WO2018225487A1 - フッ素ゴム組成物及びフッ素ゴム架橋体 - Google Patents

フッ素ゴム組成物及びフッ素ゴム架橋体 Download PDF

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WO2018225487A1
WO2018225487A1 PCT/JP2018/019449 JP2018019449W WO2018225487A1 WO 2018225487 A1 WO2018225487 A1 WO 2018225487A1 JP 2018019449 W JP2018019449 W JP 2018019449W WO 2018225487 A1 WO2018225487 A1 WO 2018225487A1
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weight
parts
fluororubber
fluorine rubber
silica
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PCT/JP2018/019449
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English (en)
French (fr)
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卓 吉田
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Nok株式会社
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Priority to CN201880037566.8A priority Critical patent/CN110709467B/zh
Priority to EP18813285.6A priority patent/EP3636712B1/en
Priority to KR1020197036184A priority patent/KR102300072B1/ko
Priority to JP2018558784A priority patent/JP6474054B1/ja
Publication of WO2018225487A1 publication Critical patent/WO2018225487A1/ja
Priority to US16/702,965 priority patent/US11384223B2/en

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Definitions

  • the present invention relates to a fluororubber composition and a cross-linked fluororubber, and more specifically, a fluororubber composition that is excellent in compression set under a steam environment, is prevented from changing in hardness under a steam environment, and is excellent in adhesiveness. And a crosslinked fluororubber.
  • the EGR valve is provided with an oil seal for preventing the exhaust gas (also referred to as EGR gas) from leaking.
  • the above-described oil seal is made of fluorine rubber having excellent heat resistance and chemical resistance.
  • Peroxide vulcanized fluororubbers use metal oxides to improve adhesion, which causes curing degradation in steam environments and oil seal sag (compression permanent). (Strain reduction) occurs.
  • the conventional fluororubber composition is excellent in compression set under a steam environment, prevents change in hardness under the steam environment, and is excellent in adhesiveness.
  • an object of the present invention is to provide a fluororubber composition and a fluororubber crosslinked product that are excellent in compression set under a steam environment, are prevented from changing in hardness under a steam environment, and are excellent in adhesiveness. .
  • a ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; A silica-aluminum silicate vinylethoxysilane reactant, Substantially free of magnesium oxide and calcium hydroxide, 8.
  • a fluororubber composition comprising 8 to 60 parts by weight of the silica-aluminum silicate vinylethoxysilane reactant with respect to 100 parts by weight of the ternary fluororubber polymer. 2.
  • a ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; A vinyl ethoxysilane reactant of silica-aluminum silicate; Containing hydrotalcite, Substantially free of magnesium oxide and calcium hydroxide, 2 to 55 parts by weight of the vinyl-ethoxysilane reaction product of silica-aluminum silicate and 0.5 to 10 parts by weight of the hydrotalcite are contained with respect to 100 parts by weight of the ternary fluororubber polymer.
  • a fluororubber composition 3. 3.
  • a cross-linked fluororubber comprising the fluororubber composition as described in any one of 1 to 3 above.
  • a fluororubber composition and a cross-linked fluororubber which are excellent in compression set under a steam environment, change in hardness under the steam environment and excellent in adhesiveness.
  • the fluororubber composition according to the first aspect contains a ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, tetrafluoroethylene, and a vinyl ethoxysilane reaction product of silica-aluminum silicate, and includes magnesium oxide. And substantially free of calcium hydroxide.
  • the fluororubber composition does not substantially contain magnesium oxide and calcium hydroxide because it does not contain magnesium oxide and calcium hydroxide or the total content thereof is ternary fluororubber polymer 100. It is 0.1 weight part or less with respect to a weight part, Preferably it is 0.05 weight part or less.
  • the fluororubber composition according to the first aspect 8 to 60 parts by weight, preferably 10 to 50 parts by weight, of the vinyl ethoxysilane reactant of silica-aluminum silicate with respect to 100 parts by weight of the ternary fluororubber polymer. Contains.
  • the ternary fluororubber polymer preferably has a fluorine content of 64 to 67% by weight from the viewpoint of remarkably exhibiting the effects of the present invention.
  • Perfluorovinyl ether which is a polymerization component in the ternary fluororubber polymer can be represented by the general formula CF 2 ⁇ CFOR f (wherein R f represents a perfluoroalkyl group having 1 to 10 carbon atoms). Examples of the perfluoroalkyl group having 1 to 10 carbon atoms include a perfluoromethyl group.
  • the ternary fluororubber polymer is preferably capable of peroxide crosslinking, and preferably contains iodine and / or bromine in the molecule as a crosslinking site.
  • ternary fluororubber polymers examples include “Viton GLT600S” (fluorine content: 64 wt%), “Viton GTL200S” (fluorine content: 64 wt%) manufactured by DuPont, and “Technoflon manufactured by Solvay Solexis, Inc. Commercial products such as “PL855” (fluorine content: 64 wt%) may be used. Two or more ternary fluororubber polymers may be used in combination.
