JP2869367B2 - Silicone rubber sponge composition and silicone rubber sponge using the same - Google Patents
Silicone rubber sponge composition and silicone rubber sponge using the sameInfo
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- JP2869367B2 JP2869367B2 JP25216395A JP25216395A JP2869367B2 JP 2869367 B2 JP2869367 B2 JP 2869367B2 JP 25216395 A JP25216395 A JP 25216395A JP 25216395 A JP25216395 A JP 25216395A JP 2869367 B2 JP2869367 B2 JP 2869367B2
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- silicone rubber
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- rubber sponge
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Description
【０００１】[0001]
【発明の技術分野】本発明は、シリコーンゴムスポンジ
組成物およびこれを用いたシリコーンゴムスポンジに係
わり、更に詳しくは、発泡性に優れ、セル構造が微細
で、スキン層の表面平滑性に優れ、また、表面粘着性が
なく、圧縮永久歪みが良好であり、また、成形時および
発泡硬化物の臭気が少なく、長時間のポストキュアーを
必要としないシリコーンゴムスポンジを得ることができ
るシリコーンゴムスポンジ組成物およびこれを用いたシ
リコーンゴムスポンジに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone rubber sponge composition and a silicone rubber sponge using the same, and more particularly, to an excellent foaming property, a fine cell structure, and an excellent surface smoothness of a skin layer. In addition, a silicone rubber sponge composition that has no surface tackiness, has good compression set, has a low odor during molding and a foamed cured product, and can obtain a silicone rubber sponge that does not require long post-curing. And a silicone rubber sponge using the same.
【０００２】[0002]
【発明の技術的背景とその問題点】従来より、シリコー
ンゴムスポンジは、耐候性・電気特性・圧縮永久歪みな
どに優れた材料としてよく知られている。このシリコー
ンゴムスポンジは、基本的に熱硬化性シリコーンゴム組
成物に有機発泡剤と硬化剤とを配合し、加熱により発泡
・硬化して得られるが、その場合、発泡性に優れ、セル
構造が微細で、スキン層の表面平滑性に優れ、また、表
面粘着性がなく、圧縮永久歪みが良好で、しかも、シリ
コーンゴム本来の特性を損なわないことが重要である。
このような観点から、従来は発泡剤としてアゾビスイソ
ブチロニトリル（ＡＩＢＮ）が一般に使用されてきた。
しかしながら、このアゾビスイソブチロニトリル（ＡＩ
ＢＮ）を用いた場合、長時間のポストキュアーが必要で
あり、このため工程時間が長くなるという問題があり、
工程時間の短縮のために、ポストキュアー時間の短縮が
望まれている。このため、発泡剤としてアゾビスイソブ
チロニトリル以外のものを用いる方法が検討され、例え
ば、アゾジカルボンアミド（ＡＤＣＡ）やジニトロソペ
ンタメチレンテトラミン（ＤＰＴ）を発泡剤として用い
る方法（特開昭55−29565 号公報）が提案されている。
しかしながら、これらの発泡剤は、アゾビスイソブチロ
ニトリルの場合のように単にシリコーンゴムコンパウン
ドに配合して熱風下で自由発泡させるだけでは、ほとん
ど発泡せず、しかも表面平滑性に著しく劣り、かつその
表面に粘着感が残るという難点があった。近時、これら
の難点を解決する方法として、架橋基を従来のビニル基
に代えて１−エチル−１−ブチニル基、エチリデンノル
ボニル基などに変更したシリコーンポリマーをベースポ
リマーとして用いる方法（特開平２−16132 号公報）
や、同架橋基をシクロヘキシル基などのシクロアルキル
基などに変更したシリコーンポリマーをベースポリマー
として用いる方法（特開平２−251542号公報）が提案さ
れている。しかしながら、これらの方法では、発泡性、
表面平滑性および表面粘着性は改善されるが、発泡剤と
してアゾビスイソブチロニトリルを使用した場合に得ら
れるスポンジ成形体に比べて圧縮永久歪み特性に著しく
劣るという欠点を有する。その他、ビニル基などの脂肪
族不飽和基を有しないシリコーンポリマー、すなわちケ
イ素原子に結合する有機基がメチル基、エチル基、プロ
ピル基、フェニル基、3,3,3 −トリフルオロプロピル基
などからのみ構成されるシリコーンポリマーをベースポ
リマーとして使用した場合の報告もあるが、この場合に
は、表面平滑性と表面粘着性の問題は解決されるが、架
橋のコントロールが極めて困難で、かつ圧縮永久歪み特
性も著しく劣っている。BACKGROUND OF THE INVENTION Conventionally, silicone rubber sponges are well known as materials having excellent weather resistance, electrical properties, compression set and the like. This silicone rubber sponge is basically obtained by blending an organic foaming agent and a curing agent into a thermosetting silicone rubber composition and foaming and curing by heating. In this case, the foaming properties are excellent and the cell structure is excellent. It is important that it is fine, has excellent surface smoothness of the skin layer, has no surface tackiness, has good compression set, and does not impair the inherent properties of silicone rubber.
From such a viewpoint, azobisisobutyronitrile (AIBN) has conventionally been generally used as a foaming agent.
