JP3676875B2 - Method for producing surface-treated carbon black for rubber reinforcement - Google Patents
Method for producing surface-treated carbon black for rubber reinforcement Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明はゴム補強用表面処理カーボンブラック（以下、単に「表面処理カーボン」と記載する）の製法に関し、更に詳しくは表面に無定形シリカを付着させたゴム補強用表面処理カーボンブラックの製法に関する。このようにして得られるゴム補強用表面処理カーボンブラックは、タイヤ用ゴム組成物をはじめとしてベルトコンベア、産業用ロールなどの各種ゴム製品用ゴム組成物に配合して、耐摩耗性、グリップ性能、低転がり抵抗性（低発熱性）などの優れたゴム物性を与えることができ、かつ従来のカーボンブラック製造設備を大きく変更することなく製造できるので低コストで製造することができる。
【０００２】
【従来の技術】
従来、カーボンブラックやシリカなどの補強性充填剤がゴム補強用に使用されてきた。これらの中でシリカは、カーボンブラックに比べて、高温（６０℃付近）でのｔａｎδが低く、低温（０℃付近）でのｔａｎδが高いという特性を持つため、例えばタイヤトレッド用ゴム組成物に用いた場合、低転がり抵抗でかつグリップ力の高いタイヤが製造できるという利点がある。しかしながら、シリカはカーボンブラックに比べて耐摩耗性に劣り、混練加工性に劣り、また電気伝導度が低いために、例えばタイヤ用に使用すると走行中にタイヤが帯電し、ラジオなどの電子機器にノイズを発生させたり、場合によっては誤動作を生じるなどの種々の問題があった。
【０００３】
顔料などの表面にシリカなどを被覆して分散性を改良したり、耐候性を向上させたりすることは、例えば特公昭５０−１４２５４号公報や特公平７−３０２６９号公報などに提案されている。例えば特公平７−３０２６９号公報には、カーボンブラックを水中に分散させ、pHを６以上に調節し、温度を７０℃以上に保ちながら珪酸ナトリウムを用いてカーボンブラックの粒子表面に無定形シリカを沈積させた粉体塗料用カーボンブラックの表面処理方法が記載されている。しかしながら、いずれの公報にも、ゴム補強用としてカーボンブラックの表面にシリカを付着せしめることについては言及されていない。
【０００４】
【発明が解決しようとする課題】
従って、本発明の目的は、シリカのもつ優れたｔａｎδ温度依存性を備えかつ耐摩耗性が良好で、しかも低電気伝導度に起因する問題のないゴム補強用表面処理カーボンブラックを現存のカーボンブラック製造設備を大幅に変更することなく廉価に製造できる造粒された（ビード化）ゴム補強用表面処理カーボンブラックの製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明に従えば、ゴム補強用表面処理カーボンブラックを製造するにあたり、カーボンブラックの造粒工程において、珪酸金属塩水溶液および酸水溶液をカーボンブラックに添加した後または添加しながら、造粒装置にて造粒することから成るゴム補強用表面処理カーボンブラックの製造方法が提供される。
【０００６】
【発明の実施の形態】
本発明者らは、前述の如く、シリカのもつ優れたｔａｎδ温度依存性を備えかつ耐摩耗性が良好で、しかも低電気伝導度に起因する問題のないゴム補強用表面処理カーボンブラックを製造する方法について鋭意検討をすすめた結果、造粒時に加える造粒用液体（通常は水及びバインダー）の代わりに水ガラス水溶液およびその中和に必要な量の硫酸その他の酸水溶液を加えることで目的のゴム補強用表面処理カーボンを製造できることを見出した。
【０００７】
本発明において原料物質として使用されるゴム補強用カーボンブラックとしては、従来からタイヤ用その他のゴム補強用カーボンとして汎用されている任意のカーボンブラックを用いることができる。好ましいカーボンブラックはＳＲＦ〜ＳＡＦグレードのものであり、ゴム組成物の用途により、種々使い分けや２種以上をブレンドすることが可能である。
【０００８】
