JP2005146099A - Low-hardness fluororubber composition - Google Patents

Low-hardness fluororubber composition Download PDF

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JP2005146099A
JP2005146099A JP2003384746A JP2003384746A JP2005146099A JP 2005146099 A JP2005146099 A JP 2005146099A JP 2003384746 A JP2003384746 A JP 2003384746A JP 2003384746 A JP2003384746 A JP 2003384746A JP 2005146099 A JP2005146099 A JP 2005146099A
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fluororubber
hardness
weight
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Mitsuru Maeda
満 前田
Akihiro Naraki
章浩 楢木
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Unimatec Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluororubber composition comprising a solid fluororubber and a liquid fluororubber as essential components, providing a vulcanized product having <50 JIS A-hardness, having excellent kneading processability and mold releasability, and providing the vulcanized product having excellent normal properties and compression set. <P>SOLUTION: The low-hardness fluororubber composition providing the vulcanized product having <50 JIS A hardness comprises (A) the solid fluororubber, (B) the liquid fluororubber and (C) a perfluoroalkane represented by the general formula: F(CF<SB>2</SB>)<SB>2n</SB>F (wherein n is an integer of 5-30), a 1H perfluoroalkane represented by the general formula: F(CF<SB>2</SB>)<SB>m</SB>H (wherein m is an integer of 10-30) or both thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、低硬度フッ素ゴム組成物に関する。更に詳しくは、固体状フッ素ゴムおよび液体状フッ素ゴムを主成分とし、JIS A硬さが50未満の加硫物を与える低硬度フッ素ゴム組成物に関する。   The present invention relates to a low hardness fluororubber composition. More specifically, the present invention relates to a low-hardness fluororubber composition that contains a solid fluororubber and a liquid fluororubber as a main component and gives a vulcanizate having a JIS A hardness of less than 50.

フッ素ゴム加硫物は、高温における耐熱性、耐薬品性、耐油性、耐候性などの点ですぐれた特性を有するため、ガスケット、Oリング、パッキンなどのシール材として、自動車工業、油圧工業、一般機械工業、航空機工業などの分野において、需要が急激に増加している。また、最近では、フッ素ゴム加硫物の上記諸特性に加えて、ガス透過性や汚染物質の発生の少なさが歓迎され、電子機器用のガスケット、パッキンなどへの用途も検討されている。   Fluoro rubber vulcanizate has excellent characteristics such as heat resistance at high temperatures, chemical resistance, oil resistance, weather resistance, etc., so as a sealing material for gaskets, O-rings, packing, etc. Demand is increasing rapidly in fields such as general machinery industry and aircraft industry. Recently, in addition to the above-mentioned characteristics of fluororubber vulcanizates, gas permeability and low generation of pollutants are welcomed, and applications for gaskets and packing for electronic devices are also being studied.

これらの機器用パッキンには、JIS A硬さで50未満の低硬度フッ素ゴムが要求されているが、通常の固体状フッ素ゴムだけでは、補強剤として一般に使用されているカーボンブラックやシリカなどを添加しない状態でも50未満の硬さであり、しかも良好なゴム物性を示すフッ素ゴム加硫成形品は得られない。   These device packings require low-hardness fluororubbers with a JIS A hardness of less than 50. However, ordinary solid fluororubbers only use carbon black, silica, etc. that are commonly used as reinforcing agents. Even when not added, a fluororubber vulcanized molded article having a hardness of less than 50 and showing good rubber properties cannot be obtained.

