JPS623182B2 - - Google Patents
Info
- Publication number
- JPS623182B2 JPS623182B2 JP54118407A JP11840779A JPS623182B2 JP S623182 B2 JPS623182 B2 JP S623182B2 JP 54118407 A JP54118407 A JP 54118407A JP 11840779 A JP11840779 A JP 11840779A JP S623182 B2 JPS623182 B2 JP S623182B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- silicone rubber
- component
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- -1 polysiloxane Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 229920002379 silicone rubber Polymers 0.000 claims description 17
- 239000004945 silicone rubber Substances 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 239000005909 Kieselgur Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- 238000012360 testing method Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- UJXFNIQSAHCTTA-UHFFFAOYSA-N 1-butylperoxyhexane Chemical compound CCCCCCOOCCCC UJXFNIQSAHCTTA-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- MLPRTGXXQKWLDM-UHFFFAOYSA-N hydroxy-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](O)(C)C1=CC=CC=C1 MLPRTGXXQKWLDM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Description
本発明は、シヤフトシール用シリコーンゴム組
成物、さらに詳しく言えば、シヤフトシールに最
適な加熱加硫型シリコーンゴム組成物に関するも
のである。
自動車の駆動部におけるシヤフトシールには、
シリコーンゴムがそのすぐれた物理特性（耐油
性、耐久性）の故にシール材として用いられるの
は広く知られている。しかしながら上記シヤフト
シールの如き長時間にわたつてシヤフト摺動面と
の摩擦が繰り返される場合には摩擦によつて発す
る騒音が人間に不快感を与え、とくに自動車にお
いては運転者の不安感を招く原因となる。また一
面では摩擦による摩耗が摺動面とシール材との間
隙を拡げるため油洩れの原因ともなりうるが、従
来のシリコーンゴム組成物ではこれらの不安要因
を充分除去するには至つていない。
本発明は、かかる欠点を改良し、接触する摺動
面との摩擦による騒音がなく、耐摩耗性、耐油
性、耐久性およびモーターオイル密封性のすぐれ
たシヤフトシール用シリコーンゴムの組成物を提
供するものである。
すなわち本発明は、
(イ) 平均単位式
RaSiO４−ａ／２
（式中Ｒは置換または非置換の一価炭化水素
基、ａは1.98〜2.02）で表わされる単位からな
るオルガノポリシロキサン生ゴム 100重量部
(ロ) 補強性シリカ系充填剤 ５〜100重量部
(ハ) けいそう土 ５〜100重量部
(ニ) 平均単位式
RbHcSiO４−ｂ−ｃ／２
（式中Ｒは置換または非置換の一価炭化水素
基、
ｂ＝１〜２、ｃ＝0.1〜1.2、ｂ＋ｃ＝1.8〜
2.2）で示されるオルガノハイドロジエンポリ
シロキサン 0.01〜10重量部
(ホ) 有機過酸化物 0.1〜10重量部
からなるシヤフトシール用シリコーンゴム組成物
に関する。
本発明を詳細に説明すると、前記(イ)成分は通常
シリコーンゴムの主原料とされる常温でガム状を
呈する高分子量の直鎖状ないしやや分岐した鎖状
オルガノポリシロキサンである。側鎖有機基とし
てはメチル基、エチル基、ビニル基、フエニル
基、トリフルオルプロピル基が例示されるが、好
ましくは全有機基の少なくとも50％はメチル基で
ある。末端封鎖基としては水酸基、アルコキシ
基、メチル基、ビニル基、フエニル基から選択・
構成されるオルガシリル基が例示されるが、特に
限定するものではない。(ロ)成分の補強性シリカ系
充填剤としては、ヒユームドリシカ、沈降法シリ
カ、これらを疎水化したものが例示される。(ロ)成
分はシリコーンゴムの機械的強度の発現に必須の
成分であり、その使用量は(イ)成分100重量部に対
して５〜100重量部であるが、好ましくは20〜70
重量部である。(ハ)成分のけいそう土はシリコーン
ゴムの硬さと耐油性の向上に必須な成分である。
