JPH0625284B2 - Silica compounded rubber composition - Google Patents
Silica compounded rubber compositionInfo
- Publication number
- JPH0625284B2 JPH0625284B2 JP59124400A JP12440084A JPH0625284B2 JP H0625284 B2 JPH0625284 B2 JP H0625284B2 JP 59124400 A JP59124400 A JP 59124400A JP 12440084 A JP12440084 A JP 12440084A JP H0625284 B2 JPH0625284 B2 JP H0625284B2
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Description
【発明の詳細な説明】 （技術分野） 本発明は天然ゴムおよびジエン系合成ゴムから成る群か
ら選ばれた少くとも１種のゴムに珪酸塩系填料およびシ
ランカツプリング剤を配合して成る作業性および加工性
の優れたゴム組成物に関するものである。Description: TECHNICAL FIELD The present invention comprises the operation of blending at least one rubber selected from the group consisting of natural rubber and diene synthetic rubber with a silicate filler and a silane coupling agent. The present invention relates to a rubber composition having excellent workability and processability.
（従来技術） 従来、カーボンブラツク配合ゴム組成物の補強性を改善
するためのカーボンブラツクの一部もしくは全部をシリ
カで置換する方法、さらにはこれを改良すべくシランカ
ツプリング剤を用いる方法が検討され、例えば特公昭５
０−２９７４１号公報にシリカカツプリング剤を補強剤
として用いることが記載されている。しかし、このシリ
カカツプリング剤系補強剤によつてもゴム組成物の破壊
特性及び作業性、加工性を高水準なものとするには不充
分である。また、特公昭５１−２０２０８号公報等にシ
リカ−シランカツプリング剤を補強剤として用いたゴム
組成物が記載されている。このようなシリカ−シランカ
ツプリング剤系補強によると配合ゴムの補強性が著しく
改善でき、破壊特性を向上させることができるが、配合
ゴムの未加硫時の流動性が著しく劣り、作業性および加
工性の低下をもたらす欠点がある。(Prior Art) Conventionally, a method of substituting a part or all of the carbon black with silica for improving the reinforcing property of a rubber composition containing carbon black, and a method of using a silane coupling agent for improving the method have been studied. For example, Japanese Patent Publication 5
The use of a silica coupling agent as a reinforcing agent is described in 0-29741. However, even this silica coupling agent-based reinforcing agent is insufficient to bring the rubber composition to high levels of fracture properties, workability and processability. Further, Japanese Patent Publication No. 51-20208 discloses a rubber composition using a silica-silane coupling agent as a reinforcing agent. Such silica-silane coupling agent system reinforcement can remarkably improve the reinforcing property of the compounded rubber and improve the fracture property, but the flowability of the compounded rubber when not vulcanized is remarkably poor, and the workability and There is a drawback that results in deterioration of workability.
（発明の目的） 本発明の目的は、シリカ−シランカツプリング剤系補強
ゴム組成物の上記欠点を解消し、カーボンブラツク補強
に勝る破壊特性を有すると同時に、作業性、加工性の改
善されたゴム組成物を提供することにある。(Object of the Invention) An object of the present invention is to solve the above-mentioned drawbacks of a silica-silane coupling agent-based reinforcing rubber composition and to have a breaking property superior to carbon black reinforcing, and at the same time, improved workability and processability. To provide a rubber composition.
