JP7425374B2 - フッ素ゴム架橋用組成物および成形品 - Google Patents
フッ素ゴム架橋用組成物および成形品 Download PDFInfo
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- JP7425374B2 JP7425374B2 JP2022550500A JP2022550500A JP7425374B2 JP 7425374 B2 JP7425374 B2 JP 7425374B2 JP 2022550500 A JP2022550500 A JP 2022550500A JP 2022550500 A JP2022550500 A JP 2022550500A JP 7425374 B2 JP7425374 B2 JP 7425374B2
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- fluororubber
- crosslinking
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Description
本開示のフッ素ゴム架橋用組成物において、架橋剤(b)の含有量が、フッ素ゴム(a)100質量部に対し、0.1~10質量部であることが好ましい。
本開示のフッ素ゴム架橋用組成物は、架橋促進剤(c)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物において、架橋促進剤(c)の含有量が、フッ素ゴム(a)100質量部に対し、0.1~10質量部であることが好ましい。
本開示のフッ素ゴム架橋用組成物は、受酸剤(d)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物において、受酸剤(d)の含有量が、フッ素ゴム(a)100質量部に対し、0.1~50質量部であることが好ましい。
本開示のフッ素ゴム架橋用組成物において、受酸剤(d)が、金属酸化物、金属水酸化物、アルカリ金属ケイ酸塩、弱酸の金属塩およびハイドロタルサイトからなる群より選択される少なくとも1種であることが好ましい。
本開示のフッ素ゴム架橋用組成物において、架橋剤(b)が、2,7-ジヒドロキシ-9H-フルオレン-9-オン、および、2,7-ジヒドロキシ-9H-フルオレン-9-オンと、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種であることが好ましい。
本開示のフッ素ゴム架橋用組成物は、ジアルキルスルホン化合物をさらに含有することが好ましい。
本開示で用いるポリオール架橋可能なフッ素ゴムは、ポリオール架橋可能な部位を有するフッ素ゴムである。本開示において、フッ素ゴムとは、非晶質フルオロポリマーである。「非晶質」とは、フルオロポリマーの示差走査熱量測定〔DSC〕(昇温速度20℃/分)あるいは示差熱分析〔DTA〕(昇温速度20℃/分)において現われた融解ピーク(ΔH)の大きさが4.5J/g以下であることをいう。フッ素ゴムは、架橋することにより、エラストマー特性を示す。エラストマー特性とは、ポリマーを延伸することができ、ポリマーを延伸するのに必要とされる力がもはや適用されなくなったときに、その元の長さを保持できる特性を意味する。
(式中、構造単位M1はビニリデンフルオライド(m1)由来の構造単位であり、構造単位M2は含フッ素エチレン性単量体(m2)由来の構造単位であり、構造単位N1は単量体(m1)および単量体(m2)と共重合可能な単量体(n1)由来の繰り返し単位である)
CF2=CFO(Rf1O)q(Rf2O)rRf3 (2)
(式中、Rf1およびRf2はそれぞれ独立に炭素数1~6の直鎖または分岐したパーフルオロアルキレン基、Rf3は炭素数1~6の直鎖または分岐したパーフルオロアルキル基、qおよびrはそれぞれ独立に0~6の整数(ただし0<q+r≦6を満たす)である)で表される含フッ素単量体、一般式(3):
CHX11=CX12Rf4 (3)
(式中、X11およびX12は、一方がHであり、他方がFであり、Rf4は炭素数1~12の直鎖または分岐したフルオロアルキル基である)で表される含フッ素単量体、フッ化ビニルなどの含フッ素単量体があげられるが、これらのなかでも、TFE、HFP、PAVEが好ましい。
CY1 2=CY1-Rf5CHR1X1 (4)
(式中、Y1は、独立に、水素原子、フッ素原子または-CH3、Rf5は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロポリオキシアルキレン基またはパーフルオロポリオキシアルキレン基、R1は、水素原子または-CH3、X1は、ヨウ素原子または臭素原子)で表されるヨウ素または臭素含有単量体、一般式(5):
CF2=CFO(CF2CF(CF3)O)m(CF2)n-X2 (5)
(式中、mは、0~5の整数、nは、1~3の整数、X2は、シアノ基、カルボキシル基、アルコキシカルボニル基、臭素原子、ヨウ素原子)で表される単量体、一般式(6):
CH2=CH(CF2)pI (6)
