JPH0848881A - Reinforcing filler for silicone rubber - Google Patents
Reinforcing filler for silicone rubberInfo
- Publication number
- JPH0848881A JPH0848881A JP18571494A JP18571494A JPH0848881A JP H0848881 A JPH0848881 A JP H0848881A JP 18571494 A JP18571494 A JP 18571494A JP 18571494 A JP18571494 A JP 18571494A JP H0848881 A JPH0848881 A JP H0848881A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- wet
- synthetic silicic
- silicone rubber
- silica
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はシリコーンゴムの補強充
填剤用に適した疎水性湿式法合成珪酸に関する。さらに
詳しくは、シリコーンゴムに配合することで、優れた加
工性と高い補強性を有するシリコーンゴム組成物を与え
る疎水性湿式法合成珪酸に関する。FIELD OF THE INVENTION The present invention relates to a hydrophobic wet-process synthetic silicic acid suitable as a reinforcing filler for silicone rubber. More specifically, the present invention relates to a hydrophobic wet method synthetic silicic acid which, when added to a silicone rubber, gives a silicone rubber composition having excellent processability and high reinforcement.
【０００２】[0002]
【従来の技術】シリコーンゴムには充填剤としてのシリ
カ粉末が必須成分である。実用的な強度を有するシリコ
ーンゴム弾性体を得るためには、通常、補強充填剤とし
て比表面積が５０ｍ2 ／ｇ以上のシリカ粉末を充填す
る。従来補強充填剤としては、一般的には、四塩化珪素
を酸素／水素炎下で加水分解して得られる乾式法のフュ
ームドシリカや、アルカリ金属けい酸塩と鉱酸とを中和
反応させて得られる湿式法合成珪酸が使用されている。
これらのシリカ粉末をシリコーンの生ゴムに配合して使
用する際には、その表面活性を抑制してシリコーン生ゴ
ムへの配合を容易にしたり、コンパウンドの貯蔵安定性
や加工性を改良したり、架橋物の物性を改良したりする
ために、湿潤剤（Ｗｅｔｔｅｒ）と呼ばれる低分子シロ
キサン、エステル、シラノール基含有シラン、アルコキ
シ含有シランなどが分散剤として使用される。2. Description of the Related Art Silica powder as a filler is an essential component of silicone rubber. In order to obtain a silicone rubber elastic body having practical strength, silica powder having a specific surface area of 50 m 2 / g or more is usually filled as a reinforcing filler. As a conventional reinforcing filler, generally, fumed silica of a dry method obtained by hydrolyzing silicon tetrachloride in an oxygen / hydrogen flame or an alkali metal silicate and a mineral acid are subjected to a neutralization reaction. Wet method synthetic silicic acid obtained by the above method is used.
When these silica powders are used by blending with the raw silicone rubber, their surface activity is suppressed to facilitate blending with the raw silicone rubber, the storage stability and processability of the compound are improved, and crosslinked products are used. In order to improve the physical properties of the above, a low molecular weight siloxane called a wetting agent (Wetter), an ester, a silanol group-containing silane, an alkoxy-containing silane or the like is used as a dispersant.
【０００３】また、湿潤剤を併用する代わりに、あらか
じめシリカ表面をシロキサンやシランで表面処理した疎
水性シリカが使用されることもあり、疎水性シリカがシ
リコーンゴムの補強充填剤として有用であることは公知
である〔例えば、特公昭３３−９２９６号、特公昭３６
−５９９１号、特公昭４９−２０７３９号〕。又、湿式
法合成珪酸をシリコーンゴム組成物の混練時に実質的に
疎水化して使用することも、特公平０４−８２０２３号
に開示されている。疎水性シリカには、フュームドシリ
カを疎水化したもの（代表的には、商品名アエロジルＲ
９７２）と、湿式法合成珪酸を疎水化したものの（代表
的には、商品名ニップシールＳＳ−３０Ｐ）がある。一
般的にフュームドシリカは、湿式法のシリカに比べ高価
であって、高い補強性と透明性が得られるが、増粘性が
高くシリコーンコンパウンドの流動性を低下させる。フ
ュームドシリカを表面処理した疎水化品は、未処理のも
のに比べれば増粘性は低いが、依然として増粘性を有す
る。In addition, instead of using a wetting agent in combination, hydrophobic silica whose silica surface is previously surface-treated with siloxane or silane may be used, and the hydrophobic silica is useful as a reinforcing filler for silicone rubber. Are known [for example, Japanese Examined Patent Publication Nos. 33-9296 and 36.
-5991, Japanese Patent Publication No. 49-20739]. It is also disclosed in Japanese Patent Publication No. 04-82023 that the wet synthetic silica is substantially hydrophobized when kneading the silicone rubber composition. The hydrophobic silica is obtained by making fumed silica hydrophobic (typically, trade name Aerosil R
972), and a wet method synthetic silicic acid made hydrophobic (typically, a trade name Nipseal SS-30P). In general, fumed silica is more expensive than wet-process silica and can provide high reinforcement and transparency, but it has a high viscosity and deteriorates the fluidity of the silicone compound. The hydrophobized product obtained by surface-treating fumed silica has a lower thickening property than the untreated product, but still has a thickening property.