そこで、本出願人は先に、アミン加硫またはポリオール加硫可能な固体状フッ素ゴム、液体状フッ素ゴム、炭素数8以上のアルキル基を有する脂肪族アミンおよびパーフルオロポリエーテルを含有する、JIS A硬さが50未満の加硫物を与える低硬度フッ素ゴム組成物を提案している。
特許第3,277,571号公報
Therefore, the present applicant has previously included a solid fluororubber capable of amine vulcanization or polyol vulcanization, a liquid fluororubber, an aliphatic amine having an alkyl group having 8 or more carbon atoms, and perfluoropolyether, JIS. A low hardness fluororubber composition that provides a vulcanizate having an A hardness of less than 50 is proposed.
Japanese Patent No. 3,277,571

かかる低硬度フッ素ゴム組成物は、金型離型性にはすぐれているが、生地混練時のロール非粘着性についての言及はなく、これ以外の従来技術においても、混練加工性および金型離型性に優れ、しかも常態物性および耐圧縮永久歪特性にすぐれた加硫物を与え得る低硬度フッ素ゴム組成物については、殆ど満足されるレベルのものが提案されていないのが現状である。   Such a low-hardness fluororubber composition is excellent in mold releasability, but there is no mention of roll non-adhesiveness during dough kneading, and in other conventional techniques, kneadability and mold releasability are not mentioned. As for the low-hardness fluororubber composition that is excellent in moldability and can give a vulcanizate excellent in normal properties and compression set properties, an almost satisfactory level has not been proposed.

本発明の目的は、固体状フッ素ゴムおよび液体状フッ素ゴムを主成分とし、JIS A硬さが50未満の加硫物を与える低硬度フッ素ゴム組成物において、混練加工性、金型離型性に優れ、かつ加硫後の常態物性及び圧縮永久歪にもすぐれた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 to provide a low-hardness fluororubber composition comprising a solid fluororubber and a liquid fluororubber as a main component and giving a vulcanizate having a JIS A hardness of less than 50, kneadability, mold releasability Another object of the present invention is to provide a fluororubber composition which is excellent in normal properties after compression and excellent in compression set.

かかる本発明の目的は、(A) 固体状フッ素ゴム、(B) 液体状フッ素ゴム、(C) 一般式F(CF2)2nF(ここでnは5〜30の整数である)で表わされるパーフルオロアルカン、一般式F(CF2)mH(ここでmは10〜30の整数である)であらわされる1Hパーフルオロアルカンまたはこれらの両者を含有する、JIS A硬さが50未満の加硫物を与える低硬度フッ素ゴム組成物によって達成される。 The object of the present invention is represented by (A) solid fluororubber, (B) liquid fluororubber, (C) general formula F (CF 2 ) 2n F (where n is an integer of 5 to 30). Perfluoroalkane, 1H perfluoroalkane represented by the general formula F (CF 2 ) m H (where m is an integer of 10 to 30), or both, JIS A hardness is less than 50 This is achieved by a low hardness fluororubber composition that provides a vulcanizate.

本発明にかかる低硬度フッ素ゴム組成物は、JIS A硬さが50未満の加硫物を与えるとともに、得られる加硫物は、混練加工性、金型離型性に優れ、かつ加硫後の常態物性及び圧縮永久歪にもすぐれているため、ガスケット、Oリング、パッキンなどのシール材として、自動車工業、油圧工業、一般機械工業、航空機工業などの分野において、有効に用いられる。   The low hardness fluororubber composition according to the present invention gives a vulcanized product having a JIS A hardness of less than 50, and the obtained vulcanized product is excellent in kneadability and mold releasability, and after vulcanization. Therefore, it is effectively used as a sealing material for gaskets, O-rings, packings and the like in fields such as the automobile industry, hydraulic industry, general machinery industry, and aircraft industry.