  • the vinyl-ethoxysilane reaction product of silica-aluminum silicate is not particularly limited as long as it is a reaction product obtained by reacting silica-aluminum silicate with vinylethoxysilane.
  • silica-aluminum silicate for example, a commercially available product such as “Citirin Z86” manufactured by Hoffman Mineral Co., Ltd. may be used.
  • a vinyl ethoxysilane reactant of silica-aluminum silicate for example, a commercially available product such as “actidyl VM” manufactured by Hoffman Mineral Co. may be used.
  • the fluororubber composition according to the second aspect comprises a ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether and tetrafluoroethylene, a vinyl-ethoxysilane reaction product of silica-aluminum silicate, and hydrotalcite. Contained and substantially free of magnesium oxide and calcium hydroxide.
  • the silica-aluminum silicate vinylethoxysilane reactant is 2 to 55 parts by weight, preferably 3 to 50 parts by weight with respect to 100 parts by weight of the ternary fluororubber polymer. And 0.5 to 10 parts by weight, preferably 1 to 9 parts by weight of the hydrotalcite.
  • the explanation about the first aspect can be used for the ternary fluororubber polymer used in the second aspect and the vinylethoxysilane reaction product of silica-aluminum silicate.
  • hydrotalcite examples include Mg 4.3 Al 2 (OH) 12.6 CO 3 .mH 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 4 .5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O , and the like.
  • hydrotalcites for example, commercially available products such as “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd. may be used.
  • the fluororubber composition according to the first aspect or the second aspect described above is preferably used after peroxide crosslinking.
  • An organic peroxide crosslinking agent can be preferably used for peroxide crosslinking.
  • the organic peroxide crosslinking agent is not particularly limited, and examples thereof include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane.
  • the organic peroxide crosslinking agent is preferably used in a proportion of 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the ternary fluororubber polymer. .
  • the fluororubber crosslinked product includes a crosslinking aid used as a general compounding agent for rubber, a reinforcing agent such as white carbon, carbon black such as MT carbon black and FEF carbon black, A filler such as graphite, a processing aid such as stearic acid, palmitic acid, and paraffin wax, an anti-aging agent, a plasticizer, zinc oxide, and the like may be appropriately added as long as the object of the present invention is not impaired.
  • the cross-linked fluororubber of the present invention is formed by cross-linking the fluororubber composition described above.
  • the crosslinking is preferably peroxide crosslinking. According to the cross-linked fluororubber of the present invention, it is excellent in compression set in a steam environment, preventing changes in hardness in a steam environment, and obtaining an effect of excellent adhesiveness.
  • each component of the fluororubber composition is kneaded using a closed kneader such as a kneader, an intermix, a Banbury mixer, or an open roll.
  • a closed kneader such as a kneader, an intermix, a Banbury mixer, or an open roll.
  • the kneaded material is dispensed into a sheet shape or formed into a predetermined shape using an extruder, a bawel apparatus or the like.
  • crosslinking molding is performed at a predetermined temperature (preferably 100 to 180 ° C.) for a predetermined time (preferably 1 to 30 minutes).
  • secondary crosslinking can be performed at a predetermined temperature (preferably 200 to 220 ° C.) for a predetermined time (preferably 1 to 10 hours) using an air oven or the like.
  • the cross-linked fluororubber of the present invention is suitably used as various seal members, particularly as an oil seal for an EGR valve.
  • the EGR valve oil seal comprising the crosslinked fluororubber of the present invention has excellent compression set in a steam environment, prevents changes in hardness in the steam environment, and has excellent adhesiveness. A good seal can be achieved in a harsh environment.
  • Example 1 Preparation of Fluororubber Composition 100 parts by weight of the following ternary fluororubber polymer C, 10 parts by weight of a silica-aluminum silicate vinylethoxysilane reaction product (“Activid VM” manufactured by Hoffman Mineral) and MT carbon black (CANCARB) 3 parts by weight of LIMITED “THERMAX N-990LSR”) and 0.1 parts by weight of zinc oxide (JIS standard “1 type” applicable quality) are blended, and further, an organic valence oxide crosslinking agent (2,5-dimethyl- 2,5-di (t-butylperoxy) hexane) (“Perhexa 25B-40” manufactured by Nippon Oil & Fats Co., Ltd.) and a predetermined compounding agent were mixed and kneaded to obtain an uncrosslinked fluororubber composition. It was.