【０００４】[0004]
【発明が解決しようとする課題】増粘性の問題に関して
は、射出成形、特に一般のミラブルゴムに比べて粘度が
ほぼ１桁低い液状ゴムの射出成形おいては、より低増粘
性であることが求められる。そのため、湿式法合成珪酸
の疎水性シリカの方がフュームドシリカの疎水性シリカ
より低増粘性であって配合の自由度が高い（加工性に優
れる）という利点がある。しかし、従来の湿式法合成珪
酸の疎水性シリカは、ゴム補強性が不充分であるという
問題がある。そこで、本発明の目的は、低増粘性であっ
て加工性に優れるという物性を維持しつつ、従来の疎水
性湿式法合成珪酸より補強性が高められた、シリコーン
ゴム用補強充填剤に適した疎水性湿式法合成珪酸を提供
することにある。即ち、本発明は、湿潤剤の添加なしに
疎水性湿式法合成珪酸のみで、優れた加工性と補強性を
有するシリコーンゴム組成物を提供することを目的とす
る。Regarding the problem of thickening, it is required to have a lower thickening in injection molding, particularly in injection molding of liquid rubber having a viscosity which is about an order of magnitude lower than that of general millable rubber. To be Therefore, the hydrophobic silica of wet-process synthetic silicic acid has an advantage that it has a lower viscosity than the hydrophobic silica of fumed silica and has a high degree of freedom in blending (excellent processability). However, the conventional wet-process synthetic silicic acid hydrophobic silica has a problem that the rubber-reinforcing property is insufficient. Therefore, the object of the present invention is suitable for a reinforcing filler for silicone rubber, which has a higher viscosity than conventional hydrophobic wet synthetic silica while maintaining the physical properties of low viscosity increase and excellent workability. It is to provide a hydrophobic wet method synthetic silicic acid. That is, it is an object of the present invention to provide a silicone rubber composition having excellent processability and reinforcing properties by using only hydrophobic wet synthetic silica without adding a wetting agent.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意研究を積み重ねた。その結果、疎水性
湿式法合成珪酸をシリコーンゴムに配合したときの、加
工性（増粘性）、及び架橋性の物性（引っ張り強度な
ど）は湿式法合成珪酸の疎水化の程度と大きく関係する
こと、及び湿式法合成珪酸の粒子性に大きく影響される
ことを見い出した。即ち、疎水化の程度と粒子性を制御
した疎水性湿式法合成珪酸をシリコーンゴムに配合する
ことで、湿潤剤の使用なしに、優れた加工性と実用的強
度を有するシリコーンゴム架橋物が得られることを見い
出して本発明を完成した。安価で実用的であるシリコー
ンオイルを表面処理剤を用いることでも、疎水化の程度
と粒子性を制御すれば、シリコーンゴム用補強充填剤と
して優れた疎水性湿式法合成珪酸を提供できることか
ら、本発明は特に有用である。[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, the processability (thickening) and crosslinkable physical properties (tensile strength, etc.) of the hydrophobic wet-process synthetic silicic acid blended with the silicone rubber are greatly related to the degree of hydrophobization of the wet-process synthetic silicic acid. It has been found that the particle properties of wet-process synthetic silicic acid are greatly affected. That is, by blending the hydrophobic wet method synthetic silicic acid in which the degree of hydrophobization and particle property is controlled with the silicone rubber, a crosslinked silicone rubber having excellent processability and practical strength can be obtained without using a wetting agent. The present invention has been completed by discovering that it is possible. Even if a surface treatment agent is used for inexpensive and practical silicone oil, it is possible to provide an excellent hydrophobic wet synthetic silica as a reinforcing filler for silicone rubber by controlling the degree of hydrophobization and particle property. The invention is particularly useful.
【０００６】本発明のシリコーンゴム用補強充填剤は、
ＢＥＴ比表面積が１００〜１５０ｍ2 ／ｇであり、ジ−
ｎ−ブチルアミン吸着量が３０〜１００ｍ・ｍｏｌ／ｋ
ｇであり、Ｍ値が５〜５５％であり、且つ二次平均粒子
径が１〜５μｍである疎水性湿式法合成珪酸であること
を特徴する。以下本発明について説明する。The reinforcing filler for silicone rubber of the present invention is
BET specific surface area is 100 to 150 m 2 / g,
Adsorption amount of n-butylamine is 30 to 100 m · mol / k
g, the M value is 5 to 55%, and the secondary average particle diameter is 1 to 5 μm. The present invention will be described below.
【０００７】本発明の疎水性湿式法合成珪酸は、ＢＥＴ
比表面積が１００〜１５０ｍ2 ／ｇの範囲である。ＢＥ
Ｔ比表面積が上記範囲より低いと補強性能が低くなり、
上記範囲を超えると加工性が低下する。ＢＥＴ比表面積
は、好ましくは１２０〜１４０ｍ2 ／ｇの範囲である。
ＢＥＴ比表面積はシリカの一次粒子の大きさ、及びその
表面状態（微細孔等）によって決定されるもので、補強
性を示す目安となるものである。表面処理することによ
り表面状態が変化し、その値は小さくなる傾向がある。The hydrophobic wet-process synthetic silicic acid of the present invention is BET
The specific surface area is in the range of 100 to 150 m 2 / g. BE
If the T specific surface area is lower than the above range, the reinforcing performance becomes low,
If it exceeds the above range, the workability is deteriorated. The BET specific surface area is preferably in the range of 120 to 140 m 2 / g.
The BET specific surface area is determined by the size of primary particles of silica and the surface condition (such as fine pores) of silica, and serves as a measure of the reinforcing property. The surface treatment changes the surface condition, and its value tends to decrease.