固体状フッ素ゴムとしては、重量平均分子量Mw(40℃、ゲルパーメーションクロマトグラフィー、溶媒テトラヒドロフラン、ポリスチレン換算;以下同じ)が約50,000〜300,000の既知のフッ素ゴム、具体的にはフッ化ビニリデンを主成分とし、これと他の含フツ素オレフイン、例えばヘキサフルオロプロペン、ペンタフルオロプロペン、トリフルオロエチレン、トリフルオロクロロエチレン、テトラフルオロエチレン、フッ化ビニル、パーフルオロ(アクリル酸エステル)、アクリル酸パーフルオロアルキル、パーフルオロ(アルキルビニルエーテル)などの少なくとも一種との共重合体、テトラフルオロエチレン-プロピレン共重合体、テトラフルオロエチレン-プロピレン-フツ化ビニリデン3元共重合体などが用いられる。また、これらのフッ素ゴムの末端には、パーオキサイド加硫可能な架橋点モノマーや臭素、ヨウ素またはこれら両者を結合させたものも用いられる。   The solid fluororubber is a known fluororubber having a weight average molecular weight Mw (40 ° C., gel permeation chromatography, solvent tetrahydrofuran, polystyrene equivalent; the same shall apply hereinafter) of about 50,000 to 300,000, specifically vinylidene fluoride. And other fluorine-containing olefins such as hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (acrylate ester), perfluoroacrylate A copolymer with at least one of alkyl, perfluoro (alkyl vinyl ether), tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-propylene-vinylidene fluoride terpolymer, and the like are used. Further, a crosslinking point monomer capable of peroxide vulcanization, bromine, iodine or a combination of both is used at the end of these fluororubbers.

一方、液体状フッ素ゴムとしては、重量平均分子量Mwが約500〜10,000のフッ素ゴム、例えば、フッ化ビニリデン-ヘキサフルオロブロペン共重合体、フッ化ビニリデン-ヘキサフルオロプロペン-テトラフルオロエチレン3元共重合体などが用いられる。   On the other hand, the liquid fluororubber is a fluororubber having a weight average molecular weight Mw of about 500 to 10,000, for example, vinylidene fluoride-hexafluorobropen copolymer, vinylidene fluoride-hexafluoropropene-tetrafluoroethylene ternary copolymer. A polymer or the like is used.

フッ素ゴム組成物の調製にあたっては、ロール作業で均一に配合剤を混ぜるための切り返し作業が重要であるが、液状フッ素ゴムを添加すると生地のこしがなくなり、ロールに生地が粘着し、切り返しができない。これは密閉式混練機を用いる場合も同様であり、生地の粘着により排出が困難となる。このため、本発明においては、上記固体状フッ素ゴムおよび液状フッ素ゴムに加えて、さらにパーフルオロアルカン類が用いられる。   In the preparation of the fluororubber composition, it is important to turn over to mix the compounding agent uniformly in the roll operation. However, when the liquid fluororubber is added, the dough does not break and the dough sticks to the roll and cannot be turned over. The same applies to the case where a closed kneader is used, and it becomes difficult to discharge due to adhesion of the dough. Therefore, in the present invention, perfluoroalkanes are further used in addition to the solid fluororubber and the liquid fluororubber.

一般式 F(CF2) 2nF で表わされるパーフルオロアルカンは、一般式 F(CF2)nI で表わされるパーフルオロアルキルヨージドをカップリングすることによって製造される化合物であり、具体的には例えばパーフルオロデカン、パーフルオロドデカン、パーフルオロヘキサデカン、パーフルオロオクタデカン、パーフルオロエイコサン、パーフルオロテトラコサン、パーフルオロオクタコサン、パーフルオロトリアコンタン、パーフルオロテトラコンタン、パーフルオロペンタコンタン、パーフルオロヘキサコンタンなどが挙げられ、これらは単独であるいは混合物として用いられる。 The perfluoroalkane represented by the general formula F (CF 2 ) 2n F is a compound produced by coupling a perfluoroalkyl iodide represented by the general formula F (CF 2 ) n I, specifically For example, perfluorodecane, perfluorododecane, perfluorohexadecane, perfluorooctadecane, perfluoroeicosane, perfluorotetracosane, perfluorooctacosane, perfluorotriacontane, perfluorotetracontan, perfluoropentacontane, perfluoro Hexacontane and the like can be mentioned, and these are used alone or as a mixture.

