JP4553094B2 - Rubber composition, vulcanizable rubber composition and vulcanized product - Google Patents
Rubber composition, vulcanizable rubber composition and vulcanized product Download PDFInfo
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- JP4553094B2 JP4553094B2 JP2002021914A JP2002021914A JP4553094B2 JP 4553094 B2 JP4553094 B2 JP 4553094B2 JP 2002021914 A JP2002021914 A JP 2002021914A JP 2002021914 A JP2002021914 A JP 2002021914A JP 4553094 B2 JP4553094 B2 JP 4553094B2
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、耐劣化油性に優れた加硫物の材料となる、酸化により劣化した潤滑油と接触するゴム部品用のゴム組成物に関する。
【0002】
【従来の技術】
近年、自動車においては、エンジンの高出力化、FF化、排ガス対策などによって、エンジンルームの熱的環境条件は過酷化している。一方、自動車用潤滑油では、ロングライフ化、低燃費化などが進められている。その結果、潤滑油は、高温条件下で交換されることなく長期間使用できることが求められている。しかし、潤滑油は空気との接触により酸化が進行し、その結果、劣化油が生成する。
【0003】
ゴムにおいては、劣化油との接触によりゴムが硬化するという問題が指摘され、また、アクリロニトリル−ブタジエン共重合ゴムを水素添加したゴムでは硬化の程度が小さいことが知られている(豊田合成技報告、Vol.26、No.2、第51〜56頁(1984))。しかし、より耐劣化油性に優れたゴム加硫物が求められている。
【0004】
【発明が解決しようとする課題】
本発明の目的は、耐劣化油性に優れた、酸化により劣化した潤滑油と接触するゴム部品用の加硫物とその材料となるゴム組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明者らは、上記課題を達成すべく鋭意検討した結果、ヨウ素価が小さく、α,β−エチレン性不飽和ニトリル単量体単位含有量の大きなニトリル基含有共重合体ゴムにエチレン性不飽和カルボン酸の金属塩とを配合して加硫させることにより、劣化油と接触しても体積が変化しにくく、硬化しにくい、クラックの発生しにくいゴム加硫物が得られることを見出し、この知見に基づいて、本発明を完成させるに至った。
【0006】
かくして本発明によれば、第一の発明として、ヨウ素価10以下、α,β−エチレン性不飽和ニトリル単量体単位含有量40〜60重量%のニトリル基含有共重合ゴム(A)100重量部に対し、α,β−エチレン性不飽和カルボン酸金属塩(B)3〜100重量部を含有してなる、酸化により劣化した潤滑油と接触するゴム部品用のゴム組成物が提供される。
また、第二の発明として、ヨウ素価10以下、α,β−エチレン性不飽和ニトリル単量体単位含有量40〜60重量%のニトリル基含有共重合ゴム(A)100重量部に対し、α,β−エチレン性不飽和カルボン酸金属塩(B)3〜100重量部および有機過酸化物加硫剤0.2〜10重量部を含有してなる、酸化により劣化した潤滑油と接触するゴム部品用の加硫性ゴム組成物が提供される。
さらに第三の発明として、該加硫性ゴム組成物を加硫してなる、酸化により劣化した潤滑油と接触するゴム部品用の加硫物が提供される。
【0007】
【発明の実施の形態】
本発明の、酸化により劣化した潤滑油と接触するゴム部品用のゴム組成物は、ヨウ素価10以下、α,β−エチレン性不飽和ニトリル単量体単位含有量40〜60重量%のニトリル基含有共重合ゴム(A)100重量部に対し、α,β−エチレン性不飽和カルボン酸金属塩(B)3〜100重量部を含有してなる。
【0008】
本発明に用いるニトリル基含有共重合ゴム(A)は、α,β−エチレン性不飽和ニトリル系単量体を他の単量体と共重合して得られるゴムであり、α,β−エチレン性不飽和ニトリル単量体単位含有量40〜60重量%、好ましくは42〜55重量%である。α,β−エチレン性不飽和ニトリル単量体含有量が少なすぎると耐劣化油性に劣り、逆に多すぎると耐寒性に劣る。α,β−エチレン性不飽和ニトリル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリルなどが挙げられ、アクリロニトリルが好ましい。
【0009】