However, this azobisisobutyronitrile (AI
When BN) is used, a long post-curing is required, and there is a problem that the process time becomes long,
In order to reduce the process time, it is desired to reduce the post cure time. For this reason, a method using a material other than azobisisobutyronitrile as a foaming agent has been studied. For example, a method using azodicarbonamide (ADCA) or dinitrosopentamethylenetetramine (DPT) as a foaming agent (Japanese Patent Laid-Open No. -29565).
However, these foaming agents hardly foam when simply blended into a silicone rubber compound and freely foamed under hot air as in the case of azobisisobutyronitrile, and furthermore, have extremely poor surface smoothness, and There was a problem that a sticky feeling remained on the surface. Recently, as a method of solving these difficulties, a method of using a silicone polymer in which a crosslinking group is replaced with a 1-ethyl-1-butynyl group, an ethylidene norbornyl group or the like instead of a conventional vinyl group as a base polymer (Japanese Patent Laid-Open No. No. 2-16132)
A method has been proposed in which a silicone polymer in which the crosslinking group is changed to a cycloalkyl group such as a cyclohexyl group or the like is used as a base polymer (JP-A-2-251542). However, in these methods, foamability,
Although the surface smoothness and the surface tackiness are improved, they have a drawback that the compression set characteristic is remarkably inferior to the sponge molded product obtained when azobisisobutyronitrile is used as a foaming agent. In addition, a silicone polymer having no aliphatic unsaturated group such as a vinyl group, i.e., an organic group bonded to a silicon atom is formed from a methyl group, an ethyl group, a propyl group, a phenyl group, a 3,3,3-trifluoropropyl group, or the like. There are reports of the use of a silicone polymer composed only of as a base polymer.In this case, the problems of surface smoothness and surface tackiness are solved, but control of crosslinking is extremely difficult and compression The distortion characteristics are also significantly inferior.
【０００３】[0003]
【発明の目的】このように、従来より、発泡倍率が高く
セル構造が均一なシリコーンゴムスポンジを得るため、
発泡剤にアゾビスイソブチロニトリルを用いる方法が多
用されてきたが、長時間のポストキュアーを必要とし生
産性に問題があることから、これに代わる技術が要求さ
れている。しかしながら、これまでに提案ないし報告さ
れているものは、発泡性、表面平滑性、表面粘着性に問
題があったり、圧縮永久歪み特性に著しく劣るなどの難
点があるなど、未だ満足し得る方法が得られていないの
が実情である。本発明はこのような従来技術の課題に対
処すべくなされたもので、発泡剤にアゾビスイソブチロ
ニトリルを用いなくとも、発泡倍率が高く、セル構造が
均一で、表面平滑性や表面粘着性に問題がなく、しかも
圧縮永久歪み特性も良好で、成形時および発泡硬化物の
臭気が少なく長時間のポストキュアーを必要としないシ
リコーンゴムスポンジを得ることのできるシリコーンゴ
ムスポンジ用組成物およびこれを用いたシリコーンゴム
スポンジを提供することを目的とする。As described above, in order to obtain a silicone rubber sponge having a high expansion ratio and a uniform cell structure,
Although a method using azobisisobutyronitrile as a foaming agent has been frequently used, a long-term post-curing is required and there is a problem in productivity, so that an alternative technique is required. However, what has been proposed or reported so far, foaming, surface smoothness, there is a problem in the surface tackiness, there are difficulties such as remarkably inferior compression set characteristics, there is still a satisfactory method. The fact is that it has not been obtained. The present invention has been made to address such problems of the prior art, and without using azobisisobutyronitrile as a foaming agent, the foaming ratio is high, the cell structure is uniform, the surface smoothness and the surface adhesion are improved. A silicone rubber sponge composition which has no problem in the properties and good compression set characteristics, and which can obtain a silicone rubber sponge which does not require a long post-curing and a low odor during molding and a foamed cured product, and An object of the present invention is to provide a silicone rubber sponge using the same.