他のシリカ系増量充填剤では、シヤフトシールと
して使用したとき摩耗性がはげしく騒音も大きく
なるが、けいそう土にはかかる弊害がみられな
い。(ハ)成分の使用量は(イ)成分100重量部に対して
５〜10重量部であるが、好ましくは20〜90重量部
である。(ニ)成分のオルガノハイドロジエンポリシ
ロキサンはシリコーンゴムに好ましいすべり性、
騒音減少性、耐摩耗性およびモーターオイルの密
封性を付与するためとくに重要な成分であつて本
発明の特徴をなす成分である。(ニ)成分は、１分子
中に少なくとも１つのケイ素原子結合水素原子を
有するオルガノハイドロジエンポリシロキサンで
ある。ケイ素原子給合水素原子は１分子中に３個
以上存在することが好ましい。本成分の添加量は
使用するオルガノハイドロジエンポリシロキサン
中のケイ素原子給水合水素原子の含有量により
0.01〜10重量部、好ましくは0.1〜10重量部の範
囲の適量を用いることができる。添加量がこの範
囲より少なすぎると目的とする効果が少なく、ま
た多すぎると加硫成形に際しての発泡、ベタツキ
の原因となる。本成分の一般式中のＲは、(イ)成分
の側鎖有機基と同様でよく、特にメチル基が好ま
しい。(ホ)成分の有機過酸化物は、シリコーンゴム
組成物を加熱硬化するために使用される従来から
公知の触媒であり、これにはベンゾイルパーオキ
サイド、ｔ−ブチルパーベンゾエート、２・４−
ジクロルベンゾイルパーオキサイド、モノクロル
ベンゾイルパーオキサイド、ジクミルパーオキサ
イド、２・５−ビス（ｔ−ブチル−パーオキシ）
−２・５−ジメチルヘキサンなどが例示される。
(イ)成分〜(ホ)成分ともおのおの一種だけ使用しても
よく、おのおの二種以上混合して使用しても良
い。本発明のシリコーンゴム組成物は、上記(イ)〜
(ホ)成分を単に配合することにより得られるが、必
要に応じて末端水酸基封鎖の低重合度ポリジメチ
ルシロキサン、ジフエニルシランジオール、ジフ
エニルメチルシラノールなどの低分子量有機けい
素化合物、マイカ粉末、黒鉛、テフロン粉末、酸
化マグネシウム、酸化亜鉛、顔料、耐熱剤、耐油
剤その他の添加剤を配合することは差し支えな
い。なお、これら(イ)〜(ホ)の成分の配合順序はとく
にこれを制限する必要はないが、通常はまず(イ)成
分と(ロ)成分をニーダミキサーなどを用いて混合
し、これにバンバリーミキサーまたは２本ロール
を用いて(ハ)成分と(ニ)成分を混合し、最後に(ホ)成分
を２本ロールを用いて混合するのが有利である。
このようにして調整されたシリコーンゴム組成
物を100℃〜200℃に数分間〜数時間加圧または非
加圧下に加熱し、さらに必要に応じて後加硫する
と硬化して機械特性、耐油性、耐摩耗性、密封性
がすぐれた騒音発生の小さいシヤフトシールに好
適なシリコーンゴム製品を与える。
つぎに本発明を実施例で説明するが、実施例中
部とあるのは重量部を意味する。
実施例 １
ジメチルシロキサン単位99、84モル％とメチル
ビニルシロキサン単位0.16モル％を有する両末端
がジメチルビニルシリル基封鎖のメチルビニルポ
リシロキサン生ゴム（25℃における可塑度160）
100部、比表面積240m2／grの沈降法
シリカ35部、けいそう土60部、ジフエニルシラ
ンジオール３部をバンバリーミキサーに投入して
良く混練し、次いで温度を170℃に上げて２時間
混練した。60℃以下に冷却してからマイカ微粉末
10部、第１表に示す量の両末端トリメチルシリル
基封鎖のメチルハイドロジエンポリシロキサン
（ジメチルシロキサン単位とメチルハイドロジエ
ンシロキサン単位とがモル比で１：１であり、粘
度が50cstである）と2.5ジメチル−2.5（ジ−ｔ
−ブチルパーオキシ）ヘキサンの50％シリコーン
オイルペースト0.5部とを添加して２本ロールで
均一に混練し、シリコーンゴム組成物とした。つ
ぎに、この組成物を170℃、10分間の条件で熱プ
レスを用いて硬化させ、さらに200℃、４時間の
条件でオーブン中で後加硫を行なつて得た厚さ２
mmのシートについて、JIS−Ｋ−6310に従つて硬
度、引張り強伸度（ダンベル３号型使用）を測定
した。また同じ組成物をオイルシール用成型金型
を用い、上記と同様の条件で加熱硬化させ、得ら
れた成型品をオイルシール試験用回転試験機に組
み込んで試験機のシヤフトを3000rpmで回転駆動
させ、５名の判定者が徐々に試験機から遠のいて
いきながら摩擦発生音の聞こえなくなる距離を測
定した。また同様の条件で24時間連続回転し、試
験用潤滑油のもれた容量を測定し、シヤフトシー
ルの密封性の目安とした。耐油特性としてはモー
ターオイル10W−30ならびにJIS膨潤油３号をそ
れぞれ環流式試験管に採り、この中へ前記条件で
加硫した試験片を浸して、試験管を恒温槽中で
150℃に加熱し70時間後における試験片の体積変
化を測定した。
比較例として、メチルハイドロジエンポリシロ
キサンを除いたほかは実施例１と同様に調整した
組成物について同様の条件で試験片を作成し同様
に測定した。これらの測定結果を第１表に示し
た。
