JPH08133721A - Granular precipitated silica and its production - Google Patents
Granular precipitated silica and its productionInfo
- Publication number
- JPH08133721A JPH08133721A JP28030194A JP28030194A JPH08133721A JP H08133721 A JPH08133721 A JP H08133721A JP 28030194 A JP28030194 A JP 28030194A JP 28030194 A JP28030194 A JP 28030194A JP H08133721 A JPH08133721 A JP H08133721A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- granular
- precipitated silicic
- rubber
- precipitated 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
Landscapes
- Silicon Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、新規な粒状沈殿ケイ酸
に関する。特に、本発明は、ゴム、プラスチック、樹脂
等の充填剤に適した大きな粒子径と高い嵩比重を有し、
しかも適度な粒子硬度を有しており、充填作業が容易で
あり、且つ粉じんの発生が著しく改善された新規な粒状
沈殿ケイ酸及びその製造方法を提供するものである。FIELD OF THE INVENTION The present invention relates to a novel granular precipitated silica. In particular, the present invention has a large particle size and a high bulk specific gravity suitable for a filler such as rubber, plastic and resin,
Further, the present invention provides a novel granular precipitated silicic acid having an appropriate particle hardness, facilitating a filling operation, and significantly improving dust generation, and a method for producing the same.
【0002】[0002]
【従来の技術】沈殿ケイ酸粉末は通称ホワイトカーボン
と呼ばれ、表面活性を有す白色度の高い粉末であり、ゴ
ム補強充填剤をはじめ農薬用分散剤、塗料、樹脂、情報
用紙、インク、歯磨き等様々な分野で使用されている。
一般的に柔らかい凝集粒で、粉体の中でも最も軽い部類
に属し、非常に飛散しやすく取扱い時に粉塵による作業
環境の悪化が問題となっている。また、粉体の嵩比重が
低く、包装や貯蔵及び輸送費用の不経済、或いは流動性
が悪くサイロの底壁等に残るなど問題点もある。このよ
うな難点を解消するために粒状品が強く要望されてい
る。2. Description of the Related Art Precipitated silicic acid powder is commonly called white carbon and is a powder with high whiteness having surface activity. It is used as a rubber reinforcing filler, agricultural chemical dispersant, paint, resin, information paper, ink, It is used in various fields such as toothpaste.
Generally, it is a soft agglomerate and belongs to the lightest class of powder, and it is very easy to scatter, and the deterioration of the working environment due to dust during handling is a problem. In addition, there are problems that the bulk specific gravity of the powder is low, the packaging, storage and transportation costs are uneconomical, or the fluidity is poor and the powder remains on the bottom wall of the silo. There is a strong demand for granular products in order to eliminate such difficulties.
【0003】[0003]
【発明が解決しようとする課題】ところで、沈殿ケイ酸
粉末をエラストマー充填剤として用いる場合、その性能
を第一に考えるならば補強効果の上から、エラストマー
中へ分散性の良い微粉体である事が望ましい。しかるに
補強性能を多少犠牲にしても前述のような難点を解消す
る為に、種々の造粒方法が提案されている。しかし、種
々の造粒方法より粒状化した場合、オープンロールやバ
ンバリーミキサー等で、ゴム等と混練した場合、沈殿ケ
イ酸粉末の分散性が損なわれ、ゴムの性質を決める、耐
摩耗性、引張り強さ、伸び、反撥弾性等の性能が著しく
低下する。例えば、特公昭56−41566号や特開平
2−302312号に開示される、高濃度沈殿ケイ酸ス
ラリーを噴霧乾燥する方法で得られる粒状品では、粒子
径が小さく、又嵩比重も低く、造粒品本来の目的である
作業性の改善や貯蔵及び輸送費の改善が不十分であっ
た。By the way, when the precipitated silicic acid powder is used as an elastomer filler, it should be a fine powder having good dispersibility in the elastomer from the viewpoint of reinforcing effect if its performance is considered first. Is desirable. However, various granulation methods have been proposed in order to solve the above-mentioned drawbacks even if the reinforcing performance is somewhat sacrificed. However, when granulated by various granulation methods, when kneaded with rubber, etc. with an open roll, Banbury mixer, etc., the dispersibility of the precipitated silicic acid powder is impaired, the properties of the rubber are determined, abrasion resistance, and tensile strength. Performances such as strength, elongation and impact resilience are significantly reduced. For example, a granular product obtained by a method of spray-drying a high-concentration precipitated silicic acid slurry disclosed in JP-B-56-41566 and JP-A-2-302312 has a small particle size and a low bulk specific gravity, Improvements in workability and storage and transportation costs, which are the original purpose of granules, were insufficient.