（発明の解決しようとする問題点） 本発明者等はシリカ−シランカツプリング剤を補強剤に
用いた場合ゴム組成物の作業性および加工性が低下する
原因につき鋭意研究を行つた結果、例えば前記特公昭５
１−２０２０８号公報に開示されているゴム組成物に補
強添加剤として用いられているシランカツプリング剤
（Ｚ−AlK−Sn−AlK−Ｚ、但しＺはシラン基、AlKはア
ルキレン基、ｎは２〜６）にみられる如く、混練時に分
子中に結合する硫黄の分離や最終段階で添加された加硫
促進剤、例えばジベンゾチアジルスルフイド（ＤＭ）、
ジフエニルグアニジン（ＤＰＧ）、Ｎ−オキシジエチレ
ンベンゾチアジルスルフエンアミド（ＮＯＢＳ）、Ｎ−
シクロヘキシルベンゾチアジルスルフエンアミド（Ｃ
Ｚ）等との相乗的反応によりシランカツプリング剤がポ
リマーとポリマー間の結合に消費され、またゴム中に配
合されたシリカ表面とシランカツプリング剤の末端基の
反応が阻害され、充填剤的補強性が低下し、シリカ自身
の表面がポリマーと物理的結合を作りやすいという潜在
的特性と相まつて配合ゴムの未加硫粘度（ムーニー粘度
が上昇し）、作業性、加工性が低下することを知見し
た。(Problems to be Solved by the Invention) As a result of intensive studies by the present inventors, for example, the reason why the workability and processability of the rubber composition are lowered when a silica-silane coupling agent is used as a reinforcing agent, for example, Saikoku Sho 5
A silane coupling agent (Z-AlK-Sn-AlK-Z, wherein Z is a silane group, AlK is an alkylene group, and n is used as a reinforcing additive in the rubber composition disclosed in JP 1-20208 A. 2-6), the separation of sulfur bound in the molecule during kneading and the vulcanization accelerator added in the final stage, such as dibenzothiazyl sulfide (DM),
Diphenyl guanidine (DPG), N-oxydiethylene benzothiazyl sulfenamide (NOBS), N-
Cyclohexylbenzothiazyl sulfenamide (C
The silane coupling agent is consumed in the bond between the polymers due to a synergistic reaction with Z) or the like, and the reaction between the surface of the silica compounded in the rubber and the terminal group of the silane coupling agent is hindered. The unvulcanized viscosity (increased Mooney viscosity), workability and processability of the compounded rubber are reduced in combination with the potential property that the reinforcing property is reduced and the surface of silica itself easily forms a physical bond with the polymer. I found out.
（問題点を解決するための手段） 次いで上記知見に基づき上記相剩的反応を防止する方法
につき研究したところ、シランカツプリング剤の結合剤
としてのシリカとの反応部分と、後添加の加硫促進剤の
反応基、チオカルバミル基を同時に一つの分子として有
するシランカツプリングを用いると、混練中はシランカ
ツプリング剤とシリカとの結合のみが主として行われ、
ポリマーとポリマーの間の結合反応が加硫工程において
行われるようになり、補強性を高度に維持しながら作業
性、加工性の改善されたゴム組成物が得られることを確
かめ本発明を達成するに至った。(Means for Solving Problems) Next, based on the above findings, a method for preventing the above-mentioned synergistic reaction was studied. As a result, a reaction portion of the silane coupling agent with silica as a binder and a vulcanization after addition were conducted. When a silane coupling having a reactive group of the accelerator and a thiocarbamyl group as one molecule at the same time is used, only the bonding between the silane coupling agent and silica is mainly performed during kneading,
The present invention has been accomplished by confirming that the bonding reaction between polymers is carried out in the vulcanization process, and that a rubber composition having improved workability and processability while maintaining a high degree of reinforcement can be obtained. Came to.