The present invention relates to a silicone rubber composition for shaft seals, and more specifically to a heat-vulcanizable silicone rubber composition that is most suitable for shaft seals. Shaft seals in automobile drive parts include:
It is widely known that silicone rubber is used as a sealing material because of its excellent physical properties (oil resistance, durability). However, when friction with the shaft sliding surface is repeated over a long period of time, such as with the shaft seal mentioned above, the noise generated by the friction causes discomfort to humans, and especially in automobiles, it causes anxiety among drivers. becomes. On the other hand, abrasion due to friction may widen the gap between the sliding surface and the sealing material, which may cause oil leakage, but conventional silicone rubber compositions have not yet been able to sufficiently eliminate these concerns. The present invention improves these drawbacks and provides a silicone rubber composition for shaft seals that is free from noise caused by friction with contacting sliding surfaces and has excellent wear resistance, oil resistance, durability, and motor oil sealing properties. It is something. That is, the present invention provides (a) Organopolysiloxane raw rubber consisting of units represented by the average unit formula RaSiO4-a/2 (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and a is 1.98 to 2.02) 100 weight Part (b) Reinforcing silica filler 5 to 100 parts by weight (c) Diatomaceous earth 5 to 100 parts by weight (d) Average unit formula RbHcSiO4-b-c/2 (in the formula, R is substituted or unsubstituted) valence hydrocarbon group, b=1-2, c=0.1-1.2, b+c=1.8-
2.2) A silicone rubber composition for shaft seals comprising 0.01 to 10 parts by weight of an organohydrodiene polysiloxane (e) and 0.1 to 10 parts by weight of an organic peroxide. To explain the present invention in detail, the component (a) is a high molecular weight linear or slightly branched chain organopolysiloxane that is gum-like at room temperature and is usually the main raw material for silicone rubber. Examples of side chain organic groups include methyl group, ethyl group, vinyl group, phenyl group, and trifluoropropyl group, and preferably at least 50% of all organic groups are methyl groups. The terminal blocking group can be selected from hydroxyl group, alkoxy group, methyl group, vinyl group, and phenyl group.
