient heat resistance at 300°C was required for semiconductor applications. It is difficult to say that it has heat resistance performance.
　一方、特許文献３には、含フッ素エラストマー100重量部に対して、イソインドリノン系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料およびアントラキノン系顔料の少なくとも一種0.5～20重量部を含有してなり、加硫製品の耐プラズマ性を向上させる含フッ素エラストマー組成物が開示されているが、圧縮永久歪率の測定が200℃、70時間で行われていることから、300℃以上はもちろん、250℃近傍においても十分な耐熱性能を有しているとは言い難い。 On the other hand, in Patent Document 3, 0.5 to 20 parts by weight of at least one of isoindolinone-based pigments, quinacridone-based pigments, diketopyrrolopyrrole-based pigments and anthraquinone-based pigments is contained in 100 parts by weight of the fluorine-containing elastomer. A fluorine-containing elastomer composition that improves the plasma resistance of vulcanized products has been disclosed. It is difficult to say that it has sufficient heat resistance even at around 250°C.
特開２００９―１６１６６２号公報JP 2009-161662 A 特開２００５―３４４０７４号公報JP-A-2005-344074 特許第４，７２０，５０１号公報Patent No. 4,720,501 特開２０１３―２１６７７１号公報JP 2013-216771 A 特許第３，０８２，６２６号公報Patent No. 3,082,626 ＷＯ２００８／０４１５５７WO2008/041557
　本発明の目的は、シアノ基を架橋性基とする含フッ素エラストマーにおいて、この加硫物がプラズマ照射条件下で使用され、300℃以上といった高温条件下においてもすぐれた耐熱性を示すといった含フッ素エラストマーを提供することにある。 An object of the present invention is to provide a fluorine-containing elastomer having a cyano group as a crosslinkable group, the vulcanizate of which is used under plasma irradiation conditions and exhibits excellent heat resistance even under high temperature conditions of 300°C or higher. To provide an elastomer.
　かかる本発明の目的は、(A)テトラフルオロエチレン60.0～80.0モル％、(B)パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)19.8～35.0モル％および(C)パーフルオロ不飽和ニトリル化合物0.2～5.0モル％の共重合組成を有する含フッ素エラストマー100重量部当り、キナクリドン0.2～0.9重量部およびビスアミドキシム化合物または2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン0.2～5重量部を配合した含フッ素エラストマー組成物によって達成される。 Such an object of the present invention is (A) 60.0 to 80.0 mol% of tetrafluoroethylene, (B) 19.8 to 35.0 mol% of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) and (C) perfluoro 0.2-0.9 parts by weight of quinacridone and bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexa per 100 parts by weight of fluorine-containing elastomer having a copolymer composition of 0.2-5.0 mol% of unsaturated nitrile compound This is achieved by a fluorine-containing elastomer composition containing 0.2 to 5 parts by weight of fluoropropane.
　本発明に係る含フッ素エラストマー組成物は、キナクリドンを特定量配合した上で、ビスアミドキシム化合物または2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンを加硫剤として加硫成形することにより、300℃といった高温下での使用においても有効な半導体製造装置用シール材を形成させることができるといったすぐれた効果を奏する。得られたシール材は、キナクリドン以外の充填剤、例えばカーボンブラック、シリカ等の無機充填剤を含有していなくともすぐれた耐熱性を示し、具体的には後記実施例に示される通り、300℃、168時間、300時間および500時間での圧縮永久歪値によって示されるような良好な高温耐熱性を示している。 The fluorine-containing elastomer composition according to the present invention is vulcanized using a bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a vulcanizing agent after blending a specific amount of quinacridone. By doing so, it is possible to form a sealing material for a semiconductor manufacturing apparatus which is effective even when used at a high temperature of 300° C., which is an excellent effect. The resulting sealing material exhibits excellent heat resistance even if it does not contain fillers other than quinacridone, such as inorganic fillers such as carbon black and silica. , 168 hours, 300 hours and 500 hours of compression set values show good high temperature heat resistance.