【０００４】[0004]
【発明の構成】本発明者らは、上記目的を達成すべく鋭
意検討した結果、発泡剤として特定量の1,1'−アゾ−ビ
ス（１−アセトキシ−１−フェニル−エタン）を用い、
さらに水素原子含有有機ケイ素化合物を配合することに
より、熱風下においても、発泡性に優れ、セル構造が微
細で、スキン層の表面平滑性に優れ、また、表面粘着性
がなく、圧縮永久歪みが良好であり、成形時の臭気も少
なく、また発泡硬化物の臭気も少なく、長時間のポスト
キュアーを必要としないシリコーンゴムスポンジを容易
に作製できることを見出し、本発明を完成するに至っ
た。即ち本発明は、 (1) 平均組成式The present inventors have conducted intensive studies to achieve the above object, and as a result, using a specific amount of 1,1'-azo-bis (1-acetoxy-1-phenyl-ethane) as a foaming agent,
In addition, by blending a hydrogen atom-containing organosilicon compound, even under hot air, it has excellent foaming properties, a fine cell structure, excellent surface smoothness of the skin layer, no surface tackiness, and no compression set. The present inventors have found that silicone rubber sponges which are good, have a low odor during molding, have a low odor of the foamed cured product, and do not require a long post-curing can be easily produced, and have completed the present invention. That is, the present invention provides:
【０００５】[0005]
【化３】 Embedded image
【０００６】（式中のR は炭素数１〜10の非置換または
置換の１価炭化水素基、a ＝1.95〜2.05）で示されるオ
ルガノポリシロキサン 100重量部に対し (2) 充填剤３〜500 重量部 (3) 1,1'−アゾ−ビス（１−アセトキシ−１−フェニル
−エタン）からなる発泡剤 0.1〜20重量部 (4) 平均組成式(Wherein R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a = 1.95 to 2.05) per 100 parts by weight of the organopolysiloxane represented by the following formula: 500 parts by weight (3) Blowing agent consisting of 1,1'-azo-bis (1-acetoxy-1-phenyl-ethane) 0.1 to 20 parts by weight (4) Average composition formula
【０００７】[0007]
【化４】 Embedded image
【０００８】（式中、 R' は置換または非置換の一価炭
化水素基、X は水素基または加水分解可能な基を表わ
す。b は０≦b ≦３、c は０＜c ＜３、d は０≦d ≦
３、ただしb ＋c ＋d は０＜b ＋c ＋d ≦４である）で
示される水素原子含有有機けい素化合物） 0.1〜20重量
部 (5) 有機過酸化物0.05〜15重量部 を配合してなるシリコーンゴムスポンジ組成物に関する
ものである。(Wherein R ′ is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrogen group or a hydrolyzable group, b is 0 ≦ b ≦ 3, c is 0 <c <3, d is 0 ≦ d ≦
3, where b + c + d is 0 <b + c + d ≦ 4) 0.1 to 20 parts by weight (5) Organic peroxide 0.05 to 15 parts by weight It relates to a silicone rubber sponge composition.
【０００９】まず、本発明のシリコーンゴムスポンジ組
成物を成す構成成分について説明する。第１成分として
のオルガノポリシロキサンは式First, components constituting the silicone rubber sponge composition of the present invention will be described. The organopolysiloxane as the first component has the formula
【００１０】[0010]
【化５】 Embedded image
【００１１】で示され、このR はメチル基、エチル基、
プロピル基、ブチル基などのアルキル基、ビニル基、ア
リル基、ブタニエル基などのアルケニル基、フェニル
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原子の一部または全部をハロゲン原
子、シアノ基などで置換したクロロメチル基、クロロプ
ロピル基、3,3,3 −トリフルオロプロピル基、２−シア
ノエチル基などから選択される炭素数１〜10の、好まし
くは炭素数１〜８の同種または異種の非置換または置換
１価炭化水素基が挙げられるが、メチル基、フェニル
基、3,3,3 −トリフルオロプロピル基、ビニル基が好ま
しい。またビニル基を 0.001モル％〜10モル％含むこと
が好ましく、さらに好ましくは0.01〜５モル％である。
0.001モル％より少ないと圧縮永久歪みが悪くなり、10
モル％を越えると機械的強度が悪くなるからである。a
は1.95〜2.05の正数であるものとされる。このものは分
子構造が直鎖状のものとすることが好ましいが、これは
分子中に一部分枝鎖状のものを含有していても問題はな
い。また、このものは分子鎖末端が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すればよいが、この
トリオルガノシリル基としてはトリメチルシリル基、ジ
メチルビニルシリル基、メチルフェニルビニルシリル
基、メチルジフェニルシリル基、メチルジビニルシリル
基、トリビニルシリル基などが例示される。なお、この
ものは重合度に特に限定はないが、好ましくは重合度30
00〜30000 より好ましくは5000〜10000 である。重合度
が3000未満であるとシリコーンゴムスポンジの機械的強
度が低下し、重合度が 30000を越えると充填剤配合が困
難となり作業性が低下する。Wherein R is a methyl group, an ethyl group,
Alkyl groups such as propyl group and butyl group, vinyl group, allyl group, alkenyl group such as butaniel group, phenyl group, aryl group such as tolyl group, or part or all of hydrogen atoms bonded to carbon atoms of these groups. A halogen atom, a chloromethyl group substituted with a cyano group, a chloropropyl group, a 3,3,3-trifluoropropyl group, a carbon number of 1 to 10 selected from a 2-cyanoethyl group and the like, preferably a carbon number of 1 to 8 same or different unsubstituted or substituted monovalent hydrocarbon groups are mentioned, and a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group and a vinyl group are preferred. Further, it preferably contains 0.001 mol% to 10 mol% of a vinyl group, and more preferably 0.01 to 5 mol%.
If it is less than 0.001 mol%, the compression set becomes poor, and
If the amount exceeds mol%, the mechanical strength becomes poor. a
Is assumed to be a positive number between 1.95 and 2.05. It is preferable that this compound has a straight-chain molecular structure, but there is no problem even if the molecule contains a partially branched-chain compound. In addition, this may be one in which the molecular chain end is blocked with a triorganosilyl group or a hydroxyl group. Examples of the triorganosilyl group include a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, and a methyldiphenylsilyl group. Group, methyldivinylsilyl group, trivinylsilyl group and the like. In addition, this is not particularly limited in the degree of polymerization, preferably a degree of polymerization 30
It is more preferably from 5000 to 10,000. If the degree of polymerization is less than 3,000, the mechanical strength of the silicone rubber sponge decreases, and if the degree of polymerization exceeds 30,000, it becomes difficult to mix the filler and the workability decreases.