Examples include organasilyl groups, but the present invention is not particularly limited thereto. Examples of the reinforcing silica-based filler as component (b) include hyaluronic acid, precipitated silica, and hydrophobized versions of these. Component (B) is an essential component for developing the mechanical strength of silicone rubber, and the amount used is 5 to 100 parts by weight, preferably 20 to 70 parts by weight, per 100 parts by weight of component (B).
Parts by weight. Component (c) diatomaceous earth is an essential component for improving the hardness and oil resistance of silicone rubber.
Other silica-based extender fillers have severe wear and noise when used as shaft seals, but diatomaceous earth does not have these problems. The amount of component (c) used is 5 to 10 parts by weight, preferably 20 to 90 parts by weight, per 100 parts by weight of component (a). Component (d) organohydrodiene polysiloxane has a slip property suitable for silicone rubber,
It is a particularly important component for imparting noise reduction properties, wear resistance, and motor oil sealing properties, and is a feature of the present invention. Component (2) is an organohydrodiene polysiloxane having at least one silicon-bonded hydrogen atom in one molecule. It is preferable that three or more silicon-attached hydrogen atoms exist in one molecule. The amount of this component added depends on the content of silicon atoms and hydrated hydrogen atoms in the organohydrodiene polysiloxane used.
Suitable amounts ranging from 0.01 to 10 parts by weight, preferably from 0.1 to 10 parts by weight may be used. If the amount added is too small than this range, the desired effect will be small, and if it is too large, it will cause foaming and stickiness during vulcanization molding. R in the general formula of this component may be the same as the side chain organic group of component (a), and is particularly preferably a methyl group. The organic peroxide of component (e) is a conventionally known catalyst used for heat curing silicone rubber compositions, and includes benzoyl peroxide, t-butyl perbenzoate, 2.4-
Dichlorobenzoyl peroxide, monochlorobenzoyl peroxide, dicumyl peroxide, 2,5-bis(t-butyl-peroxy)
-2,5-dimethylhexane and the like are exemplified.
Each of the components (a) to (e) may be used alone, or two or more of each may be used in combination. The silicone rubber composition of the present invention comprises the above (a) to
It can be obtained by simply blending the components (e), and if necessary, low molecular weight organosilicon compounds such as low polymerization degree polydimethylsiloxane with end-blocked hydroxyl groups, diphenylsilanediol, diphenylmethylsilanol, mica powder, Graphite, Teflon powder, magnesium oxide, zinc oxide, pigments, heat resistant agents, oil resistant agents, and other additives may be blended. Note that there is no particular restriction on the order in which these components (A) to (E) are mixed, but usually, components (A) and (B) are first mixed using a kneader mixer, etc. It is advantageous to mix components (c) and (d) using a Banbury mixer or two rolls, and finally mix component (e) using a two rolls. The silicone rubber composition prepared in this way is heated to 100°C to 200°C for several minutes to several hours under pressure or without pressure, and if necessary is post-vulcanized to harden and improve mechanical properties and oil resistance. To provide a silicone rubber product suitable for a shaft seal with excellent wear resistance, sealing performance, and low noise generation. Next, the present invention will be explained with reference to Examples, in which "parts by weight" are meant in the middle part of the examples. Example 1 Methylvinylpolysiloxane raw rubber with dimethylvinylsilyl groups blocked at both ends and having 99, 84 mol% dimethylsiloxane units and 0.16 mol% methylvinylsiloxane units (plasticity 160 at 25°C)
100 parts, specific surface area 240 m 2 /gr sedimentation method: 35 parts of silica, 60 parts of diatomaceous earth, and 3 parts of diphenylsilanediol were put into a Banbury mixer and kneaded well, then the temperature was raised to 170°C and kneaded for 2 hours. did. Mica fine powder after cooling to below 60℃
10 parts, the amount of methylhydrodiene polysiloxane endblocked with trimethylsilyl groups at both ends as shown in Table 1 (the molar ratio of dimethylsiloxane units to methylhydrodienesiloxane units is 1:1, and the viscosity is 50 cst) and 2.5 Dimethyl-2.5 (di-t
0.5 part of 50% silicone oil paste (butylperoxy)hexane was added and kneaded uniformly with two rolls to obtain a silicone rubber composition. Next, this composition was cured using a hot press at 170°C for 10 minutes, and then post-vulcanized in an oven at 200°C for 4 hours to obtain a thickness of 2.