ニトリル基含有共重合ゴム(A)において、α,β−エチレン性不飽和ニトリル系単量体と共重合させる単量体としては、共役ジエン系単量体、非共役ジエン系単量体、α−オレフィンなどが例示される。共役ジエン系単量体としては、例えば、1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエンなどが挙げられ、1,3−ブタジエンが好ましい。非共役ジエン系単量体は、好ましくは炭素数が5〜12のものであり、1,4−ペンタジエン、1,4−ヘキサジエン、ビニルノルボルネン、ジシクロペンタジエンなどが例示される。α−オレフィンとしては、炭素数が2〜12のものが好ましく、エチレン、プロピレン、1−ブテン、4−メチル−1−ペンテン、1−ヘキセン、1−オクテンなどが例示される。さらに、芳香族ビニル系単量体、フッ素含有ビニル系単量体、α,β−エチレン性不飽和モノカルボン酸、α,β−エチレン性不飽和多価カルボン酸またはその無水物、共重合性の老化防止剤などを共重合してもよい。
【0010】
芳香族ビニル系単量体としては、例えば、スチレン、α−メチルスチレン、ビニルピリジンなどが挙げられる。フッ素含有ビニル系単量体としては、例えば、フルオロエチルビニルエーテル、フルオロプロピルビニルエーテル、o−トリフルオロメチルスチレン、ペンタフルオロ安息香酸ビニル、ジフルオロエチレン、テトラフルオロエチレンなどが挙げられる。α,β−エチレン性不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸などが挙げられる。α,β−エチレン性不飽和多価カルボン酸としては、例えば、イタコン酸、フマル酸、マレイン酸などが挙げられる。α,β−エチレン性不飽和多価カルボン酸無水物としては、例えば、無水イタコン酸、無水マレイン酸などが挙げられる。共重合性の老化防止剤としては、例えば、N−(4−アニリノフェニル)アクリルアミド、N−(4−アニリノフェニル)メタクリルアミド、N−(4−アニリノフェニル)シンナムアミド、N−(4−アニリノフェニル)クロトンアミド、N−フェニル−4−(3−ビニルベンジルオキシ)アニリン、N−フェニル−4−(4−ビニルベンジルオキシ)アニリンなどが挙げられる。
【0011】
ニトリル基含有共重合ゴム(A)のヨウ素価は、10以下である。ヨウ素価が大きすぎると耐劣化油性に劣るという問題を生じる。ニトリル基含有共重合ゴム(A)のヨウ素が大きすぎる場合には、通常の水素添加処理を行なうことにより、主鎖の不飽和結合を飽和させ、ヨウ素価を小さくすればよい。
【0012】
ニトリル基含有共重合ゴム(A)のムーニー粘度ML1+4,(100℃)は、好ましくは10〜300、より好ましくは20〜250、特に好ましくは30〜200である。ムーニー粘度が小さすぎると加硫物の機械的物性が劣る場合があり、逆に大きすぎると加工性に劣る場合がある。
【0013】
本発明に用いるα,β−エチレン性不飽和カルボン酸金属塩(B)を構成するα,β−エチレン性不飽和カルボン酸は、少なくとも1価のフリーのカルボキシル基を有するものであって、α,β−エチレン性不飽和モノカルボン酸、α,β−エチレン性不飽和ジカルボン酸、α,β−エチレン性不飽和ジカルボン酸モノエステルなどが例示される。α,β−エチレン性不飽和モノカルボン酸としては、アクリル酸、メタクリル酸、クロトン酸、3−ブテン酸などが挙げられる。α,β−エチレン性不飽和ジカルボン酸としては、マレイン酸、フマル酸、イタコン酸などが挙げられる。α,β−エチレン性不飽和ジカルボン酸モノエステルとしては、マレイン酸モノメチル、マレイン酸モノエチル、イタコン酸モノメチル、イタコン酸モノエチルなどが挙げられる。これらの中で、加硫物の強度特性の点からエステル基を持たないα,β−エチレン性不飽和カルボン酸が好ましく、α,β−エチレン性不飽和モノカルボン酸がより好ましく、メタクリル酸が特に好ましい。
【0014】
α,β−エチレン性不飽和カルボン酸金属塩(B)を構成する金属としては、加硫物の強度特性の点から、好ましくは、亜鉛、マグネシウム、カルシウム、バリウム、チタン、クロム、鉄、コバルト、ニッケル、アルミニウム、錫、鉛が挙げられ、より好ましくは亜鉛、マグネシウム、カルシウム、アルミニウムが挙げられ、さらに好ましくは亜鉛、マグネシウム、カルシウムおよびアルミニウムが挙げられ、特に好ましくは亜鉛である。
【0015】
α,β−エチレン性不飽和カルボン酸金属塩(B)は、ニトリル基含有共重合ゴム(A)に、α,β−エチレン性不飽和カルボン酸と前記金属または金属化合物とを配合して、ゴム組成物の製造時にニトリル基含有共重合ゴム(A)中で両者を反応させて、金属塩(B)を生成させてもよい。このような方法で生成された金属塩(B)は、細かくなり、分散させやすく好ましい。金属塩(B)を生成させるのに用いられる金属化合物としては、前記金属の酸化物、水酸化物、炭酸塩などが挙げられ、特に酸化亜鉛、炭酸亜鉛が好ましい。
【0016】
ニトリル基含有共重合ゴム(A)中にα,β−エチレン性不飽和カルボン酸と金属または金属化合物とを配合してα,β−エチレン性不飽和カルボン酸金属塩(B)を生成させる場合には、α,β−エチレン性不飽和カルボン酸1モルに対して、金属または金属化合物を金属量として0.5〜3.2モル、好ましくは0.7〜2.5モル配合して反応させる。金属または金属化合物量が少なすぎても多すぎても、α,β−エチレン性不飽和カルボン酸が金属または金属化合物と反応しにくくなる。ただし、金属化合物として、酸化亜鉛、炭酸亜鉛、水酸化亜鉛などを用いる場合は、それら単独でもゴムの配合剤として加硫促進剤として機能するので、上記範囲の上限を超えても、配合組成によっては問題を生じない場合がある。
【0017】