本発明に従って、造粒されたゴム補強用表面処理カーボンブラックを製造する一般的な方法について説明する。先ず珪酸金属塩、例えば珪酸ナトリウム、メタ珪酸ナトリウム、珪酸マグネシウム、珪酸カルシウムを秤量し、水で希釈する。希釈濃度にはとくに限定はないが、好ましくは１〜５重量％程度である。表面処理反応工程で珪酸金属塩水溶液と同時に添加する酸水溶液（例えば硫酸など）の濃度にも特に限定はないが、珪酸金属塩水溶液の濃度とほぼ同程度の濃度でそれぞれほぼ同量の添加によりpHが変化しない濃度に調整するのが好ましい。また、これらのいずれか一方または両方に、通常カーボンブラックの造粒に使用されるバインダー（例えば糖蜜、リグニンスルホン酸など）などを添加することができる。
【０００９】
本発明の特徴は前記珪酸金属塩水溶液及び酸水溶液を通常のカーボンブラックの製造に使用される造粒工程（連続式又はバッチ式のいずれでもよい）の前、または造粒中、に添加し、カーボンブラックの表面にシリカを付着させた表面処理カーボンブラックを製造することにある。
珪酸金属塩水溶液の添加量または添加速度はカーボンブラックの供給量または供給速度と付着させるシリカの量に依存する。また同時に添加する酸水溶液の添加量または添加速度についても珪酸金属塩水溶液の添加量、添加速度及びカーボンブラックの最終pH値に依存する。因みにゴム補強用カーボンブラックの場合には、ゴム配合時に加硫挙動に影響を与えないようにするために一般的にはpH７付近とするのが普通である。
【００１０】
前述のようにして珪酸金属塩水溶液および酸水溶液が添加されたカーボンブラックは、例えば有刺型スクリュー式造粒装置などを用いて適当な温度（例えば６０℃〜２００℃）で攪拌、造粒するとともに、表面処理される。カーボンブラックに対する珪酸金属塩水溶液の添加量には特に限定はないが、好ましくはカーボンブラック重量に対してSiＯ2 量として０．５〜５０重量％、更に好ましくは０．５〜３０重量％である。一方、酸水溶液の添加量は添加した珪酸金属塩を中和するのに必要な量である。珪酸金属塩の添加量が少な過ぎると所望の効果が得にくくなり、逆に多過ぎると電気伝導度が低下するので好ましくない。なお、珪酸金属塩水溶液の添加量および酸水溶液の添加量の合計量は好ましくは、カーボンブラックに対して、５０〜２００重量％である。
【００１１】
本発明に係るシリカ表面処理ゴム補強用のカーボンブラックは架橋可能な任意のゴム成分に配合して耐摩耗性、グリップ性能、転がり抵抗などに優れたゴム組成物を得ることができる。そのような架橋可能なゴムとしては、例えば天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム、アクリロニトリロブタジエンゴム、クロロプレンゴム、エチレン−プロピレン共重合体ゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、イソプレン−ブタジエン共重合体ゴム、クロロスルホン化ポリエチレン、アクリルゴム、エピクロルヒドリンゴム、多硫化ゴム、シリコーンゴム、フッ素ゴム、ウレタンゴムなどを用いることができ、これらは単独又は任意のブレンドとして用いることができ、ブレンドを用いる場合にはそのブレンド比には特に制限はない。
【００１２】
本発明に従ったシリカ表面処理カーボンブラックは、ゴム成分１００重量部に対しシリカ表面処理カーボンブラックを１０〜２００重量部、更に好ましくは１５〜１５０重量部配合するのが好ましい。この配合量が少な過ぎるとゴムを十分に補強できないため、例えば耐摩耗性などが悪化する。逆に多過ぎると硬度が高くなり過ぎたり加工性が低下する等、ゴム材料としての実用性が乏しくなるおそれがあるので好ましくない。前記ゴム組成物には前記シリカ表面処理カーボンブラックの他にゴム組成物に通常配合される任意のカーボンブラック又は／及びシリカを併用することができる。
【００１３】
前記ゴム組成物には、前記ゴム、シリカを表面に付着させたカーボンブラックなどに加えて、ゴム工業で通常使用される任意の配合剤、例えば硫黄、有機過酸化物、軟化剤、老化防止剤、加硫促進剤、充填剤、可塑剤、シランカップリング剤等を必要に応じて、通常の配合量の範囲で適宜配合することができる。
【００１４】
【実施例】
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。
【００１５】
実施例１〜６及び比較例１〜２
シリカ表面処理カーボンブラックの調製
以下の方法により表面処理カーボンブラックを製造した。
カーボンブラックとしては表Ｉに示すＨＡＦ（Ｎ３３９）およびＩＳＡＦ（Ｎ２２０）の２種類を使用した。