The hardness and tensile strength and elongation (using dumbbell type 3) of the sheet of mm were measured according to JIS-K-6310. In addition, the same composition was heated and cured using an oil seal mold under the same conditions as above, and the molded product obtained was installed in a rotation testing machine for oil seal testing, and the shaft of the testing machine was rotated at 3000 rpm. Five judges gradually moved away from the test machine and measured the distance at which the frictional sound could no longer be heard. In addition, the shaft was rotated continuously for 24 hours under the same conditions, and the leakage volume of the test lubricating oil was measured, which was used as a guideline for the sealing performance of the shaft seal. For oil resistance, motor oil 10W-30 and JIS swelling oil No. 3 were placed in a reflux test tube, a test piece vulcanized under the above conditions was immersed in the test tube, and the test tube was placed in a constant temperature bath.
The volume change of the test piece was measured after 70 hours of heating to 150°C. As a comparative example, a test piece was prepared under the same conditions as in Example 1 for a composition prepared in the same manner as in Example 1, except that methylhydrodiene polysiloxane was omitted, and the test pieces were measured in the same manner. The results of these measurements are shown in Table 1.
【表】
実施例 ２
ジメチルシロキサン単位95.0モル％、メチルビ
ニルシロキサン単位0.2モル％とメチルフエニル
シロキサン単位4.8モル％よりなり両末端がジメ
チルビニルシリル基封鎖のメチルフエニルビニル
ポリシロキサン生ゴム（25℃における可塑度
130）、比表面積200m2／grのフユームドシリカ50
部、両末端水酸基の低重合度ポリジメチルシロキ
サン10部、ビニルトリエトキシシラン0.5部、テ
フロン粉末（三井フロロケミカル製テフロン6CJ
粉末）0.5部とをニーダーミキサーに投入し均一
になるまで混練した。次いで温度を150℃に上げ
て２時間混練した。60℃以下に冷却してからけい
そう土20部ベンガラ0.5部、第２表に示す量のメ
チルハイドロジエンシクロテトラシロキサンと
２・４ジクロルベンゾイルパーオキサイド0.6部
を添加して２本ロールで均一に混合し、シリコー
ンゴム組成物とした。つぎに、この組成物を120
℃、10分間の条件で熱プレスを用いて硬化させ、
さらに250℃、４時間の条件でオーブン中で後加
硫酸を行ない、実施例１と全く同様の測定を行な
つた。比較例としてメチルハイドロジエンシクロ
テトラシロキサンを添加しなかつたことを除い
て、上述した条件と全く同じ条件で作製した組成
物についても同様の条件で試験片を作成し同様に
測定した。これらの測定結果を第２表に示した。[Table] Example 2 Methylphenylvinyl polysiloxane raw rubber consisting of 95.0 mol% dimethylsiloxane units, 0.2 mol% methylvinylsiloxane units, and 4.8 mol% methylphenylsiloxane units, with both ends blocked by dimethylvinylsilyl groups (25°C plasticity in
130), fumed silica 50 with a specific surface area of 200 m 2 /gr.
