JP6435666B2 - Fluoro rubber composition - Google Patents
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本発明は、フッ素ゴム組成物に関する。さらに詳しくは、オイルシール等の成形材料などとして用いられるフッ素ゴム組成物に関する。 The present invention relates to a fluororubber composition. More specifically, the present invention relates to a fluororubber composition used as a molding material such as an oil seal.
フッ素ゴムは耐油性、耐燃料油性にすぐれていることから、自動車、産業機械等の幅広い分野で、Oリング、パッキン等のシール材料として用いられており、例えばオイルシールは、自動車、産業機械等の分野で重要な機械部品として広く用いられている。 Fluororubber has excellent oil resistance and fuel oil resistance, so it is used as a sealing material for O-rings, packing, etc. in a wide range of fields such as automobiles and industrial machines. For example, oil seals are used in automobiles, industrial machines, etc. It is widely used as an important machine part in the field.
本出願人は先に、シール材料として、ゴム100重量部当り、アスペクト比8以上の針状または繊維状の充填剤を1〜100重量部含有するゴム組成物を提案しており、その実施例にはフッ化ビニリデン(VdF)-ヘキサフルオロプロピレン(HFP)２元共重合ゴムにアスペクト比8のウォラストナイトを配合せしめたフッ素ゴム組成物が開示されている(特許文献１)。また、フッ化ビニリデン(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)３元共重合ゴムを用いたフッ素ゴム組成物もシール材料として一般的に用いられている。 The present applicant has previously proposed a rubber composition containing 1 to 100 parts by weight of an acicular or fibrous filler having an aspect ratio of 8 or more per 100 parts by weight of rubber as a sealing material. Discloses a fluororubber composition in which wollastonite having an aspect ratio of 8 is blended with a vinylidene fluoride (VdF) -hexafluoropropylene (HFP) binary copolymer rubber (Patent Document 1). Further, a fluororubber composition using a vinylidene fluoride (VdF) -hexafluoropropylene (HFP) -tetrafluoroethylene (TFE) terpolymer rubber is also generally used as a sealing material.
しかしながら、これらの２元系あるいは３元系フッ素ゴム組成物から加硫成形されたフッ素ゴムは、潤滑油に含まれる塩基性添加剤への耐性の点においては十分ではなく、塩基性添加剤が大量に含まれる潤滑油をシール対象とした箇所への用途には改良が求められている。近年、機器の長寿命化が求められており、耐熱性、耐摩耗性など耐久性にすぐれるフッ素ゴム組成物を、ギア油などの添加剤が大量に含まれるシール用途に適用できれば機器の長寿命化に貢献することが可能となる。 However, fluororubbers vulcanized and molded from these binary or ternary fluororubber compositions are not sufficient in terms of resistance to basic additives contained in lubricating oils. There is a need for improvement in applications where a large amount of lubricating oil is to be sealed. In recent years, there has been a demand for longer life of equipment, and if a fluororubber composition with excellent durability such as heat resistance and wear resistance can be applied to sealing applications containing a large amount of additives such as gear oil, the length of the equipment will be increased. It is possible to contribute to life extension.
本発明の目的は、耐熱性、耐摩耗性などの耐久性にすぐれるとともに、耐潤滑油性、シール性をも十分に満足し得る、オイルシールなどのシールの成形材料などとして好適に用いられるフッ素ゴム組成物を提供することにある。 The object of the present invention is suitably used as a molding material for a seal such as an oil seal, which has excellent durability such as heat resistance and wear resistance, and can sufficiently satisfy lubricating oil resistance and sealability. The object is to provide a fluororubber composition.
かかる本発明の目的は、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-エチレン-パーフルオロ(アルキルビニルエーテル)5元共重合体よりなるフッ素ゴム100重量部当り、平均粒子径が6〜35μmの珪藻土、ウォラストナイト、タルク、グラファイトおよび炭素繊維の少なくとも一種を3〜60重量部含有せしめたフッ素ゴム組成物によって達成される。 The object of the present invention is to provide diatomaceous earth having an average particle diameter of 6 to 35 μm per 100 parts by weight of fluororubber comprising a quinarypolymer of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-ethylene-perfluoro (alkyl vinyl ether). , A fluororubber composition containing 3 to 60 parts by weight of at least one of wollastonite, talc, graphite and carbon fiber.