　本発明で用いられる含フッ素エラストマーは、(A)テトラフルオロエチレン60.0～80.0モル％、好ましくは60～68.8モル％、(B)パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)19.8～35.0モル％、好ましくは31～35モル％、および(C)パーフルオロ不飽和ニトリル化合物0.2～5.0モル％、好ましくは0.5～3.0モル％の共重合組成を有する。 The fluorine-containing elastomer used in the present invention comprises (A) 60.0 to 80.0 mol %, preferably 60 to 68.8 mol % of tetrafluoroethylene, and (B) perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether). It has a copolymer composition of 19.8 to 35.0 mol%, preferably 31 to 35 mol%, and (C) a perfluorounsaturated nitrile compound of 0.2 to 5.0 mol%, preferably 0.5 to 3.0 mol%.
　(A)成分のテトラフルオロエチレンの共重合割合がこれよりも低いと、耐熱性の面で劣り、またシリコン、金属、シリカガラス等への粘着性が強くなり、一方これよりも高い共重合割合では、エラストマーというよりは樹脂的挙動を示すため、シール性能が悪化し、また加工性に劣るようになる。 If the copolymerization ratio of tetrafluoroethylene of the component (A) is lower than this, the heat resistance will be inferior and the adhesiveness to silicon, metal, silica glass, etc. will be strong. However, since it behaves more like a resin than an elastomer, the sealing performance deteriorates and the workability deteriorates.
　また、(B)成分のパーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)の共重合割合がこれよりも低いと、相対的にテトラフルオロエチレンの共重合割合が増加することもあって、共重合体が樹脂に近い状態となり、シール性能の低下が著しくなる。一方、これよりも共重合割合が高いと、特に粘着性が著しく悪化するようになる。 If the copolymerization ratio of component (B) perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether) is lower than this, the copolymerization ratio of tetrafluoroethylene may relatively increase. As a result, the copolymer is in a state close to that of a resin, resulting in a significant decrease in sealing performance. On the other hand, if the copolymerization ratio is higher than this, the tackiness in particular will be remarkably deteriorated.
　(B)成分共単量体のパーフルオロ(低級アルキルビニルエーテル)としては、一般にはパーフルオロ(メチルビニルエーテル)、パーフルオロ(エチルビニルエーテル)、パーフルオロ(プロピルビニルエーテル)等が用いられる。また、パーフルオロ(低級アルコキシ低級アルキルビニルエーテル)としては、例えば次のようなものが用いられ、
Figure JPOXMLDOC01-appb-I000001
これらの中で、特にCnF2n+1基がCF3基であるものが好んで用いられる。 As the perfluoro (lower alkyl vinyl ether) as the component (B) comonomer, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether) and the like are generally used. Further, as the perfluoro (lower alkoxy lower alkyl vinyl ether), for example, the following are used,
Figure JPOXMLDOC01-appb-I000001
Among these, those in which the C n F 2n+1 group is a CF 3 group are particularly preferred.
  また、架橋サイト単量体としての(C)成分共単量体のパーフルオロ不飽和ニトリル化合物としては、次のようなものが用いられる。
Figure JPOXMLDOC01-appb-I000002
Also, as the perfluorounsaturated nitrile compound of the (C) component comonomer as the cross-linking site monomer, the following compounds are used.
Figure JPOXMLDOC01-appb-I000002
　なお、(C)成分のパーフルオロ不飽和ニトリル化合物の共重合量は、架橋性基として必要な0.2～5.0モル％、好ましくは0.5～3.0モル％とされる。 The copolymerization amount of the perfluorounsaturated nitrile compound as component (C) is 0.2 to 5.0 mol%, preferably 0.5 to 3.0 mol%, which is necessary for the crosslinkable group.
