JPS6320463B2 - - Google Patents
Info
- Publication number
- JPS6320463B2 JPS6320463B2 JP23034583A JP23034583A JPS6320463B2 JP S6320463 B2 JPS6320463 B2 JP S6320463B2 JP 23034583 A JP23034583 A JP 23034583A JP 23034583 A JP23034583 A JP 23034583A JP S6320463 B2 JPS6320463 B2 JP S6320463B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silicone rubber
- curing
- composition
- parts
- 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
- 239000000203 mixture Substances 0.000 claims description 31
- 229920002379 silicone rubber Polymers 0.000 claims description 26
- 239000004945 silicone rubber Substances 0.000 claims description 26
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 4
- 229920003257 polycarbosilane Polymers 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- -1 polysiloxane Polymers 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([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
- 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
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱硬化性シリコーンゴム組成物、特に
はすぐれた硬化促進効果をもつ熱硬化性シリコー
ンゴム組成物に関するものである。
熱硬化性シリコーンゴムについてはその目的、
用途によつて各種のものが使用されているが、通
常、これらはいずれも有機過酸化物系の硬化触媒
の存在下での100〜400℃の加熱によつて硬化され
ている。この有機過酸化物としてはベンゾイルパ
ーオキサイド、ジクミルパーオキサイド、ジター
シヤリーブチルパーオキサイド、ビス―２，４−
ジクロロベンゾイルパーオキサイド、ターシヤリ
ーブチルパーベンゾエートなどが常用されている
のであるが、これらは加熱されると常温では飛散
しにくい分解残渣を発生するため、加硫硬化後の
シリコーンゴムが物性の低下したものになるとい
う不利を与えることがあり、またこのシリコーン
ゴム組成物が特にフエニル基またはトリフルオロ
プロピル基を含有するものであるときにはその硬
化速度が遅く成形に時間がかかるという欠点があ
る。
このため、この種の熱硬化性シリコーンゴム組
成物についてはオルガノハイドロジエンポリシロ
キサンとカルシウム系化合物とを添加することに
よつて硬化速度を促進させ、有機過酸化物の添加
量を1/2〜1/3に減少させるようにした組成物も提
案されている（特公昭52−27180号公報参照）が、
これには配合が煩雑となりコストも高くなるとい
う不利があつた。
本発明はこのような不利を解決した熱硬化性シ
リコーンゴム組成物に関するものであり、これは
(A)平均組成式が
The present invention relates to a thermosetting silicone rubber composition, and particularly to a thermosetting silicone rubber composition having an excellent curing accelerating effect. Regarding thermosetting silicone rubber, its purpose,
Various types are used depending on the purpose, but all of these are usually cured by heating at 100 to 400°C in the presence of an organic peroxide-based curing catalyst. Examples of this organic peroxide include benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, bis-2,4-
Dichlorobenzoyl peroxide, tertiary butyl perbenzoate, etc. are commonly used, but when heated, they generate decomposition residues that are difficult to scatter at room temperature, so silicone rubber after vulcanization and curing may have deteriorated physical properties. In addition, especially when the silicone rubber composition contains a phenyl group or a trifluoropropyl group, there is a disadvantage that the curing speed is slow and molding takes time. Therefore, for this type of thermosetting silicone rubber composition, the curing speed is accelerated by adding organohydrodiene polysiloxane and a calcium-based compound, and the amount of organic peroxide added is reduced by 1/2 to 1/2. A composition in which the amount is reduced to 1/3 has also been proposed (see Japanese Patent Publication No. 52-27180);
This had the disadvantage that the formulation was complicated and the cost was high. The present invention relates to a thermosetting silicone rubber composition that solves these disadvantages.