本発明に係るフッ素ゴム組成物は、フッ素ゴム共重合モノマーとしてフッ化ビニリデン、ヘキサフルオロプロピレン、テトラフルオロエチレン、パーフルオロ(アルキルビニルエーテル)に加えて、ポリマー主鎖に塩基による攻撃の保護ポリマーとして働くと考えられるエチレンを導入しているため、フッ素ゴムの特性を保持しつつ、共重合モノマーとしてエチレンを用いていない２元共重合体あるいは３元共重合体フッ素ゴムに比べて耐塩基性を向上せしめ、硬化劣化を著しく抑制することができるといったすぐれた効果を奏する。 In addition to vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, perfluoro (alkyl vinyl ether) as a fluororubber copolymerization monomer, the fluororubber composition according to the present invention functions as a protective polymer against attack by a base in the polymer main chain. Because of the introduction of ethylene, improved base resistance compared to binary or ternary copolymer fluororubbers that do not use ethylene as a comonomer while maintaining the properties of fluororubber It has an excellent effect of being able to significantly suppress deterioration due to caking.
フッ素ゴムとしては、フッ化ビニリデン〔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〕-エチレン〔E〕-パーフルオロ(アルキルビニルエーテル)〔FAVE〕5元共重合体、好ましくはVdF-HFP-TFE-E-パーフルオロ(メチルビニルエーテル)〔FMVE〕5元共重合体が用いられ、これは例えば市販品であるSolvey製品Thecnoflon BR9151などをそのまま用いることができる。ここで、エチレンが共重合されていないフッ素ゴムを用いた場合には、その加硫成形品であるシール材は本発明の目的とする耐久性を達成することができない。かかる5元共重合体は、好ましくは有機過酸化物架橋剤-多官能性不飽和化合物共架橋剤よりなる架橋系によって架橋される。 Fluoro rubber includes vinylidene fluoride [VdF] -hexafluoropropylene [HFP] -tetrafluoroethylene [TFE] -ethylene [E] -perfluoro (alkyl vinyl ether) [FAVE] terpolymer, preferably VdF- HFP-TFE-E-perfluoro (methyl vinyl ether) [FMVE] terpolymer is used. For example, commercially available Solvey product Thecnoflon BR9151 can be used as it is. Here, in the case of using a fluororubber that is not copolymerized with ethylene, the sealing material that is a vulcanized molded product cannot achieve the durability intended by the present invention. Such a ternary copolymer is preferably crosslinked by a crosslinking system comprising an organic peroxide crosslinking agent-polyfunctional unsaturated compound co-crosslinking agent.
フッ素ゴムには、充填剤として平均粒子径(レーザー散乱法により測定)が6〜35μmの珪藻土、ウォラストナイト(CaO・SiO2)、タルク〔Mg3Si3O10(OH)2〕、グラファイト、マイカおよび炭素繊維の少なくとも一種、好ましくは珪藻土、ウォラストナイト、タルク、グラファイトおよび炭素繊維が、フッ素ゴム100重量部当り1〜60重量部、好ましくは3〜50重量部の割合で配合される。これらの充填剤の量がこれより少ない割合で用いられると、この加硫成形物は本発明の目的とするシール性能を達成することができず、一方これより多い割合で用いられると、組成物が硬くなり過ぎてしまい、成形性に悪影響を及ぼすようになる。ここで、充填剤が繊維状の場合には、平均粒子径とは、その平均繊維長を意味している。 Fluororubber contains diatomite, wollastonite (CaO · SiO 2 ), talc (Mg 3 Si 3 O 10 (OH) 2 ), graphite, having an average particle size (measured by laser scattering method) of 6 to 35 μm as fillers. , At least one of mica and carbon fiber, preferably diatomaceous earth, wollastonite, talc, graphite and carbon fiber are blended in an amount of 1 to 60 parts by weight, preferably 3 to 50 parts by weight per 100 parts by weight of fluororubber . If the amount of these fillers is used in a smaller proportion, this vulcanized molded product cannot achieve the sealing performance intended by the present invention, whereas if it is used in a proportion higher than this, the composition Becomes too hard, which adversely affects moldability. Here, when the filler is fibrous, the average particle diameter means the average fiber length.