【0004】又、特開昭54−110200号には、沈
殿ケイ酸スラリーをフィルタープレスで濾別、洗浄して
得られるフィルターケークに、必要により粉末状沈降珪
酸を混合して、固体含量が28〜40重量%になるよう
に調整し、造粒機で圧縮成形し、乾燥することで顆粒状
のケイ酸を得る方法が記載されている。しかし、沈殿ケ
イ酸のフィルターケークの含水量は一般に約80%であ
り、ケーク単独ではペースト状、更にはスラリーとなり
顆粒状に成形することが困難である。そのため、実際に
は、粉末状沈降珪酸を混合して固体含量を所定範囲に調
整する必要がある。Further, in Japanese Patent Laid-Open No. 54-110200, a filter cake obtained by filtering and washing a precipitated silicic acid slurry with a filter press is mixed with powdered precipitated silicic acid if necessary to obtain a solid content of 28. A method for obtaining granular silicic acid by adjusting the content to be 40% by weight, compression molding with a granulator, and drying is described. However, the water content of the filter cake of precipitated silicic acid is generally about 80%, and it is difficult for the cake alone to be formed into a paste or a slurry into granules. Therefore, in practice, it is necessary to mix powdery precipitated silicic acid to adjust the solid content within a predetermined range.
【0005】本発明者らが、沈殿ケイ酸のフィルターケ
ークに乾燥粉末を混合して含水率を低下させることで顆
粒状に成形し易くする方法を試みたところ、粉末状沈降
珪酸をフィルターケークと均一に混合することは困難で
あった。さらに、この方法により得られた顆粒状のケイ
酸は、ゴムに添加した場合、所望の物性が安定して得ら
れないという問題があった。The inventors of the present invention tried a method of mixing dry powder into a filter cake of precipitated silicic acid to reduce the water content, thereby facilitating molding into a granular form. It was difficult to mix uniformly. Further, the granular silicic acid obtained by this method has a problem that when it is added to rubber, desired physical properties cannot be stably obtained.
【0006】そこで本発明の目的は、ゴムに添加した場
合、微粉体を用いた場合と変わらない物性を有する、顆
粒状の沈殿ケイ酸を提供することにある。さらに詳しく
は、本発明は、ゴムに添加した場合に微粉体を用いた場
合と変わらない物性、即ち、分散性、強度、耐摩耗等が
得られる新規な顆粒状の沈殿ケイ酸及びその製造方法を
提供することにある。Therefore, it is an object of the present invention to provide a granular precipitated silicic acid which has the same physical properties as those when a fine powder is used when added to rubber. More specifically, the present invention provides a novel granular precipitated silicic acid which has the same physical properties as those when a fine powder is used when added to rubber, that is, dispersibility, strength, abrasion resistance and the like, and a method for producing the same. To provide.
【0007】[0007]
【課題を解決するための手段】本発明は、粒子径が50
0μm〜5mmの範囲に入る粒子の占める割合が80重
量%以上であり、且つ粒子硬度が10〜30gfである
ことを特徴とする粒状沈殿ケイ酸に関する。The present invention has a particle size of 50.
The present invention relates to a granular precipitated silicic acid characterized in that the proportion of particles falling within the range of 0 μm to 5 mm is 80% by weight or more and the particle hardness is 10 to 30 gf.
【0008】さらに本発明は、好ましくは、嵩比重が2
50〜500g/リットルの範囲であり、BET比表面
積が100〜300m2 /gの範囲である粒状沈殿ケイ
酸である。Further, the present invention preferably has a bulk specific gravity of 2
It is a granular precipitated silicic acid having a BET specific surface area of 50 to 500 g / liter and a BET specific surface area of 100 to 300 m 2 / g.
【0009】更に本発明は、湿式法沈殿ケイ酸のフィル
ターケークを水分が50〜75%の範囲になるように乾
燥し、次いで得られた沈殿ケイ酸ケークを造粒すること
を特徴とする、前記本発明の粒状沈殿ケイ酸の製造方法
に関する。以下、本発明を更に詳細に説明する。Further, the present invention is characterized in that the wet-process precipitated silica filter cake is dried so that the water content is in the range of 50 to 75%, and then the obtained precipitated silica cake is granulated. The present invention relates to the method for producing granular precipitated silicic acid according to the present invention. Hereinafter, the present invention will be described in more detail.