それぞれのカーボンブラックを反応炉で生成しバグフィルターで捕集後、造粒工程へ送る。造粒装置（有刺型スクリュー式造粒装置）へカーボンブラックを導入する直前に５重量％のＪＩＳ１号珪酸ナトリウムの水溶液および２，５重量％硫酸水溶液をカーボンブラック全体に均一に噴霧した。ＪＩＳ１号珪酸ナトリウムの水溶液の噴霧量は所望のＳｉＯ2 処理量によって変化させた。すなわち、ＪＩＳ１号珪酸ナトリウムに含まれるＳｉＯ2 量が３６．５重量％とし、この全量が析出によりカーボンブラック表面に付着されるとしてカーボンブラックの搬送速度より計算により噴霧量を求めた。その後、このカーボンブラックを造粒装置（有刺型スクリュー式造粒装置）へ搬送し通常の方法により造粒を行い表面処理カーボンブラックを得た。造粒装置（有刺型スクリュー式造粒装置）から出てきた直後の表面処理カーボンブラックの温度は約７０〜８０℃であった。
【００１６】
表面処理カーボンブラックの特性測定法
１）シリカ含量
表面処理カーボンブラック試料を電気炉中で６００℃で灰化し、その灰分をフッ化水素処理しその減量をシリカ分としてもとの表面処理カーボンに対する重量分率として示した。
２）窒素比表面積（Ｎ2 ＳＡ）
ＡＳＴＭ Ｄ３０３７の方法に従って測定した。
３）ヨウ素吸着量
ＪＩＳ Ｋ６２２１に従って測定した。
【００１７】
ゴム物性測定法
以下の配合表に従って各種ゴム組成物を常法に従ってバンバリーミキサー及びロール機で混練して調製した（加硫条件：１６０℃×３０分）。
１）引張り強さ
ＪＩＳ Ｋ６３０１に準拠して測定した。
２）耐摩耗性指数
ランボーン摩耗試験機を使用して荷重５kg、スリップ率２５％、時間４分、室温の条件で測定し摩耗減量を指数として示した。なお、数字が大きい程耐摩耗性が良好であることを示す。
３）ｔａｎδ
（株）東洋精機製作所製、粘弾性スペクトロメータを用いて、振幅±２％、周波数２０Hz、静歪み１０％で測定した。
４）体積固有電気抵抗
ＡＳＴＭ Ｄ９９１またはＪＩＳ Ｋ６９１１に準拠して測定した。
【００１９】
補強性充填剤の種類、及びそれを前記配合表に示す配合にて調整した組成物の測定結果を表Ｉに示す。
【００２０】
【表１】
【発明の効果】
表Ｉの結果から明らかなように、本発明に係る方法で製造された造粒されたビード状のゴム補強用表面処理カーボンブラックを用いた各実施例では、従来の例である比較例１及び２に比較して、高温域（６０℃）でｔａｎδが低く、低温域（０℃）でｔａｎδが高いというシリカの特性を備えながら、耐摩耗性が良好で、電気抵抗の低いゴム配合物が得られる。
すなわち例えばタイヤのトレッドゴムとして使用した場合高グリップでかつ抵燃費性にすぐれかつ耐摩耗性が良好で、電気抵抗が高いことによるラジオノイズや電子機器への悪影響もないという性能を示すゴム組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a rubber-treated surface-treated carbon black (hereinafter simply referred to as “surface-treated carbon”), and more particularly to a method for producing a rubber-reinforced surface-treated carbon black having amorphous silica attached to the surface. The rubber-treated surface-treated carbon black thus obtained is blended with various rubber products for rubber products such as a rubber composition for tires, belt conveyors, industrial rolls, etc., and wear resistance, grip performance, Excellent rubber physical properties such as low rolling resistance (low heat build-up) can be provided, and the conventional carbon black production facility can be produced without greatly changing, and therefore can be produced at low cost.