従つて本発明は、天然ゴムおよびジエン系合成ゴムから
成る群から選ばれた少なくとも１種のゴム１００重量部
に対して電子顕微鏡で測定した平均基本粒径が３０ｍμ
以下、ＢＥＴ法で測定した比表面積１３０m2／ｇ以上、
シリカ（ＳｉＯ２）含分８０％以上で表わされる範囲の
珪酸塩系填料（細粉状活性沈殿珪酸、以後シリカとい
う）を１〜１００重量部と次の一般式 （式中Ｒ１；炭素数１〜４のアルキル基 炭素数５〜８のシクロアルキル基または
フェニル基 Ｒ２；炭素数１〜４のアルキル基 炭素数５〜８のシクロアルキル基または
フェニル基 Ｒ３；炭素数１〜８の２価の直鎖または分枝鎖の、場
合により環状の炭化水素基 ｍ ；１，２または３ ｎ ；２〜６までの値 この際Ｒ４，Ｒ５は炭素数１〜４の直鎖または分枝鎖の
炭化水素基もしくはフエニル基を表わし、同一または異
なるものを示す。）で表わされる結合剤を0.1〜２０重
量部配合してなるシリカ配合ゴム組成物に係るものであ
る。Therefore, the present invention has an average basic particle diameter of 30 mμ measured by an electron microscope with respect to 100 parts by weight of at least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber.
Hereinafter, a specific surface area of 130 m 2 / g or more measured by the BET method,
1 to 100 parts by weight of a silicate-based filler (finely powdered active precipitated silicic acid, hereinafter referred to as silica) having a silica (SiO 2 ) content of 80% or more and the following general formula: (In the formula, R 1 ; alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms or phenyl group R 2 ; alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms or phenyl group R 3 ; C 1-8 divalent linear or branched, optionally cyclic hydrocarbon group m; 1, 2 or 3 n; values up to 2-6 In this case, R 4 and R 5 represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms or a phenyl group, and are the same or different. The present invention relates to a silica-containing rubber composition obtained by mixing 0.1 to 20 parts by weight of a binder represented by the formula (1).
ここでＢＥＴ法とは、ブルナウアー−エメツト−テーラ
ー(Brunauer-Emmett-Teller)法の略で、ＡＳＴＭ Ｄ−
３０３７−８１にその測定方法が規定されているもので
ある。Here, the BET method is an abbreviation for the Brunauer-Emmett-Teller method, which is ASTM D-
The measuring method is specified in 3037-81.
本発明で使用するシリカは、ＢＥＴ吸着比表面積を１３
０m2／ｇ以上、電子顕微鏡で測定した平均基本粒子径を
３０ｍμ以下とするが、このように規定することにより
ゴム組成物の破壊強度を高度に維持できるためである。
またシリカ表面のＯＨ基とカツプリング剤ポリマーの結
合を増大させることにより高い破壊強度を維持するため
に、そのシリカ含分を８０％以上とする必要がある。The silica used in the present invention has a BET adsorption specific surface area of 13
The average basic particle diameter measured by an electron microscope is 0 m 2 / g or more, and the average basic particle diameter is 30 mμ or less. This is because the breaking strength of the rubber composition can be maintained at a high level by such a definition.
Further, in order to maintain a high breaking strength by increasing the bond between the OH groups on the silica surface and the coupling agent polymer, the silica content must be 80% or more.
シリカの配合量は、ゴム分１００重量部に対して１重量
部未満では効果がなく、１００重量部を越えると未加硫
時の粘度が高くなり、ゴム組成物の加工性、作業性が悪
くなるので、１〜１００重量部とする。If the compounding amount of silica is less than 1 part by weight with respect to 100 parts by weight of the rubber content, there is no effect, and if it exceeds 100 parts by weight, the viscosity in the unvulcanized state becomes high, resulting in poor processability and workability of the rubber composition. Therefore, it is 1 to 100 parts by weight.
本発明においては上記ゴム分としては、天然ゴムおよび
ジエン系合成ゴムの内のいずれか１種または２種以上を
使用するが、ここでジエン系ゴムとは、広い意味に解さ
れるもので、例えばスチレンブタジエンゴム（ＳＢ
Ｒ）、ポリブタジエンゴム（ＢＲ）、ポリイソプレンゴ
ム（ＩＲ）、アクリロニトリル−ブタジエンゴム等のみ
ならず、エチレンプロピレンゴム（ＥＰＤＭ）およびハ
ロゲン化ブチルゴム等も含まれる。In the present invention, as the rubber component, any one kind or two or more kinds of natural rubber and diene-based synthetic rubber is used. Here, the diene-based rubber is understood in a broad sense. For example, styrene butadiene rubber (SB
R), polybutadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile-butadiene rubber and the like, as well as ethylene propylene rubber (EPDM) and halogenated butyl rubber and the like.