  • a silica-aluminum silicate vinylethoxysilane reaction product (“Activid VM” manufactured by Hoffman Mineral) and
  • Ternary fluororubber polymer A Ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; fluorine content 64% by weight (“Viton GLT600S” manufactured by DuPont)
  • Ternary fluororubber polymer B Ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; fluorine content 64% by weight (“Viton GTL200S” manufactured by DuPont)
  • -Ternary fluororubber polymer C ternary fluororubber polymer consisting of vinylidene fluoride, perfluorovinyl ether, tetrafluoroethylene; fluorine content 64 wt% ("Technoflon PL855" manufactured by Solvay Solexis)
  • test piece Using the fluorororubber composition, a test piece for adhesive evaluation, a test piece for compression set evaluation in a steam environment, and a test piece for evaluation of hardness change prevention in a steam environment It was prepared by the following method.
  • Test piece for evaluating adhesiveness The above fluororubber composition was formed into an oil seal shape of ⁇ 85 mm, and this was press-crosslinked and adhered to a steel plate at 180 ° C. for 3 minutes, thereby testing for adhesiveness evaluation. I got a piece.
  • Test piece for evaluation of compression set under steam environment The fluororubber composition was formed into an O-ring shape having a wire diameter of 3.1 mm, and this was press-crosslinked at 180 ° C. for 3 minutes, and then 200 A test piece for evaluation of compression set in a steam environment was obtained by holding for 5 hours in an atmosphere of ° C.
  • Test piece for evaluation of hardness change prevention in steam environment The above fluororubber composition was molded into a sheet having a thickness of 2 mm, this was press-crosslinked at 180 ° C. for 3 minutes, and then in an atmosphere at 200 ° C. By holding for 5 hours, a test piece for evaluation of hardness change prevention in a steam environment was obtained.
  • Compression set under steam environment was measured according to JIS K6262: 2013.
  • the test environment was a steam environment with a humidity of 95%, the test temperature was 80 ° C., and the test time was 96 hours.
  • the following evaluation criteria were used. ⁇ Evaluation criteria> AA: Compression set (%) is 0% or more and 25% or less.
  • C Compression set (%) is more than 31% and 100% or less.
  • Hardness change prevention in steam environment The hardness change in a steam environment was measured based on JISK6258: 2010. The test environment was a steam environment with a humidity of 95%, the test temperature was 80 ° C., and the test time was 192 hours. Based on the measured change in hardness (Hw) (Points), the following evaluation criteria were used. ⁇ Evaluation criteria> AA: Hardness change (Hw) (Points) is ⁇ 0. A: Hardness change (Hw) (Points) is -5 or more and -1 or less. B: Hardness change (Hw) (Points) is +1 or more and +5 or less. C: Hardness change (Hw) (Points) is more than +5 and +10 or less.
  • Example 2 In Example 1, each test piece was prepared in the same manner as in Example 1 except that the amount of silica-aluminum silicate vinylethoxysilane reactant was changed to 15 parts by weight. And evaluated. The results are shown in Table 1.
  • Example 3 In Example 1, each test piece was prepared in the same manner as in Example 1 except that the amount of the silica-aluminum silicate vinylethoxysilane reactant was changed to 30 parts by weight. And evaluated. The results are shown in Table 1.
  • Example 4 In Example 3, instead of MT carbon black, 2 parts by weight of FEF carbon black (“Seast GS-O” manufactured by Tokai Carbon Co., Ltd.) was blended, and the blending of zinc oxide was omitted. Each test piece was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 In Example 1, instead of the ternary fluorororubber polymer C, 100 parts by weight of a polymer composed of 50 parts by weight of the ternary fluororubber polymer A and 50 parts by weight of the ternary fluororubber polymer B was used.
  • the blending amount of the vinyl ethoxysilane reactant of silica-aluminum silicate was changed to 5 parts by weight, and further hydrotalcite (Mg 4.3 Al 2 (OH) 12.6 CO 3 ⁇ mH 2 O) (Kyowa) 3 parts by weight of “DHT-4A” manufactured by Chemical Industry Co., Ltd., 6 parts by weight of magnesium oxide (“Kyowa Mag 150” manufactured by Kyowa Chemical Industry Co., Ltd.), and 3 parts by weight of calcium hydroxide (“CALDIC 2000” manufactured by Omi Chemical Industry Co., Ltd.)
  • DHT-4A Al 2 (OH) 12.6 CO 3 ⁇ mH 2 O
  • CALDIC 2000 calcium hydroxide manufactured by Omi Chemical Industry Co., Ltd.
  • Comparative Example 2 In Comparative Example 1, each test piece was prepared in the same manner as in Comparative Example 1 except that the blending of magnesium oxide was omitted, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 3 In Comparative Example 1, each test piece was prepared in the same manner as in Comparative Example 1 except that the blending of hydrotalcite, magnesium oxide and calcium hydroxide was omitted, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 each test piece was prepared in the same manner as in Example 1 except that the compounding amount of the vinyl ethoxysilane reactant of silica-aluminum silicate was changed to 5 parts by weight. And evaluated. The results are shown in Table 1.