【００１２】(2) 成分の充填剤は、シリコーンゴムスポ
ンジの補強、増粘、加工性向上などの目的で添加される
ものであり、通常シリコーンゴムに配合するものであれ
ば特に限定はなく、これには、フュームドシリカ、湿式
シリカ、表面を疎水化処理したフュームドシリカや湿式
シリカ、石英微粉末、けいそう土、タルク、クレー、カ
ーボンブラック、炭酸カルシウム、酸化亜鉛、酸化マグ
ネシウムなどが例示される。これらの充填剤は、そのま
ま使用してもよく、またオルガノシロキサン、ポリオル
ガノシロキサン、ヘキサオルガノジシラザン等により表
面処理されたものを用いてもよい。この充填剤の配合量
は、(1) 成分のオルガノポリシロキサン 100重量部に対
して３重量部未満では目的とする補強性が得られず、加
工性も不充分であり、 500重量部を越えると吐出性など
の加工特性や機械的強度が低下することから３〜500 重
量部が好ましいが、より好ましくは５〜300 重量部であ
る。The filler of the component (2) is added for the purpose of reinforcing the silicone rubber sponge, increasing the viscosity, improving the processability, etc., and is not particularly limited as long as it is usually compounded with the silicone rubber. Examples include fumed silica, wet silica, fumed silica whose surface has been hydrophobized, wet silica, quartz fine powder, diatomaceous earth, talc, clay, carbon black, calcium carbonate, zinc oxide, magnesium oxide, etc. Is done. These fillers may be used as they are, or may be surface-treated with organosiloxane, polyorganosiloxane, hexaorganodisilazane, or the like. If the amount of the filler is less than 3 parts by weight with respect to 100 parts by weight of the organopolysiloxane of the component (1), the desired reinforcing property cannot be obtained, the workability is insufficient, and the amount exceeds 500 parts by weight. The amount is preferably from 3 to 500 parts by weight, more preferably from 5 to 300 parts by weight, since processing characteristics such as dischargeability and mechanical strength are lowered.
【００１３】次に第３成分の1,1'−アゾ−ビス（１−ア
セトキシ−１−フェニル−エタン）は、発泡シリコーン
ゴムスポンジを得るための必須のものであり、加熱する
ことにより分解し、発泡性に優れ、セル構造が微細で、
スキン層の平滑性また、表面粘着性がなく圧縮永久歪み
が良好であり、シリコーンゴムスポンジを容易に作製で
きるという特性を有する。またこの発泡剤の添加量は、
(1) 成分のオルガノポリシロキサン 100重量部に対し、
0.1〜20重量部が好ましい。 0.1重量部より少なくなる
と発泡倍率の高いシリコーンゴムスポンジの形成が困難
であり、20重量部を越えて添加すると、得られるシリコ
ーンゴムスポンジの物性が低下する。さらに好ましくは
0.5 〜10重量部である。また、この発泡剤の平均粒径は
200μm以下が好ましく、より好ましくは 100μm 以下
である。 200μm より大きいと微細なセルが得られない
からである。The third component, 1,1'-azo-bis (1-acetoxy-1-phenyl-ethane), is essential for obtaining a foamed silicone rubber sponge, and is decomposed by heating. , Excellent foaming properties, fine cell structure,
Smoothness of the skin layer. Also, it has good compression set without surface tackiness, and has characteristics that a silicone rubber sponge can be easily produced. Also, the amount of this foaming agent
(1) With respect to 100 parts by weight of the organopolysiloxane of the component,
0.1-20 parts by weight are preferred. If the amount is less than 0.1 part by weight, it is difficult to form a silicone rubber sponge having a high expansion ratio, and if the amount exceeds 20 parts by weight, the physical properties of the obtained silicone rubber sponge deteriorate. More preferably
It is 0.5 to 10 parts by weight. The average particle size of this blowing agent is
It is preferably 200 μm or less, more preferably 100 μm or less. If the thickness is larger than 200 μm, a fine cell cannot be obtained.
【００１４】(4) 成分としての水素原子含有有機けい素
化合物は上記した式(2) で示されるものである。これを
配合することにより、(3) 成分の発泡剤の分解時に発生
する酢酸臭を低減させるためのものであり、これにより
ポストキュアーの時間の短縮化が可能となるものであ
る。(4) The hydrogen-containing organosilicon compound as a component is represented by the above formula (2). By blending this, the acetic acid odor generated when the foaming agent of the component (3) is decomposed is reduced, whereby the post-curing time can be shortened.
【００１５】式中、R'で示される置換または非置換の一
価炭化水素基としては、上記R で例示した基と同様の基
を挙げることができ、またX で示される水酸基または加
水分解可能な基としては、メトキシ基、エトキシ基、プ
ロポキシ基などのアルコキシ基、アセトキシ基などのア
シロキシ基、アミノ基、アミノキシ基、ケトオキシム
基、アミド基、アルケニルオキシ基などをあげることが
できる。In the formula, examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R 'include the same groups as those exemplified above for R, and a hydroxyl group represented by X or a hydrolyzable group Examples of such a group include an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, an acyloxy group such as an acetoxy group, an amino group, an aminooxy group, a ketoxime group, an amide group, and an alkenyloxy group.
【００１６】b 、c 、d およびb ＋c ＋d は前記の通り
である。B, c, d and b + c + d are as described above.