金属塩(B)は、取り扱いの問題を生じない限り、細かなものが好ましく、粒子径20μm以上の粒子の含有量を5%以下としたものが好ましい。そのためには、金属塩(B)をニトリル基含有ゴム(A)に配合する場合には金属塩を、金属塩(B)をニトリル基含有ゴム(A)で生成する場合には金属化合物を、風力分級装置で分級する、ふるい分級装置で分級するなどの方法によって、細かくすればよい。
【0018】
ニトリル基含有共重合ゴム(A)100重量部に対するα,β−エチレン性不飽和カルボン酸金属塩(B)の含有量は、3〜100重量部、好ましくは10〜80重量部、より好ましくは25〜70重量部である。含有量が少なすぎると強度が劣り、逆に多すぎると混練が困難になる。
【0019】
本発明のゴム組成物には、一般的なゴムに使用される配合剤、例えば、カーボンブラック、シリカ、短繊維などの補強剤、炭酸カルシウム、クレー、タルク、ケイ酸カルシウムなどの充填剤、可塑剤、顔料、老化防止剤、粘着付与剤、加工助剤、スコーチ防止剤などや樹脂を含有してもよい。また、ニトリル基含有共重合ゴム(A)以外のゴムや樹脂を本発明の効果を実質的に阻害しない範囲で含有してもよい。
【0020】
本発明のゴム組成物の調製方法は特に限定されず、一般的なゴム組成物の調製方法に従って、各成分を配合し、混練すればよい。
【0021】
本発明の加硫性ゴム組成物は、上記ゴム組成物であり、かつニトリル基含有共重合ゴム(A)100重量部当たり、有機過酸化物加硫剤0.2〜10重量部を含有するものである。
【0022】
本発明で用いる有機過酸化物加硫剤としては、ゴム工業分野で加硫剤として使用されているものが好ましく、例えば、ジアルキルパーオキサイド類、ジアシルパーオキサイド類、パーオキシエステル類などが挙げられ、好ましくはジアルキルパーオキサイド類である。ジアルキルパーオキサイド類としては、例えば、ジクミルパーオキサイド、ジ−t−ブチルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)−3−ヘキシン、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、1,3−ビス(t−ブチルパーオキシイソプロピル)ベンゼンなどが挙げられる。ジアシルパーオキサイド類として、例えば、ベンゾイルパーオキサイド、イソブチリルパーオキサイドなどが挙げられる。パーオキシエステル類としては、例えば、2,5−ジメチル−2,5−ビス(ベンゾイルパーオキシ)ヘキサン、t−ブチルパーオキシイソプロピルカーボネートなど)などが挙げられる。ニトリル基含有共重合ゴム(A)100重量部に対する有機過酸化物加硫剤の配合量は、0.2〜10重量部、好ましくは0.3〜7重量部、特に好ましくは0.5〜5重量部である。有機過酸化物加硫剤の配合量が少なすぎると、加硫密度が低下し、圧縮永久ひずみが大きくなる。有機過酸化物加硫剤の配合量が多すぎると、加硫物のゴム弾性が不十分となる場合がある。
【0023】
有機過酸化物加硫剤を使用する場合は、通常、加硫助剤を併用する。加硫助剤としては、酸化亜鉛、酸化マグネシウム、トリアリルシアヌレート、トリメチロールプロパントリメタクリレート、N,N’−m−フェニレンビスマレイミドなどを用いることが好ましい。加硫助剤は、クレー、炭酸カルシウム、シリカなどに分散させ、ゴム組成物の加工性を改良したものを使用してもよい。加硫助剤の種類および配合量は特に限定されず、加硫物の用途、要求性能、加硫剤の種類、加硫助剤の種類などに応じて決めればよい。
【0024】
本発明の加硫性ゴム組成物を調製する方法は、一般の加硫性ゴム組成物の調製方法と同じである。すなわち、加硫剤、加硫助剤などの配合以降は、混練中に加硫しないように、加硫開始温度以下に維持して混練すればよい。
【0025】
本発明の加硫物は、前述の加硫性ゴム組成物を加硫したものである。ゴム組成物を加硫する方法は、加硫性ゴム組成物を加熱すればよい。一般的には、成形しておいて加熱するか、成形と同時に加熱する。
【0026】
加硫時の温度は、好ましくは100〜200℃、より好ましくは130〜195℃、特に好ましくは140〜190℃である。温度が低すぎると加硫時間が長時間必要となったり、加硫密度が低くなったりする場合がある。温度が高すぎる場合は、成形不良になる場合がある。
【0027】
また、加硫時間は、加硫方法、加硫温度、形状などにより異なるが、1分間〜4時間が加硫密度と生産効率の面から好ましい。
【0028】
加硫するための加熱方法としては、プレス加熱、蒸気加熱、オーブン加熱、熱風加熱などのゴムの加硫に用いられる方法から適宜選択すればよい。
【0029】
【発明の効果】
本発明の、ゴム部品用の加硫物は、酸化により劣化した潤滑油に対する耐性に優れる。その特性を活かして、自動車、船舶、および工業用機械などの潤滑油と接触するゴム部品、例えば、自動車の駆動系のホース、パッキン、シールなどに使用される。
【0030】
【実施例】
以下に実施例、比較例を挙げて本発明を具体的に説明する。なお、部または配合に関わる%は、特に記載しない限り、重量基準である。また、測定は、下記の方法で行なった。
【0031】
(1)常態特性