【0010】本発明の粒状沈殿ケイ酸は、粒子径が50
0μm〜5mmの範囲に入る粒子の占める割合が80重
量%以上である。粒子径が500μm以下の粒状沈殿ケ
イ酸はこれまでも、エラストマー充填剤として使用され
ている。また、更に粒子径の小さい沈殿ケイ酸は、塗
料、特殊紙、フィルム等比較的滑らかな表面状態が求め
られる分野で使用されている。しかし、粒子径が500
μm以上の粒子の占める割合が上記範囲以下では、微粉
が多いために取扱い時に粉塵の発生による作業環境の悪
化が難点とである。それに対して、本発明では粒子径が
小さくとも500μmである粒子が80%以上ある粒状
沈殿ケイ酸であり、ゴム、樹脂等のエラストマー充填剤
としての作業性を改善し、また貯蔵及び輸送費を改善す
るものである。The granular precipitated silica of the present invention has a particle size of 50.
The proportion of particles falling within the range of 0 μm to 5 mm is 80% by weight or more. Granular precipitated silicic acid having a particle diameter of 500 μm or less has been used as an elastomer filler until now. Precipitated silicic acid having a smaller particle size is used in fields such as paints, special papers, and films that require a relatively smooth surface condition. However, the particle size is 500
When the proportion of particles having a size of μm or more is less than the above range, it is difficult to deteriorate the working environment due to the generation of dust during handling because the amount of fine powder is large. On the other hand, the present invention is a granular precipitated silicic acid having 80% or more of particles having a particle size of at least 500 μm, which improves workability as an elastomer filler for rubber, resin, etc., and also reduces storage and transportation costs. It will improve.
【0011】一方、粒子径が5mmを超える粒子径が多
い沈殿ケイ酸では、エラストマー中への充填が限られた
時間で行われる為に分散不良となるという問題が起こ
る。従って、500μm〜5mmの範囲に入る粒子の占
める割合が80重量%以上であることが必要である。本
発明の粒状沈殿ケイ酸は、好ましくは粒子径が500μ
m〜5mmの範囲に入る粒子の占める割合が85重量%
以上である。On the other hand, in the case of precipitated silicic acid having a large particle size of more than 5 mm, the problem arises that the dispersion is poor because the filler is filled in the elastomer for a limited time. Therefore, it is necessary that the proportion of particles falling within the range of 500 μm to 5 mm is 80% by weight or more. The granular precipitated silicic acid of the present invention preferably has a particle size of 500μ.
The proportion of particles within the range of m to 5 mm is 85% by weight.
That is all.
【0012】また、本発明の粒状沈殿ケイ酸は、粒子硬
度が10〜30gfの範囲である。粒子硬度は30gf
以下であれば、実質的にゴム等への分散性が未造粒物と
同等である。また、粒子硬度が30gfを超える沈殿ケ
イ酸は、比較的嵩比重も高く輸送中の粉化も少ないが、
分散性が悪くゴム物性の劣化原因となり、本発明の目的
とする用途分野では使用できない。一方、粒子硬度が1
0gf未満では、ゴム物性への影響は殆どないが、粉化
し易く、取り扱い時に粉塵の発生が多くなり、作業環境
の悪化の原因となる。本発明の粒状沈殿ケイ酸は、粒子
硬度が好ましくは15〜25gfの範囲である。The granular precipitated silicic acid of the present invention has a particle hardness of 10 to 30 gf. Particle hardness is 30gf
When it is below, the dispersibility in rubber or the like is substantially equal to that of the ungranulated product. Further, the precipitated silicic acid having a particle hardness of more than 30 gf has a relatively high bulk specific gravity and little powdering during transportation,
It has poor dispersibility and causes deterioration of the physical properties of rubber, and cannot be used in the intended application field of the present invention. On the other hand, the particle hardness is 1
When it is less than 0 gf, the physical properties of rubber are hardly affected, but it is easily pulverized, and dust is often generated during handling, which causes deterioration of working environment. The granular precipitated silica of the present invention preferably has a particle hardness in the range of 15 to 25 gf.