[0002]
[Prior art]
Conventionally, reinforcing fillers such as carbon black and silica have been used for rubber reinforcement. Among these, silica has the characteristics that tan δ at a high temperature (around 60 ° C.) is low and tan δ at a low temperature (around 0 ° C.) is high compared with carbon black. When used, there is an advantage that a tire having low rolling resistance and high grip force can be manufactured. However, silica is inferior to carbon black in abrasion resistance, inferior in kneading workability, and has low electrical conductivity. For example, when used for tires, the tires are charged during running, and are used in electronic devices such as radios. There have been various problems such as generation of noise and malfunction in some cases.
[0003]
For example, Japanese Patent Publication No. 50-14254 and Japanese Patent Publication No. 7-30269 propose to improve the dispersibility and improve the weather resistance by coating the surface of a pigment or the like with silica. . For example, in Japanese Patent Publication No. 7-30269, carbon black is dispersed in water, the pH is adjusted to 6 or higher, and amorphous silica is added to the surface of the carbon black particles using sodium silicate while maintaining the temperature at 70 ° C. or higher. A method for surface treatment of deposited carbon black for powder coating is described. However, none of the publications mentions attaching silica to the surface of carbon black for reinforcing rubber.
[0004]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a surface-treated carbon black for rubber reinforcement that has excellent tan δ temperature dependency of silica, has good wear resistance, and has no problems caused by low electrical conductivity. An object of the present invention is to provide a method for producing a granulated (beaded) rubber-treated surface-treated carbon black for reinforcing rubber that can be produced at low cost without greatly changing the production equipment.
[0005]
[Means for Solving the Problems]
According to the present invention, in the production of the rubber-reinforced surface-treated carbon black, in the granulating step of the carbon black, after adding or adding the aqueous silicate metal salt solution and the aqueous acid solution to the carbon black, A method for producing a rubber-reinforced surface-treated carbon black comprising granulating is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the present inventors produce a surface-treated carbon black for rubber reinforcement that has excellent tan δ temperature dependency of silica, has good wear resistance, and has no problems due to low electrical conductivity. As a result of diligent investigations on the method, instead of the granulating liquid (usually water and binder) added during granulation, an aqueous glass solution and an amount of sulfuric acid or other acid solution required for neutralization are added. It has been found that surface-treated carbon for rubber reinforcement can be produced.
[0007]
As the carbon black for reinforcing rubber used as a raw material in the present invention, any carbon black conventionally used as a rubber reinforcing carbon for tires and other rubbers can be used. Preferred carbon black is of the SRF to SAF grade, and it is possible to use various types or blend two or more types depending on the use of the rubber composition.
[0008]
A general method for producing a granulated rubber-reinforced surface-treated carbon black according to the present invention will be described. First, a metal silicate salt such as sodium silicate, sodium metasilicate, magnesium silicate, or calcium silicate is weighed and diluted with water. The dilution concentration is not particularly limited, but is preferably about 1 to 5% by weight. There is no particular limitation on the concentration of the acid aqueous solution (for example, sulfuric acid, etc.) added simultaneously with the aqueous silicate metal salt solution in the surface treatment reaction step. It is preferable to adjust the concentration so that the pH does not change. Moreover, a binder (for example, molasses, lignin sulfonic acid, etc.) usually used for granulation of carbon black can be added to one or both of these.