  • Comparative Examples 1 and 2 containing magnesium oxide and calcium hydroxide are inferior in compression set in a steam environment and cannot prevent a change in hardness in the steam environment.
  • the content of the vinyl ethoxysilane reactant of silica-aluminum silicate is not in the range of 8 to 60 parts by weight as compared with the fluororubber composition (Examples 1 to 4) according to the first aspect of the present invention. In Comparative Examples 3 and 4, it can be seen that the adhesiveness is poor.
  • Example 5 Silica-aluminum silicate vinyl ethoxysilane reaction product (made by Hoffman Mineral Co., Ltd.) was added to 50 parts by weight of the following ternary fluororubber polymer A and 50 parts by weight of the following ternary fluororubber polymer B.
  • Actidyl VM ”) 5 parts by weight, hydrotalcite (Mg 4.3 Al 2 (OH) 12.6 CO 3 ⁇ mH 2 O) (Kyowa Chemical Industry Co., Ltd.“ DHT-4A ”) 6 parts by weight, MT carbon 3 parts by weight of black (“THERMAX N-990LSR” manufactured by CANCARB LIMITED) and 0.1 parts by weight of zinc oxide (JIS standard “1 type” applicable quality) are blended, and an organic peroxide crosslinking agent (2, 5 -Dimethyl-2,5-di (t-butylperoxy) hexane) (Nippon Yushi Co., Ltd.
  • Ternary fluororubber polymer A Ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; fluorine content 64% by weight (“Viton GLT600S” manufactured by DuPont)
  • Ternary fluororubber polymer B Ternary fluororubber polymer composed of vinylidene fluoride, perfluorovinyl ether, and tetrafluoroethylene; fluorine content 64% by weight (“Viton GTL200S” manufactured by DuPont)
  • Example 6 In Example 5, each test piece was produced in the same manner as in Example 5 except that the amount of hydrotalcite was changed to 9 parts by weight, and evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 (Comparative Example 5) In Example 5, the amount of hydrotalcite was changed to 3 parts by weight, and further 6 parts by weight of magnesium oxide (“Kyowa Mag 150” manufactured by Kyowa Chemical Industry Co., Ltd.) and calcium hydroxide (“CALDIC 2000” manufactured by Omi Chemical Industry Co., Ltd.) ]) Each test piece was prepared in the same manner as in Example 5 except that 3 parts by weight were blended, and evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 6 (Comparative Example 6) In Example 5, each test piece was prepared in the same manner as in Example 5 except that the amount of hydrotalcite was changed to 3 parts by weight and that 3 parts by weight of calcium hydroxide was further added. And evaluated in the same manner. The results are shown in Table 2.
  • Example 7 each test piece was prepared in the same manner as in Example 5 except that the amount of hydrotalcite was changed to 12 parts by weight, and evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Comparative Examples 5 and 6 containing magnesium oxide and calcium hydroxide are inferior in compression set in a steam environment and cannot prevent a change in hardness in the steam environment.