【0013】本発明の粒状沈殿ケイ酸は、嵩比重が25
0〜500g/リットルの範囲であることが好ましい。
嵩比重が250g/リットル以上である沈殿ケイ酸造粒
物であれば、実質的に粉塵の発生は少なく作業環境は改
善され、さらに、貯蔵や輸送費の点でも優れている。ま
た、嵩比重が500g/リットル以下であれば、エラス
トマー中への分散性も良好に保てるからである。より好
ましい嵩比重は300〜400g/リットルの範囲であ
る。The granular precipitated silica of the present invention has a bulk specific gravity of 25.
It is preferably in the range of 0 to 500 g / liter.
The precipitated silicic acid granulated product having a bulk specific gravity of 250 g / liter or more has substantially no generation of dust, improves the working environment, and is also excellent in storage and transportation costs. Further, if the bulk specific gravity is 500 g / liter or less, the dispersibility in the elastomer can be kept good. A more preferable bulk specific gravity is in the range of 300 to 400 g / liter.
【0014】本発明の粒状沈殿ケイ酸は、BET比表面
積が、特にゴム補強充填剤として補強効果が充分発揮し
得るという観点から、100〜300m2 /gの範囲で
あることが好ましい。好ましくは、BET比表面積は1
50〜250m2 /gの範囲である。The granular precipitated silicic acid of the present invention preferably has a BET specific surface area of 100 to 300 m 2 / g from the viewpoint that the reinforcing effect as a rubber reinforcing filler can be sufficiently exhibited. Preferably, the BET specific surface area is 1
It is in the range of 50 to 250 m 2 / g.
【0015】以下、本発明の粒状沈殿ケイ酸の製造方法
について説明する。湿式法沈殿ケイ酸のフィルターケー
クの水分は一般に約80%である。本発明者らの検討の
結果、このフィルターケークの水分を多くとも75%に
なるように乾燥することによって、フィルターケークが
ペースト状からスラリー状となることなしに造粒が可能
であることを見出した。一方、乾燥したフィルターケー
クの水分が50%未満になると、造粒して得られる粒状
物の粒子硬度が高くなり過ぎ、本発明の所定の範囲の粒
子硬度を有する粒状沈殿ケイ酸が得られなくなる。粒子
硬度が高くなり過ぎるとゴム等への分散が悪く、ゴム本
来の物性である耐摩耗性、引っ張り強度等が劣化する。
フィルターケークの乾燥の程度は、好ましくは70〜6
0%の範囲である。The method for producing the granular precipitated silica of the present invention will be described below. The water content of wet process precipitated silica filter cakes is generally about 80%. As a result of investigations by the present inventors, it was found that by drying the filter cake so that the water content is at most 75%, it is possible to granulate the filter cake from a paste form to a slurry form. It was On the other hand, when the water content of the dried filter cake is less than 50%, the particle hardness of the granules obtained by granulation becomes too high, and the granular precipitated silicic acid having the particle hardness in the predetermined range of the present invention cannot be obtained. . When the particle hardness is too high, the dispersion in rubber or the like is poor and the original physical properties of rubber, such as abrasion resistance and tensile strength, are deteriorated.
The dryness of the filter cake is preferably 70-6.
It is in the range of 0%.
【0016】本発明の方法で用いる湿式法沈殿ケイ酸
は、まずケイ酸アルカリと鉱酸を反応させて得られるも
のである。反応後、得られた沈殿ケイ酸スラリーを濾過
及び洗浄することにより、沈殿ケイ酸フィルターケーク
を得る。沈殿ケイ酸スラリーを得る反応方法は、例えば
ケイ酸ソーダと硫酸とを反応させて微細な水和ケイ酸ス
ラリーを生成させる反応工程までは、特公昭38−17
651号及び特公昭54−25235号等に開示されて
いる公知の方法等と同様な操作により行われるが、望ま
しくは、ケイ酸ナトリウムと硫酸を同時滴下する反応方
法である。また、濾過及び洗浄はフィルタープレスやベ
ルトフィルター等を使用して工業的に大量処理すること
が可能である。The wet method precipitated silicic acid used in the method of the present invention is obtained by first reacting an alkali silicate and a mineral acid. After the reaction, the obtained precipitated silica slurry is filtered and washed to obtain a precipitated silica filter cake. As a reaction method for obtaining a precipitated silicic acid slurry, for example, up to a reaction step of reacting sodium silicate and sulfuric acid to produce a fine hydrated silicic acid slurry, JP-B-38-17 is used.