次にシリカと一緒に配合される結合剤としてのシランカ
ツプリング剤は、前記一般式で示されるもので、従来シ
リカ−シランカツプリング剤系に使用されてきたものと
全く構造を異にし、末端にシリカと反応する基Ｒ１Ｏと
他端に、加硫促進剤の残基Ｘを一分子中に有し、混練り
中は基Ｒ１Ｏによるシリカ表面との結合、加硫中は基Ｘ
が加硫促進剤として機能し分子中の硫黄によるポリマー
とポリマーの間の結合を行う作用を有するもので、例え
ば次に示す化合物が含まれる。Next, the silane coupling agent as a binder to be blended together with silica is represented by the above-mentioned general formula, and has a completely different structure from that conventionally used in a silica-silane coupling agent system. Has a group R 1 O that reacts with silica and a residue X of a vulcanization accelerator in one molecule at the other end, and is bonded to the silica surface by the group R 1 O during kneading and the group during the vulcanization. X
Acts as a vulcanization accelerator and has an action of forming a bond between polymers by sulfur in the molecule, and includes, for example, the compounds shown below.
１ ２ ３ ４ ５ ６ ７ ８ ９ １０ 上記結合剤はゴム分１００重量部に対し２０重量部より
多く添加すると加硫後のゴムの破壊強度が低下し、0.1
重量部未満では添加した効果が得られないので、0.1〜
２０重量部とする。1 Two Three Four 5 6 7 8 9 10 If more than 20 parts by weight of the above binder is added to 100 parts by weight of rubber, the breaking strength of the rubber after vulcanization will decrease, and
If it is less than 10 parts by weight, the effect of addition cannot be obtained.
20 parts by weight.
本発明のゴム組成物には、通常更に加硫促進剤を、ゴム
分１００重量部に0.1〜5.0重量部添加するが、5.0重量
部以上では、加硫ゴムのモジユラスが高くなりすぎ、ゴ
ム焼けの原因となり、0.1重量部未満では添加する効果
が得られない。また硫黄は必ずしも配合する必要はない
が、４重量部以下の分量で、加硫促進剤とのバランスを
とりながら配合し、ゴム架橋を調整することができる。A vulcanization accelerator is usually added to the rubber composition of the present invention in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the rubber component. However, when the amount is 5.0 parts by weight or more, the modulus of the vulcanized rubber becomes too high and the rubber burns. If the amount is less than 0.1 part by weight, the effect of addition cannot be obtained. Further, it is not always necessary to add sulfur, but it is possible to adjust the rubber cross-linking by adding 4 parts by weight or less while keeping the balance with the vulcanization accelerator.
本発明のゴム組成物には、この他通常使用されている配
合剤、例えばプロセスオイル、老化防止剤、酸化防止剤
等を適宜添加することができる。To the rubber composition of the present invention, other commonly used compounding agents such as process oil, antiaging agent, antioxidant and the like can be appropriately added.
以上の構成から成る本発明のゴム組成物は、補強性が著
しく改善され、破壊特性が向上し且つ優れた作業性およ
び加工性を有するので、各種タイヤ部材、特にトレツド
ゴムおよびサイドトレツドゴムとして、或いはまた各種
工業製品、例えばホース、ベルト、防振ゴム、制振材等
として広く使用が可能である。The rubber composition of the present invention having the above-mentioned constitution has remarkably improved reinforcing properties, improved fracture properties, and excellent workability and processability. Therefore, various tire members, particularly as a tread rubber and a side tread rubber, Alternatively, it can be widely used as various industrial products such as hoses, belts, anti-vibration rubbers, and damping materials.