また、一般式 F(CF2)mH で表わされる1Hパーフルオロアルカンは、パーフルオロアルキルハライドを亜鉛と反応させることによって製造される化合物であり、具体的には例えば1Hパーフルオロデカン、1Hパーフルオロドデカン、1Hパーフルオロヘキサデカン、1Hパーフルオロオクタデカン、1Hパーフルオロエイコサン、1Hパーフルオロテトラコサン、1Hパーフルオロオクタコサン、1Hパーフルオロトリアコンタンなどが挙げられ、これらは単独であるいは混合物として用いられる。
特開平5−320078号公報
In addition, 1H perfluoroalkane represented by the general formula F (CF 2 ) m H is a compound produced by reacting perfluoroalkyl halide with zinc. Specifically, for example, 1H perfluorodecane, 1H perfluorodecane, Fluorododecane, 1H perfluorohexadecane, 1H perfluorooctadecane, 1H perfluoroeicosane, 1H perfluorotetracosane, 1H perfluorooctacosane, 1H perfluorotriacontane and the like can be mentioned, and these can be used alone or as a mixture .
JP-A-5-320078

以上の必須成分は、(A) 固体状フッ素ゴム100重量部に対して、(B) 液体状フッ素ゴムが50〜100重量部、好ましくは70〜90重量部および(C) パーフルオロアルカン、1Hパーフルオロアルカンまたはこれらの両者が0.5〜10重量部、好ましくは4〜6重量部の割合で用いられる。(B)成分がこれ以上の使用割合では、良好な物性が得られないようになり、一方これ以下の使用割合では、加硫物のJIS A硬さが50より大となる。また、(C)成分がこれ以下の使用割合では、生地混練時のロール非粘着性が得られず、一方これより多い使用割合で用いられると、物性が低下するようになる。   The above essential components are (A) 50 to 100 parts by weight, preferably 70 to 90 parts by weight of liquid fluororubber with respect to 100 parts by weight of solid fluororubber and (C) perfluoroalkane, 1H. Perfluoroalkane or both of them is used in a proportion of 0.5 to 10 parts by weight, preferably 4 to 6 parts by weight. When the component (B) is used in an amount higher than this, good physical properties cannot be obtained. On the other hand, when the component is used at an amount less than this, the JIS A hardness of the vulcanizate is greater than 50. Further, when the component (C) is used at a ratio below this, roll non-adhesiveness at the time of kneading the dough cannot be obtained. On the other hand, when the component is used at a ratio higher than this, the physical properties are lowered.

なお、一般式F(CF2)2nF(ここでnは5〜30の整数である)で表わされるパーフルオロアルカン、一般式F(CF2)mH(ここでmは10〜30の整数である)であらわされる1Hパーフルオロアルカンまたはこれらの両者を含有するフッ素ゴム組成物は、本出願人によって提案されているが、この組成物は加硫成型時において金型離型性にすぐれ、しかも硬さ変化のない加硫物を与えるとされているが、生地混練時のロール非粘着性についての言及はなく、また得られる加硫物のJIS A硬さは70前後であることが示されている。
特開平7−224200号公報
A perfluoroalkane represented by the general formula F (CF 2 ) 2n F (where n is an integer of 5 to 30), a general formula F (CF 2 ) m H (where m is an integer of 10 to 30) The fluororubber composition containing 1H perfluoroalkane or both of these is proposed by the present applicant, and this composition has excellent mold releasability at the time of vulcanization molding, In addition, although it is said that a vulcanizate with no change in hardness is given, there is no mention of roll non-stickiness during dough kneading, and the JIS A hardness of the obtained vulcanizate is around 70. Has been.
JP 7-224200 A

以上の各成分を必須成分とする組成物中には、充填剤、補強剤としてのカーボンブラック、シリカ、グラファイト、クレー、タルク、けいそう土、硫酸バリウム、酸化チタンなどの添加が可能であり、補強効果の大きいカーボンブラック、シリカなどの場合には、硬さの上昇がみられるため、フッ素ゴム合計量100重量部当り約10重量部以下、好ましくは約5重量部以下にとどめることが望ましい。   In the composition containing each of the above components as essential components, fillers, carbon black as a reinforcing agent, silica, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium oxide, etc. can be added, In the case of carbon black, silica, etc., which have a large reinforcing effect, an increase in hardness is observed, so it is desirable to keep the amount to about 10 parts by weight or less, preferably about 5 parts by weight or less per 100 parts by weight of the total amount of fluororubber.