  • Comparative Example 7 where the hydrotalcite content is not in the range of 0.5 to 10 parts by weight, It turns out that it is inferior to the compression set in an environment.

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Abstract

本発明は、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるフッ素ゴム組成物及びフッ素ゴム架橋体を提供することを課題とし、フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、ハイドロタルサイトとを含有し、酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、３元系フッ素ゴムポリマー１００重量部に対して、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を２～５５重量部、ハイドロタルサイトを０．５～１０重量部含有することを特徴とするフッ素ゴム組成物により解決される。

Description

フッ素ゴム組成物及びフッ素ゴム架橋体
　本発明は、フッ素ゴム組成物及びフッ素ゴム架橋体に関し、より詳しくは、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるフッ素ゴム組成物及びフッ素ゴム架橋体に関する。
　従来、内燃機関の燃焼室より排出される排気ガスの一部を内燃機関の吸気系に再循環させる排気再循環（Exhaust Gas Recirculation；ＥＧＲ）バルブが知られている（特許文献１）。
　ＥＧＲバルブには、前記排気ガス（ＥＧＲガスともいう）の漏れを防止するためのオイルシールが設けられる。
　ＥＧＲバルブの内部は、排気ガスや凝縮水に接触する過酷な環境となることから、上述したオイルシールには、耐熱、耐薬品性に優れたフッ素ゴムが使用されている。
　また、上述したオイルシールは、蒸気にもさらされることから、耐スチーム性も要求される。一般にポリオール架橋されたフッ素ゴムは、受酸剤として配合するＭｇＯに起因して、耐スチーム性に劣る。そのため、スチーム環境ではパーオキサイド架橋系のフッ素ゴムが使用される。
特開２０１５－１２４６４０号公報 ＷＯ２００６／００６４６８（フッ素ゴム組成物）
　パーオキサイド加硫系のフッ素ゴムにおいては、接着性を向上させるために金属酸化物が使用されているが、それが起因して、スチーム環境での硬化劣化、およびオイルシールのへたり（圧縮永久ひずみ低下）が発生する。
　よって、従来のフッ素ゴム組成物においては、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるものが望まれた。
　そこで本発明の課題は、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるフッ素ゴム組成物及びフッ素ゴム架橋体を提供することにある。
　また本発明の他の課題は、以下の記載によって明らかとなる。
　上記課題は、以下の各発明によって解決される。
１．
　フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、
　シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物とを含有し、
　酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
　前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を８～６０重量部含有することを特徴とするフッ素ゴム組成物。
２．
　フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、
　シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、
　ハイドロタルサイトとを含有し、
　酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
　前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を２～５５重量部、前記ハイドロタルサイトを０．５～１０重量部含有することを特徴とするフッ素ゴム組成物。
３．
　前記３元系フッ素ゴムポリマーは、フッ素含有量が６４～６７重量％であることを特徴とする前記１又は２記載のフッ素ゴム組成物。
４．
　前記１～３の何れかに記載のフッ素ゴム組成物を架橋してなることを特徴とするフッ素ゴム架橋体。
　本発明によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるフッ素ゴム組成物及びフッ素ゴム架橋体を提供することができる。
　以下に、本発明を実施するための形態について詳しく説明する。
　まず、本発明の第１態様に係るフッ素ゴム組成物について説明する。
　第１態様に係るフッ素ゴム組成物は、フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物とを含有し、酸化マグネシウム及び水酸化カルシウムを実質的に含有しない。
　ここで、フッ素ゴム組成物が酸化マグネシウム及び水酸化カルシウムを実質的に含有しないというのは、酸化マグネシウム及び水酸化カルシウムを含有しないか、これらの合計の含有量が、３元系フッ素ゴムポリマー１００重量部に対して、０．１重量部以下、好ましくは０．０５重量部以下であることである。
　第１態様に係るフッ素ゴム組成物は、前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を８～６０重量部、好ましくは１０～５０重量部含有する。
　これにより、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られる。