　これら各単量体を用いての共重合反応は、一般にステンレス鋼製オートクレーブ中に水、パーフルオロオクタン酸アンモニウム等の含フッ素系乳化剤およびリン酸二水素カリウム等の緩衝剤を仕込んだ後、テトラフルオロエチレン、パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)およびパーフルオロ不飽和ニトリル化合物を順次仕込み、約50～80℃に昇温させた後、過硫酸アンモニウム等のラジカル発生剤および亜硫酸ナトリウム等の還元剤より形成されるレドックス系開始剤を添加することにより行われる。反応圧力は、約0.75～0.85MPa程度に保たれることが好ましく、このため反応の進行と共に低下する反応容器内圧力を上げるため、これら3種の単量体混合物を追加分添しながら反応を行うことが好ましい。 The copolymerization reaction using each of these monomers is generally carried out by charging water, a fluorine-containing emulsifier such as ammonium perfluorooctanoate, and a buffering agent such as potassium dihydrogen phosphate into a stainless steel autoclave. Fluoroethylene, perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether) and perfluoro unsaturated nitrile compound are sequentially charged, heated to about 50-80°C, and then a radical generator such as ammonium persulfate is added. and a redox initiator formed from a reducing agent such as sodium sulfite. The reaction pressure is preferably maintained at about 0.75 to 0.85 MPa. Therefore, in order to increase the internal pressure of the reaction vessel, which decreases with the progress of the reaction, the reaction is continued while additionally adding these three monomer mixtures. preferably.
　以上の成分を必須成分とする３元共重合体中には、共重合反応を阻害せずかつ加硫物性を損なわない程度(約20モル％以下)の他のフッ素化オレフィンや各種ビニル化合物などを共重合させることもできる。他のフッ素化オレフィンとしては、例えばフッ化ビニリデン、モノフルオロエチレン、トリフルオロエチレン、トリフルオロプロピレン、ペンタフルオロプロピレン、ヘキサフルオロプロピレン、ヘキサフルオロイソブチレン、クロロトリフルオロエチレン、ジクロロジフルオロエチレン等が用いられ、またビニル化合物としては、例えばエチレン、プロピレン、1-ブテン、イソブチレン、メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン、トリフルオロスチレン等が用いられる。 In the terpolymer having the above components as essential components, other fluorinated olefins and various vinyl compounds, etc., to the extent that they do not interfere with the copolymerization reaction and do not impair the physical properties of vulcanization (about 20 mol% or less) can also be copolymerized. Examples of other fluorinated olefins include vinylidene fluoride, monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, chlorotrifluoroethylene, and dichlorodifluoroethylene. Examples of vinyl compounds include ethylene, propylene, 1-butene, isobutylene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, and trifluorostyrene.
　かかる3元共重合体よりなる含フッ素エラストマーには、キナクリドン(融点390℃)が含フッ素エラストマー100重量部当り0.2～0.9重量部、好ましくは0.2～0.8重量部、さらに好ましくは0.2～0.4重量部の割合で用いられる。キナクリドンがこれより少ない割合で用いられると、300℃以上といった高温条件下における耐熱性が劣るようになり、一方これより多い割合で用いられると、分散性に欠けるようになり、その結果目視できる凝集塊が生じ、ひいては破断起点となりうるようになってしまう。 In the fluoroelastomer comprising such a terpolymer, quinacridone (melting point: 390°C) is added in an amount of 0.2 to 0.9 parts by weight, preferably 0.2 to 0.8 parts by weight, more preferably 0.2 to 0.4 parts by weight, per 100 parts by weight of the fluoroelastomer. used at a rate of If the quinacridone is used in a smaller proportion, the heat resistance at high temperatures of 300°C or higher becomes poor, while if the quinacridone is used in a larger proportion, the dispersibility becomes poor, resulting in visible agglomeration. Lumps are formed, which in turn can become fracture initiation points.