加硫系については特に指定がなく、アミン加硫、ポリオール加硫、パーオキサイド加硫など任意の加硫方法をとることができ、これらの加硫系に必要な配合剤、例えば加硫剤、加硫促進剤、受酸剤などが配合される。   The vulcanization system is not particularly specified, and any vulcanization method such as amine vulcanization, polyol vulcanization, peroxide vulcanization, etc. can be used. The compounding agents necessary for these vulcanization systems, such as vulcanizing agents, Vulcanization accelerator, acid acceptor, etc. are blended.

アミン加硫の加硫剤としては、4,4′-メテレンビス(シクロヘキシルアミン)カーバメート、へキサメチレンジアミンカーバメート、N,N′-ジシンナミリデン-1,6-ヘキサンジアミンなどが用いられ、ポリオール加硫の架橋剤としては、2,2-ビス(4-ヒドロキシフェニル)プロパン〔ビスフェノールA〕、2,2-ビス(4-ヒドロキシフェニル)パーフルオロプロパン〔ビスフェノールAF〕、ヒドロキノン、カテコール、レゾルシン、4,4′-ジヒドロキシジフェニル、4,4′-ジヒドロキシジフェニルメタン、4,4′-ジヒドロキシジフェニルスルホン、2,2-ビス(4-ヒドロキシフェニル)ブタンなどのポリヒドロキシ芳香族化合物あるいはそれらのアルカリ金属塩またはアルカリ土類金属塩が用いられ、またパーオキサイド加硫の際の多官能性不飽和化合物、共架橋剤および有機過酸化物としては、一般に用いられている任意のものを用いることができる。   As the vulcanizing agent for amine vulcanization, 4,4′-methylenebis (cyclohexylamine) carbamate, hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexanediamine and the like are used. As the crosslinking agent, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane (bisphenol AF), hydroquinone, catechol, resorcin, 4,4 Polyhydroxyaromatic compounds such as' -dihydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, 2,2-bis (4-hydroxyphenyl) butane, or alkali metal salts or alkaline earth thereof Metal salts are used, and polyfunctional unsaturated compounds, co-crosslinking agents and organic compounds during peroxide vulcanization As the oxide, it can be used any of those commonly used.

加硫促進剤としては、ポリヒドロキシ芳香族化合物またはその金属塩が加硫剤として用いられたとき、各種の第4級アンモニウム塩または第4級ホスホニウム塩などが、フッ素ゴム合計量100重量部当り約0.1〜10重量部、好ましくは約0.1〜2重量部の割合で用いられる。また、受酸剤としては、各種の2価金属の酸化物または水酸化物が、フッ素ゴム合計量100重量部当り約1〜30重量部、好ましくは約3〜20重量部の割合で用いられる。共架橋剤は、フッ素ゴム合計量100重量部当り約0.5〜10重量部、好ましくは約0.5〜6重量部の割合で、また有機過酸化物は、フッ素ゴム合計量100重量部当り約0.1〜5重量部、好ましくは約0.5〜3重量部の割合で、それぞれ用いられる。   As a vulcanization accelerator, when a polyhydroxy aromatic compound or a metal salt thereof is used as a vulcanizing agent, various quaternary ammonium salts or quaternary phosphonium salts are used per 100 parts by weight of the total amount of fluororubber. About 0.1 to 10 parts by weight, preferably about 0.1 to 2 parts by weight is used. As the acid acceptor, various divalent metal oxides or hydroxides are used at a ratio of about 1 to 30 parts by weight, preferably about 3 to 20 parts by weight per 100 parts by weight of the total amount of fluororubber. . The co-crosslinking agent is about 0.5 to 10 parts by weight, preferably about 0.5 to 6 parts by weight per 100 parts by weight of fluororubber, and the organic peroxide is about 0.1 to about 100 to 100 parts by weight of fluororubber. 5 parts by weight, preferably about 0.5 to 3 parts by weight, are used respectively.