（発明の実施例） 次に本発明を実施例および比較例により説明する。(Examples of the Invention) Next, the present invention will be described with reference to Examples and Comparative Examples.
第１表に示す配合（重量部）で２１種類のゴム組成物を
つくつた。尚表中シリカ種は次に示すものを用いた。Twenty-one rubber compositions were prepared with the formulations (parts by weight) shown in Table 1. The following silica species were used in the table.
また第１表の組成物には、第２，３表に示すように次の
シランカツプリング剤： Ｉ．HS・CH2・CH2・CH2・Si・(OCH3)3日本ユニカ（株）製、 商品名Ａ−１８９ II． III．H2NCH2・CH2・CH2・Si・(OC2H5)3日本ユニカ（株）
製、 商品名Ａ−１１００ IV Ｖ． （硫黄原子が１個の場合は、加硫速度の遅れが著しく、
通常の加硫条件で十分な物性を発揮することは難し
い。） をゴム組成物No.１〜１４については第２表に示すよう
に各々6.0重量部を配合し、No.１５〜２１については第
３表に示すように各々１２重量部を配合した。このよう
にして得られたゴム組成物およびシランカツプリングを
配合しないゴム組成物につき、破壊強度とムーニー粘度
を測定し得られた結果を第２表および第３表に示す。こ
こで、破壊強度はJISK6301に準じ、またムーニー粘度は
JISK6300に準じて測定した値である。 The compositions in Table 1 also contained the following silane coupling agents as shown in Tables 2 and 3: HS · CH 2 · CH 2 · CH 2 · Si · (OCH 3) 3 Nippon Unica Co., Ltd. under the trade name of A-189 II. III. H 2 NCH 2・ CH 2・ CH 2・ Si ・ (OC 2 H 5 ) 3 Nihon Unica Co., Ltd.
Product name: A-1100 IV V. (When there is only one sulfur atom, the vulcanization rate is significantly delayed,
It is difficult to exhibit sufficient physical properties under normal vulcanization conditions. ) Was blended in an amount of 6.0 parts by weight for each of the rubber compositions Nos. 1 to 14 and 12 parts by weight for each of the rubber compositions No. 15 to 21 as shown in Table 3. Tables 2 and 3 show the results obtained by measuring the breaking strength and Mooney viscosity of the rubber composition thus obtained and the rubber composition containing no silane coupling. Here, the breaking strength is in accordance with JIS K6301, and the Mooney viscosity is
It is a value measured according to JIS K6300.
（発明の効果） 本発明のゴム組成物は、特定のシリカと前記一般式 で表わされるシランカツプリング剤を結合剤として配合
した構成としたため、従来のシリカ−シランカツプリン
グ剤によると本来シリカとポリマーの結合に使われるも
のが、ポリマー間に使用され、充填剤による補強効果が
低減し、作業性、加工性が低下したのに対し、本発明で
は使用するシランカツプリング剤において結合剤として
のシリカとの反応部分と、加硫促進剤の残基である反応
基を一つの分子に存在させ安定化させることにより、架
橋反応の開始が抑制され、第２表、第３表に示す如く、
補強効果が制限されることなく破壊特性が著しく向上
し、同時に上記本発明で用いるシランカツプリング剤は
常温で液状であり、アロマオイル、スピンドルオイル等
の様な軟化効果を有するのでシリカ自身の表面がポリマ
ーと物理的結合をするという本質的問題も回避され作業
性および加工性が著しく改善されるという効果が得られ
る。 (Effects of the Invention) The rubber composition of the present invention comprises a specific silica and the above general formula Since the silane coupling agent represented by the formula is used as a binder, the conventional silica-silane coupling agent, which is originally used to bond silica and polymer, is used between the polymers and the reinforcing effect of the filler. However, in the present invention, the silane coupling agent used in the present invention has a reaction part with silica as a binder and a reactive group which is a residue of the vulcanization accelerator. By allowing it to exist in one molecule and stabilizing it, the initiation of the crosslinking reaction is suppressed, and as shown in Tables 2 and 3,
The fracture effect is remarkably improved without limiting the reinforcing effect, and at the same time, the silane coupling agent used in the present invention is a liquid at room temperature and has a softening effect such as aroma oil, spindle oil, etc. The essential problem of physical bond with the polymer is avoided, and the workability and processability are significantly improved.