【０００８】ジ−ｎ−ブチルアミン吸着量は３０〜１０
０ｍ・ｍｏｌ／ｋｇの範囲である。ジ−ｎ−ブチルアミ
ン吸着量が上記範囲より低いと、疎水化度が高く、増粘
性は低いが、補強性能も低くなる。又、上記範囲を超え
て高くなると、疎水化度が低く、補強性能は高くなる
が、加工性が低下する。ジ−ｎ−ブチルアミン吸着量
は、好ましくは３０〜５０・ｍｏｌ／ｋｇの範囲てあ
る。尚、ジ−ｎ−ブチルアミン吸着量（以下、「ＤＢＡ
吸着量」ということがある）は、疎水性の度合を表す指
標である。通常のシリカはその表面上に多量のシラノー
ル基が存在して、親水性を示すことが知られている。ま
だジ−ｎ−ブチルアミンはイオン結合的にシリカ粒子表
面上に吸着されることも知られている（R.Meyer:kautsc
huku.Gummi,7[8],180 ─182WT(1954) ）。このため、疎
水性に表面処理されたシリカに残存するシラノール基に
結合するジ−ｎ−ブチルアミンの量から、シリカの疎水
性の度合を知ることができる。The amount of di-n-butylamine adsorbed is 30 to 10
The range is 0 m · mol / kg. When the amount of adsorbed di-n-butylamine is lower than the above range, the degree of hydrophobicity is high and the viscosity increase is low, but the reinforcing performance is also low. On the other hand, if it exceeds the above range, the hydrophobicity is low and the reinforcing performance is high, but the workability is lowered. The amount of adsorbed di-n-butylamine is preferably in the range of 30 to 50 · mol / kg. In addition, the amount of adsorbed di-n-butylamine (hereinafter, "DBA
Sometimes referred to as "adsorption amount") is an index indicating the degree of hydrophobicity. It is known that ordinary silica has a large amount of silanol groups on its surface and exhibits hydrophilicity. It is also known that di-n-butylamine is ionically adsorbed on the surface of silica particles (R. Meyer: kautsc.
huku.Gummi, 7 [8], 180 ─182WT (1954)). Therefore, the degree of hydrophobicity of silica can be known from the amount of di-n-butylamine bonded to the silanol groups remaining in the hydrophobically surface-treated silica.
【０００９】疎水化度を示すＭ値は、５〜５５％の範囲
である。この範囲より低いと、疎水化度が低く、補強性
能は高いが、加工性が悪くなる。一方、この範囲を超え
て高くなると、増粘性は低いが補強性能も低くなる。Ｍ
値は、好ましくは３０〜５０％の範囲である。尚、Ｍ値
は、処理粉体が湿潤しはじめる水とメタノールの混合溶
液のメタノール濃度を容量％で表示した値である。従っ
て、Ｍ値により、ジ−ｎ−ブチルアミン吸着量と同様に
疎水化の度合を知ることができる。Ｍ値が高い程、疎水
性は高い。ＤＢＡ吸着量とＭ値のふたつの値によって、
シリカの疎水性を表現することができる。The M value showing the degree of hydrophobicity is in the range of 5 to 55%. When it is lower than this range, the hydrophobicity is low and the reinforcing performance is high, but the workability is deteriorated. On the other hand, when the content is higher than this range, the viscosity increase is low, but the reinforcing performance is low. M
The value is preferably in the range of 30-50%. The M value is a value in which the concentration of methanol in a mixed solution of water and methanol at which the treated powder begins to wet is expressed in volume%. Therefore, the degree of hydrophobization can be known from the M value in the same manner as the amount of adsorbed di-n-butylamine. The higher the M value, the higher the hydrophobicity. By the two values of DBA adsorption amount and M value,
The hydrophobicity of silica can be expressed.
【００１０】本発明の疎水性湿式法合成珪酸の二次平均
粒子径は１〜５μｍの範囲、好ましくは２〜４μｍの範
囲でる。特に、二次平均粒子径とともに粗大粒子の除去
を目的に分級を施したものがさらに好ましい。二次平均
粒子径が上記範囲より粗くなると目的とする補強性が得
られない。従来シリコーンゴムに汎用されている湿式法
合成珪酸であるニップシールＬＰの二次平均粒子径は約
８μｍであるが、本発明の目的の補強性を得るにはさら
に調整された粒子性が必要である。当然のことである
が、極端に粗くなると分散不良の問題を招き、補強性が
悪くなる。一方、上記範囲より二次平均粒子径が小さく
なっても、補強性能がさらに向上することはなく、かえ
って、粉塵飛散が大きくなり、作業性が悪くなるという
欠点を招く。二次平均粒子径はシリカの分散性に関与す
るものである。一般にシリカは究極の粒子である一次粒
子が複雑に結合凝集したいわゆる二次凝集粒子として存
在する。この複雑な粒子構造と表面活性により補強性が
支配されると考えられるため二次粒子の平均粒子径を整
えることは、補強性に重要な因子であると考えられる。The secondary average particle diameter of the hydrophobic wet synthetic silica of the present invention is in the range of 1 to 5 μm, preferably 2 to 4 μm. In particular, those subjected to classification for the purpose of removing coarse particles as well as the secondary average particle diameter are more preferable. If the secondary average particle diameter becomes coarser than the above range, the desired reinforcing property cannot be obtained. The secondary average particle size of nip seal LP, which is a wet-process synthetic silicic acid that has been widely used in conventional silicone rubber, is about 8 μm, but further adjusted particle properties are required to obtain the reinforcing property for the purpose of the present invention. . As a matter of course, if it becomes extremely rough, it causes a problem of poor dispersion and deteriorates the reinforcing property. On the other hand, even if the secondary average particle diameter is smaller than the above range, the reinforcing performance is not further improved, but rather the dust scattering is increased and the workability is deteriorated. The secondary average particle diameter is related to the dispersibility of silica. Generally, silica exists as so-called secondary agglomerated particles in which primary particles, which are the ultimate particles, are complexly bound and agglomerated. Since the reinforcing property is considered to be governed by this complicated particle structure and surface activity, it is considered that adjusting the average particle size of the secondary particles is an important factor for the reinforcing property.