1 part, 10 parts of low-polymerization polydimethylsiloxane with hydroxyl groups at both ends, 0.5 part of vinyltriethoxysilane, Teflon powder (Teflon 6CJ manufactured by Mitsui Fluorochemicals)
0.5 part of powder) was placed in a kneader mixer and kneaded until uniform. Then, the temperature was raised to 150°C and kneading was continued for 2 hours. After cooling to below 60°C, add 20 parts of diatomaceous earth, 0.5 part of red iron, methyl hydrodiene cyclotetrasiloxane in the amount shown in Table 2, and 0.6 part of 2,4 dichlorobenzoyl peroxide, and mix uniformly with two rolls. and mixed to form a silicone rubber composition. Next, add this composition to 120
Cure using a heat press for 10 minutes.
Furthermore, post-sulfurization was carried out in an oven at 250° C. for 4 hours, and the same measurements as in Example 1 were carried out. As a comparative example, a test piece was prepared under the same conditions as above for a composition prepared under exactly the same conditions as described above, except that methylhydrogencyclotetrasiloxane was not added, and measurements were made in the same manner. The results of these measurements are shown in Table 2.
【表】【table】
Claims (1)
基、ａは1.98〜2.02）で表わされる単位からな
るオルガノポリシロキサン生ゴム 100重量部 (ロ) 補強性シリカ系充填剤 ５〜100重量部 (ハ) けいそう土 ５〜100重量部 (ニ) 平均単位式 RbHcSiO４−ｂ−ｃ／２ （式中Ｒは置換または非置換の一価炭化水素
基、 ｂ＝１〜２、ｃ＝0.1〜1.2、ｂ＋ｃ＝1.8〜
2.2）で示されるオルガノハイドロジエンポリ
シロキサン 0.01〜10重量部 (ホ) 有機過酸化物 0.1〜10重量部 からなるシヤフトシール用シリコーンゴム組成
物。[Scope of Claims] 1 (a) Organopolysiloxane raw rubber consisting of units represented by the average unit formula RaSiO4-a/2 (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and a is 1.98 to 2.02) 100 parts by weight (b) Reinforcing silica filler 5 to 100 parts by weight (c) Diatomaceous earth 5 to 100 parts by weight (d) Average unit formula RbHcSiO4-b-c/2 (in the formula, R is substituted or unsubstituted) Monovalent hydrocarbon group, b=1-2, c=0.1-1.2, b+c=1.8-
2.2) A silicone rubber composition for shaft seals comprising 0.01 to 10 parts by weight of an organohydrodiene polysiloxane (e) and 0.1 to 10 parts by weight of an organic peroxide.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11840779A JPS5643351A (en) | 1979-09-14 | 1979-09-14 | Silicone rubber composition for sealing shaft |
| GB8029205A GB2060667B (en) | 1979-09-14 | 1980-09-10 | Silicone rubber composition for drive shaft seals |
| CA000360008A CA1162687A (en) | 1979-09-14 | 1980-09-10 | Silicone rubber composition for drive shaft seals |
| DE19803034232 DE3034232A1 (en) | 1979-09-14 | 1980-09-11 | ORGANOPOLYSILOXANE RUBBER FOR DRIVE SHAFT SEALS |
| BE0/202083A BE885210A (en) | 1979-09-14 | 1980-09-12 | SILICONE RUBBER COMPOSITION FOR DRIVE SHAFT SEALS AND SEALS OBTAINED |
| IT24633/80A IT1141044B (en) | 1979-09-14 | 1980-09-12 | SILICONIC RUBBER COMPOSITION FOR DRIVE SHAFT |
| FR8019715A FR2464976A1 (en) | 1979-09-14 | 1980-09-12 | SILICONE RUBBER COMPOSITION FOR DRIVE SHAFT JOINTS AND JOINTS OBTAINED |
| SE8006416A SE8006416L (en) | 1979-09-14 | 1980-09-12 | SILICONE RUBBER COMPOSITION FOR DRIVE SHAFT SEALS |
| SU802980757A SU978734A3 (en) | 1979-09-14 | 1980-09-12 | Composition for sealing rotating shafts |