【００１７】このような水素原子含有有機けい素化合物
としては、例えば下記に示すような化合物をあげること
ができる。Examples of such a hydrogen atom-containing organic silicon compound include the following compounds.
【００１８】なお、以下の記載における化学式中のMe、
Et、PrまたはPhはそれぞれメチル基、エチル基、プロピ
ル基またはフェニル基を示したものである。In the following description, Me,
Et, Pr, and Ph represent a methyl group, an ethyl group, a propyl group, or a phenyl group, respectively.
【００１９】HSi(OMe)3 、HSi(OEt)3 、HSi(OPr)3 、Me
HSi(OMe)2 、MeHSi(OEt)2 、Me2HSiOMe 、Me2HSiOEt 、
Me3SiOSi(Me)2H、HSi[-OSi(Me)2H]3、MeSi[-OSi(Me)2H]
3 、ViSi[-OSi(Me)2H]3 、PhSi[-OSi(Me)2H]3 、HSi (OMe) 3 , HSi (OEt) 3 , HSi (OPr) 3 , Me
HSi (OMe) 2, MeHSi ( OEt) 2, Me 2 HSiOMe, Me 2 HSiOEt,
Me 3 SiOSi (Me) 2 H, HSi [-OSi (Me) 2 H] 3 , MeSi [-OSi (Me) 2 H]
3 , ViSi [-OSi (Me) 2 H] 3 , PhSi [-OSi (Me) 2 H] 3 ,
【００２０】[0020]
【化６】 Embedded image
【００２１】Me2HSiO0.5とSiO2とからなる共重合体等が
例示される。また、このものの配合量は上記(1) 成分10
0 重量部に対して 0.1〜20重量部の範囲とされるが、こ
れは 0.1重量部より少ない量では、臭気を減少させる効
果が小さく、20部より多いと微細均一なセルが得られな
いことがありまた機械的強度や耐熱性が悪くなることが
あるからである。より好ましくは 0.2〜10重量部であ
る。Examples of the copolymer include Me 2 HSiO 0.5 and SiO 2 . In addition, the compounding amount of this is the above (1) component 10
The range is 0.1 to 20 parts by weight with respect to 0 parts by weight.If the amount is less than 0.1 part by weight, the effect of reducing odor is small, and if it is more than 20 parts, fine uniform cells cannot be obtained. This is because mechanical strength and heat resistance may deteriorate. More preferably, it is 0.2 to 10 parts by weight.
【００２２】(5) 成分の有機過酸化物としては、通常シ
リコーンゴムの加硫に使用されている従来公知のものを
使用でき、これには例えば、ベンゾイルパーオキサイ
ド、2,4 −ジクロロベンゾイルパーオキサイド、モノク
ロロベンゾイルパーオキサイド、2,5 −ジメチル−2,5
−ジ−ｔ−ブチルパーオキシヘキサン、ｔ−ブチルパー
オキシベンゾエート、ｔ−ブチルパーオキシ−２−エチ
ルヘキサノエート、ジクミルパーオキサイド、クミル−
ｔ−ブチルパーオキサイド等の有機過酸化物加硫剤が用
いられ、熱空気加硫を行う場合には、ベンゾイルペルオ
キシド、2,4 −ジクロロベンゾイルペルオキシド等のジ
アシル系有機過酸化物が一般的である。なお、これらの
有機過酸化物加硫剤は、１種または２種以上の混合物と
して用いられる。(5) 成分の有機過酸化物の配合量は、
(1) 成分のシリコーンベースポリマー 100重量部に対
し、0.05〜15重量部の範囲が好ましい。有機過酸化物の
配合量が0.05未満では加硫が十分に行われず、15重量部
を越えて配合してもそれ以上の格別な効果がないばかり
か、得られたシリコーンゴムの物性に悪影響を与えるこ
とがあるからである。また、より微細なセルを有し、高
い発泡倍率を有するスポンジを得るためには、硬化剤と
して、ベンゾイルパーオキサイド、2,4 −ジクロロベン
ゾイルパーオキサイド、モノクロロベンゾイルパーオキ
サイドなどのジアシル系有機過酸化物と他の有機過酸化
物を併用することが効果的である。As the organic peroxide (5), conventionally known ones usually used for vulcanization of silicone rubber can be used. Examples thereof include benzoyl peroxide and 2,4-dichlorobenzoyl peroxide. Oxide, monochlorobenzoyl peroxide, 2,5-dimethyl-2,5
-Di-t-butylperoxyhexane, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, cumyl-
When an organic peroxide vulcanizing agent such as t-butyl peroxide is used and hot air vulcanization is performed, diacyl organic peroxides such as benzoyl peroxide and 2,4-dichlorobenzoyl peroxide are generally used. is there. In addition, these organic peroxide vulcanizing agents are used as one kind or as a mixture of two or more kinds. (5) The compounding amount of the organic peroxide of the component is
(1) The range is preferably 0.05 to 15 parts by weight based on 100 parts by weight of the silicone base polymer as the component. If the compounding amount of the organic peroxide is less than 0.05, the vulcanization is not sufficiently performed, and if the compounding amount exceeds 15 parts by weight, not only no further special effect is exerted, but also the physical properties of the obtained silicone rubber are adversely affected. This is because it may be given. In order to obtain a sponge having a finer cell and a high expansion ratio, a diacyl organic peroxide such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide or monochlorobenzoyl peroxide is used as a curing agent. It is effective to use the compound in combination with another organic peroxide.