　なお、特許文献４には、架橋性基としてシアノ基を有するパーフルオロエラストマー100重量部に、本発明においても加硫剤として用いるビスアミドキシム化合物加硫剤0.2～5重量部および融点300℃ 以上の着色剤0.005～0.3重量部を配合してなるパーフルオロエラストマー組成物が開示され、着色剤として、キナクリドンが挙げられている。この特許文献に開示された発明では、キナクリドンの添加が着色を目的とするに止まっており、実施例では本発明で規定する添加量を下回る0.1重量部が用いられた態様が示されているに過ぎず、そこには耐熱性の改善を目的とする本願発明の技術的思想は開示されているものではない。 In Patent Document 4, 100 parts by weight of a perfluoroelastomer having a cyano group as a crosslinkable group, 0.2 to 5 parts by weight of a bisamidoxime compound vulcanizing agent, which is also used as a vulcanizing agent in the present invention, and a melting point of 300°C or higher are added. A perfluoroelastomer composition comprising 0.005 to 0.3 parts by weight of a colorant is disclosed, and the colorant is quinacridone. In the invention disclosed in this patent document, the addition of quinacridone is only for the purpose of coloring, and the examples show an aspect in which 0.1 part by weight, which is less than the amount specified in the present invention, is used. However, it does not disclose the technical idea of the present invention for the purpose of improving heat resistance.
　また、この特許文献では(B)成分であるパーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)が30～24モル％の共重合組成を有するパーフルオロエラストマーが用いられており、これよりも共重合割合が高いと特に粘着性が著しく悪化するようになると述べられている。これに対して本発明では、特に粘着性を悪化させることなく(B)成分の好ましい範囲を31～35モル％に設定しており、これは(A)成分の好ましい範囲を60～68.8モル％と設定したことも関連している。 In addition, in this patent document, a perfluoroelastomer having a copolymer composition of 30 to 24 mol % of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether) as component (B) is used. It is stated that if the copolymerization ratio is higher than this, the tackiness will be significantly deteriorated. In contrast, in the present invention, the preferred range of component (B) is set to 31 to 35 mol% without particularly deteriorating the adhesiveness, which means that the preferred range of component (A) is 60 to 68.8 mol%. It is also related to setting
　含フッ素エラストマーには、特許文献５～６に記載される如き、一般式
　　　HON=C(NH2)(CF2)nC(NH2)=NOH
　　　　　　　　　　n：1～10
で表されるビスアミドキシム化合物または2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンが加硫剤として、含フッ素エラストマー100重量部当り0.2～5重量部、好ましくは0.5～2重量部の割合で添加して用いられる。 The fluorine - containing elastomer includes a
n: 1 to 10
A bisamidoxime compound represented by or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane as a vulcanizing agent is 0.2 to 5 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. It is used by adding in the proportion of parts by weight.
　なお、この特許文献５の実施例に示されている組成物は、カーボンブラックが補強材として配合されているため、高度に清浄性が要求される用途等一部の用途においてはその適用が難しい可能性があり、また実施例中の275℃または300℃、70時間における圧縮永久歪の値から耐熱性に対するさらなる向上が求められる。また、特許文献６では、シリカを必須としており、やはり耐プラズマ性の点で課題が残っている。 It should be noted that the composition shown in the examples of Patent Document 5 contains carbon black as a reinforcing material, so it is difficult to apply it in some applications such as applications that require a high degree of cleanliness. Further improvement in heat resistance is required from the values of compression set at 275°C or 300°C for 70 hours in the examples. Moreover, in Patent Document 6, silica is essential, and the problem still remains in terms of plasma resistance.
　以上の必須成分よりなる含フッ素エラストマー組成物の調製は、例えば2本ロール等を用いて約30～100℃で混練することにより行われ、それの架橋は、約100～250℃で約10～120分間加熱することによって行われる。二次加硫を行う場合には、約90～300℃で行われ、下記実施例に記載される如く、段階的な昇温でオーブン加硫が行われることが好ましい。 Preparation of the fluorine-containing elastomer composition comprising the above essential components is carried out, for example, by kneading using a twin roll or the like at about 30 to 100°C, and cross-linking is carried out at about 100 to 250°C for about 10 to 10°C. It is carried out by heating for 120 minutes. If secondary vulcanization is carried out, it is carried out at about 90°-300° C., and oven vulcanization is preferably carried out with a stepwise temperature increase as described in the examples below.