[0009]
A feature of the present invention is that the metal silicate aqueous solution and the acid aqueous solution are added before or during the granulation step (which may be either a continuous type or a batch type) used in the production of ordinary carbon black, The object is to produce a surface-treated carbon black in which silica is adhered to the surface of the carbon black.
The addition amount or addition rate of the aqueous silicate metal salt solution depends on the supply amount or supply rate of carbon black and the amount of silica to be deposited. Further, the addition amount or addition rate of the acid aqueous solution added at the same time also depends on the addition amount, addition rate, and final pH value of the carbon black. Incidentally, in the case of carbon black for reinforcing rubber, generally, the pH is generally around 7 so as not to affect the vulcanization behavior when the rubber is blended.
[0010]
The carbon black to which the aqueous silicate metal salt solution and the aqueous acid solution are added as described above is stirred and granulated at an appropriate temperature (for example, 60 ° C. to 200 ° C.) using, for example, a barbed screw granulator. Together with the surface treatment. The amount of the aqueous silicate metal salt solution added to the carbon black is not particularly limited, but is preferably 0.5 to 50% by weight, more preferably 0.5 to 30% by weight as the amount of SiO 2 with respect to the weight of the carbon black. . On the other hand, the addition amount of the acid aqueous solution is an amount necessary for neutralizing the added silicate metal salt. If the addition amount of the silicate metal salt is too small, it is difficult to obtain a desired effect, and conversely, if the addition amount is too large, the electric conductivity is lowered, which is not preferable. In addition, the total amount of the addition amount of the silicate metal salt aqueous solution and the addition amount of the acid aqueous solution is preferably 50 to 200% by weight with respect to the carbon black.
[0011]
The carbon black for reinforcing a silica surface-treated rubber according to the present invention can be blended with any crosslinkable rubber component to obtain a rubber composition excellent in abrasion resistance, grip performance, rolling resistance and the like. Examples of such crosslinkable rubbers include natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), butyl rubber (IIR), and halogenated. Butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene Copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, etc. can be used, these can be used alone or as any blend, When to use There is no particular limitation to the blend ratio.
[0012]
The silica surface-treated carbon black according to the present invention is preferably blended in an amount of 10 to 200 parts by weight, more preferably 15 to 150 parts by weight, based on 100 parts by weight of the rubber component. If the blending amount is too small, the rubber cannot be sufficiently reinforced, so that, for example, the wear resistance is deteriorated. On the other hand, if the amount is too large, it is not preferable because the practicality as a rubber material may be poor, such as excessively high hardness or reduced workability. In addition to the silica surface-treated carbon black, any carbon black or / and silica usually compounded in the rubber composition can be used in combination with the rubber composition.
[0013]
In addition to the rubber and carbon black with silica attached to the surface, the rubber composition includes any compounding agent commonly used in the rubber industry, such as sulfur, organic peroxides, softeners, anti-aging agents. Further, a vulcanization accelerator, a filler, a plasticizer, a silane coupling agent, and the like can be appropriately blended within a range of a normal blending amount as necessary.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
[0015]
Examples 1-6 and Comparative Examples 1-2
Preparation of silica surface-treated carbon black Surface-treated carbon black was produced by the following method.
Two types of carbon black, HAF (N339) and ISAF (N220) shown in Table I, were used.