調製した加硫性ゴム組成物を170℃で20分間、プレス圧10MPaで加硫を行い、厚さ2mmのシートを得た。このシートを用いて打ち抜いて、JIS K6251の引張試験用試験片を作製した。この試験片を用いて、JIS K6251に従い、加硫物の引張強さおよび伸びを測定し、JIS K6253に従い、マイクロサイズ国際ゴム硬さ計を用いて、加硫物の硬さ(IRHD マイクロ)を測定した。
【0032】
(2)耐油性
JIS K6258に従い、150℃の試験用潤滑油IRM902油に試験片を168時間浸せきし、浸せき前後の体積を測定し、浸せき前に対する体積変化率を%で表した。また、上記常態物性の硬さ測定と同様に浸せき後の硬さを測定し、浸せき前に対する変化を測定した。耐油性の測定においては、体積変化率および硬さ変化の絶対値が小さいほど、耐油性に優れる。
【0033】
(3)耐劣化油性
浸せきしている間、試験用潤滑油IRM902油1200mlに対し、1分当たり50mlの空気を定速度で吹き込む以外は、上記耐油性の測定と同様に処理し、各物性を測定した。なお、通常は、伸びの測定時、クラックが発生した時点で破断するが、耐劣化油性の測定においては、表面にクラックが発生しても破断しなかったので、併せて、クラック発生時の伸びの大きさを測定した。耐劣化油性の測定においては、体積変化率および硬さ変化の絶対値が小さく、クラック発生時の伸びが大きいほど、耐劣化油性に優れる。
【0034】
実施例1
ニトリル基含有共重合ゴムA(Zetpol 1000L、日本ゼオン社製、アクリロニトリル−ブタジエン共重合ゴム水素添加物、ヨウ素価7以下、アクリロニトリル単位含有量44重量%、ムーニー粘度ML1+4,(100℃)70)100部に、メタクリル酸亜鉛15部、亜鉛華1号10部、SRFカーボンブラック(旭カーボン社製、旭#50)20部、トリス(2−エチルヘキシル)トリメリテート8部、置換ジフェニルアミン(老化防止剤、ユニロイヤル社製、ナウガード445)1.5部、2−メルカプトベンゾチアゾール亜鉛塩(老化防止剤)1.5部および1,3−ビス(t−ブチルパーオキシイソプロピル)ベンゼン(有機過酸化物)40%品(ハーキュレス社製、バルカップ40KE)6部(有機過酸化物量2.4部)を配合し、50℃でロール混練して、加硫性ゴム組成物を調製した。この加硫性ゴム組成物を170℃で20分間、10MPaの圧力でプレスすることにより加硫し、厚さ2mmのシートとし、3号形ダンベルを用いて打ち抜いて、試験片を作製した。この試験片を用いて、常態物性、耐油性および耐劣化油性を測定した。結果を表1に示す。
【0035】
実施例2
ニトリル基含有共重合ゴムAの代わりにニトリル基含有共重合ゴムB(Zetpol 1010、日本ゼオン社製、アクリロニトリル−ブタジエン共重合ゴム水素添加物、ヨウ素価10、アクリロニトリル単位含有量44重量%、ムーニー粘度ML1+4,(100℃)85)を用いる以外は、実施例1と同様に処理した。結果を表1に示す。
【0036】
比較例1
メタクリル酸亜鉛を配合せず、カーボンブラックの量を20部から40部に変える以外は、実施例1と同様に処理した。結果を表1に示す。
【0037】
比較例2
ニトリル基含有共重合ゴムAの代わりにニトリル基含有共重合ゴムc(Zetpol 1020、日本ゼオン社製、アクリロニトリル−ブタジエン共重合ゴム水素添加物、ヨウ素価24、アクリロニトリル単位含有量44重量%、ムーニー粘度ML1+4,(100℃)78)を用いる以外は、実施例1と同様に処理した。結果を表1に示す。
【0038】
比較例3
ニトリル基含有共重合ゴムAの代わりにニトリル基含有共重合ゴムd(Zetpol 2000、日本ゼオン社製、アクリロニトリル−ブタジエン共重合ゴム水素添加物、ヨウ素価4、アクリロニトリル単位含有量36重量%、ムーニー粘度ML1+4,(100℃)85)を用いる以外は、実施例1と同様に処理した。結果を表1に示す。
【0039】
【表1】
【0040】
α,β−エチレン性不飽和カルボン酸金属塩を含有しない比較例1の加硫物は、カーボンブラックの量を変えて、硬さを他の実施例、比較例に近づけて測定したが、引張強度、伸びが小さく、耐劣化油性の測定において、硬さ変化が大きく、小さな伸びでクラックが発生する。ヨウ素価が20より大きなニトリル基含有共重合ゴムを用いた比較例2のゴム加硫物は、伸びが小さく、耐劣化油性の測定において、小さな伸びでクラックが発生する。α,β−エチレン性不飽和ニトリル単量体単位含有量が40重量%未満のニトリル基含有共重合ゴムを用いた比較例3のゴム加硫物は、耐油性の測定において、体積変化率の絶対値が大きく、耐劣化油性の測定において、体積変化率の絶対値が大きく、小さな伸びでクラックが発生する。
【0041】
それに対し、本発明の加硫物(実施例1および2)は、耐劣化油性の測定において、体積および硬さが変化しにくく、クラックが発生しにくい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber composition for a rubber part that comes into contact with a lubricating oil deteriorated by oxidation , which is a material of a vulcanizate having excellent resistance to deterioration oil.