【００２３】また、本発明のシリコーンゴムスポンジ組
成物には、上記 (1)〜(5) の他に、酸化チタン、水酸化
セリウム、酸化セリウム、酸化鉄、白金化合物、加工助
剤、シランカップリング剤なども配合することができ
る。さらに、カーボン、フェライト粉末などを配合し、
高周波誘電加熱による成形も可能である。Further, in addition to the above (1) to (5), the silicone rubber sponge composition of the present invention further comprises titanium oxide, cerium hydroxide, cerium oxide, iron oxide, a platinum compound, a processing aid, a silane cup. A ring agent and the like can also be blended. Furthermore, compounding carbon, ferrite powder, etc.
Molding by high-frequency dielectric heating is also possible.
【００２４】上記のようにして得られたシリコーンゴム
スポンジ組成物はついで発泡硬化させてシリコーンゴム
発泡体とされるが、この発泡硬化は公知の方法で行えば
よい。すなわち、この発泡硬化は金型成形、押出し成形
などで行えばよく、金型成形の場合は上記したシリコー
ンゴム発泡体組成物を、金型にその全容積の1/5 〜4/5
程度に充填したのち 100〜200 ℃で１〜30分間加熱すれ
ばよく、押出し成形とするときには 200〜400 ℃の温度
で10秒〜15分、発泡と同時に常圧熱気加硫させればよい
が、これは流動床加熱式あるいは高周波加硫式で行なっ
てもよい。なお、このようにして作られたシリコーンゴ
ムスポンジはチューブ状、ロッド状、シート状など任意
の形状に成形すればよい。そして得られたシリコーンゴ
ムスポンジは、ガスケット、プリンター、ＰＰＣなどの
ＯＡ機器の現像ロール、転写ロール、クリーニングロー
ル、加圧ロール、紙送りロール、断熱材、クッション材
などとして非常に有用である。The silicone rubber sponge composition obtained as described above is then foamed and cured to obtain a silicone rubber foam. The foaming and curing may be performed by a known method. In other words, the foam hardening may be performed by mold molding, extrusion molding, or the like.In the case of mold molding, the silicone rubber foam composition described above is placed in a mold at 1/5 to 4/5 of its total volume.
After filling, heat at 100 to 200 ° C for 1 to 30 minutes, and for extrusion, at 200 to 400 ° C for 10 seconds to 15 minutes. This may be carried out by a fluidized bed heating method or a high frequency vulcanization method. The silicone rubber sponge thus produced may be formed into an arbitrary shape such as a tube, a rod, and a sheet. The obtained silicone rubber sponge is very useful as a developing roll, a transfer roll, a cleaning roll, a pressure roll, a paper feed roll, a heat insulating material, a cushioning material, etc. of OA equipment such as a gasket, a printer and a PPC.
【００２５】[0025]
【実施例】以下、実施例により本発明を更に具体的に説
明するが、本発明はこれらに限定されるものではない。
尚、実施例中の部は重量部を表す。 実施例１ 分子鎖両末端がジメチルビニルシリル基で封鎖されたジ
メチルシロキサン単位99.73モル％、メチルビニルシロ
キサン単位0.25モル％からなる重合度約7000のオルガノ
ポリシロキサン 100部に、ヒュームドシリカ アエロジ
ル200 （日本アエロジル製）40部と、加工助剤として分
子鎖両末端が水酸基で封鎖された重合度約10のジメチル
シロキサン４部をオープニーダーで混合し 150℃で２時
間加熱処理しベースコンパウンド１を作製した。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The parts in the examples represent parts by weight. Example 1 100 parts of an organopolysiloxane having a degree of polymerization of about 7000, comprising 99.73 mol% of dimethylsiloxane units and 0.25 mol% of methylvinylsiloxane units, both ends of which are blocked with a dimethylvinylsilyl group, and fumed silica Aerosil 200 ( 40 parts of Nippon Aerosil) and 4 parts of dimethylsiloxane having a polymerization degree of about 10 and both ends of which are blocked with hydroxyl groups as a processing aid are mixed in an open kneader and heated at 150 ° C. for 2 hours to prepare a base compound 1. did.
【００２６】次いで、２本ロールにてこのベースコンパ
ウンド 100部に、1,1'−アゾ−ビス（１−アセトキシ−
１−フェニル−エタン）（平均粒径70μm ）５部、メチ
ルハイドロジェンポリシロキサンNext, 1,1'-azo-bis (1-acetoxy-) was added to 100 parts of the base compound using two rolls.