Claims (1)
群から選ばれた少なくとも１種のゴム100重量部に対し
て、電子顕微鏡で測定した平均基本粒径が30ｍμ以下、
ＢＥＴ法で測定した比表面積130m2／ｇ以上、シリカ
（ＳｉＯ２）含分80％以上で表わされる範囲の珪酸塩系
填料を１〜100重量部と、次の一般式 （式中Ｒ１；炭素数１〜４のアルキル基 炭素数５〜８のシクロアルキル基 またはフェニル基 Ｒ２；炭素数１〜４のアルキル基 炭素数５〜８のシクロアルキル基 またはフェニル基 Ｒ３；炭素数１〜８の２価の直鎖または分枝鎖の、場
合により環状の炭化水素基 ｍ ；１，２または３ ｎ ；２〜６までの値 この際Ｒ４，Ｒ５は炭素数１〜４の直鎖または分枝鎖の
炭化水素基もしくはフェニル基を表わし、同一または異
なるものを示す。）で表わされる結合剤を0.1〜20重量
部配合してなるシリカ配合ゴム組成物。1. An average basic particle diameter measured by an electron microscope of 30 mμ or less based on 100 parts by weight of at least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber,
1 to 100 parts by weight of a silicate-based filler having a specific surface area of 130 m 2 / g or more and a silica (SiO 2 ) content of 80% or more as measured by the BET method, and the following general formula: (In the formula, R 1 ; alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms or phenyl group R 2 ; alkyl group having 1 to 4 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms or phenyl group R 3 ; C 1-8 divalent linear or branched, optionally cyclic hydrocarbon group m; 1, 2 or 3 n; values up to 2-6 In this case, R 4 and R 5 represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms or a phenyl group, and are the same or different. ) A silica-containing rubber composition comprising 0.1 to 20 parts by weight of a binder represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59124400A JPH0625284B2 (en) | 1984-06-19 | 1984-06-19 | Silica compounded rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59124400A JPH0625284B2 (en) | 1984-06-19 | 1984-06-19 | Silica compounded rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS614742A JPS614742A (en) | 1986-01-10 |
| JPH0625284B2 true JPH0625284B2 (en) | 1994-04-06 |
Family
ID=14884501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59124400A Expired - Lifetime JPH0625284B2 (en) | 1984-06-19 | 1984-06-19 | Silica compounded rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625284B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5663358A (en) * | 1996-01-22 | 1997-09-02 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon disulfide compounds |
| JP3479084B2 (en) | 1996-06-26 | 2003-12-15 | 株式会社ブリヂストン | Rubber composition |
| FR2839720B1 (en) * | 2002-05-15 | 2005-07-22 | Rhodia Chimie Sa | ORGANOSILIC COMPOUNDS USED IN PARTICULAR AS A COUPLING AGENT, ELASTOMERIC COMPOSITIONS CONTAINING SAME AND ARTICLES THEREOF (S) PREPARED FROM SUCH COMPOSITIONS |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55131029A (en) * | 1979-03-30 | 1980-10-11 | Phillips Petroleum Co | Manufacture of silica reinforced rubber and compound suitable for use as coupling agent |
-
1984
- 1984-06-19 JP JP59124400A patent/JPH0625284B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55131029A (en) * | 1979-03-30 | 1980-10-11 | Phillips Petroleum Co | Manufacture of silica reinforced rubber and compound suitable for use as coupling agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS614742A (en) | 1986-01-10 |
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