なお、特許文献１には、鉄道車両用正・逆両回転用オイルシールの成形材料として、フッ素ゴム(VdF-HFP共重合体)100重量部当り、アスペクト比8以上のウォラストナイト1〜100重量部を添加し、それを混練して調製されたフッ素ゴム組成物が開示されているが、本発明で用いられている５元共重合体については何ら教示されてはいない。この文献で開示されている２元共重合体や一般的にシール材料として用いられる３元共重合体を用いた場合には、平均繊維径が6μm以上の珪藻土、ウォラストナイト、タルク、グラファイト、マイカおよび炭素繊維の少なくとも一種を用いた場合であっても、後記比較例２〜３に示されるように例えば200時間以上といった耐久時間を達成することは難しくなる。 Patent Document 1 discloses a wollastonite 1 to 100 having an aspect ratio of 8 or more per 100 parts by weight of fluororubber (VdF-HFP copolymer) as a molding material for forward and reverse rotation oil seals for railway vehicles. Although a fluororubber composition prepared by adding parts by weight and kneading them is disclosed, there is no teaching about the ternary copolymer used in the present invention. When the binary copolymer disclosed in this document or the ternary copolymer generally used as a sealing material is used, diatomaceous earth, wollastonite, talc, graphite, having an average fiber diameter of 6 μm or more, Even when at least one of mica and carbon fiber is used, it is difficult to achieve a durability time of, for example, 200 hours or more as shown in Comparative Examples 2 to 3 below.
また、特許文献２では、フッ化ビニリデン、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)、CF2=CFO[CF2CF(CF3)O]nCF3およびRfX(Rfは炭素数2〜8の不飽和フルオロ炭化水素基であり、基中に1個以上のエーテル結合を有していてもよく、Xは臭素またはヨウ素である)を共重合成分とする含フッ素エラストマーが開示されている。しかるに、この場合にも特許文献１記載の２元共重合体フッ素ゴムあるいは３元共重合体フッ素ゴムと同様に、例えばVdF-HFP結合が、潤滑油などに含まれる塩基性の添加剤によりフッ化水素の脱離反応が起こり、C=C二重結合が生成してしまい、この二重結合にアミンが付加することで硬化劣化が生じることとなる。これに対して本発明では、共重合成分としてエチレンを用いたフッ素ゴムを選択することにより、ポリマー主鎖のVdF含有量あるいはVdF-HFP結合を減らすことで、耐塩基性を向上せしめ、硬化劣化を著しく抑制することを可能にしているといった点で、公知のフッ素ゴム組成物とは大きく相違している。 In Patent Document 2, vinylidene fluoride, tetrafluoroethylene, perfluoro (methyl vinyl ether), CF 2 = CFO [CF 2 CF (CF 3 ) O] nCF 3 and RfX (Rf is a non-carbon having 2 to 8 carbon atoms). There is disclosed a fluorine-containing elastomer having a copolymer component as a saturated fluorohydrocarbon group, which may have one or more ether bonds in the group, and X is bromine or iodine. However, in this case as well, as in the binary copolymer fluororubber or ternary copolymer fluororubber described in Patent Document 1, for example, a VdF-HFP bond is blocked by a basic additive contained in a lubricating oil or the like. The elimination reaction of hydride occurs and a C = C double bond is generated, and an amine is added to this double bond, resulting in curing deterioration. On the other hand, in the present invention, by selecting a fluororubber using ethylene as a copolymerization component, the VdF content of the polymer main chain or the VdF-HFP bond is reduced, thereby improving the base resistance and curing deterioration. Is significantly different from the known fluororubber composition in that it is possible to remarkably suppress the above.
以上の必須成分よりなるフッ素ゴム組成物には、加硫操作上、物性上、機能上などから要求される各種配合剤が添加され、例えばフッ素ゴム加硫に用いられるポリオール系または有機過酸化物系加硫剤、4級オニウム塩等の加硫助剤、多官能性不飽和化合物共架橋剤、カーボンブラック等の必須成分以外の補強剤または充填剤、2価金属の酸化物、水酸化物またはハイドロタルサイト等の受酸剤、その他必要な配合剤が配合された上で、オープンロール、ニーダなどを用いる任意の混練手段により組成物の調製が行われ、約160〜200℃、約3〜30分間のヒートプレスおよび必要に応じて約150〜250℃、約0.5〜24時間の二次加硫を行うことにより、オイルシールなどのシール材へと加硫成形される。 To the fluororubber composition comprising the above essential components, various compounding agents required for vulcanization operation, physical properties, and functions are added. For example, polyol-based or organic peroxide used for fluororubber vulcanization -Based vulcanizing agents, vulcanizing aids such as quaternary onium salts, polyfunctional unsaturated compound co-crosslinking agents, reinforcing agents or fillers other than essential components such as carbon black, divalent metal oxides, hydroxides Alternatively, an acid acceptor such as hydrotalcite and other necessary compounding agents are blended, and then the composition is prepared by any kneading means using an open roll, a kneader, and the like, and about 160 to 200 ° C., about 3 It is vulcanized and formed into a sealing material such as an oil seal by performing a heat press for ˜30 minutes and optionally performing secondary vulcanization at about 150 to 250 ° C. for about 0.5 to 24 hours.