(A) The average composition formula is
【式】（ここにＲは非置
換または置換の１価炭化水素基、ｍは1.98〜2.2
の正数）で示されるオルガノポリシロキサン100
重量部、(B)分子中に少なくとも２個の≡SiH基を
含むポリシルアルキレンシロキサン、ポリシラ
ン、ポリカルボシランまたはこれらの混合物0.01
〜５重量部、(C)有機過酸化物0.05〜５重量部とか
らなることを特徴とするものである。
本発明者らは熱硬化性シリコーンゴム組成物中
の有機過酸化物の分解残渣残留による不利を解決
する手法について種々検討した結果、この組成物
に≡SiH基を有するポリシルアルキレンシロキサ
ンを添加すればシリコーンゴムの硬化速度を著し
く促進させることができ、有機過酸化物の配合量
を1/5程度にまで減少させることができること、
また発泡し易いシリコーンゴム組成物を発泡のお
それなく硬化させることができ、さらには硬化速
度の遅いフエニル基、フルオロアルキル基含有シ
リコーンゴム組成物をも速く硬化させることがで
きるということを見出すとともに、この≡SiH基
含有ポリシルアルキレンシロキサンはこれを≡
SiH基を有するポリシラン、ポリカルボシランと
してもよいということを確認して本発明を完成さ
せた。
本発明の組成物を構成する(A)成分としてのオル
ガノポリシロキサンは通常シリコーンオイルまた
はシリコーン生ゴムと称されている平均組成式が
[Formula] (where R is an unsubstituted or substituted monovalent hydrocarbon group, m is 1.98 to 2.2
Organopolysiloxane 100 (positive number)
Part by weight, (B) Polysylalkylene siloxane, polysilane, polycarbosilane or mixture thereof containing at least two ≡SiH groups in the molecule 0.01
5 parts by weight, and 0.05 to 5 parts by weight of (C) organic peroxide. The present inventors have investigated various methods for solving the disadvantages caused by residual decomposition residues of organic peroxides in thermosetting silicone rubber compositions. The curing speed of silicone rubber can be significantly accelerated, and the amount of organic peroxide added can be reduced to about 1/5;
In addition, we have discovered that easily foamable silicone rubber compositions can be cured without fear of foaming, and that phenyl group- and fluoroalkyl group-containing silicone rubber compositions that have a slow curing rate can also be cured quickly. This ≡SiH group-containing polysylalkylene siloxane is ≡
The present invention was completed by confirming that polysilanes and polycarbosilanes having SiH groups can be used. The organopolysiloxane as component (A) constituting the composition of the present invention has an average compositional formula that is usually referred to as silicone oil or silicone raw rubber.
【式】で示される直鎖状のオルガノポリ
シロキサンで、このＲがメチル基、エチル基、プ
ロピル基などのアルキル基、シクロヘキシル基な
どのシクロアルキル基、ビニル基、アリル基など
のアルケニル基、フエニル基、トリル基などのア
リール基、またはこれらの基の炭素原子に結合し
た水素基の１部をハロゲン原子、シアノ基などで
置換したクロロメチル基、３，３，３―トリフル
オロプロピル基などとされるものであるが、通常
はその少なくとも50モル％がメチル基で０〜５モ
ル％のビニル基、０〜50モル％のフエニル基を含
むものとされる。また、このオルガノポリシロキ
サンはその末端がトリメチルシリル基、ジメチル
ビニルシリル基、メチルジビニルシリル基、メチ
ルフエニルビニルシリル基のようなトリオルガノ
シリル基または水酸基で封鎖されたものとされる
が、この組成物を硬化して得られるシリコーンゴ
ムの強度を低下させないために少なくとも
100000cSの粘度をもつものとすることがよい。
また、本発明の組成物における(B)成分は前記し
たようにポリシルアルキレンシロキサン、ポリシ