組成物の調製は、ミキシングロールなどを用いて行われ、調製された組成物の加硫は、一般にプレス加硫および加熱オーブン中での二次加硫によって行われるが、射出成形も可能である。   The composition is prepared using a mixing roll or the like, and the vulcanization of the prepared composition is generally performed by press vulcanization and secondary vulcanization in a heating oven, but injection molding is also possible. .

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1〜4、比較例1〜4
固体状フッ素ゴムA(アミン加硫、ポリオール加硫用):フッ化ビニリデン-ヘキサフルオロプロペン(モル比78:22)共重合体(重量平均分子量Mw200,000)
固体状フッ素ゴムB(パーオキサイド加硫用):フッ化ビニリデン-ヘキサフルオロプロペン-テトラフルオロエチレン(モル比68:16:16)3元共重合体(重量平均分子量Mw160,000)
液体状フッ素ゴム:フッ化ビニリデン-ヘキサフルオロプロペン(モル比78:22)共重合体(重量平均分子量Mw 6,000)
上記固体状フッ素ゴム、液体状フッ素ゴムおよび下記表1に示される配合処方の各種配合剤(いずれも重量部)を、8インチミキシングロールで混練し、低硬度フッ素ゴム組成物を調製した。生地混練時のロール非粘着性については○(粘着なし)、△(粘着小)、×(粘着大)の3段階で評価した。得られた結果は、下記表1に示される。なお、実施例1〜3において、パーフルオロアルカンを用いない場合には、混練性が著しく悪化するため、比較例1〜3においては、液状フッ素ゴムが減量されて用いられた。
表1
実施例 比較例
配合処方 1 2 3 4 1 2 3 4 5
固体状フッ素ゴムA 100 100 100 100 100 100 100
固体状フッ素ゴムB 100 100
液体状フッ素ゴム 80 80 80 80 60 60 60 40 80
MTカーボンブラック 2 2 2 2 2 2 2 2 2
水酸化カルシウム 12 12 12 12 12
酸化マグネシウム 5 5 5 5 5
亜鉛華 15 6 15 6
4,4´-メチレンビス(シクロ 2 2
ヘキシルアミン)カーバメート
ビスフェノールAF 3 3 3 3 3
ベンジルトリフェニル 2.5 2.5 2.5 2.5 2.5
ホスホニウムクロライド
トリアリルイソシアヌレート 10 10
(日本化成製品TAICM-60)
有機過酸化物(日本油脂製品 2 2
パーヘキサ25B-40)
F(CF2)24F-F(CF2)12H(重量比1:1) 5 5 5 5
F(CF2)24F 5
Examples 1-4, Comparative Examples 1-4
Solid fluororubber A (for amine vulcanization and polyol vulcanization): Vinylidene fluoride-hexafluoropropene (molar ratio 78:22) copolymer (weight average molecular weight Mw 200,000)
Solid fluororubber B (for peroxide vulcanization): Vinylidene fluoride-hexafluoropropene-tetrafluoroethylene (molar ratio 68:16:16) terpolymer (weight average molecular weight Mw 160,000)
Liquid fluororubber: Vinylidene fluoride-hexafluoropropene (molar ratio 78:22) copolymer (weight average molecular weight Mw 6,000)
The above solid fluororubber, liquid fluororubber and various compounding agents (all by weight) shown in Table 1 below were kneaded with an 8-inch mixing roll to prepare a low-hardness fluororubber composition. The roll non-adhesiveness at the time of kneading the dough was evaluated in three stages: ○ (no adhesion), Δ (small adhesion), and x (high adhesion). The obtained results are shown in Table 1 below. In Examples 1 to 3, when perfluoroalkane was not used, the kneadability was remarkably deteriorated. Therefore, in Comparative Examples 1 to 3, the liquid fluororubber was used in a reduced amount.
Table 1
Example Comparative Example
Formulation 1 2 3 4 1 2 3 4 5
Solid fluororubber A 100 100 100 100 100 100 100
Solid fluororubber B 100 100
Liquid fluororubber 80 80 80 80 60 60 60 40 80
MT carbon black 2 2 2 2 2 2 2 2 2
Calcium hydroxide 12 12 12 12 12
Magnesium oxide 5 5 5 5 5
Zinc flower 15 6 15 6
4,4´-methylenebis (cyclo 2 2
(Hexylamine) Carbamate Bisphenol AF 3 3 3 3 3
Benzyltriphenyl 2.5 2.5 2.5 2.5 2.5
Phosphonium chloride triallyl isocyanurate 10 10
(Nippon Kasei product TAICM-60)
Organic peroxide (Japanese fat products 2 2
Perhexa 25B-40)
F (CF 2 ) 24 FF (CF 2 ) 12 H (weight ratio 1: 1) 5 5 5 5
F (CF 2 ) 24 F 5