| AU62370/80A AU535241B2 (en) | 1979-09-14 | 1980-09-12 | Silicone rubber composition |
| BR8005897A BR8005897A (en) | 1979-09-14 | 1980-09-15 | COMPOSITION OF SILICON RUBBER AND DRIVE SHAFT SEAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11840779A JPS5643351A (en) | 1979-09-14 | 1979-09-14 | Silicone rubber composition for sealing shaft |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5643351A JPS5643351A (en) | 1981-04-22 |
| JPS623182B2 true JPS623182B2 (en) | 1987-01-23 |
Family
ID=14735874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11840779A Granted JPS5643351A (en) | 1979-09-14 | 1979-09-14 | Silicone rubber composition for sealing shaft |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5643351A (en) |
| AU (1) | AU535241B2 (en) |
| BE (1) | BE885210A (en) |
| BR (1) | BR8005897A (en) |
| CA (1) | CA1162687A (en) |
| DE (1) | DE3034232A1 (en) |
| FR (1) | FR2464976A1 (en) |
| GB (1) | GB2060667B (en) |
| IT (1) | IT1141044B (en) |
| SE (1) | SE8006416L (en) |
| SU (1) | SU978734A3 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0112396B1 (en) * | 1982-06-15 | 1988-02-24 | Toray Silicone Co., Ltd. | Composition for forming releasable film |
| DE3243194A1 (en) * | 1982-11-23 | 1984-05-24 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING SILICONE RUBBER VOLCANISATES |
| FR2557121B1 (en) * | 1983-12-21 | 1986-10-10 | Rhone Poulenc Spec Chim | HOT VULCANIZABLE ORGANOPOLYSILOXANIC ELASTOMERIC COMPOSITIONS WITH IMPROVED PHYSICAL CHARACTERISTICS |
| US4774281A (en) * | 1987-09-04 | 1988-09-27 | Dow Corning Corporation | Low compression set silicone rubber |
| US5380770A (en) * | 1992-04-09 | 1995-01-10 | General Electric Company | Heat cured silicone rubber compositions containing a potassium aluminosilicate filler which provides resistance to hydrocarbon oils and adjustable shrinkage |
| KR20010069668A (en) * | 2001-04-26 | 2001-07-25 | 이명수 | a composition seal for rotation |
| JP4520159B2 (en) * | 2004-01-07 | 2010-08-04 | 信越化学工業株式会社 | Silicone rubber composition |
| US20100225067A1 (en) * | 2009-03-06 | 2010-09-09 | Gm Global Technology Operations, Inc. | Coated ring seal |
| WO2018092490A1 (en) * | 2016-11-17 | 2018-05-24 | 信越化学工業株式会社 | Addition-curable liquid silicone rubber composition for automobile oil filter sealing member, and automobile oil filter sealing member |
| RU2720195C2 (en) * | 2018-08-09 | 2020-04-27 | Общество с ограниченной ответственностью "Изотроп" | Heat-conducting compound |
| RU2720194C2 (en) * | 2018-08-09 | 2020-04-27 | Общество с ограниченной ответственностью "Изотроп" | Composite heat-conducting material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5340050A (en) * | 1976-09-27 | 1978-04-12 | Toray Silicone Co Ltd | Heat-curable silicone rubber composition |
| JPS5388055A (en) * | 1977-01-13 | 1978-08-03 | Toray Silicone Co Ltd | Silicone rubber composition for shaft sealing |
| JPS5448870A (en) * | 1977-09-26 | 1979-04-17 | Toshiba Silicone | Method of forming silicone rubber tube |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865778A (en) * | 1974-02-07 | 1975-02-11 | Gen Electric | Heat vulcanizable silicone rubber compositions resistant to oil degradation |
-
1979