(式中、pは1~10の整数)で表される単量体などがあげられ、たとえば特公平5-63482号公報、特開平7-316234号公報に記載されているようなパーフルオロ(6,6-ジヒドロ-6-ヨード-3-オキサ-1-ヘキセン)やパーフルオロ(5-ヨード-3-オキサ-1-ペンテン)などのヨウ素含有単量体、特開平4-217936号公報記載のCF2=CFOCF2CF2CH2Iなどのヨウ素含有単量体、特開昭61-55138号公報に記載されている4-ヨード-3,3,4,4-テトラフルオロ-1-ブテンなどのヨウ素含有単量体、特開平4-505341号公報に記載されている臭素含有単量体、特開平4-505345号公報、特開平5-500070号公報に記載されているようなシアノ基含有単量体、カルボキシル基含有単量体、アルコキシカルボニル基含有単量体などがあげられる。これらをそれぞれ単独で、または任意に組合わせて用いることができる。
またビスオレフィン化合物としては特開平8-12726号公報に記載されたものを用いることができる。
本開示のフッ素ゴム架橋用組成物は、架橋剤を含有する。架橋剤は、下記一般式(b)で示される化合物、および、前記化合物と、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種である。
本開示のフッ素ゴム架橋用組成物は、架橋促進剤を含むことが好ましい。架橋促進剤を用いると、フッ素ゴム主鎖の脱フッ酸反応における分子内二重結合の形成を促進することにより架橋反応を促進することができる。架橋剤として、一般式(b)で示される化合物、および、一般式(b)で示される化合物と、アルカリ金属またはアルカリ土類金属またはオニウム化合物との塩から選択される1種の化合物を用いる場合には、架橋促進剤を架橋剤とともに用いることが好ましい。架橋剤としてオニウム塩を用いる場合でも、架橋促進剤を架橋剤とともに用いることができるが、必ずしも用いる必要はない。架橋条件や成形品の物性により適宜架橋促進剤の量を調整することができる。架橋促進剤を増量すれば、架橋反応は早くなり、またはより低温で架橋できるようになるが、圧縮永久歪み特性は悪化する傾向にある。逆に架橋促進剤を減量すれば架橋反応は遅くなるが、圧縮永久歪み特性は良くなる傾向にある。
本開示のフッ素ゴム架橋用組成物は、受酸剤をさらに含有してもよい。受酸剤を含有することにより、フッ素ゴム架橋用組成物の架橋反応が一層円滑に進行し、高温での圧縮永久歪み特性が一層向上する。
フッ素ゴム架橋用組成物は、必要に応じてフッ素ゴム架橋用組成物に配合される通常の添加物、たとえば充填剤(カーボンブラック、瀝青炭、硫酸バリウム、珪藻土、焼成クレー、タルク等)、加工助剤(ワックス等)、可塑剤、着色剤、安定剤、粘着性付与剤(クマロン樹脂、クマロン・インデン樹脂等)、離型剤、導電性付与剤、熱伝導性付与剤、表面非粘着剤、柔軟性付与剤、耐熱性改善剤、難燃剤、発泡剤、国際公開第2012/023485号に記載の酸化防止剤などの各種添加剤を配合することができ、前記のものとは異なる常用の架橋剤、架橋促進剤を1種またはそれ以上配合してもよい。
フッ素ゴム架橋用組成物を架橋することにより、本開示の成形品を得ることができる。また、フッ素ゴム架橋用組成物を成形し、架橋することによっても、本開示の成形品を得ることができる。フッ素ゴム架橋用組成物は、従来公知の方法で成形することができる。成形および架橋の方法および条件としては、採用する成形および架橋において公知の方法および条件の範囲内でよい。成形および架橋の順序は限定されず、成形した後架橋してもよいし、架橋した後成形してもよいし、成形と架橋とを同時に行ってもよい。
ブーツは、たとえば、等速ジョイントブーツ、ダストカバー、ラックアンドピニオンステアリングブーツ、ピンブーツ、ピストンブーツなどの自動車用ブーツ、農業機械用ブーツ、産業車両用ブーツ、建築機械用ブーツ、油圧機械用ブーツ、空圧機械用ブーツ、集中潤滑機用ブーツ、液体移送用ブーツ、消防用ブーツ、各種液化ガス移送用ブーツなどの各種産業用ブーツなどの複雑形状成形体として好ましく用いることができる。
19F-NMR(Bruker社製AC300P型)を用いて測定した。
19F-NMRにて測定されたフッ素ゴムの組成から計算によって求めた。
ASTM D1646-15およびJIS K6300-1:2013に準拠して測定した。測定温度は100℃である。
示差走査熱量計(メトラー・トレド社製、DSC822e、もしくは、日立ハイテクサイエンス社製、X-DSC7000)を用い、試料10mgを20℃/分で昇温することによりDSC曲線を得て、DSC曲線の二次転移前後のベースラインの延長線と、DSC曲線の変曲点における接線との交点を示す温度をガラス転移温度とした。
示差走査熱量計(メトラー・トレド社製:DSC822e、もしくは、日立ハイテクサイエンス社製、X-DSC7000)を用い、試料10mgを20℃/分で昇温することによりDSC曲線を得て、DSC曲線において現われた融解ピーク(ΔH)の大きさから融解熱を算出した。
フッ素ゴム架橋用組成物について、一次架橋時に加硫試験機(エムアンドケー社製 MDR H2030)を用いて、180℃で架橋曲線を求め、トルクの変化より、最大トルク(MH)および最適架橋時間(T90)を求めた。