【００１１】本発明の疎水性湿式法合成珪酸は、公知の
製造方法により製造することができる。例えば、湿式法
合成珪酸を得るための製造方法は、アルカリ金属珪酸塩
水溶液と鉱酸とを反応させて沈殿析出させる場合、通常
市販のケイ酸ソーダ及び硫酸などが一般的に使用され
る。沈殿析出させる方法としては、例えば所定の濃度に
調整されたケイ酸ソーダ溶液が張り込まれた反応槽中
に、一定の温度を保ちながら硫酸が数段階に分けて添加
される片側添加反応方式、あるいはあらかじめ一定量の
温水が張り込まれた反応槽中に、一定のｐＨ及び温度を
保ちながらケイ酸ソーダ溶液及び硫酸が一定時間添加さ
れる同時添加方式などがある。The hydrophobic wet method synthetic silicic acid of the present invention can be produced by a known production method. For example, in the production method for obtaining wet-process synthetic silicic acid, commercially available sodium silicate and sulfuric acid are generally used when an aqueous solution of an alkali metal silicate and a mineral acid are reacted to cause precipitation. As a method of causing precipitation, for example, in a reaction tank filled with a sodium silicate solution adjusted to a predetermined concentration, sulfuric acid is added in several steps while maintaining a constant temperature, a one-sided addition reaction method, Alternatively, there is a simultaneous addition method in which a sodium silicate solution and sulfuric acid are added for a certain period of time while maintaining a certain pH and temperature in a reaction tank in which a certain amount of warm water has been previously filled.
【００１２】沈殿析出させた後に、濾過、乾燥、粉砕、
さらに必要に応じ分級して湿式法合成珪酸を得ることが
できる。但し、二次平均粒子径は、流体エネルギーミル
等を使用して粒子を粉砕することで、１〜５μｍの範囲
に調整することができる。さらに必要に応じて、風力式
分級機等を使用して分級することで、所望の二次平均粒
子径を有する合成珪酸を得ることができる。尚、本発明
の疎水性湿式法合成珪酸を得る方法における粒子性の調
整（粉砕及び分級）は、疎水化の前後のいずれで行って
も良い。After precipitation, filtration, drying, crushing,
Further, if necessary, classification can be carried out to obtain a wet synthetic silica. However, the secondary average particle diameter can be adjusted in the range of 1 to 5 μm by crushing the particles using a fluid energy mill or the like. Further, if necessary, classification can be performed using a wind power classifier or the like to obtain a synthetic silicic acid having a desired secondary average particle diameter. The adjustment of the particle properties (pulverization and classification) in the method for obtaining the hydrophobic wet synthetic silica of the present invention may be performed before or after the hydrophobization.
【００１３】湿式法合成珪酸の疎水化は、例えば、湿式
法合成珪酸をシリコーンオイルを用いて表面処理するこ
とが行える。例えば、特公昭４２−２６１７９号に開示
されているように、５０センチストークスの粘度を持っ
たジメチルポリシロキサンオイルを湿式法合成珪酸に噴
霧し、２５０〜３５０°Ｃの温度で約１／２〜２時間加
熱して疎水性の湿式法合成珪酸を得ることができる。Hydrophobicization of the wet method synthetic silicic acid can be carried out, for example, by subjecting the wet method synthetic silicic acid to a surface treatment with silicone oil. For example, as disclosed in Japanese Examined Patent Publication (Kokoku) No. 42-26179, dimethylpolysiloxane oil having a viscosity of 50 centistokes is sprayed onto a wet-process synthetic silicic acid, and a temperature of 250 to 350 ° C. It is possible to obtain a hydrophobic wet synthetic silica by heating for 2 hours.
【００１４】本発明において表面処理剤として用いられ
るシリコーンオイルとしては、ジメチルシリコーンオイ
ル、メチルフェニルシリコーンオイル、メチルハイドロ
ジェンシリコーンオイルのようなストレートシリコンオ
イルと称されるものや、特殊な有機基を分子構造中に含
む変性シリコーンオイルと称されるもの等を特に制限な
く用いることができる。但し、疎水化の効果及びその実
用目的より、ストレートシリコーンオイルが望ましく、
中でもジメチルシリコーンオイルが好適に使用される。
その分子量としては小さすぎても、大きすぎても疎水化
の効果が劣るため、通常、分子量５００〜５０００の範
囲のものが好適に使用される。The silicone oil used as the surface treatment agent in the present invention includes those called straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, and molecules with special organic groups. What is called a modified silicone oil contained in the structure can be used without particular limitation. However, in view of the effect of hydrophobization and its practical purpose, straight silicone oil is desirable,
Among them, dimethyl silicone oil is preferably used.
If the molecular weight is too small or too large, the effect of hydrophobizing is inferior, so that one having a molecular weight of 500 to 5000 is usually preferably used.