ラン、ポリカルボシランから選択されるが、これ
らはその分子中に少なくとも２個のけい素原子に
結合した水素基としての≡SiH結合を含むものと
する必要がある。これらのシロキサン、シランは
その分子中に少なくとも１個の
（ここにＲは前記に同じ、ａ＝0.1〜1.2、ｂ＝１
〜２、ｃ＝0.01〜1.0、ａ＋ｂ＝1.8〜3.0、ｎ＝１
〜10）を有する有機けい素化合物であり、これに
はつぎのものが例示される。
この(B)成分を前記した(A)成分に添加した組成物
は後記する有機過酸化物を添加し加熱することに
よつて硬化されるが、これは(B)成分の添加によつ
て硬化速度が著しく促進されるのでこの有機過酸
化物の添加量を従来法にくらべて1/5〜1/2量に減
少しても得られるシリコーンゴムの機械的物性を
実質的に支障のない範囲とすることができるし、
これによつて発泡し易いシリコーンゴム組成物を
発泡のおそれなしに硬化させることができ、さら
には硬化速度の遅いフエニル基、トリフルオロプ
ロピル基のような基を含むシリコーンゴム組成物
の成形時間が短縮されるという有用性を与えられ
る。なお、この(B)成分の(A)成分に対する配合量は
少なすぎると上記した効果が充分に達成されず、
逆に多すぎると本発明の組成物から得られる硬化
したシリコーンゴムの電気特性、耐スチーム性な
どの諸物性が低下するので、(A)成分100重量部に
対し0.01〜５重量部の範囲とすることが必要とさ
れる。
また、この(C)成分としての有機過酸化物はこの
シリコーンゴム組成物を硬化させるための必須成
分とされるもので、従来公知のベンゾイルパーオ
キサイド、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―ｔ―ブチルパーオキサイド、ｔ―ブチルパー
ベンゾエート、２，５―ジメチル―２，５―（ジ
―ｔ―ブチルパーオキシ）ヘキシン、１，１―ビ
ス（ｔ―ブチルパーオキシ）３，３，５―トリメ
チルシクロヘキサン、ジクミルパーオキサイドな
どが例示されるが、これらは上記した(A)成分100
重量部に対し0.05〜５重量部の範囲で添加すれば
よい。
本発明の熱硬化性シリコーンゴム組成物は上記
した(A)〜(C)成分を混練りすることによつて得ら
れ、その配合の順序に特に制限はないが、通常の
用途に際しては(A)成分と後記する任意成分として
の微粉末状シリカ充填剤とを予じめ均一に混合
し、ついでこれに(B)および(C)成分を混合すること
によつて行なわれる。なお、この組成物は前記し
たようにこの(C)成分である有機過酸化物の添加量
を減少させるとシリコーンゴム成形品の硬度が若
干低下することがあるが、この場合には(B)成分を
ビニル基を含有するものとすればよい。また、本
発明の組成物は基本的には上記した(A)〜(C)成分か
ら構成されるが、硬化後の機械的強度を向上させ
るために微粉末状シリカ充填剤を添加することは
任意であり、これには従来シリコーンゴム組成物
用として公知のヒユームドシリカ、沈降シリカ、
石英粉末、けいそう土などが例示されるが、これ
らは粒子径が大きいと硬化後のシリコーンゴムの
機械的強度が低下するので、150m2／ｇ以上の表
面積をもつ微粉末状のものとする必要があり、(A)
成分100重量部に対し５〜400重量部の範囲で添加
すればよい。なお、この組成物には必要に応じア
ルコキシシラン、末端シラノールジメチルポリシ
ロキサン、ジフエニルシランジオールなどのソフ
ナー類、耐熱性向上剤、架橋剤、着色剤など、さ
らには接着助剤としてのカーボンフアンクシヨナ
ルシランなどを添加してもよく、また充填剤とし
て当業界においてよく用いられている準補強剤と
しての炭酸カルシウム、セライト、タルク、クレ
イ、マイカ、水酸化アルミニウムなどを添加して
もよい。
本発明の組成物はモールド成型、押出し成型、
カレンダー成型など種々の加工法によつて成型さ
れるが、いずれの場合も硬化促進効果が充分に発
揮されて成型品を得ることができ、通常のシリコ
ーンゴムの応用される用途に広く供することがで
きる。
つぎに本発明の実施例をあげるが、例中におけ
る部は重量部を、粘度は25℃での測定値を示した
ものであり、このシリコーンゴム組成物の硬化特
性はODR（東洋精機社製商品名）での測定結果
を、またこの組成物を硬化させて得たシリコーン
ゴム成型品の物性値はJIS Ｋ 6301に準拠した方
法での測定値を示したものである。
実施例１〜７、比較例１〜３
（CH3）2SiO単位99.75モル％、（CH2＝CH）
CH3SiO単位0.25モル％からなり、末端がトリメ
チルシリル基で封鎖された粘度が10000000cSの
オルガノポリシロキサン100部に末端に水酸基を
有する低分子量のジメチルポリシロキサン５部お
よび湿式シリカ40部とをミキサーで均一になるま
で混練し、150℃で２時間処理して揮発性成分と
水分を除去してベースコンパウンドを作つた。
つぎに、このベースコンパウンドに、第１表に
示した量の下記の≡SiH基含有シリコーン化合物
と２，５―ジメチル―２，５―ジ―ｔ―ブチルパ
ーオキサイドとを室温で添加し、二本ロールで均
一に混合させたのち、この硬化特性を測定し、つ
いでこれを圧力30Kg／cm2、165℃の条件下で10分
間加圧加熱して成型品とし、さらに200℃で４時
間ポストキユアをしてからこの物性を測定したと
ころ、硬化特性は第１図、第２図に示したとおり
であり、物性値については第１表に併記したとお
りの結果が得られた。
なお、本例では比較のために≡SiH基含有シリ
コーン化合物を添加しないもの（比較例１）、お