　３元系フッ素ゴムポリマーは、本発明の効果を顕著に発揮する観点で、フッ素含有量が６４～６７重量％であることが好ましい。
　３元系フッ素ゴムポリマーにおける重合成分であるパーフルオロビニルエーテルは、一般式ＣＦ２＝ＣＦＯＲｆ（式中、Ｒｆは炭素数１～１０のパーフルオロアルキル基を表す）で表すことができる。前記炭素数１～１０のパーフルオロアルキル基としては、例えばパーフルオロメチル基等が挙げられる。
　３元系フッ素ゴムポリマーは、パーオキサイド架橋可能であることが好ましく、架橋サイトとして分子中にヨウ素及び／又は臭素を含有するものであることが好ましい。
　このような３元系フッ素ゴムポリマーとして、例えば、デュポン社製「バイトンＧＬＴ６００Ｓ」（フッ素含有量６４重量％）、「バイトンＧＴＬ２００Ｓ」（フッ素含有量６４重量％）、ソルベイソレクシス社製「テクノフロンＰＬ８５５」（フッ素含有量６４重量％）等の市販品を用いてもよい。３元系フッ素ゴムポリマーは、２種以上を混合して用いてもよい。
　シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物は、シリカ‐ケイ酸アルミニウムと、ビニルエトキシシランとを反応させて得られる反応物であれば格別限定されない。シリカ‐ケイ酸アルミニウムとして、例えば、ホフマンミネラル社製「シチリンＺ８６」等の市販品を用いてもよい。また、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物として、例えば、ホフマンミネラル社製「アクチジルＶＭ」等の市販品を用いてもよい。
　次に、本発明の第２態様に係るフッ素ゴム組成物について説明する。
　第２態様に係るフッ素ゴム組成物は、フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、ハイドロタルサイトとを含有し、酸化マグネシウム及び水酸化カルシウムを実質的に含有しない。
　第２態様に係るフッ素ゴム組成物は、前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を２～５５重量部、好ましくは３～５０重量部含有し、前記ハイドロタルサイト類を０．５～１０重量部、好ましくは１～９重量部含有する。
　これにより、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られる。
　第２態様に用いられる３元系フッ素ゴムポリマー及びシリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物については、第１態様についてした説明を援用することができる。
　第２態様に用いられるハイドロタルサイトとしては、例えば、Ｍｇ４．３Ａｌ２（ＯＨ）１２．６ＣＯ３・ｍＨ２Ｏ、Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ、Ｍｇ４．５Ａｌ２（ＯＨ）１３ＣＯ３・３．５Ｈ２Ｏ等が挙げられる。ハイドロタルサイト類として、例えば、協和化学工業社製「ＤＨＴ－４Ａ」等の市販品を用いてもよい。
　以上に説明した第１態様又は第２態様に係るフッ素ゴム組成物は、パーオキサイド架橋して用いられることが好ましい。
　パーオキサイド架橋には、有機過酸化物架橋剤を好ましく用いることができる。
　有機過酸化物架橋剤は格別されず、例えば２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン等が挙げられる。
　有機過酸化物架橋剤は、３元系フッ素ゴムポリマー１００重量部に対して、０．５～５重量部の割合で用いることが好ましく、１～３重量部の割合で用いられることが更に好ましい。
　フッ素ゴム架橋体には、以上に説明した成分以外に、ゴムの一般的な配合剤として用いられている架橋助剤、ホワイトカーボン等の補強剤、ＭＴカーボンブラックやＦＥＦカーボンブラック等のカーボンブラック、グラファイト等の充填剤、ステアリン酸、パルミチン酸、パラフィンワックス等の加工助剤、老化防止剤、可塑剤、酸化亜鉛等を本発明の目的を損なわない範囲で適宜添加してもよい。
　本発明のフッ素ゴム架橋体は、以上に説明したフッ素ゴム組成物を架橋してなる。架橋は、上述したようにパーオキサイド架橋であることが好ましい。本発明のフッ素ゴム架橋体によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られる。
　フッ素ゴム架橋体を製造する好ましい方法においては、まず、フッ素ゴム組成物の各成分をニーダ、インターミックス、バンバリーミキサ等の密閉式混練機又はオープンロールを用いて混練する。次いで、混練物をシート状に分出するか、あるいは押出機、バウエル装置等を用いて所定の形状にする。次いで、圧縮プレス、注入成形機、射出成形機等を用いて、所定温度（好ましくは１００～１８０℃）で所定時間（好ましくは１～３０分間）、架橋成形する。更に、所定温度（好ましくは２００～２２０℃）で所定時間（好ましくは１～１０時間）、エアオーブン等を用いて二次架橋することができる。
　本発明のフッ素ゴム架橋体は、各種シール部材、特にＥＧＲバルブ用オイルシールとして好適に用いられる。本発明のフッ素ゴム架橋体からなるＥＧＲバルブ用オイルシールは、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れるため、ＥＧＲバルブの過酷な環境下において良好なシールを達成することができる。
　以下に、本発明の実施例について説明するが、本発明はかかる実施例により限定されない。
　以下は、第１態様に関する例証である。
（実施例１）
１．フッ素ゴム組成物の調製
　下記３元系フッ素ゴムポリマーＣ　１００重量部に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物（ホフマンミネラル社製「アクチジルＶＭ」）１０重量部と、ＭＴカーボンブラック（ＣＡＮＣＡＲＢ　ＬＩＭＩＴＥＤ社製「ＴＨＥＲＭＡＸ　Ｎ－９９０ＬＳＲ」）３重量部、酸化亜鉛（ＪＩＳ規格「１種」該当品質）０．１重量部を配合し、更に、有機価酸化物架橋剤（２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン）（日本油脂社製「パーヘキサ２５Ｂ－４０」）２重量部と共に所定の配合剤を配合して混練し、未架橋のフッ素ゴム組成物を得た。