得られた各種の低硬度フッ素ゴム組成物を、150℃で15分間プレス加硫し、次いで200℃のオーブン中で10時間の二次加硫を行い、各加硫物の諸特性をJIS K-6301に従って測定した。圧縮永久歪は、P-24のOリングを同じ条件で加硫して製作し、これを175℃、120時間、25%圧縮の条件下で測定した。更に、P−24 Oリング10個取りで、バリ部分の厚みが0.06mmのバリとOリングとが−体成形できる金型を用いて、外部離型剤なしの条件下でプレス加硫を行い、Oリングとバリ部とが一体に離型できるか否かを測定した。このような操作を5回くり返し、金型上に残存するOリングの割合を離型率とし、金型離型性の目安とした。得られた結果は、下記表2に示される。
表2
実施例 比較例
測定項目 1 2 3 4 1 2 3 4 5
〔成型時〕
生地混練時の非粘着性 ○ △ △ ○ × × × ○ ×
離型率 (%) 0 30 30 0 100 100 100 100 100
〔加硫物〕
硬さ (JIS A) 40 43 41 40 47 46 49 51 39
100%モジュラス (MPa) 0.6 0.8 0.6 0.6 0.5 0.8 0.6 1.0 0.5
引張強さ (MPa) 6.8 7.2 7.3 6.7 7.0 7.4 7.3 9.3 6.9
伸び (%) 510 530 500 500 500 550 490 490 520
圧縮永久歪 (%) 31 52 55 31 30 53 54 28 32
The various low-hardness fluororubber compositions obtained were press vulcanized at 150 ° C for 15 minutes, followed by secondary vulcanization in an oven at 200 ° C for 10 hours. Measured according to -6301. The compression set was produced by vulcanizing a P-24 O-ring under the same conditions, and this was measured under conditions of 175 ° C., 120 hours, 25% compression. Furthermore, press vulcanization is performed under conditions without external release agent using a mold that can form burrs and O-rings with a burr thickness of 0.06 mm with 10 P-24 O-rings. Then, it was measured whether or not the O-ring and the burr part could be released from each other. Such an operation was repeated 5 times, and the ratio of the O-ring remaining on the mold was defined as the mold release rate, which was used as a guide for the mold releasability. The obtained results are shown in Table 2 below.
Table 2
Example Comparative Example
Measurement item 1 2 3 4 1 2 3 4 5
[When molding]
Non-adhesiveness during dough kneading ○ △ △ ○ × × × ○ ×
Mold release rate (%) 0 30 30 0 100 100 100 100 100
[Vulcanized product]
Hardness (JIS A) 40 43 41 40 47 46 49 51 39
100% modulus (MPa) 0.6 0.8 0.6 0.6 0.5 0.8 0.6 1.0 0.5
Tensile strength (MPa) 6.8 7.2 7.3 6.7 7.0 7.4 7.3 9.3 6.9
Elongation (%) 510 530 500 500 500 550 490 490 520
Compression set (%) 31 52 55 31 30 53 54 28 32