[0002]
[Prior art]
In recent years, in automobiles, the thermal environmental conditions in the engine room have become severe due to high engine output, FF conversion, exhaust gas countermeasures, and the like. On the other hand, for automobile lubricants, long life and low fuel consumption are being promoted. As a result, it is required that the lubricating oil can be used for a long time without being replaced under high temperature conditions. However, the lubricating oil is oxidized by contact with air, and as a result, deteriorated oil is generated.
[0003]
In rubber, it has been pointed out that the rubber is cured by contact with deteriorated oil, and it is known that the degree of curing is small in rubber obtained by hydrogenating acrylonitrile-butadiene copolymer rubber (Toyoda Gosei Technical Report). Vol. 26, No. 2, pp. 51-56 (1984)). However, there is a demand for rubber vulcanizates that are more excellent in resistance to deterioration oil.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a vulcanizate for rubber parts which is excellent in resistance to deterioration oil and which comes into contact with a lubricating oil deteriorated by oxidation, and a rubber composition as a material thereof.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an ethylene-based copolymer rubber having a small iodine value and a large content of an α, β-ethylenically unsaturated nitrile monomer unit has an ethylenic content. By mixing and vulcanizing with a metal salt of a saturated carboxylic acid, it is found that a rubber vulcanizate is obtained that is less likely to change in volume even when in contact with deteriorated oil, hard to harden, and hard to crack. Based on this finding, the present invention has been completed.
[0006]
Thus, according to the present invention, as a first invention, a nitrile group-containing copolymer rubber (A) having an iodine value of 10 or less and an α, β-ethylenically unsaturated nitrile monomer unit content of 40 to 60 wt% (A) 100 wt. Provided is a rubber composition for rubber parts that contacts 3 to 100 parts by weight of the α, β-ethylenically unsaturated carboxylic acid metal salt (B) with respect to parts and contacts with a lubricating oil deteriorated by oxidation. .
Moreover, as 2nd invention, with respect to 100 weight part of nitrile group containing copolymer rubber (A) whose iodine number is 10 or less and whose content of α, β-ethylenically unsaturated nitrile monomer unit is 40 to 60% by weight, , Β-ethylenically unsaturated carboxylic acid metal salt (B) 3 to 100 parts by weight and organic peroxide vulcanizing agent 0.2 to 10 parts by weight, rubber in contact with lubricating oil deteriorated by oxidation Vulcanizable rubber compositions for parts are provided.
Furthermore, as a third invention, there is provided a vulcanized product for rubber parts which comes into contact with a lubricating oil deteriorated by oxidation , which is obtained by vulcanizing the vulcanizable rubber composition.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The rubber composition for rubber parts in contact with a lubricating oil deteriorated by oxidation of the present invention has a nitrile group having an iodine value of 10 or less and an α, β-ethylenically unsaturated nitrile monomer unit content of 40 to 60% by weight. It contains 3 to 100 parts by weight of the α, β-ethylenically unsaturated carboxylic acid metal salt (B) with respect to 100 parts by weight of the containing copolymer rubber (A).
[0008]
The nitrile group-containing copolymer rubber (A) used in the present invention is a rubber obtained by copolymerizing an α, β-ethylenically unsaturated nitrile monomer with another monomer, and α, β-ethylene. The unsaturated nitrile monomer unit content is 40 to 60% by weight, preferably 42 to 55% by weight. If the content of the α, β-ethylenically unsaturated nitrile monomer is too small, the oil resistance is poor, and conversely if it is too much, the cold resistance is poor. Examples of the α, β-ethylenically unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is preferable.