　次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
　参考例
　内容積10Lのステンレス鋼製オートクレーブ中に、蒸留水5.0kg、パーフルオロオクタン酸アンモニウム90gおよびリン酸二水素カリウム78gを仕込んだ後、オートクレーブ内を窒素で置換し、次いで減圧した。そこに、
　　　テトラフルオロエチレン〔TFE〕　　　　　　　　　　　　　　130g
　　　パーフルオロ(メチルビニルエーテル)〔PMVE〕　　　 　　　　130g
　　　パーフルオロ(3-オキサ-8-シアノ-1-オクテン)〔CPeVE〕　　　 15g
　　　　　　　CF2=CFO(CF2)4CN
を順次仕込み、60℃に昇温させた後、過硫酸アンモニウム7gおよび亜硫酸ナトリウム1gを溶解させた0.3Lの水溶液を添加し、重合反応を開始させた。 Reference Example A stainless steel autoclave having an internal volume of 10 L was charged with 5.0 kg of distilled water, 90 g of ammonium perfluorooctanoate and 78 g of potassium dihydrogen phosphate. there,
Tetrafluoroethylene [TFE] 130g
Perfluoro(methyl vinyl ether) [PMVE] 130g
Perfluoro(3-oxa-8-cyano-1-octene) [CPeVE] 15g
CF2 =CFO( CF2 ) 4CN
were sequentially charged and the temperature was raised to 60° C., 0.3 L of aqueous solution in which 7 g of ammonium persulfate and 1 g of sodium sulfite were dissolved was added to initiate the polymerization reaction.
　重合反応中、TFEを92～100g/hr、PMVEを92～100g/hr、CPeVEを3.9～4.3g/hrの分添速度でそれぞれ添加し、その間のオートクレーブの圧力を0.78～0.87MPaに保った。重合反応開始時から8.9時間後に分添を停止し、そのままの状態をさらに1時間保った。オートクレーブを冷却し、残ガスをパージして、固形分濃度25重量％の水性ラテックスを7.7kg得た。得られた水性ラテックスを、26重量％塩化マグネシウム水溶液0.5Lとエタノール6Lと混合液中に加えて凝析させた後水洗し、110℃で10時間の乾燥を行って、白色のゴム状3元共重合体を2kg(収率99％)得た。 During the polymerization reaction, TFE was added at 92-100g/hr, PMVE at 92-100g/hr, and CPeVE at 3.9-4.3g/hr, respectively, while the autoclave pressure was maintained at 0.78-0.87MPa. . After 8.9 hours from the start of the polymerization reaction, the partial addition was stopped, and the state was maintained for an additional hour. The autoclave was cooled and purged of residual gas to obtain 7.7 kg of aqueous latex having a solids concentration of 25% by weight. The resulting aqueous latex was added to a mixture of 0.5 L of a 26% by weight magnesium chloride aqueous solution and 6 L of ethanol to coagulate, washed with water, and dried at 110°C for 10 hours to give a white rubbery ternary 2 kg of copolymer was obtained (yield 99%).
　このゴム状3元共重合体は、ムーニー粘度ML1+10(121℃)が88で、赤外線吸収スペクトルおよびNMR分析から、次のような組成であることが確認された。
　　　　　　　　　　　　TFE　　  65.4モル％
　　　　　　　　　　　　FMVE　　 33.3モル％
　　　　　　　　　　　　CPeVE　　 1.3モル％ This rubber-like terpolymer had a Mooney viscosity ML 1+10 (121° C.) of 88, and was confirmed to have the following composition from infrared absorption spectrum and NMR analysis.