【００１５】シリコーンオイル疎水化処理によって、ジ
−ｎ−ブチルアミン吸着量は低下し、Ｍ値は増加する
（疎水化が進む）。一方、シリコーンオイル疎水化処理
によって、ＢＥＴ比表面積は低下する。従って、湿式法
合成珪酸とシリコーンオイルとの混合割合は、本発明の
目標とする疎水化度を考慮し、かつ使用する湿式法合成
珪酸のＢＥＴ比表面積に応じて適宣変量する。例えば、
比較的高いＢＥＴ比表面積を有する湿式法合成珪酸をシ
リコーンオイル疎水化処理する場合、比較的多めのシリ
コーンオイルを用いても、所定範囲内のＢＥＴ比表面積
を有する疎水化湿式法合成珪酸が得られ、得られる疎水
化湿式法合成珪酸は比較的高い疎水化度を有することに
なる。ＢＥＴ比表面積が約２００ｍ2 ／ｇを示す未処理
の湿式法合成珪酸については、例えば湿式法合成珪酸１
００重量部に対して４〜１０重量部程度のシリコーンオ
イルを用いることで、所定の範囲の物性を有する本発明
の疎水化湿式法合成珪酸が得られる。By the hydrophobic treatment of silicone oil, the amount of adsorbed di-n-butylamine is decreased and the M value is increased (hydrophobicization is promoted). On the other hand, the BET specific surface area is reduced by the hydrophobic treatment of silicone oil. Therefore, the mixing ratio of the wet method synthetic silicic acid and the silicone oil is appropriately adjusted in consideration of the target degree of hydrophobicity of the present invention and according to the BET specific surface area of the wet method synthetic silicic acid used. For example,
When wet-process synthetic silicic acid having a relatively high BET specific surface area is subjected to a hydrophobic treatment with silicone oil, even if a relatively large amount of silicone oil is used, a hydrophobized wet-process synthetic silicic acid having a BET specific surface area within a predetermined range can be obtained. The obtained hydrophobized synthetic silica has a relatively high degree of hydrophobicity. For the unprocessed wet-process synthetic silicic acid having a BET specific surface area of about 200 m 2 / g, for example, wet-process synthetic silicic acid 1
By using about 4 to 10 parts by weight of silicone oil with respect to 00 parts by weight, the hydrophobized wet process synthetic silicic acid of the present invention having physical properties within a predetermined range can be obtained.
【００１６】本発明の疎水化湿式法合成珪酸であるシリ
コーンゴム用補強充填剤は、種々のシリコーンゴムに適
用することができる。例えば、メチルビニルシリコーン
ゴム、メチルフェニルビニルシリコーンゴム、メチルフ
ロロアルキルシリコーンゴム等に代表されるミラブルタ
イプシリコーンゴムや液状シリコーンゴムである。ま
た、本発明の充填剤のシリコーンゴムに対する充填量
は、補強性と加工性等を考慮して適宜決定されるが、例
えば、通常シリコーンゴム１００重量部に対して２０〜
６０重量部の範囲である。The reinforcing filler for silicone rubber which is the hydrophobized wet method synthetic silicic acid of the present invention can be applied to various silicone rubbers. For example, it is a millable type silicone rubber or a liquid silicone rubber represented by methyl vinyl silicone rubber, methylphenyl vinyl silicone rubber, methyl fluoroalkyl silicone rubber and the like. Further, the filling amount of the filler of the present invention with respect to the silicone rubber is appropriately determined in consideration of the reinforcing property and the processability, and, for example, it is usually 20 to 100 parts by weight of the silicone rubber.
It is in the range of 60 parts by weight.
【００１７】粘度特性（加工性）は、後述するシリコー
ンゴムコンパウンドのムーニー粘度測定によって評価す
ることができる。ＭＬ1 ＋1 1 のムーニー粘度値が高い
と、シリカの増粘性が高く、低いとシリカの増粘性が低
いことを示す。本発明の充填剤を用いると、未処理の湿
式法合成珪酸に湿潤剤を併用をした場合と同等又はそれ
以下のムーニー粘度値を示すシリコーンゴムコンパウン
ドが得られる。The viscosity characteristics (workability) can be evaluated by measuring the Mooney viscosity of the silicone rubber compound described later. A high Mooney viscosity value of ML 1 +1 1 indicates a high viscosity increase of silica, and a low Mooney viscosity value indicates a low viscosity increase of silica. When the filler of the present invention is used, a silicone rubber compound having a Mooney viscosity value equal to or less than that when a wetting agent is used in combination with untreated wet synthetic silica is obtained.
【００１８】[0018]
【実施例】以下、本発明を更に具体的に説明するため実
施例を示すが、本発明はこれらの実施例に限定されるも
のではない。尚、以下の実施例における部は、すべて重
量部であるまた、実施例及び比較例における各種物性測
定と試験は、下記の方法によって行なった。 １）ＢＥＴ比表面積 カンターソープ（米国Ｑｕａｎｔａｃｈｒｏｍｅ社製）
を用いて１点法により測定した。 ２）ＤＢＡ吸着量 乾燥試料２５０ｍｇを精秤し、これに５０ｍｌのＮ／５
００ ジ−ｎ−ブチルアミン溶液（石油ベンジン溶媒）
を加え、２０℃で約２時間放置する。この上澄液２５ｍ
ｌにクロロホルム５ｍｌ、指示薬（クリスタルバイオレ
ット）２〜３滴を加え、紫色が青色に変わるまでＮ／１
００ 過塩素酸溶液（無水酢酸溶媒）で滴定し、この時
の滴定値をＡｍｌとする。別にブランクを行いＢｍｌと
し、次式によってＤＢＡ吸着量を算出した。 ＤＢＡ吸着量（ｍ・ｍｏｌ／ｋｇ）＝８０（Ｂ−Ａ）ｆ 但し、ｆはＮ／１００ 過塩素酸溶液の力価EXAMPLES Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these examples. All parts in the following examples are parts by weight, and various physical property measurements and tests in the examples and comparative examples were carried out by the following methods. 1) BET specific surface area Canter soap (manufactured by Quantachrome, USA)
Was measured by the one-point method. 2) DBA adsorption amount 250 mg of dry sample was precisely weighed and 50 ml of N / 5 was added to it.