[0009]
In the nitrile group-containing copolymer rubber (A), monomers to be copolymerized with the α, β-ethylenically unsaturated nitrile monomer include conjugated diene monomers, non-conjugated diene monomers, α -Olefin and the like are exemplified. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-butadiene is preferable. The non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentadiene, 1,4-hexadiene, vinylnorbornene, and dicyclopentadiene. As an alpha olefin, a C2-C12 thing is preferable and ethylene, propylene, 1-butene, 4-methyl-1- pentene, 1-hexene, 1-octene etc. are illustrated. Furthermore, aromatic vinyl monomers, fluorine-containing vinyl monomers, α, β-ethylenically unsaturated monocarboxylic acids, α, β-ethylenically unsaturated polyvalent carboxylic acids or anhydrides thereof, copolymerizability An anti-aging agent or the like may be copolymerized.
[0010]
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl pyridine and the like. Examples of the fluorine-containing vinyl monomer include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, tetrafluoroethylene, and the like. Examples of the α, β-ethylenically unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid include itaconic acid, fumaric acid, maleic acid and the like. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid anhydride include itaconic anhydride and maleic anhydride. Examples of copolymerizable anti-aging agents include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4 -Anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
[0011]
The iodine value of the nitrile group-containing copolymer rubber (A) is 10 or less. If the iodine value is too large, there is a problem that the oil resistance is poor. When the iodine of the nitrile group-containing copolymer rubber (A) is too large, the main chain unsaturated bond may be saturated to reduce the iodine value by performing a normal hydrogenation treatment.
[0012]
The Mooney viscosity ML 1 + 4 (100 ° C.) of the nitrile group-containing copolymer rubber (A) is preferably 10 to 300, more preferably 20 to 250, and particularly preferably 30 to 200. If the Mooney viscosity is too small, the mechanical properties of the vulcanizate may be inferior, whereas if it is too large, the processability may be inferior.
[0013]
The α, β-ethylenically unsaturated carboxylic acid constituting the α, β-ethylenically unsaturated carboxylic acid metal salt (B) used in the present invention has at least a monovalent free carboxyl group, , Β-ethylenically unsaturated monocarboxylic acid, α, β-ethylenically unsaturated dicarboxylic acid, α, β-ethylenically unsaturated dicarboxylic acid monoester and the like. Examples of the α, β-ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and 3-butenoic acid. Examples of the α, β-ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like. Examples of the α, β-ethylenically unsaturated dicarboxylic acid monoester include monomethyl maleate, monoethyl maleate, monomethyl itaconate, monoethyl itaconate and the like. Among these, α, β-ethylenically unsaturated carboxylic acid having no ester group is preferable from the viewpoint of strength characteristics of the vulcanizate, α, β-ethylenically unsaturated monocarboxylic acid is more preferable, and methacrylic acid is preferable. Particularly preferred.
[0014]
The metal constituting the α, β-ethylenically unsaturated carboxylic acid metal salt (B) is preferably zinc, magnesium, calcium, barium, titanium, chromium, iron, cobalt from the viewpoint of the strength characteristics of the vulcanizate. , Nickel, aluminum, tin, and lead, more preferably zinc, magnesium, calcium, and aluminum, still more preferably zinc, magnesium, calcium, and aluminum, and particularly preferably zinc.
[0015]
The α, β-ethylenically unsaturated carboxylic acid metal salt (B) is prepared by blending the nitrile group-containing copolymer rubber (A) with the α, β-ethylenically unsaturated carboxylic acid and the metal or metal compound, The metal salt (B) may be produced by reacting both in the nitrile group-containing copolymer rubber (A) during the production of the rubber composition. The metal salt (B) produced by such a method is preferable because it is fine and easy to disperse. Examples of the metal compound used to produce the metal salt (B) include the metal oxides, hydroxides, carbonates, and the like, and zinc oxide and zinc carbonate are particularly preferable.
[0016]
When α, β-ethylenically unsaturated carboxylic acid metal salt (B) is produced by blending α, β-ethylenically unsaturated carboxylic acid and metal or metal compound in nitrile group-containing copolymer rubber (A) Is reacted with 0.5 to 3.2 moles, preferably 0.7 to 2.5 moles of metal or metal compound as metal amount per mole of α, β-ethylenically unsaturated carboxylic acid. Let If the amount of the metal or metal compound is too small or too large, the α, β-ethylenically unsaturated carboxylic acid becomes difficult to react with the metal or metal compound. However, when zinc oxide, zinc carbonate, zinc hydroxide or the like is used as the metal compound, it functions as a vulcanization accelerator as a rubber compounding agent alone, so even if it exceeds the upper limit of the above range, it depends on the compounding composition. May not cause problems.
[0017]
The metal salt (B) is preferably fine as long as it does not cause a problem in handling, and the content of particles having a particle diameter of 20 μm or more is preferably 5% or less. For this purpose, when the metal salt (B) is blended with the nitrile group-containing rubber (A), the metal salt is used. When the metal salt (B) is produced with the nitrile group-containing rubber (A), the metal compound is used. What is necessary is just to make it fine by methods, such as classifying with a wind classifier and classifying with a sieve classifier.