TFE 65.4 mol%
FMVE 33.3 mol%
CPeVE 1.3 mol%
　実施例１
　テトラフルオロエチレン-パーフルオロ(メチルビニルエーテル)- パーフルオロ(3-オキサ-8-シアノ-1-オクテン)〔モル比65.4：33.3：1.3〕3元共重合体100重量部に、キナクリドン0.30重量部およびビスアミドキシム化合物 HON=C(NH2)(CF2)4C(NH2)=NOH 0.7重量部を加え、2本ロールミル上で30～100℃の温度で混練した。混練物を180℃で30分間プレス加硫(一次加硫)した後、次の条件下でのオーブン加硫(二次加硫)を行った。
    90℃で4時間
    90℃から204℃迄6時間かけて昇温
    204℃で18時間
    204℃から298℃迄3時間かけて昇温
    298℃で8時間 Example 1
100 parts by weight of tetrafluoroethylene-perfluoro(methyl vinyl ether)-perfluoro(3-oxa-8-cyano-1-octene) [molar ratio 65.4:33.3:1.3] terpolymer, 0.30 parts by weight of quinacridone and 0.7 parts by weight of the bisamidoxime compound HON=C(NH 2 )(CF 2 ) 4 C(NH 2 )=NOH was added and kneaded on a two-roll mill at a temperature of 30-100°C. After press vulcanization (primary vulcanization) of the kneaded material at 180° C. for 30 minutes, oven vulcanization (secondary vulcanization) was performed under the following conditions.
90°C for 4 hours 90°C to 204°C over 6 hours 204°C for 18 hours 204°C to 298°C over 3 hours 298°C for 8 hours
  実施例２
  実施例１において、ビスアミドキシム化合物の代わりに2,2-ビス(3-アミノ-4-ヒドロキシフェニル) ヘキサフルオロプロパン3.0重量部が、またキナクリドン量が0.40重量部に、それぞれ変更されて用いられた。 Example 2
In Example 1, 3.0 parts by weight of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was used instead of the bisamidoxime compound, and the amount of quinacridone was changed to 0.40 parts by weight. .
  比較例１
  実施例１において、キナクリドン量が0.05重量部に変更されて用いられた。 Comparative example 1
In Example 1, the amount of quinacridone was changed to 0.05 parts by weight.
  比較例２
  実施例１において、キナクリドン量が0.1重量部に変更されて用いられた。 Comparative example 2
In Example 1, the amount of quinacridone was changed to 0.1 parts by weight.
  比較例３
  実施例１において、キナクリドン量が1.0重量部に変更されて用いられた。 Comparative example 3
In Example 1, the amount of quinacridone was changed to 1.0 part by weight.
  比較例４
  実施例２において、キナクリドンが用いられなかった。 Comparative example 4
In Example 2, no quinacridone was used.
　以上の各実施例および比較例で得られた加硫成形物について、次の各項目の測定を行った。
　　　常態物性：ASTM D2240に対応するJIS K6253-3(硬度)
　　　　　　　　ISO 37に対応するJIS K6251(引張試験)
　　　　　　　　　硬度は75以下が好ましい
　　　圧縮永久歪：ASTM Method B；P-24 Ｏリングについて、300℃で168、
　　　　　　　　　300、500時間の条件下で測定
　　　　　　　　　　300℃、500時間で70％以下が好ましく、50％以下が
　　　　　　　　　　さらに好ましい
　　　キナクリドンの分散性：2本ロールミル上で混練した後、混練物を2mm
　　　　　　　　　　　　　　の厚みで分出し、この混練物中1kgに目視で
　　　　　　　　　　　　　　きる凝集塊を評価
　　　　　　　　　　　　　　　凝集塊は破断起点となりうることから、
　　　　　　　　　　　　　　　凝集塊1kg当り5個以下をOK、6個以上をNG
　　　　　　　　　　　　　　　と評価 The following items were measured for the vulcanized moldings obtained in the above examples and comparative examples.
Normal physical properties: JIS K6253-3 (hardness) corresponding to ASTM D2240
JIS K6251 (tensile test) corresponding to ISO 37
Hardness is preferably 75 or less Compression set: ASTM Method B; 168 at 300°C for P-24 O-ring
Measured under conditions of 300 and 500 hours At 300°C for 500 hours, it is preferably 70% or less, more preferably 50% or less Dispersibility of quinacridone: After kneading on a two-roll mill,
Thickness of 1 kg is separated out, and the aggregates visible in 1 kg of this kneaded material are evaluated.