00 Di-n-butylamine solution (petroleum benzine solvent)
Is added and the mixture is left to stand at 20 ° C. for about 2 hours. 25m of this supernatant
Chloroform (5 ml) and indicator (Crystal Violet) (2 to 3 drops) were added to 1L until the purple color changed to blue.
00 Titrate with a perchloric acid solution (acetic anhydride solvent), and the titration value at this time is Aml. Separately, it was blanked to Bml, and the DBA adsorption amount was calculated by the following formula. DBA adsorption amount (m · mol / kg) = 80 (BA) f where f is the titer of N / 100 perchloric acid solution
【００１９】３）Ｍ値 メタノールの濃度を５容量％の間隔で変化させた水との
混合溶液を調製し、これを容積１０ｍｌの試験管に５ｍ
ｌ入れる。次いで供試粉体を０．１〜０．２ｇ入れ、振
り混ぜ静置後観察し、粉体が懸濁する最小のメタノール
の濃度を知り、これをＭ値とする。 ４）二次粒子の平均粒子径 コールターカウンターＴＡ−ＩＩ（Ｃｏｕｒｕｔｅｒ
Ｅｌｅｃｔｏｒｏｎｉｃｓ Ｉｎｃ．製）を用いて、３
０μｍアパーチャーチューブ（比較例１と比較例４は７
０μｍ）により測定した。試料の分散は、４０秒間の超
音波分散を行い、分散液は付属のＩｓｏｔｏｎＩＩ液を
使用した。3) M value A mixed solution with water in which the concentration of methanol was changed at intervals of 5% by volume was prepared, and this was put into a test tube having a volume of 10 ml for 5 m
l Next, 0.1 to 0.2 g of the test powder is added, shaken, allowed to stand and then observed, and the minimum concentration of methanol in which the powder is suspended is known, and this is taken as the M value. 4) Average particle diameter of secondary particles Coulter counter TA-II (Couruter)
Electriconics Inc. 3)
0 μm aperture tube (Comparative Example 1 and Comparative Example 4 are 7
0 μm). The sample was dispersed by ultrasonic wave for 40 seconds, and the attached Isoton II solution was used as the dispersion.
【００２０】５）シリコーンゴムの粘度特性 シリコーンゴムコンパウンドは、混練後２４時間経時し
たものについて、ムーニー粘度測定機（型式ＳＭＶ−２
００島津製作所製）を使用し、温度１００℃、Ｌロータ
ーを用いて測定し、ＭＬ1 ＋1 1 の数値で示した。 ６）ゴム補強特性の測定 ＪＩＳ Ｋ−６３０１の架橋ゴム物性試験方法に従って
実施した。5) Viscosity characteristics of silicone rubber The silicone rubber compound is a Mooney viscosity measuring device (model SMV-2) which has been aged for 24 hours after kneading.
(Manufactured by Shimadzu Co., Ltd.) at a temperature of 100 ° C. using an L rotor, and indicated by a numerical value of ML 1 +1 1 . 6) Measurement of rubber-reinforcing property It was carried out according to the method for testing physical properties of crosslinked rubber in JIS K-6301.
【００２１】実施例１ ＢＥＴ比表面積２００ｍ2 ／ｇ、ＤＢＡ吸着量２８０ｍ
・ｍｏｌ／ｋｇの湿式法合成珪酸、ニップシールＬＰ
（日本シリカ工業社製）を粉砕、分級し二次平均粒子径
が３．５μｍのものを得た。これを流動式混合機（株式
会社三井三池製作所製、ヘンシェルミキサー）に仕込
み、ジメチルシリコーンオイルＫＦ９６（信越化学工業
社製）６部を投入し５分間混合攪拌した後、２５０℃で
２時間熱処理し疎水性の湿式法合成珪酸を得た。この疎
水性湿式法合成珪酸に特性値を表１に示した。シリコー
ン生ゴムに対し、４０部の上記疎水性湿式法合成珪酸を
６インチロールで、混練し、１５０℃で２時間加熱処理
した。得られたシリコーンゴムコンパウンドを静置し、
２４時間経時後ムーニー粘度を測定し表１に示した。次
に、架橋ゴム物性を測定するために、架橋剤０．５部を
前記ロールで混練し、一次架橋１７０℃で１０分、二次
架橋を２００℃で４時間それぞれ実施した後、ゴムの引
っ張り強度の補強特性を測定した（以下、評価法は実施
例、比較例とも同様）。結果を表１に示した。Example 1 BET specific surface area 200 m 2 / g, DBA adsorption amount 280 m
・ Mol / kg wet synthetic silica, nip seal LP
(Manufactured by Nippon Silica Industry Co., Ltd.) was pulverized and classified to obtain a secondary average particle diameter of 3.5 μm. This was charged in a fluid mixer (Mitsui Miike Seisakusho, Henschel Mixer), 6 parts of dimethyl silicone oil KF96 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, mixed and stirred for 5 minutes, and then heat-treated at 250 ° C. for 2 hours. A hydrophobic wet process synthetic silicic acid was obtained. The characteristic values of this hydrophobic wet method synthetic silicic acid are shown in Table 1. 40 parts of the above-mentioned hydrophobic wet synthetic silica was kneaded with a silicone raw rubber by a 6-inch roll and heat-treated at 150 ° C. for 2 hours. The silicone rubber compound obtained is allowed to stand,
The Mooney viscosity was measured after 24 hours and is shown in Table 1. Next, in order to measure the physical properties of the crosslinked rubber, 0.5 part of a crosslinking agent was kneaded with the roll, primary crosslinking was carried out at 170 ° C. for 10 minutes, and secondary crosslinking was carried out at 200 ° C. for 4 hours. The reinforcing property of strength was measured (hereinafter, the evaluation method is the same as in Examples and Comparative Examples). The results are shown in Table 1.