よび特公昭52−27180号公報で公知の≡SiH基含
有シリコーン化合物を添加したもの（比較例２、
３）についても同様に処理し、この結果を第１
図、第１表に併記した。
（各例における≡SiH基含有シリコーン化合物
の種類）
実施例１…A linear organopolysiloxane represented by the formula, where R is an alkyl group such as a methyl group, an ethyl group, or a propyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group, or a phenyl group. aryl groups such as tolyl groups, or chloromethyl groups and 3,3,3-trifluoropropyl groups in which part of the hydrogen group bonded to the carbon atom of these groups is substituted with a halogen atom, cyano group, etc. However, usually at least 50 mol% of the methyl group is contained, 0 to 5 mol% of vinyl groups, and 0 to 50 mol% of phenyl groups. Furthermore, the terminals of this organopolysiloxane are said to be capped with a triorganosilyl group such as a trimethylsilyl group, dimethylvinylsilyl group, methyldivinylsilyl group, or methylphenylvinylsilyl group, or a hydroxyl group; In order not to reduce the strength of the silicone rubber obtained by curing the product, at least
It is preferable to have a viscosity of 100000cS. In addition, component (B) in the composition of the present invention is selected from polysylalkylene siloxane, polysilane, and polycarbosilane as described above, and these have hydrogen bonded to at least two silicon atoms in the molecule. It is necessary to include a ≡SiH bond as a group. These siloxanes and silanes have at least one molecule in their molecules. (Here, R is the same as above, a=0.1~1.2, b=1
~2, c=0.01~1.0, a+b=1.8~3.0, n=1
~10), and examples thereof include the following. A composition in which component (B) is added to component (A) described above is cured by adding an organic peroxide described later and heating; The speed is significantly accelerated, so even if the amount of organic peroxide added is reduced to 1/5 to 1/2 compared to the conventional method, the mechanical properties of the silicone rubber obtained can be reduced to a range without substantially affecting the mechanical properties. and
This allows silicone rubber compositions that tend to foam easily to be cured without the fear of foaming, and also allows molding time for silicone rubber compositions containing groups such as phenyl groups and trifluoropropyl groups that have a slow curing rate. given the usefulness of being shortened. In addition, if the amount of component (B) added to component (A) is too small, the above effects will not be fully achieved.