[0018]
The content of the α, β-ethylenically unsaturated carboxylic acid metal salt (B) relative to 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 3 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 25 to 70 parts by weight. If the content is too small, the strength is inferior. On the other hand, if the content is too large, kneading becomes difficult.
[0019]
The rubber composition of the present invention includes compounding agents used in general rubbers, for example, reinforcing agents such as carbon black, silica and short fibers, fillers such as calcium carbonate, clay, talc and calcium silicate, plastics Agents, pigments, anti-aging agents, tackifiers, processing aids, scorch inhibitors, and resins may be included. Moreover, you may contain rubber | gum and resin other than a nitrile group containing copolymer rubber (A) in the range which does not inhibit the effect of this invention substantially.
[0020]
The method for preparing the rubber composition of the present invention is not particularly limited, and each component may be blended and kneaded according to a general method for preparing a rubber composition.
[0021]
The vulcanizable rubber composition of the present invention is the above rubber composition and contains 0.2 to 10 parts by weight of an organic peroxide vulcanizing agent per 100 parts by weight of the nitrile group-containing copolymer rubber (A). Is.
[0022]
As the organic peroxide vulcanizing agent used in the present invention, those used as a vulcanizing agent in the rubber industry are preferable, and examples thereof include dialkyl peroxides, diacyl peroxides, and peroxyesters. Preferably, dialkyl peroxides are used. Examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, and 2,5-dimethyl. Examples include -2,5-di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene. Examples of diacyl peroxides include benzoyl peroxide and isobutyryl peroxide. Examples of peroxyesters include 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, and the like. The compounding amount of the organic peroxide vulcanizing agent with respect to 100 parts by weight of the nitrile group-containing copolymer rubber (A) is 0.2 to 10 parts by weight, preferably 0.3 to 7 parts by weight, particularly preferably 0.5 to 5 parts by weight. If the amount of the organic peroxide vulcanizing agent is too small, the vulcanization density is lowered and the compression set is increased. If the amount of the organic peroxide vulcanizing agent is too large, the rubber elasticity of the vulcanizate may be insufficient.
[0023]
When using an organic peroxide vulcanizing agent, a vulcanization aid is usually used in combination. As the vulcanization aid, it is preferable to use zinc oxide, magnesium oxide, triallyl cyanurate, trimethylolpropane trimethacrylate, N, N′-m-phenylenebismaleimide and the like. A vulcanization aid may be used which is dispersed in clay, calcium carbonate, silica or the like to improve the processability of the rubber composition. The type and blending amount of the vulcanization aid are not particularly limited, and may be determined according to the use of the vulcanizate, the required performance, the type of the vulcanization agent, the type of the vulcanization aid, and the like.
[0024]
The method for preparing the vulcanizable rubber composition of the present invention is the same as the method for preparing a general vulcanizable rubber composition. That is, after blending a vulcanizing agent, a vulcanizing aid, etc., the kneading may be carried out while maintaining the vulcanization start temperature or lower so as not to vulcanize during kneading.
[0025]
The vulcanized product of the present invention is obtained by vulcanizing the aforementioned vulcanizable rubber composition. The rubber composition may be vulcanized by heating the vulcanizable rubber composition. Generally, it is molded and heated, or is heated simultaneously with the molding.
[0026]
The temperature during vulcanization is preferably 100 to 200 ° C, more preferably 130 to 195 ° C, and particularly preferably 140 to 190 ° C. If the temperature is too low, the vulcanization time may be required for a long time or the vulcanization density may be lowered. If the temperature is too high, molding failure may occur.
[0027]
The vulcanization time varies depending on the vulcanization method, vulcanization temperature, shape and the like, but is preferably 1 minute to 4 hours from the viewpoint of vulcanization density and production efficiency.
[0028]
The heating method for vulcanization may be appropriately selected from methods used for rubber vulcanization, such as press heating, steam heating, oven heating, and hot air heating.
[0029]
【The invention's effect】
Of the present invention, it vulcanizates for rubber components, excellent resistance to lubricating oil deteriorated by oxidation. Taking advantage of its characteristics, it is used for rubber parts that come into contact with lubricating oil such as automobiles, ships, and industrial machines, for example, hose, packing, seals, etc. of automobile drive systems.
[0030]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition,% related to parts or blending is based on weight unless otherwise specified. Moreover, the measurement was performed by the following method.
[0031]
(1) Normal characteristics The vulcanizable rubber composition prepared was vulcanized at 170 ° C. for 20 minutes at a press pressure of 10 MPa to obtain a sheet having a thickness of 2 mm. The sheet was punched out to produce a test piece for tensile test of JIS K6251. Using this test piece, the tensile strength and elongation of the vulcanizate were measured according to JIS K6251, and the hardness of the vulcanized product (IRHD Micro) was measured using a micro-size international rubber hardness tester according to JIS K6253. It was measured.