5 parts of 1-phenyl-ethane) (average particle size 70 μm), methyl hydrogen polysiloxane
【００２７】[0027]
【化７】 Embedded image
【００２８】2,4 −ジクロロベンゾイルパーオキサイド
0.2部、2,5 −ビス−（ｔ−ブチルパーオキシ）−2,5
−ジメチルヘキサン 0.5部を添加混練した。次に、上記
シリコーンゴムコンパウンドを押し出し機に供給し、毎
分５ｍで連続押し出しを行い、外径30mm、内径15mmの断
面を持つチューブ状のシリコーンゴムコンパウンドを得
た。これを、長さ50cmに切断し、 200℃の乾燥機に10分
間放置し、シリコーンゴムスポンジを得た。得られたシ
リコーンゴムスポンジについて、比重、表面状態、セル
状態、圧縮永久歪み、臭気を評価した。結果を表１に示
した。 比較例１ 実施例１において、メチルハイドロジェンポリシロキサ
ンを配合しなかった以外は実施例１と同様に評価した。
結果を表１に示した。 比較例２ 実施例１において、1,1'−アゾ−ビス（１−アセトキシ
−１−フェニル−エタン）の代りにアゾビスイソブチロ
ニトリル（大塚化学製）を用いた以外は実施例１と同様
に評価した。結果を表１に示した。 比較例３ 実施例１において、1,1'−アゾ−ビス（１−アセトキシ
−１−フェニル−エタン）の代りにアゾジカルボンアミ
ド（三協化成製）を用いた以外は実施例１と同様とし
た。結果を表１に示した。2,4-dichlorobenzoyl peroxide
0.2 parts, 2,5-bis- (t-butylperoxy) -2,5
-0.5 parts of dimethylhexane was added and kneaded. Next, the silicone rubber compound was supplied to an extruder and continuously extruded at a rate of 5 m / min to obtain a tubular silicone rubber compound having an outer diameter of 30 mm and an inner diameter of 15 mm. This was cut into a length of 50 cm and left in a dryer at 200 ° C. for 10 minutes to obtain a silicone rubber sponge. About the obtained silicone rubber sponge, specific gravity, surface state, cell state, compression set, and odor were evaluated. The results are shown in Table 1. Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that methyl hydrogen polysiloxane was not blended.
The results are shown in Table 1. Comparative Example 2 Example 1 was the same as Example 1 except that azobisisobutyronitrile (manufactured by Otsuka Chemical) was used in place of 1,1′-azo-bis (1-acetoxy-1-phenyl-ethane). It was evaluated similarly. The results are shown in Table 1. Comparative Example 3 In the same manner as in Example 1 except that azodicarbonamide (manufactured by Sankyo Kasei) was used instead of 1,1′-azo-bis (1-acetoxy-1-phenyl-ethane). did. The results are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例２ 分子鎖両末端がトリメチルシリル基で封鎖されたジメチ
ルシロキサン単位99.8モル％、メチルビニルシロキサン
単位 0.2モル％から成る、重合度約8000のオルガノポリ
シロキサン100 部に、ジメチルジクロロシランで疎水化
処理されたフュームドシリカ：アエロジルR-972(日本ア
エロジル製）45部、加工助剤として両末端をメトキシ基
で封鎖された重合度約８のジメチルシロキサン２部をニ
ーダーにて混練りし、ベースコンパウンド２を得た。次
いで２本ロールにてベースコンパウンド３ 100 部に、
1,1'−アゾ−ビス（１−アセトキシ−１−フェニル−エ
タン）（平均粒径 100μm ）３部、ベンゾイルパーオキ
サイド 0.2部、ジクミルパーオキサイド 1.0部、メチル
ハイドロジェンポリシロキサンExample 2 100 parts of an organopolysiloxane having a degree of polymerization of about 8000 and comprising 99.8 mol% of dimethylsiloxane units and 0.2 mol% of methylvinylsiloxane units, both ends of the molecular chain of which are capped with trimethylsilyl groups, is treated with dimethyldichlorosilane. Fumed silica subjected to hydrophobic treatment: 45 parts of Aerosil R-972 (manufactured by Nippon Aerosil) and 2 parts of dimethylsiloxane having a polymerization degree of about 8 and having both ends blocked with methoxy groups as a processing aid are kneaded in a kneader. Thus, a base compound 2 was obtained. Then, 2 rolls of base compound 3 100 parts,
1,1′-azo-bis (1-acetoxy-1-phenyl-ethane) (average particle size 100 μm) 3 parts, benzoyl peroxide 0.2 part, dicumyl peroxide 1.0 part, methyl hydrogen polysiloxane
【００３１】[0031]
【化８】 Embedded image
【００３２】ベンゾイルパーオキサイド 0.3部、ジクミ
ルパーオキサイド１部を添加混合し、実施例１と同様な
方法でシリコーンゴムスポンジを得て実施例１と同様に
評価した。結果を表２に示した。 実施例３ 実施例２において、メチルハイドロジェンポリシロキサ
ンを２部とした以外は同様に評価した。結果を表２に示
した。 実施例４ 実施例２において、メチルハイドロジェンポリシロキサ
ンを５部とした以外は同様に評価した。結果を表２に示
した。 比較例４ 実施例２においてメチルハイドロジェンポリシロキサン
をジメチルポリシロキサンThen, 0.3 parts of benzoyl peroxide and 1 part of dicumyl peroxide were added and mixed, and a silicone rubber sponge was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 3 In the same manner as in Example 2, except that methyl hydrogen polysiloxane was used in an amount of 2 parts, the same evaluation was performed. The results are shown in Table 2. Example 4 Evaluation was made in the same manner as in Example 2, except that 5 parts of methyl hydrogen polysiloxane was used. The results are shown in Table 2. Comparative Example 4 In Example 2, methyl hydrogen polysiloxane was replaced with dimethyl polysiloxane.