Each carbon black is produced in a reactor, collected by a bag filter, and sent to the granulation process. Immediately before the introduction of carbon black into a granulator (barbed screw granulator), 5% by weight of JIS No. 1 sodium silicate aqueous solution and 2,5% by weight sulfuric acid aqueous solution were uniformly sprayed on the entire carbon black. The spray amount of the aqueous solution of JIS No. 1 sodium silicate was changed depending on the desired SiO 2 treatment amount. That is, the amount of SiO 2 contained in JIS No. 1 sodium silicate was 36.5% by weight, and the spray amount was determined by calculation from the transport speed of carbon black, assuming that this total amount was deposited on the carbon black surface by precipitation. Thereafter, the carbon black was conveyed to a granulator (barbed screw granulator) and granulated by a usual method to obtain surface-treated carbon black. The temperature of the surface-treated carbon black immediately after coming out of the granulator (barbed screw granulator) was about 70 to 80 ° C.
[0016]
Characteristic measurement method of surface-treated carbon black 1) Silica content Surface-treated carbon black sample is ashed in an electric furnace at 600 ° C, the ash content is treated with hydrogen fluoride, and the weight loss with respect to the original surface-treated carbon as silica content. Expressed as a fraction.
2) Nitrogen specific surface area (N 2 SA)
Measured according to the method of ASTM D3037.
3) Iodine adsorption amount Measured according to JIS K6221.
[0017]
Method for measuring rubber physical properties Various rubber compositions were prepared by kneading with a Banbury mixer and a roll machine according to a conventional method according to the following composition table (vulcanization conditions: 160C x 30 minutes).
1) Tensile strength Measured according to JIS K6301.
2) Abrasion resistance index Using a Lambourne abrasion tester, the measurement was performed under the conditions of a load of 5 kg, a slip rate of 25%, a time of 4 minutes, and room temperature, and the wear loss was shown as an index. In addition, it shows that abrasion resistance is so favorable that a number is large.
3) tan δ
Using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., the amplitude was ± 2%, the frequency was 20 Hz, and the static strain was 10%.
4) Volume specific electric resistance Measured according to ASTM D991 or JIS K6911.
[0019]
Table I shows the types of reinforcing fillers and the measurement results of the compositions prepared with the formulations shown in the formulation table.
[0020]
[Table 1]
【The invention's effect】
As is apparent from the results in Table I, in each of the examples using the granulated bead-shaped surface-treated carbon black for reinforcing rubber produced by the method according to the present invention, Comparative Example 1 and Compared to 2, a rubber compound having good wear resistance and low electrical resistance while having the characteristics of silica that tan δ is low in the high temperature region (60 ° C.) and tan δ is high in the low temperature region (0 ° C.). can get.
That is, for example, when used as a tread rubber of a tire, a rubber composition that exhibits high grip, excellent fuel economy, good wear resistance, and no adverse effects on radio noise and electronic equipment due to high electrical resistance. Is obtained.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10973696A JP3676875B2 (en) | 1996-04-30 | 1996-04-30 | Method for producing surface-treated carbon black for rubber reinforcement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10973696A JP3676875B2 (en) | 1996-04-30 | 1996-04-30 | Method for producing surface-treated carbon black for rubber reinforcement |
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| Publication Number | Publication Date |
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| JPH09296071A JPH09296071A (en) | 1997-11-18 |
| JP3676875B2 true JP3676875B2 (en) | 2005-07-27 |
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| JP10973696A Expired - Lifetime JP3676875B2 (en) | 1996-04-30 | 1996-04-30 | Method for producing surface-treated carbon black for rubber reinforcement |
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| KR100321269B1 (en) | 1997-04-30 | 2002-09-09 | 요코하마 고무 가부시키가이샤 | Manufacture method of modified carbon black for rubber reinforcement, Rubber composition containing modified carbon black for rubber reinforcement and manufacturing method thereof |
| EP2075291B1 (en) | 2006-10-20 | 2014-04-23 | Denki Kagaku Kogyo Kabushiki Kaisha | Granular acetylene black, process for production thereof, and composition |
| JP5280016B2 (en) * | 2007-05-11 | 2013-09-04 | 大日精化工業株式会社 | Coating liquid |
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