[0032]
(2) Oil resistance According to JIS K6258, the test piece was immersed in a test lubricating oil IRM902 oil at 150 ° C. for 168 hours, the volume before and after the immersion was measured, and the volume change rate before immersion was expressed in%. Further, the hardness after immersion was measured in the same manner as the measurement of hardness of the normal physical properties, and the change relative to that before immersion was measured. In the measurement of oil resistance, the smaller the absolute value of volume change rate and hardness change, the better the oil resistance.
[0033]
(3) Deterioration of oil resistance While immersed in 1200 ml of lubricating oil for testing IRM902 oil, the same treatment as in the above oil resistance measurement was performed except that 50 ml of air was blown at a constant speed. It was measured. In addition, it usually breaks when a crack occurs when measuring the elongation, but in the measurement of resistance to deterioration oil, it does not break even if a crack occurs on the surface. The size of was measured. In the measurement of the resistance to deterioration oil, the absolute value of the volume change rate and the hardness change is small, and the greater the elongation at the time of crack occurrence is, the better the deterioration oil resistance is.
[0034]
Example 1
Nitrile group-containing copolymer rubber A (Zetpol 1000L, manufactured by Nippon Zeon Co., Ltd., hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value of 7 or less, acrylonitrile unit content 44% by weight, Mooney viscosity ML 1 + 4 , (100 ° C.) 70) 100 parts, zinc methacrylate 15 parts, zinc white No. 1 10 parts, SRF carbon black (Asahi Carbon Co., Ltd., Asahi # 50) 20 parts, tris (2-ethylhexyl) trimellitate 8 parts, substituted diphenylamine (anti-aging) Agent, 1.5 parts by Nauvard 445 manufactured by Uniroyal, 1.5 parts 2-mercaptobenzothiazole zinc salt (anti-aging agent) and 1,3-bis (t-butylperoxyisopropyl) benzene (organic peroxidation) Product) 40% product (Hercules Co., Ltd., Valcup 40KE) 6 parts (organic peroxide amount 2.4 parts) Compounded, and kneading at 50 ° C., to prepare a vulcanizable rubber composition. This vulcanizable rubber composition was vulcanized by pressing it at 170 ° C. for 20 minutes at a pressure of 10 MPa to form a sheet having a thickness of 2 mm and punched out using a No. 3 type dumbbell to prepare a test piece. Using this test piece, normal properties, oil resistance and resistance to deterioration oil were measured. The results are shown in Table 1.
[0035]
Example 2
Instead of nitrile group-containing copolymer rubber A, nitrile group-containing copolymer rubber B (Zetpol 1010, manufactured by Nippon Zeon Co., Ltd., hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 10, acrylonitrile unit content 44% by weight, Mooney viscosity The treatment was performed in the same manner as in Example 1 except that ML 1 + 4 , (100 ° C.) 85) was used. The results are shown in Table 1.
[0036]
Comparative Example 1
The same treatment as in Example 1 was conducted except that zinc methacrylate was not blended and the amount of carbon black was changed from 20 parts to 40 parts. The results are shown in Table 1.
[0037]
Comparative Example 2
Nitrile group-containing copolymer rubber c instead of nitrile group-containing copolymer rubber A (Zetpol 1020, manufactured by Nippon Zeon Co., Ltd., hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 24, acrylonitrile unit content 44% by weight, Mooney viscosity The treatment was performed in the same manner as in Example 1 except that ML 1 + 4 , (100 ° C.) 78) was used. The results are shown in Table 1.
[0038]
Comparative Example 3
Nitrile group-containing copolymer rubber d (Zetpol 2000, manufactured by Nippon Zeon Co., Ltd., hydrogenated acrylonitrile-butadiene copolymer rubber, iodine value 4, acrylonitrile unit content 36% by weight, Mooney viscosity instead of nitrile group-containing copolymer rubber A The treatment was performed in the same manner as in Example 1 except that ML 1 + 4 , (100 ° C.) 85) was used. The results are shown in Table 1.
[0039]
[Table 1]
[0040]
The vulcanizate of Comparative Example 1 containing no α, β-ethylenically unsaturated carboxylic acid metal salt was measured by changing the amount of carbon black and bringing the hardness close to that of other Examples and Comparative Examples. The strength and elongation are small, and in the measurement of resistance to deterioration oil, the hardness change is large, and cracks are generated with small elongation. The rubber vulcanizate of Comparative Example 2 using a nitrile group-containing copolymer rubber having an iodine value greater than 20 has a small elongation, and cracks are generated with a small elongation in the measurement of resistance to deterioration oil. The rubber vulcanizate of Comparative Example 3 using a nitrile group-containing copolymer rubber having an α, β-ethylenically unsaturated nitrile monomer unit content of less than 40% by weight has a volume change rate in oil resistance measurement. The absolute value is large, and in the measurement of resistance to deterioration oil, the absolute value of the volume change rate is large, and cracks occur with small elongation.
[0041]
On the other hand, the vulcanizates of the present invention (Examples 1 and 2) are less likely to change in volume and hardness and are less likely to crack in the measurement of resistance to deterioration oil.
Claims (3)
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