【００３３】[0033]
【化９】 Embedded image
【００３４】とした以外は実施例２と同様に評価した。
結果を表２に示した。 比較例５ 実施例２においてメチルハイドロジェンポリシロキサン
を配合しなかった以外は同様に評価した。結果を表２に
示した。Evaluation was made in the same manner as in Example 2 except that
The results are shown in Table 2. Comparative Example 5 Evaluation was made in the same manner as in Example 2 except that methyl hydrogen polysiloxane was not blended. The results are shown in Table 2.
【００３５】[0035]
【表２】 [Table 2]
【００３６】実施例５ 実施例１で用いたオルガノポリシロキサン 100部にアセ
チレンブラック（電気化学工業製）30部をオープンニー
ダーにて混練しベースコンパウンド３を得た。ついで、
このベースコンパウンド３ 100部に、２本ロールで1,1'
−アゾ−ビス（１−アセトキシ−１−フェニル−エタ
ン）（平均粒径90μm ）を２部、メチルハイドロジェン
ポリシロキサンExample 5 A base compound 3 was obtained by kneading 100 parts of the organopolysiloxane used in Example 1 with 30 parts of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) using an open kneader. Then
100 parts of this base compound 3, 1,1 'with 2 rolls
2 parts of azo-bis (1-acetoxy-1-phenyl-ethane) (average particle size 90 μm), methyl hydrogen polysiloxane
【００３７】[0037]
【化１０】 Embedded image
【００３８】ｔ−ブチルパーオキシ−２−エチルヘキサ
ノエート１部、2,5 −ジメチル−2,5−ジ−ｔ−ブチル
パーオキシヘキサン 1.5 部を均一になるまで混合し
た。得られたコンパウンドを50×50×10mmのシートに分
出し、このシートを電子レンジ内に収納し、周波数2450
MHz 、出力 600Ｗで２分間加熱し、シリコーンゴムスポ
ンジを得て実施例１と同様に評価した。結果を表３に示
した。 実施例６ 実施例５において1,1'−アゾ−ビス（１−アセトキシ−
１−フェニル−エチル）を４部とした以外は同様に評価
した。結果を表３に示した。 比較例６ 実施例５においてメチルハイドロジェンポリシロキサン
を25部とした以外は同様に評価した。結果を表３に示し
た。One part of t-butylperoxy-2-ethylhexanoate and 1.5 parts of 2,5-dimethyl-2,5-di-t-butylperoxyhexane were mixed until uniform. The obtained compound is divided into sheets of 50 × 50 × 10 mm, and the sheets are stored in a microwave oven, and the frequency is set to 2450.
The mixture was heated at 600 MHz for 2 minutes at an output of 600 W to obtain a silicone rubber sponge, which was evaluated in the same manner as in Example 1. The results are shown in Table 3. Example 6 In Example 5, 1,1′-azo-bis (1-acetoxy-
The same evaluation was performed except that 4 parts of 1-phenyl-ethyl) was used. The results are shown in Table 3. Comparative Example 6 Evaluation was made in the same manner as in Example 5 except that 25 parts of methyl hydrogen polysiloxane was used. The results are shown in Table 3.
【００３９】[0039]
【表３】 [Table 3]
Claims (2)
化水素基、a ＝1.95〜2.05）で示されるオルガノポリシ
ロキサン 100重量部に対し (2) 充填剤３〜500 重量部 (3) 1,1'−アゾ−ビス（１−アセトキシ−１−フェニル
−エタン）からなる発泡剤 0.1〜20重量部 (4) 平均組成式 【化２】 （式中、 R' は置換または非置換の一価炭化水素基、X
は水素基または加水分解可能な基を表わす。b は０≦b
≦３、c は０＜c ＜３、d は０≦d ≦３、ただしb ＋c
＋d は０＜b ＋c ＋d ≦４である）で示される水素原子
含有有機けい素化合物） 0.1〜20重量部 (5) 有機過酸化物0.05〜15重量部を配合してなるシリコ
ーンゴムスポンジ組成物。(1) Average composition formula (R in the formula is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a = 1.95 to 2.05) 100 parts by weight of an organopolysiloxane represented by the following formula: (2) 3 to 500 parts by weight of a filler (3) A foaming agent comprising 1,1'-azo-bis (1-acetoxy-1-phenyl-ethane) 0.1 to 20 parts by weight (4) Average composition formula (Wherein R ′ is a substituted or unsubstituted monovalent hydrocarbon group, X
Represents a hydrogen group or a hydrolyzable group. b is 0 ≦ b
≦ 3, c is 0 <c <3, d is 0 ≦ d ≦ 3, where b + c
+ D is 0 <b + c + d ≦ 4) 0.1 to 20 parts by weight (5) Silicone rubber sponge composition containing 0.05 to 15 parts by weight of an organic peroxide .
組成物を発泡硬化させて得られるシリコーンゴムスポン
ジ。2. A silicone rubber sponge obtained by foaming and curing the silicone rubber sponge composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25216395A JP2869367B2 (en) | 1995-09-29 | 1995-09-29 | Silicone rubber sponge composition and silicone rubber sponge using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25216395A JP2869367B2 (en) | 1995-09-29 | 1995-09-29 | Silicone rubber sponge composition and silicone rubber sponge using the same |
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| Publication Number | Publication Date |
|---|---|
| JPH0995552A JPH0995552A (en) | 1997-04-08 |
| JP2869367B2 true JP2869367B2 (en) | 1999-03-10 |
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ID=17233369
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