It is carried out by the same operation as the known method disclosed in Japanese Patent Publication No. 651 and Japanese Patent Publication No. 54-25235, etc., but a reaction method of simultaneously dropping sodium silicate and sulfuric acid is preferable. Further, filtration and washing can be industrially carried out in large quantities by using a filter press, a belt filter or the like.
【0017】得られた沈殿ケイ酸フィルターケークは、
乾燥することにより、所定範囲に含水量を調整する(半
乾燥する)。この乾燥に用いる乾燥機には特に制限はな
いが、例えば、通常の箱型乾燥機等を用いることができ
る。フィルターケークを所定含水量に乾燥するする本発
明の方法は、沈殿ケイ酸ケークに乾燥粉を加えて練り混
む方法や乾燥粉に水を加えて調整する方法に比べ、得ら
れる粒状物をゴムに添加した場合、安定したエラストマ
ー物性を得ることができる。The resulting precipitated silica filter cake is
The water content is adjusted to a predetermined range by drying (semi-drying). The dryer used for this drying is not particularly limited, but, for example, an ordinary box dryer or the like can be used. The method of the present invention for drying the filter cake to a predetermined water content is a method in which dry powder is added to the precipitated silicic acid cake and kneaded, or a method in which water is added to the dry powder to adjust the resulting particulate matter to rubber. When added, stable elastomer physical properties can be obtained.
【0018】所定の水分量に乾燥した沈殿ケイ酸フィル
ターケークは、常法により粒状化することができる。例
えば、水分を調整した沈殿ケイ酸フィルターケークをニ
ーダー等の混合機を通し、更に押出し造粒機を用いて粒
状化し、バンド式乾燥機等の乾燥物に衝撃をあまり与え
ない方法により乾燥することで、本発明の粒状沈殿ケイ
酸を得ることができる。尚、押出し造粒機の場合、成形
孔の板厚は成形孔径と同一又は若干厚い方が、成形物の
形状が良く微粉発生を押さえる点で望ましい。The precipitated silicic acid filter cake dried to a predetermined water content can be granulated by a conventional method. For example, pass the precipitated silicic acid filter cake whose water content is adjusted through a mixer such as a kneader, granulate using an extrusion granulator, and dry by a method that does not give much impact to the dried product such as a band dryer. Thus, the granular precipitated silica of the present invention can be obtained. In the case of an extrusion granulator, it is desirable that the plate thickness of the molding hole is equal to or slightly larger than the diameter of the molding hole in order to improve the shape of the molded product and suppress the generation of fine powder.
【0019】造粒機を通して粒状化した後の乾燥機は、
乾燥物の移動や衝撃が少なく微粉発生の少ない箱型乾燥
機やバンド乾燥又はターボドライヤー等の使用が望まし
い。また乾燥時間は、特開昭54−110200号で示
されているように短時間乾燥ではなく、5〜10時間の
ゆっくりした乾燥時間をとることで、適度な粒子硬度を
示しエラストマー中への分散性の良い粒状品を得ること
ができる。The dryer after granulation through the granulator is
It is desirable to use a box dryer, a band dryer, a turbo dryer or the like, which has less movement and impact of the dried material and less generation of fine powder. The drying time is not a short time drying as shown in JP-A-54-110200, but a slow drying time of 5 to 10 hours is taken to obtain an appropriate particle hardness and to disperse it in the elastomer. A granular product with good properties can be obtained.
【0020】[0020]
【発明の効果】本発明によれば、従来品と同様なエラス
トマー補強効果を有しながら、従来の粉状品での難点で
あった粉塵の発生を抑え、作業環境の改善や、貯蔵タン
クや輸送費用の低減、或いは流動性良好な卓越した新規
な粒状沈殿ケイ酸が得られる。EFFECTS OF THE INVENTION According to the present invention, while having an elastomer reinforcing effect similar to that of the conventional product, generation of dust, which was a difficulty in the conventional powder product, is suppressed, the working environment is improved, and the storage tank and An excellent novel granular precipitated silicic acid with low transportation cost or good fluidity can be obtained.