厚さ2mmの架橋シートを用いて、引張試験機(エー・アンド・デイ社製テンシロンRTG-1310)を使用して、JIS K6251:2010に準じて、500mm/分の条件下、ダンベル6号にて、23℃における100%モジュラス(M100)、引張強さおよび切断時伸びを測定した。
<硬さ>
厚さ2mmの架橋シートを3枚重ねて、JIS K6251-3:2012に準じて、デュロメータ硬さ(タイプA、3秒後の値)を測定した。
圧縮永久歪み測定用小形試験片を用いて、JIS K6262:2013のA法に準じて、圧縮率25%、試験温度200℃、試験時間72時間で測定した。
フッ素ゴムA:フッ化ビニリデン/ヘキサフルオロプロピレン共重合体
フッ化ビニリデン/ヘキサフルオロプロピレンのモル比:78/22(モル%)
フッ素含有率:66質量%
ムーニー粘度(ML1+10(100℃)):69
ガラス転移温度:-18℃
融解熱:セカンドランでは認めず
フッ素ゴムB:フッ化ビニリデン/ヘキサフルオロプロピレン/テトラフルオロエチレン共重合体
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のモル比:58/22/20(モル%)
フッ素含有率:69質量%
ムーニー粘度(ML1+10(100℃)):42
ガラス転移温度:-13℃
融解熱:セカンドランでは認めず
水酸化カルシウム
酸化マグネシウム
スルホラン
架橋促進剤A:ベンジルジメチルオクタデシルアンモニウムクロリド91質量%とイソプロピルアルコール9質量%との混合物
架橋促進剤B:ベンジルトリフェニルホスホニウムクロリド(BTPPC)
架橋促進剤C:8-ベンジル-1,8-ジアザビシクロ[5,4,0]-7-ウンデセニウムクロリド(DBU-B)
架橋剤-2:2,4’-ジヒドロキシベンゾフェノン
架橋剤-3:4,4’-ジヒドロキシベンゾフェノン
架橋剤-4:2,4’-ジヒドロキシジフェニルスルホン
架橋剤-5:ビス(4-ヒドロキシフェニル)スルホン
架橋剤-6:2,6-ジヒドロキシアントラセン
架橋剤-7:ハイドロキノン
架橋剤-8:4,4’-ジヒドロキシジフェニルエーテル
表1~4の処方に従ってそれぞれの成分を配合し、オープンロール上で混練りして、フッ素ゴム架橋用組成物を調製した。得られたフッ素ゴム架橋用組成物の最大トルク(MH)および最適架橋時間(T90)を表1~4に示す。次に、180℃で20分間の一次架橋(プレス架橋)、および、230℃で24時間の二次架橋(オーブン架橋)により、フッ素ゴム架橋用組成物を架橋させ、架橋シート(厚さ2mm)および圧縮永久歪み測定用小形試験片を得た。得られた架橋シートの評価結果および圧縮永久歪み試験の結果を表1~4に示す。
ガラス容器中で、ベンジルトリフェニルホスホニウムクロリド(BTPPC)3.00g(7.71mmol)をメタノール25.0gに溶解させ、これに2,7-ジヒドロキシ-9H-フルオレン-9-オン6.50g(30.6mmol)を室温下攪拌しながら加えた。これをアルミ製容器に移し、90℃の熱盤上で攪拌しながら加熱してメタノールを留去し濃縮した。さらにこの濃縮物を120℃のオーブン中16時間加熱して乾固させ、2,7-ジヒドロキシ-9H-フルオレン-9-オンとBTPPCの混合物である混合物A9.40gを得た。2,7-ジヒドロキシ-9H-フルオレン-9-オンとBTPPCを合わせた回収率は98.9質量%であった。さらに混合物Aのうち1.00gを120℃のオーブン中1時間加熱して得られた固形物の質量も1.00gであり、熱処理前後で質量の変化はなかった。
Claims (10)
- フッ素ゴム(a)が、ビニリデンフルオライド単位を含む請求項1に記載のフッ素ゴム架橋用組成物。
- 架橋促進剤(c)をさらに含有する請求項1または2に記載のフッ素ゴム架橋用組成物。
- 架橋促進剤(c)の含有量が、フッ素ゴム(a)100質量部に対し、0.1~10質量部である請求項3に記載のフッ素ゴム架橋用組成物。
- 受酸剤(d)をさらに含有する請求項1~4のいずれかに記載のフッ素ゴム架橋用組成物。
- 受酸剤(d)の含有量が、フッ素ゴム(a)100質量部に対し、0.1~50質量部である請求項5に記載のフッ素ゴム架橋用組成物。
- 受酸剤(d)が、金属酸化物、金属水酸化物、アルカリ金属ケイ酸塩、弱酸の金属塩およびハイドロタルサイトからなる群より選択される少なくとも1種である請求項5または6に記載のフッ素ゴム架橋用組成物。
- 架橋剤(b)が、2,7-ジヒドロキシ-9H-フルオレン-9-オン、および、2,7-ジヒドロキシ-9H-フルオレン-9-オンと、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種である請求項1~7のいずれかに記載のフッ素ゴム架橋用組成物。
- ジアルキルスルホン化合物をさらに含有する請求項1~8のいずれかに記載のフッ素ゴム架橋用組成物。
- 請求項1~9のいずれかに記載のフッ素ゴム架橋用組成物から得られる成形品。
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