【００２２】比較例１ 実施例１において粒子性を調整した後、疎水化した湿式
法合成珪酸に代えて、未処理の湿式法合成珪酸であるニ
ップシールＬＰ（前出）を用いて、シリコーンゴムへの
配合評価を行った。シリコーン生ゴムに対し、４０部の
ニップシールＬＰと、湿潤剤として両末端にヒドロキシ
ル基を有するジメチルポリシキサン４部を６インチロー
ルで混練した。以下実施例１と同様にして評価を行い、
その結果を表１に示した。Comparative Example 1 After the particle properties were adjusted in Example 1, the unprocessed wet-process synthetic silicic acid was replaced by Nipseal LP (described above) to replace the hydrophobized wet-process synthetic silicic acid into silicone rubber. Was evaluated. 40 parts of nip seal LP and 4 parts of dimethylpolysiloxane having hydroxyl groups at both ends as a wetting agent were kneaded with a silicone rubber by a 6 inch roll. Evaluation is performed in the same manner as in Example 1 below.
The results are shown in Table 1.
【００２３】比較例２ 実施例１におけるジメチルシリコーンオイルＫＦ９６
（前出）の添加量を１２部に代えた以外は、実施例１と
同様にして評価を行い、その結果を表１に示した。 比較例３ 実施例１におけるジメチルシリコーンオイルＫＦ９６
（前出）の添加量を３部に代えた以外は、実施例１と同
様にして評価を行い、その結果を表１に示した。 比較例４ 実施例１における疎水性湿式法合成珪酸の製造におい
て、粉砕、分級を行わなかった以外は、実施例１と同様
にして評価を行い、その結果を表１に示した。Comparative Example 2 Dimethyl silicone oil KF96 in Example 1
Evaluations were performed in the same manner as in Example 1 except that the addition amount of (described above) was changed to 12 parts, and the results are shown in Table 1. Comparative Example 3 Dimethyl silicone oil KF96 in Example 1
Evaluation was carried out in the same manner as in Example 1 except that the addition amount of (described above) was changed to 3 parts, and the results are shown in Table 1. Comparative Example 4 In the production of the hydrophobic wet method synthetic silicic acid in Example 1, evaluation was performed in the same manner as in Example 1 except that pulverization and classification were not performed, and the results are shown in Table 1.
【００２４】実施例２ ＢＥＴ比表面積１４０ｍ2 ／ｇ、ＤＢＡ吸着量２３０ｍ
・ｍｏｌ／ｋｇ、二次平均粒子径が２．３μｍの湿式法
合成珪酸、ニップシールＥ−２００Ａ（日本シリカ工業
社製）を流動式混合機（株式会社三井三池製作所製、ヘ
ンシェルミキー）に仕込み、ジメチルシリコーンオイル
ＫＦ９６（信越化学工業社製）５部を投入し５分間混合
攪拌した後、２５０℃で２時間熱処理し疎水性の湿式法
合成珪酸を得た。以下実施例１と同様にして評価を行
い、その結果を表２に示した。Example 2 BET specific surface area 140 m 2 / g, DBA adsorption amount 230 m
-Mole / kg, wet synthetic silica having a secondary average particle diameter of 2.3 μm, Nipseal E-200A (manufactured by Nippon Silica Industry Co., Ltd.) was charged into a fluid mixer (Mitsui Miike Seisakusho, Henschel Mickey). 5 parts of dimethyl silicone oil KF96 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, mixed and stirred for 5 minutes, and then heat-treated at 250 ° C. for 2 hours to obtain hydrophobic wet-process synthetic silicic acid. Evaluations were performed in the same manner as in Example 1, and the results are shown in Table 2.
【００２５】比較例５ 実施例２においてＥ−２００Ａを疎水化した疎水性の湿
式法合成珪酸に代えて、未処理の湿式法合成珪酸である
ニップシールＥ−２００Ａ（前出）を用いて、シリコー
ンゴムへの配合評価を行った。シリコーン生ゴムの対
し、４０部のニップシールＬＰと、潤滑剤として両末端
にヒドロキシル基を有するジメチルポリシロキサン４部
を６インチロールで混練した。以下実施例２と同様にし
て評価を行い、その結果を表２に示した。Comparative Example 5 In place of the hydrophobic wet-process synthetic silicic acid obtained by hydrophobizing E-200A in Example 2, Nipseal E-200A (above-mentioned) which is an unprocessed wet-process synthetic silicic acid was used, and silicone was used. The compounding evaluation to rubber was performed. 40 parts of nip seal LP against silicone raw rubber and 4 parts of dimethylpolysiloxane having hydroxyl groups at both ends as a lubricant were kneaded with a 6-inch roll. Evaluations were performed in the same manner as in Example 2, and the results are shown in Table 2.
【００２６】比較例６ 実施例２におけるジメチルシリコーンオイルＫＦ９６
（前出）の添加量を８部に代えた以外は、実施例２と同
様にして評価を行い、その結果を表２に示した。 比較例７ 実施例２におけるジメチルシリコーンオイルＫＦ９６
（前出）の添加量を３部に代えた以外は、実施例２と同
様にして評価を行い、その結果を表２に示した。Comparative Example 6 Dimethyl silicone oil KF96 in Example 2
Evaluations were performed in the same manner as in Example 2 except that the addition amount of (described above) was changed to 8 parts, and the results are shown in Table 2. Comparative Example 7 Dimethyl silicone oil KF96 in Example 2
Evaluation was carried out in the same manner as in Example 2 except that the addition amount of (described above) was changed to 3 parts, and the results are shown in Table 2.