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.
実施例１
フッ素ゴム(VdF-HFP-TFE-E-FMVE５元共重合体： 100重量部
Solvey製品Tecnoflon BR9151)
珪藻土(中央シリカ製品シリカ6B；平均粒子径 6.4μm) 30 〃
N990カーボンブラック 5 〃
トリアリルイソシアヌレート(日本化成製品TAIC) 2 〃
有機過酸化物(日本油脂製品パーヘキサ25B-40) 2 〃
以上の各成分をニーダおよびオープンロールを用いて混練し、180℃、10分間の一次加硫および200℃、24時間の二次加硫を行い、内径85mm、外径105mm、幅13mmのオイルシールを加硫成形した。
Example 1
Fluoro rubber (VdF-HFP-TFE-E-FMVE ternary copolymer: 100 parts by weight
Solvey product Tecnoflon BR9151)
Diatomaceous earth (central silica product silica 6B; average particle size 6.4μm) 30 〃
N990 carbon black 5 〃
Triallyl isocyanurate (Nippon Kasei products TAIC) 2 〃
Organic peroxides (NIPPON YILLOW PRODUCT PERHEXA 25B-40) 2 〃
The above components are kneaded using a kneader and an open roll, subjected to primary vulcanization at 180 ° C for 10 minutes and secondary vulcanization at 200 ° C for 24 hours, and an oil seal with an inner diameter of 85 mm, an outer diameter of 105 mm, and a width of 13 mm Was vulcanized and molded.
実施例２
実施例１において、珪藻土の代わりにウォラストナイト(NYCO Minerals製品NYAD400；平均繊維径7μm、平均繊維長35μm、アスペクト比5))が同量(30重量部)用いられた。
Example 2
In Example 1, the same amount (30 parts by weight) of wollastonite (NYCO Minerals product NYAD400; average fiber diameter 7 μm, average fiber length 35 μm, aspect ratio 5) was used instead of diatomaceous earth.
実施例３
実施例１において、珪藻土の代わりにタルク(浅田製粉製品タルクSW-H；平均粒子径14μm)が同量(30重量部)用いられた。
Example 3
In Example 1, the same amount (30 parts by weight) of talc (Asada Milled Product Talc SW-H; average particle size 14 μm) was used instead of diatomaceous earth.
実施例４
実施例１において、珪藻土の代わりにグラファイト(日本黒鉛製品CPB6S；平均粒子径12μm)が同量(30重量部)用いられた。
Example 4
In Example 1, the same amount (30 parts by weight) of graphite (Japanese graphite product CPB6S; average particle size of 12 μm) was used instead of diatomaceous earth.
実施例５
実施例１において、珪藻土の代わりに炭素繊維(大阪ガスケミカル製品ドナカーボS2404N；平均繊維径 13μm)20重量部が用いられた。
Example 5
In Example 1, 20 parts by weight of carbon fiber (Osaka Gas Chemical Product DonaCarbo S2404N; average fiber diameter 13 μm) was used instead of diatomaceous earth.
比較例１
実施例１において、珪藻土が用いられず、N990カーボンブラック量が35重量部に変更されて用いられた。
Comparative Example 1
In Example 1, diatomaceous earth was not used, and the amount of N990 carbon black was changed to 35 parts by weight.
比較例２
実施例１において、フッ素ゴムとしてVdF-HFP２元共重合体(ダイキン製品DAIEL G-801)が同量(100重量部)用いられた。
Comparative Example 2
In Example 1, the same amount (100 parts by weight) of VdF-HFP binary copolymer (Daikin product DAIEL G-801) was used as the fluororubber.
比較例３
実施例１において、フッ素ゴムとしてVdF-HFP-TFE３元共重合体(ダイキン製品DAIEL G-9074)が同量(100重量部)用いられた。
Comparative Example 3
In Example 1, the same amount (100 parts by weight) of VdF-HFP-TFE terpolymer (Daikin product DAIEL G-9074) was used as the fluororubber.