Claims (2)

(A) 固体状フッ素ゴム、(B) 液体状フッ素ゴム、(C) 一般式F(CF2)2nF(ここでnは5〜30の整数である)で表わされるパーフルオロアルカン、一般式F(CF2)mH(ここでmは10〜30の整数である)であらわされる1Hパーフルオロアルカンまたはこれらの両者を含有する、JIS A硬さが50未満の加硫物を与える低硬度フッ素ゴム組成物。 (A) Solid fluororubber, (B) Liquid fluororubber, (C) Perfluoroalkane represented by the general formula F (CF 2 ) 2n F (where n is an integer of 5 to 30), general formula Low hardness that gives a vulcanized product containing a 1H perfluoroalkane represented by F (CF 2 ) m H (where m is an integer of 10 to 30) or both of which have a JIS A hardness of less than 50 Fluoro rubber composition. (A) 固体状フッ素ゴム100重量部に対して、(B) 液体状フッ素ゴム50〜100重量部および(C) パーフルオロアルカン、1Hパーフルオロアルカンまたはこれらの両者を0.5〜10重量部の割合で含有する請求項1記載の低硬度フッ素ゴム組成物。
(A) Ratio of 50 to 100 parts by weight of liquid fluororubber and (C) 0.5 to 10 parts by weight of perfluoroalkane, 1H perfluoroalkane, or both of these with respect to 100 parts by weight of solid fluororubber The low-hardness fluororubber composition according to claim 1, which is contained in
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006001363A1 (en) * 2004-06-28 2006-01-05 Daikin Industries, Ltd. Fluorine-containing elastomer composition and molded article made therefrom
WO2006120818A1 (en) * 2005-05-11 2006-11-16 Nok Corporation Polyol-crosslinkable fluororubber composition
WO2008093803A1 (en) * 2007-02-01 2008-08-07 Nok Corporation Crosslinked fluororubber for rotational sliding sealing and process for producing the same
WO2009113193A1 (en) * 2008-03-11 2009-09-17 Nok株式会社 Process for producing rotating/sliding seal and rotating/sliding seal
JP2017183161A (en) * 2016-03-31 2017-10-05 住友理工株式会社 Seal member for fuel cell and manufacturing method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006001363A1 (en) * 2004-06-28 2006-01-05 Daikin Industries, Ltd. Fluorine-containing elastomer composition and molded article made therefrom
JPWO2006001363A1 (en) * 2004-06-28 2008-04-17 ダイキン工業株式会社 Fluorine-containing elastomer composition and molded article comprising the same
US7879948B2 (en) 2004-06-28 2011-02-01 Daikin Industries, Ltd. Fluorine containing elastomer composition and molded article comprising the same
JP4840138B2 (en) * 2004-06-28 2011-12-21 ダイキン工業株式会社 Fluorine-containing elastomer composition and molded article comprising the same
WO2006120818A1 (en) * 2005-05-11 2006-11-16 Nok Corporation Polyol-crosslinkable fluororubber composition
US7816454B2 (en) 2005-05-11 2010-10-19 Nok Corporation Polyol-crosslinkable fluoro-rubber composition
WO2008093803A1 (en) * 2007-02-01 2008-08-07 Nok Corporation Crosslinked fluororubber for rotational sliding sealing and process for producing the same
WO2009113193A1 (en) * 2008-03-11 2009-09-17 Nok株式会社 Process for producing rotating/sliding seal and rotating/sliding seal
JP5131347B2 (en) * 2008-03-11 2013-01-30 Nok株式会社 Manufacturing method of rotary sliding seal and rotary sliding seal
JP2017183161A (en) * 2016-03-31 2017-10-05 住友理工株式会社 Seal member for fuel cell and manufacturing method thereof

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