【００２７】[0027]
【表１】 （ ）内は、未処理の湿式法合成珪酸の物性値。[Table 1] The values in parentheses are the physical properties of untreated wet-process synthetic silicic acid.
【００２８】[0028]
【表２】 （ ）内は、未処理の湿式法合成珪酸の物性値。[Table 2] The values in parentheses are the physical properties of untreated wet-process synthetic silicic acid.
【００２９】表１の結果から、実施例１は、比較例１
（未処理の湿式法合成珪酸と湿潤剤の併用）に比べて、
加工性も補強性も遜色のないことが分かる。比較例２
は、疎水化度が高すぎると加工性は良いが、補強性が劣
ることが分かる。比較例３は、疎水化度が低すぎると補
強性は高いが、加工性が悪いことが代わる。比較例４
は、従来の粒子性を有するものでは、疎水化度を調整し
ても補強性が不充分であることが分かる。表２の結果か
らも、実施例２は、比較例５（未処理の湿式法合成珪酸
と潤滑剤の併用）に比べて、加工性も補強性も遜色のな
いことが分かる。比較例６は、疎水化度が高すぎると加
工性は良いが、補強性が劣ることが分かる。比較例７
は、疎水化が低すぎると補強性は高いが、加工性が悪い
ことが分かる。From the results of Table 1, Example 1 is comparative example 1
(Compared with untreated wet method synthetic silicic acid and wetting agent)
It can be seen that workability and reinforcement are comparable. Comparative Example 2
It can be seen that when the hydrophobicity is too high, the workability is good, but the reinforcing property is poor. In Comparative Example 3, when the degree of hydrophobicity is too low, the reinforcing property is high, but the workability is poor. Comparative Example 4
It can be seen that, with the conventional particles, the reinforcing property is insufficient even if the hydrophobicity is adjusted. The results in Table 2 also show that Example 2 is comparable in processability and reinforcement to Comparative Example 5 (combined use of untreated wet synthetic silica and a lubricant). In Comparative Example 6, when the degree of hydrophobicity is too high, the workability is good, but the reinforcing property is poor. Comparative Example 7
It can be seen that when the hydrophobicity is too low, the reinforcing property is high, but the processability is poor.
【００３０】[0030]
【発明の効果】以上の説明から明らかなように、本発明
のシリコーンゴム用補強充填剤を用いると、優れた加工
性と、高い補強性とを有するシリコーンゴム組成物が得
られる。As is apparent from the above description, when the reinforcing filler for silicone rubber of the present invention is used, a silicone rubber composition having excellent processability and high reinforcing property can be obtained.
Claims (2)
ｇであり、ジ−ｎ−ブチルアミン吸着量が３０〜１００
ｍ・ｍｏｌ／ｋｇであり、Ｍ値が５〜５５％であり、且
つ二次平均粒子径が１〜５μｍである疎水性湿式法合成
珪酸であることを特徴するシリコーンゴム用補強充填
剤。1. A BET specific surface area of 100 to 150 m 2 /
g, and the adsorbed amount of di-n-butylamine is 30 to 100.
A reinforcing filler for silicone rubber, which is a hydrophobic wet-process synthetic silicic acid having m · mol / kg, an M value of 5 to 55%, and a secondary average particle diameter of 1 to 5 μm.
湿式法合成珪酸である請求項１記載の充填剤。2. The filler according to claim 1, which is a wet-process synthetic silicic acid surface-treated with silicone oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18571494A JP3203292B2 (en) | 1994-08-08 | 1994-08-08 | Reinforcing filler for silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18571494A JP3203292B2 (en) | 1994-08-08 | 1994-08-08 | Reinforcing filler for silicone rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0848881A true JPH0848881A (en) | 1996-02-20 |
| JP3203292B2 JP3203292B2 (en) | 2001-08-27 |
Family
ID=16175572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18571494A Expired - Fee Related JP3203292B2 (en) | 1994-08-08 | 1994-08-08 | Reinforcing filler for silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3203292B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339431C (en) * | 2003-06-06 | 2007-09-26 | 株式会社德山 | Filler for clear rubber |
| KR20140017437A (en) * | 2012-08-01 | 2014-02-11 | 쇼와 덴코 패키징 가부시키가이샤 | Cover material for preventing the contents adhering |
| JP2014031179A (en) * | 2012-08-01 | 2014-02-20 | Showa Denko Packaging Co Ltd | Contents adhering prevention lid member |
| JP2017061345A (en) * | 2016-12-16 | 2017-03-30 | 昭和電工パッケージング株式会社 | Lid material for preventing adhesion of content |
| JPWO2015115184A1 (en) * | 2014-01-31 | 2017-06-22 | サンノプコ株式会社 | Hydrophobic fine-grain wet silica, production method thereof and antifoaming agent |
-
1994
- 1994-08-08 JP JP18571494A patent/JP3203292B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339431C (en) * | 2003-06-06 | 2007-09-26 | 株式会社德山 | Filler for clear rubber |
| KR20140017437A (en) * | 2012-08-01 | 2014-02-11 | 쇼와 덴코 패키징 가부시키가이샤 | Cover material for preventing the contents adhering |
| JP2014031179A (en) * | 2012-08-01 | 2014-02-20 | Showa Denko Packaging Co Ltd | Contents adhering prevention lid member |
| JPWO2015115184A1 (en) * | 2014-01-31 | 2017-06-22 | サンノプコ株式会社 | Hydrophobic fine-grain wet silica, production method thereof and antifoaming agent |
| JP2017061345A (en) * | 2016-12-16 | 2017-03-30 | 昭和電工パッケージング株式会社 | Lid material for preventing adhesion of content |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3203292B2 (en) | 2001-08-27 |
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