- 1979-09-14 JP JP11840779A patent/JPS5643351A/en active Granted
-
1980
- 1980-09-10 GB GB8029205A patent/GB2060667B/en not_active Expired
- 1980-09-10 CA CA000360008A patent/CA1162687A/en not_active Expired
- 1980-09-11 DE DE19803034232 patent/DE3034232A1/en active Granted
- 1980-09-12 SU SU802980757A patent/SU978734A3/en active
- 1980-09-12 AU AU62370/80A patent/AU535241B2/en not_active Ceased
- 1980-09-12 IT IT24633/80A patent/IT1141044B/en active
- 1980-09-12 SE SE8006416A patent/SE8006416L/en unknown
- 1980-09-12 BE BE0/202083A patent/BE885210A/en not_active IP Right Cessation
- 1980-09-12 FR FR8019715A patent/FR2464976A1/en active Granted
- 1980-09-15 BR BR8005897A patent/BR8005897A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5340050A (en) * | 1976-09-27 | 1978-04-12 | Toray Silicone Co Ltd | Heat-curable silicone rubber composition |
| JPS5388055A (en) * | 1977-01-13 | 1978-08-03 | Toray Silicone Co Ltd | Silicone rubber composition for shaft sealing |
| JPS5448870A (en) * | 1977-09-26 | 1979-04-17 | Toshiba Silicone | Method of forming silicone rubber tube |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8024633A0 (en) | 1980-09-12 |
| FR2464976B1 (en) | 1983-08-05 |
| AU6237080A (en) | 1981-03-19 |
| BR8005897A (en) | 1981-03-31 |
| IT1141044B (en) | 1986-10-01 |
| BE885210A (en) | 1981-03-12 |
| AU535241B2 (en) | 1984-03-08 |
| DE3034232A1 (en) | 1981-04-02 |
| GB2060667B (en) | 1983-10-19 |
| CA1162687A (en) | 1984-02-21 |
| GB2060667A (en) | 1981-05-07 |
| DE3034232C2 (en) | 1991-04-18 |
| SU978734A3 (en) | 1982-11-30 |
| FR2464976A1 (en) | 1981-03-20 |
| JPS5643351A (en) | 1981-04-22 |
| SE8006416L (en) | 1981-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4753978A (en) | Curable organosiloxane compositions | |
| EP0051369B1 (en) | Curable fluorinated silicone elastomer | |
| JPH09136961A (en) | High-vinyl-content low-molecular-weight liquid resin for injection molding | |
| JPH0514742B2 (en) | ||
| JPH0341109B2 (en) | ||
| JPH07216233A (en) | Fluorosilicone rubber composition | |
| JPS623182B2 (en) | ||
| JPH0741627A (en) | Rubber composition | |
| US4766170A (en) | Heat curing organopolysiloxane composition | |
| US4116920A (en) | Silicone rubber composition useful in shaft seals | |
| JPH07149987A (en) | Rubber composition | |
| JPS6241263A (en) | Dynamic fatigue-resistant silicone rubber composition | |
| US4022747A (en) | Silicone rubber compositions | |
| EP0604997A2 (en) | Room temperature vulcanizable organopolysiloxane compositions | |
| JPH0791473B2 (en) | Curable silicone rubber composition and cured product | |
| JPS6157868B2 (en) | ||
| JP2626407B2 (en) | Rubber contact | |
| US5340872A (en) | Silicone rubber compositions and their cured products | |
| TW202309198A (en) | Fluorosilicone rubber composition and cured molded product | |
| JPH0781077B2 (en) | Silicone rubber composition and cured product | |
| JP2840939B2 (en) | Silicone rubber composition | |
| JP2885002B2 (en) | Silicone rubber composition | |
| JP2616284B2 (en) | Method for producing silicone rubber composition | |
| JP3365785B2 (en) | Method for producing fluorosilicone rubber composition | |
| JP3157529B2 (en) | Silicone rubber composition |