On the other hand, if the amount is too high, the physical properties such as electrical properties and steam resistance of the cured silicone rubber obtained from the composition of the present invention will deteriorate. It is necessary to do so. In addition, the organic peroxide as component (C) is considered to be an essential component for curing this silicone rubber composition, and conventionally known benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, monochlorobenzoyl peroxide, etc. benzoyl peroxide,
Di-t-butyl peroxide, t-butyl perbenzoate, 2,5-dimethyl-2,5-(di-t-butylperoxy)hexyne, 1,1-bis(t-butylperoxy) 3,3 , 5-trimethylcyclohexane, dicumyl peroxide, etc., which are 100% of the above-mentioned component (A).
It may be added in an amount of 0.05 to 5 parts by weight. The thermosetting silicone rubber composition of the present invention is obtained by kneading the above-mentioned components (A) to (C), and there is no particular restriction on the order of blending. This is carried out by uniformly mixing component ) and a finely powdered silica filler as an optional component to be described later in advance, and then mixing components (B) and (C) therewith. As mentioned above, in this composition, if the amount of organic peroxide, which is component (C), is reduced, the hardness of the silicone rubber molded product may decrease slightly, but in this case, (B) The component may contain a vinyl group. Furthermore, although the composition of the present invention is basically composed of the above-mentioned components (A) to (C), a fine powdered silica filler may be added to improve the mechanical strength after curing. Optional, including fumed silica, precipitated silica, conventionally known for use in silicone rubber compositions,
Examples include quartz powder and diatomaceous earth, but if the particle size is large, the mechanical strength of the silicone rubber after curing will decrease, so use a fine powder with a surface area of 150 m 2 /g or more. Must be (A)
It may be added in an amount of 5 to 400 parts by weight per 100 parts by weight of the components. This composition may optionally contain softeners such as alkoxysilane, terminal silanol dimethylpolysiloxane, and diphenylsilane diol, heat resistance improvers, crosslinking agents, coloring agents, and carbon glue as an adhesion aid. Silane, etc. may be added, and calcium carbonate, celite, talc, clay, mica, aluminum hydroxide, etc., which are semi-reinforcing agents often used in the art as fillers, may also be added. The composition of the present invention can be molded, extruded,
It can be molded by various processing methods such as calendar molding, but in any case, it is possible to obtain a molded product with a sufficient curing accelerating effect, and it can be used in a wide range of applications for ordinary silicone rubber. can. Next, examples of the present invention will be given. Parts in the examples are parts by weight, and viscosity is a value measured at 25°C. The curing characteristics of this silicone rubber composition are ODR (manufactured by Toyo Seiki Co., Ltd. (trade name) and the physical property values of a silicone rubber molded product obtained by curing this composition are shown as measured by a method based on JIS K 6301. Examples 1 to 7, Comparative Examples 1 to 3 (CH 3 ) 2 SiO units 99.75 mol%, (CH 2 =CH)
100 parts of an organopolysiloxane containing 0.25 mol% of CH 3 SiO units and having a viscosity of 1,000,000 cS and whose terminals are capped with trimethylsilyl groups, 5 parts of low molecular weight dimethylpolysiloxane having a hydroxyl group at its terminals, and 40 parts of wet silica are mixed in a mixer. The mixture was kneaded until homogeneous and treated at 150° C. for 2 hours to remove volatile components and water to prepare a base compound. Next, to this base compound were added the following ≡SiH group-containing silicone compound and 2,5-dimethyl-2,5-di-t-butyl peroxide in the amounts shown in Table 1 at room temperature. After uniformly mixing with this roll, the curing characteristics were measured, and then the product was heated under pressure of 30 kg/cm 2 and 165°C for 10 minutes to form a molded product, and then post-cured at 200°C for 4 hours. After this, the physical properties were measured, and the curing characteristics were as shown in FIGS. 1 and 2, and the physical property values were as shown in Table 1. In this example, for comparison, ≡SiH group-containing silicone compound was not added (Comparative Example 1), and ≡SiH group-containing silicone compound known in Japanese Patent Publication No. 52-27180 was added (Comparative Example 2). ,
3) is processed in the same way, and this result is used as the first
They are also listed in the figure and Table 1. (Type of ≡SiH group-containing silicone compound in each example) Example 1...