5 or less per 1 kg of aggregates are OK, 6 or more are NG
and evaluated
　以上の各実施例および比較例で得られた結果は、次の表に示される。なお、比較例４の300℃、500時間後の圧縮永久歪は、Ｏリング表面がメルトしてしまい測定不可であった。

　　　　　　　　　　　　　　表
Figure JPOXMLDOC01-appb-I000003
The results obtained in each of the above examples and comparative examples are shown in the following table. The compression set of Comparative Example 4 after 500 hours at 300° C. could not be measured because the O-ring surface melted.

table
Figure JPOXMLDOC01-appb-I000003
　本発明で用いられる含フッ素エラストマーに、特定量のキナクリドンとビスアミドキシム化合物または2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンを配合してなる組成物を加硫成形して得られたＯリング等のシール材は、300℃以上といった高温条件下においても変色あるいはブルームを生じることがなく、耐熱性に優れ、良好なシール性を保持し得る。 A composition obtained by blending a specific amount of quinacridone and a bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with the fluorine-containing elastomer used in the present invention is vulcanized and molded. The resulting sealing material such as an O-ring does not discolor or bloom even under high temperature conditions of 300° C. or higher, has excellent heat resistance, and can maintain good sealing performance.
　そのため、プラズマ照射用途である半導体製造装置用のシール材等として有効に用いられる。また、シリコンウェハーの表面処理加工室の面シール、例えばチャンバーとチャンバーとの連結面あるいはチャンバーとゲート(扉)との接合面に適用され、真空を維持するためのＯリングやパッキン等としても、有効に用いられる。 Therefore, it is effectively used as a sealing material for semiconductor manufacturing equipment, which is used for plasma irradiation. In addition, it is applied to the surface seal of a silicon wafer surface treatment processing chamber, for example, the connection surface between chambers or the joint surface between a chamber and a gate (door), and as an O-ring or packing for maintaining vacuum. Effectively used.

Claims (11)

  1. 　(A)テトラフルオロエチレン60.0～80.0モル％、(B)パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)19.8～35.0モル％および(C)パーフルオロ不飽和ニトリル化合物0.2～5.0モル％の共重合組成を有する含フッ素エラストマー100重量部当り、キナクリドン0.2～0.9重量部およびビスアミドキシム化合物または2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン0.2～5重量部を配合した含フッ素エラストマー組成物。 (A) 60.0 to 80.0 mol% of tetrafluoroethylene, (B) 19.8 to 35.0 mol% of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy lower alkyl vinyl ether), and (C) 0.2 to 5.0 mol% of a perfluorounsaturated nitrile compound. 0.2 to 0.9 parts by weight of quinacridone and 0.2 to 5 parts by weight of bisamidoxime compound or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane per 100 parts by weight of fluorine-containing elastomer having a copolymer composition of mol % A fluorine-containing elastomer composition containing
  2. 　(A)テトラフルオロエチレン60.0～68.8モル％、(B)パーフルオロ(低級アルキルビニルエーテル)またはパーフルオロ(低級アルコキシ低級アルキルビニルエーテル)31.0～35.0モル％および(C)パーフルオロ不飽和ニトリル化合物0.2～5.0モル％の共重合組成を有する含フッ素エラストマーが用いられた請求項１記載の含フッ素エラストマー組成物。 (A) 60.0 to 68.8 mol% of tetrafluoroethylene, (B) 31.0 to 35.0 mol% of perfluoro (lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether), and (C) 0.2 to 5.0 perfluorounsaturated nitrile compound. 2. The fluorine-containing elastomer composition according to claim 1, wherein a fluorine-containing elastomer having a copolymer composition of mol % is used.
  3. 　ビスアミドキシム化合物が、一般式
    　　　HON=C(NH2)(CF2)nC(NH2)=NOH
    (ここで、nは1～10の整数である)で表される化合物である請求項１記載の含フッ素エラストマー組成物。     Bisamidoxime compounds have the general formula HON=C( NH2 )( CF2 ) nC ( NH2 )=NOH
    2. The fluoroelastomer composition according to claim 1, which is a compound represented by (where n is an integer of 1 to 10).