・３元系フッ素ゴムポリマーＡ：フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマー；フッ素含有量６４重量％（デュポン社製「バイトンＧＬＴ６００Ｓ」）
・３元系フッ素ゴムポリマーＢ：フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマー；フッ素含有量６４重量％（デュポン社製「バイトンＧＴＬ２００Ｓ」）
・３元系フッ素ゴムポリマーＣ：フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマー；フッ素含有量６４重量％（ソルベイソレクシス社製「テクノフロンＰＬ８５５」）
２．試験片の作製
　上記フッ素ゴム組成物を用いて、接着性評価用の試験片、スチーム環境下での圧縮永久歪み評価用の試験片、スチーム環境下での硬さ変化防止評価用の試験片を、以下の方法により作製した。
（１）接着性評価用の試験片
　上記フッ素ゴム組成物をφ８５ｍｍのオイルシールの形状に成形し、これを鋼板に対して１８０℃で３分間プレス架橋接着することによって、接着性評価用の試験片を得た。
（２）スチーム環境下での圧縮永久歪み評価用の試験片
　上記フッ素ゴム組成物を線径３．１ｍｍのＯリングの形状に成形し、これを１８０℃で３分間プレス架橋し、その後、２００℃の雰囲気下で５時間保持することによって、スチーム環境下での圧縮永久歪み評価用の試験片を得た。
（３）スチーム環境下での硬さ変化防止評価用の試験片
　上記フッ素ゴム組成物を２ｍｍ厚のシートに成形し、これを１８０℃で３分間プレス架橋し、その後、２００℃の雰囲気下で５時間保持することによって、スチーム環境下での硬さ変化防止評価用の試験片を得た。
３．評価方法
（１）接着性
　上記接着性評価用の試験片において、接着されているオイルシールをペンチで剥離し、ゴムが残留した面積率として、Ｒ残率（％）を測定した。測定されたＲ残率（％）に基づいて以下の評価基準で評価した。
＜評価基準＞
　ＡＡ：Ｒ残率（％）が８０％以上、１００％以下である。
　Ａ：Ｒ残率（％）が６０％以上、８０％未満である。
　Ｂ：Ｒ残率（％）が４５％以上、６０％未満である。
　Ｃ：Ｒ残率（％）が０％以上、４５％未満である。
（２）スチーム環境下での圧縮永久歪み
　スチーム環境下での圧縮永久歪み（％）を、ＪＩＳ　Ｋ６２６２：２０１３に準拠して測定した。試験環境は、湿度９５％のスチーム環境、試験温度は８０℃、試験時間は９６時間とした。測定された圧縮永久歪み（％）に基づいて以下の評価基準で評価した。
＜評価基準＞
　ＡＡ：圧縮永久歪み（％）が０％以上、２５％以下である。
　Ａ：圧縮永久歪み（％）が２５％超、２８％以下である。
　Ｂ：圧縮永久歪み（％）が２８％超、３１％以下である。
　Ｃ：圧縮永久歪み（％）が３１％超、１００％以下である。
（３）スチーム環境下での硬さ変化防止
　スチーム環境下での硬さ変化を、ＪＩＳ　Ｋ６２５８：２０１０に準拠して測定した。試験環境は、湿度９５％のスチーム環境、試験温度は８０℃、試験時間は１９２時間とした。測定された硬さ変化（Ｈｗ）（Ｐｏｉｎｔｓ）に基づいて以下の評価基準で評価した。
＜評価基準＞
　ＡＡ：硬さ変化（Ｈｗ）（Ｐｏｉｎｔｓ）が±０である。
　Ａ：硬さ変化（Ｈｗ）（Ｐｏｉｎｔｓ）が－５以上、－１以下である。
　Ｂ：硬さ変化（Ｈｗ）（Ｐｏｉｎｔｓ）が＋１以上、＋５以下である。
　Ｃ：硬さ変化（Ｈｗ）（Ｐｏｉｎｔｓ）が＋５超、＋１０以下である。
（４）総合評価
　上記（１）～（３）の評価結果に基づいて以下の評価基準で総合評価を行った。
＜評価基準＞
　ＡＡ：上記（１）～（３）の評価がＡ以上のみである。
　Ａ：上記（１）～（３）の評価としてＡ以上を含み、Ｃを含まない。
　Ｂ：上記（１）～（３）の評価がＢのみである。
　Ｃ：上記（１）～（３）の評価としてＣを含む。
　以上の結果を表１に示す。
（実施例２）
　実施例１において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を１５重量部に代えたこと以外は、実施例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（実施例３）
　実施例１において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を３０重量部に代えたこと以外は、実施例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（実施例４）
　実施例３において、ＭＴカーボンブラックに代えて、ＦＥＦカーボンブラック（東海カーボン社製「シーストＧＳ－Ｏ」）２重量部を配合し、酸化亜鉛の配合を省略したこと以外は、実施例３と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（比較例１）
　実施例１において、上記３元系フッ素ゴムポリマーＣに代えて、３元系フッ素ゴムポリマーＡ　５０重量部、及び、上記３元系フッ素ゴムポリマーＢ　５０重量部からなるポリマー１００重量部を用い、更に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を５重量部に代え、更に、ハイドロタルサイト（Ｍｇ４．３Ａｌ２（ＯＨ）１２．６ＣＯ３・ｍＨ２Ｏ）（協和化学工業社製「ＤＨＴ－４Ａ」）を３重量部と、酸化マグネシウム（協和化学工業社製「キョーワマグ１５０」）６重量部と、水酸化カルシウム（近江化学工業社製「ＣＡＬＤＩＣ　２０００」）３重量部とを配合したこと以外は、実施例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（比較例２）
　比較例１において、酸化マグネシウムの配合を省略したこと以外は、比較例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（比較例３）
　比較例１において、ハイドロタルサイト、酸化マグネシウム及び水酸化カルシウムの配合を省略したこと以外は、比較例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
（比較例４）
　実施例１において、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の配合量を５重量部に代えたこと以外は、実施例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表１に示す。
[規則91に基づく訂正 31.08.2018]　
Figure WO-DOC-TABLE-1
＜評価＞