【式】 実施例２…【formula】 Example 2...
【式】 実施例３…【formula】 Example 3...
【式】 実施例４〜７… 比較例２…[Formula] Examples 4 to 7... Comparative example 2...
【式】 比較例３… [Formula] Comparative example 3...
【表】【table】
第１図、第２図は実施例１〜７、比較例１〜３
のシリコーンゴム組成物の硬化速度のODRチヤ
ートを示したものである。
Figures 1 and 2 are Examples 1 to 7 and Comparative Examples 1 to 3.
This figure shows an ODR chart of the curing speed of the silicone rubber composition.
Claims (1)
基、ｍは1.98〜2.2の正数）で示されるオルガ
ノポリシロキサン 100重量部 (B) １分子中に少なくとも２個の≡SiH結合を有
するポリシルアルキレンシロキサン、ポリシラ
ン、ポリカルボシランもしくはこれらの混合物
0.01〜５重量部 (C) 有機過酸化物 0.05〜５重量部 からなることを特徴とする加熱硬化性シリコーン
ゴム組成物。[Claims] 1 (A) Organopolysiloxane whose average compositional formula is represented by [Formula] (where R is an unsubstituted or substituted monovalent hydrocarbon group, m is a positive number from 1.98 to 2.2) 100 weight Part (B) Polysylalkylene siloxane, polysilane, polycarbosilane or a mixture thereof having at least two ≡SiH bonds in one molecule
0.01-5 parts by weight (C) A heat-curable silicone rubber composition comprising 0.05-5 parts by weight of organic peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23034583A JPS60120755A (en) | 1983-12-05 | 1983-12-05 | Thermosetting silicone rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23034583A JPS60120755A (en) | 1983-12-05 | 1983-12-05 | Thermosetting silicone rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60120755A JPS60120755A (en) | 1985-06-28 |
| JPS6320463B2 true JPS6320463B2 (en) | 1988-04-27 |
Family
ID=16906389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23034583A Granted JPS60120755A (en) | 1983-12-05 | 1983-12-05 | Thermosetting silicone rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60120755A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0219115U (en) * | 1988-07-25 | 1990-02-08 | ||
| JPH03202891A (en) * | 1989-12-29 | 1991-09-04 | Matsushita Electric Ind Co Ltd | Display device |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62263254A (en) * | 1986-05-08 | 1987-11-16 | Shin Etsu Chem Co Ltd | Silicone rubber composition |
| DE3726010A1 (en) * | 1987-08-05 | 1989-02-16 | Wacker Chemie Gmbh | HEAT-CURABLE ORGANOPOLYSILOXANE COMPOSITIONS |
| EP0431173B1 (en) * | 1989-05-29 | 1995-08-02 | Kanegafuchi Chemical Industry Co., Ltd. | Curing agent, method of preparation thereof, and curable composition prepared therefrom |
| US5409995A (en) * | 1989-05-29 | 1995-04-25 | Kanegafuchi Chemical Industry Co., Ltd. | Curing agent, preparation thereof and curable composition comprising the same |
| JP2937228B2 (en) * | 1994-07-20 | 1999-08-23 | 矢崎総業株式会社 | Sealing parts for connector waterproofing |
| JP2937229B2 (en) * | 1994-08-02 | 1999-08-23 | 矢崎総業株式会社 | Sealing parts for connector waterproofing |
| US7071244B2 (en) * | 2002-12-03 | 2006-07-04 | Staar Surgical Company | High refractive index and optically clear copoly (carbosilane and siloxane) elastomers |
-
1983
- 1983-12-05 JP JP23034583A patent/JPS60120755A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0219115U (en) * | 1988-07-25 | 1990-02-08 | ||
| JPH03202891A (en) * | 1989-12-29 | 1991-09-04 | Matsushita Electric Ind Co Ltd | Display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60120755A (en) | 1985-06-28 |
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