  4. 　キナクリドン以外の充填剤を含有しない請求項１または２記載の含フッ素エラストマー組成物。 The fluorine-containing elastomer composition according to claim 1 or 2, which contains no filler other than quinacridone.
  5. 　請求項１、２、３または４の請求項記載の含フッ素エラストマー組成物を加硫成形して得られた着色成形物。 A colored molded article obtained by vulcanizing and molding the fluorine-containing elastomer composition according to claim 1, 2, 3 or 4.
  6. 　圧縮永久歪が300℃、500時間で50％以下であり、ゴム硬度(Duro A)が75以下である請求項５記載の着色成形物。 The colored molding according to claim 5, which has a compression set of 50% or less at 300°C for 500 hours and a rubber hardness (Duro A) of 75 or less.
  7. 　シール材として用いられる請求項５記載の着色成形物。 The colored molding according to claim 5, which is used as a sealing material.
  8. 　プラズマ照射用途に用いられる請求項７記載の着色シール材。 The colored sealing material according to claim 7, which is used for plasma irradiation applications.
  9. 　半導体製造装置用として用いられる請求項８記載の着色シール材。 The colored sealing material according to claim 8, which is used for semiconductor manufacturing equipment.
  10. 　シリコンウェハーの表面処理加工室の面シールとして用いられる請求項９記載の着色シール材。 The colored sealing material according to claim 9, which is used as a face seal for a silicon wafer surface treatment chamber.
  11. 　ゲートバルブ用途に用いられる請求項８記載の着色シール材。 The colored sealing material according to claim 8, which is used for gate valve applications.
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JPS56166251A (en) * 1980-04-23 1981-12-21 Du Pont Fluoroelastomer composition
WO2004094527A1 (en) * 2003-04-22 2004-11-04 Daikin Industries Ltd. Fluorine-containing elastomer composition with excellent plasma-aging prevention effect and shaped article made thereof
JP2008500408A (en) * 2004-03-31 2008-01-10 グリーン， ツイード オブ デラウェア， インコーポレイテッド Fast-curing fluoroelastomer composition, adhesive fluoroelastomer composition, and method of bonding fluoroelastomer composition
JP2008001894A (en) * 2006-05-26 2008-01-10 Daikin Ind Ltd Fluorine-containing elastomer composition excellent in plasma resistance property and sealing material comprising the same
JP2011516693A (en) * 2008-04-08 2011-05-26 グリーン， ツイード オブ デラウェア， インコーポレイテッド Oxygen-resistant plasma composition characterized by low viscosity and related methods
JP2013216771A (en) * 2012-04-09 2013-10-24 Unimatec Co Ltd Perfluoroelastomer composition
JP2017214556A (en) * 2016-05-30 2017-12-07 日本バルカー工業株式会社 Perfluoroelastomer composition and seal material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56166251A (en) * 1980-04-23 1981-12-21 Du Pont Fluoroelastomer composition
WO2004094527A1 (en) * 2003-04-22 2004-11-04 Daikin Industries Ltd. Fluorine-containing elastomer composition with excellent plasma-aging prevention effect and shaped article made thereof
JP2008500408A (en) * 2004-03-31 2008-01-10 グリーン， ツイード オブ デラウェア， インコーポレイテッド Fast-curing fluoroelastomer composition, adhesive fluoroelastomer composition, and method of bonding fluoroelastomer composition
JP2008001894A (en) * 2006-05-26 2008-01-10 Daikin Ind Ltd Fluorine-containing elastomer composition excellent in plasma resistance property and sealing material comprising the same
JP2011516693A (en) * 2008-04-08 2011-05-26 グリーン， ツイード オブ デラウェア， インコーポレイテッド Oxygen-resistant plasma composition characterized by low viscosity and related methods
JP2013216771A (en) * 2012-04-09 2013-10-24 Unimatec Co Ltd Perfluoroelastomer composition
JP2017214556A (en) * 2016-05-30 2017-12-07 日本バルカー工業株式会社 Perfluoroelastomer composition and seal material

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