　表１より、本発明の第１態様に係るフッ素ゴム組成物（実施例１～４）によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られることがわかる。
　これに対して、酸化マグネシウム、水酸化カルシウムを含有する比較例１、２では、スチーム環境下での圧縮永久歪みに劣り、スチーム環境下での硬さ変化を防止できないことがわかる。
　また、本発明の第１態様に係るフッ素ゴム組成物（実施例１～４）と比較して、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物の含有量が８～６０重量部の範囲ではない比較例３、４では、接着性に劣ることがわかる。
　以下は、第２態様に関する例証である。
（実施例５）
　下記３元系フッ素ゴムポリマーＡ　５０重量部、及び、下記３元系フッ素ゴムポリマーＢ　５０重量部からなるポリマー１００重量部に、シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物（ホフマンミネラル社製「アクチジルＶＭ」）５重量部と、ハイドロタルサイト（Ｍｇ４．３Ａｌ２（ＯＨ）１２．６ＣＯ３・ｍＨ２Ｏ）（協和化学工業社製「ＤＨＴ－４Ａ」）６重量部、ＭＴカーボンブラック（ＣＡＮＣＡＲＢ　ＬＩＭＩＴＥＤ社製「ＴＨＥＲＭＡＸ　Ｎ－９９０ＬＳＲ」）３重量部、酸化亜鉛（ＪＩＳ規格「１種」該当品質）０．１重量部を配合し、更に、有機過酸化物架橋剤（２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン）（日本油脂社製「パーヘキサ２５Ｂ－４０」）２重量部と共に所定の配合剤を配合して混練し、未架橋のフッ素ゴム組成物を得た。得られたフッ素ゴム組成物を用いて、実施例１と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表２に示す。
・３元系フッ素ゴムポリマーＡ：フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマー；フッ素含有量６４重量％（デュポン社製「バイトンＧＬＴ６００Ｓ」）
・３元系フッ素ゴムポリマーＢ：フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマー；フッ素含有量６４重量％（デュポン社製「バイトンＧＴＬ２００Ｓ」）
（実施例６）
　実施例５において、ハイドロタルサイトの配合量を９重量部に代えたこと以外は、実施例５と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表２に示す。
（比較例５）
　実施例５において、ハイドロタルサイトの配合量を３重量部に代え、更に、酸化マグネシウム（協和化学工業社製「キョーワマグ１５０」）６重量部と、水酸化カルシウム（近江化学工業社製「ＣＡＬＤＩＣ　２０００」）３重量部を配合したこと以外は、実施例５と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表２に示す。
（比較例６）
　実施例５において、ハイドロタルサイトの配合量を３重量部に代え、更に、水酸化カルシウム３重量部を配合したこと以外は、実施例５と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表２に示す。
（比較例７）
　実施例５において、ハイドロタルサイトの配合量を１２重量部に代えたこと以外は、実施例５と同様にして各試験片を作製し、実施例１と同様にして評価した。結果を表２に示す。
[規則91に基づく訂正 31.08.2018]　
Figure WO-DOC-TABLE-2
＜評価＞
　表２より、本発明の第２態様に係るフッ素ゴム組成物（実施例５、６）によれば、スチーム環境下での圧縮永久歪みに優れ、スチーム環境下での硬さ変化が防止され、且つ接着性に優れる効果が得られることがわかる。
　これに対して、酸化マグネシウム、水酸化カルシウムを含有する比較例５、６では、スチーム環境下での圧縮永久歪みに劣り、スチーム環境下での硬さ変化を防止できないことがわかる。
　また、本発明の第２態様に係るフッ素ゴム組成物（実施例５、６）と比較して、ハイドロタルサイトの含有量が０．５～１０重量部の範囲ではない比較例７では、スチーム環境下での圧縮永久歪みに劣ることがわかる。

Claims (4)

  1. 　フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、
    　シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物とを含有し、
    　酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
    　前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を８～６０重量部含有することを特徴とするフッ素ゴム組成物。
  2. 　フッ化ビニリデン、パーフルオロビニルエーテル、テトラフルオロエチレンから成る３元系フッ素ゴムポリマーと、
    　シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物と、
    　ハイドロタルサイトとを含有し、
    　酸化マグネシウム及び水酸化カルシウムを実質的に含有せず、
    　前記３元系フッ素ゴムポリマー１００重量部に対して、前記シリカ‐ケイ酸アルミニウムのビニルエトキシシラン反応物を２～５５重量部、前記ハイドロタルサイトを０．５～１０重量部含有することを特徴とするフッ素ゴム組成物。
  3. 　前記３元系フッ素ゴムポリマーは、フッ素含有量が６４～６７重量％であることを特徴とする請求項１又は２記載のフッ素ゴム組成物。
  4. 　請求項１～３の何れかに記載のフッ素ゴム組成物を架橋してなることを特徴とするフッ素ゴム架橋体。
PCT/JP2018/019449 2017-06-06 2018-05-21 フッ素ゴム組成物及びフッ素ゴム架橋体 WO2018225487A1 (ja)

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KR1020197036184A KR102300072B1 (ko) 2017-06-06 2018-05-21 불소 고무 조성물 및 불소 고무 가교체
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