以上の各実施例および比較例で得られたオイルシールを用いて、常態物性の測定、浸せき試験およびオイルシール密封試験を行った。
常態物性(硬度 Hs)：JIS K6253：1997に準拠し、タイプAデュロメータを用い
て瞬時の硬さを測定した
浸せき試験：工業用ギア油(ロイヤルパープル製品ギヤープレミアム320)に150℃
、140時間浸せき前後の伸びを測定し、変化率を算出した
また、浸せき後の試験片について180°の角度で屈曲を行い、クラッ
クの発生がみられなかったものを○、クラックの発生がみられたもの
を×と評価した
オイルシール密封試験：オイルシールを回転試験機にセットし、工業用ギア油(ギ
ヤープレミアム320)を回転軸を中心とした状態で密封し、
試験温度130℃、回転数6000rpm(周速26.7m／秒)の条件下
で200時間運転を行い、油漏れの有無を確認した
油漏れなしであれば、密封性の効果が明確であるといえる
Using the oil seals obtained in each of the above Examples and Comparative Examples, normal property measurements, immersion tests, and oil seal sealing tests were performed.
Normal state physical properties (hardness Hs): Conforms to JIS K6253: 1997, using type A durometer
Instantaneous hardness measured by immersion test: 150 ° C in industrial gear oil (Royal Purple Product Gear Premium 320)
The elongation before and after immersion for 140 hours was measured and the rate of change was calculated.
Also, bend the specimen after immersion at an angle of 180 ° to
No crack was observed, ○, crack was observed
Oil seal sealing test: An oil seal was set on a rotating test machine and industrial gear oil (G
Yer Premium 320) is sealed around the rotation axis,
Conditions of test temperature 130 ℃, rotation speed 6000rpm (circumferential speed 26.7m / sec)
Ran for 200 hours and checked for oil leaks
If there is no oil leak, it can be said that the sealing effect is clear.
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。
表
実 施 例 比 較 例
測定・評価項目 １ ２ ３ ４ ５ １ ２ ３
〔常態物性〕
硬さ(デュロメーターA) 75 75 75 77 75 77 78 81
〔浸せき試験〕
伸び変化率 (％) -31 -32 -29 -28 -30 -28 -96 -79
180°屈曲後 ○ ○ ○ ○ ○ ○ × ×
〔オイルシール密封試験〕
油漏れ なし なし なし なし なし あり あり あり
The results obtained in the above examples and comparative examples are shown in the following table.
table
Example comparison example
Measurement / evaluation items 1 2 3 4 5 1 2 3
[Normal properties]
Hardness (Durometer A) 75 75 75 77 75 77 78 81
[Immersion test]
Rate of change in elongation (%) -31 -32 -29 -28 -30 -28 -96 -79
After bending 180 ° ○ ○ ○ ○ ○ ○ × ×
[Oil seal sealing test]
Oil leak No No No No No Yes Yes Yes
Claims (4)
Diatomaceous earth, wollastonite, talc having an average particle size of 6 to 35 μm per 100 parts by weight of fluororubber consisting of quinarypolymer of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-ethylene-perfluoro (alkyl vinyl ether), A fluororubber composition containing 3 to 60 parts by weight of at least one of graphite, mica and carbon fiber.
The sealing material according to claim 3, which is used as an oil seal.
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| JP6625329B2 (en) * | 2015-02-23 | 2019-12-25 | 光洋シーリングテクノ株式会社 | Rubber composition and oil seal |
| CN108699313A (en) * | 2016-03-01 | 2018-10-23 | Nok株式会社 | Fluoro-rubber composite and crosslinked fluororubber |
| KR20200059225A (en) * | 2017-10-06 | 2020-05-28 | 에이지씨 가부시키가이샤 | Fluorine-containing copolymer composition and metal rubber laminate |
| KR20200065681A (en) * | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Composition for sealing member of continuous steel plate passing apparatus and continuous steel plate passing apparatus comprising the same |
| JP2023159467A (en) * | 2020-07-27 | 2023-11-01 | Nok株式会社 | Rubber molded product |
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| IT1247934B (en) * | 1991-05-15 | 1995-01-05 | Ausimont Spa | VINYLIDENFLUORIDE-BASED FLUOROELASTOMERS, EQUIPPED WITH SUPERIOR BASIC RESISTANCE |
| JP5294551B2 (en) * | 2006-09-07 | 2013-09-18 | Ｎｏｋ株式会社 | Oil seal for both forward and reverse rotation |
| WO2014175079A1 (en) * | 2013-04-26 | 2014-10-30 | Nok株式会社 | Fluorine-containing rubber composition |
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