【0021】[0021]
【実施例】以下、本発明を実施例及び比較例を挙げて更
に具体的に説明する。なお、実施例及び比較例における
粒子径、嵩比重、BET比表面積及び粒子硬度の測定は
次の方法で行った。 (I)粒子径の測定 ロータップ式標準ふるい振とう機(筒井理化学機器
(株)社製)を用いて5mm、500μm網目の篩をセ
ットし、試料100gを入れ5分間振動した後、篩上の
試料重量を測定し、500μm〜5mm範囲の割合を表
した。 (II)嵩比重の測定 JIS K−5101(顔料試験法)に規定するカサ試
験法に準じ測定した。 (Loose Weight法) (III)BET比表面積の測定 カンターソーブ(米国Quantachrome社製)
を用いて1点法により測定した。EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. The particle diameter, bulk specific gravity, BET specific surface area and particle hardness in Examples and Comparative Examples were measured by the following methods. (I) Measurement of particle size Using a low-tap standard sieve shaker (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.), a sieve with a mesh of 5 mm and 500 μm was set, 100 g of a sample was put therein, and the mixture was vibrated for 5 minutes and then on the sieve. The sample weight was measured and the ratio in the range of 500 μm to 5 mm was expressed. (II) Measurement of bulk specific gravity It was measured according to the bulk test method defined in JIS K-5101 (pigment test method). (Loose Weight method) (III) Measurement of BET specific surface area Cantersorb (manufactured by Quantachrome, USA)
Was measured by the one-point method.
【0022】(IV)粒子硬度の測定 JIS K−6221(造粒粒子の硬さ)試験法に準
じ、粒子径1mmの粒子を上皿天秤に乗せ、粒に垂直に
力を加え粒が破壊する時の荷重を読み取る、これを20
点行い、その平均値をもって粒子硬度とし、単位はgf
で表す。 (V)作業時の粉塵性 試料100gをディスポカップに入れ、約30cmの高
さより試料を受け皿にゆっくり注ぎ、その時の粉塵発生
度合いを調べた。粉塵の発生度合いを◎、○、×で表示
した。 (VI)ゴム物性試験 1)加硫ゴム片の目視判定及び加硫物性より、ゴム中の
粒状ケイ酸の分散性(分散均一性)が優れているものは
○、普通のものは△、悪いものは×の判定で表示した。 2)引っ張り強度 JIS K6301の試験法に準じ測定した。 3)耐摩耗性 アクロン型摩耗試験機を用いて、傾角15°、分銅6ポ
ンド、試験回数1000回転での摩耗容積を測定した。(IV) Measurement of particle hardness According to JIS K-6221 (hardness of granulated particles), particles having a particle diameter of 1 mm are placed on an upper balance and a force is applied vertically to the particles to break the particles. Read the load at time, this is 20
The particle hardness is determined by the average value, and the unit is gf.
It is represented by. (V) Dustiness during work 100 g of the sample was put in a disposable cup, the sample was slowly poured into a saucer from a height of about 30 cm, and the degree of dust generation at that time was examined. The degree of dust generation is indicated by ◎, ○, ×. (VI) Rubber physical property test 1) From the visual judgment and vulcanized physical properties of vulcanized rubber pieces, those having excellent dispersibility (dispersion uniformity) of granular silicic acid in the rubber are ◯, ordinary ones are Δ, and poor. The thing was displayed by the judgment of x. 2) Tensile strength Measured according to the JIS K6301 test method. 3) Abrasion resistance Using an Akron type abrasion tester, the abrasion volume was measured at an inclination angle of 15 °, a weight of 6 pounds, and a test frequency of 1000 revolutions.
【0023】実施例1 90℃に加熱した温水17,200mlに、3号ケイ酸
ナトリウム溶液(Na2 O約7%、SiO2 約22%)
637mlを加え攪拌しながら、次いで3号ケイ酸ナト
リウム溶液(前記と同濃度)5,970mlと48%硫
酸約1,200mlを、反応液のpHが9〜11を保つ
ように60分間で同時注加した。更に48%硫酸を注加
して反応液の酸性化を行った。酸性化終了時のpHは約
3.0とした。得られた沈殿ケイ酸スラリーをフィルタ
ープレスで濾別し、温水で充分洗浄を行い湿潤フィルタ
ーケークを得た。この時のケーク水分は80%であっ
た。このフィルターケークを不二パウダル社製ディスク
ペレッター(F−5型)押し出し造粒機を用いて粒状に
成形しようと試みた。しかし、成形時にペースト状、更
にはスラリー状になってしまった。そのまま乾燥する
と、不均一な径の粒子や一つの塊となってしまい、形状
の良い粒子に成形することは困難であった。Example 1 No. 3 sodium silicate solution (about 7% Na 2 O, about 22% SiO 2 ) was added to 17,200 ml of warm water heated to 90 ° C.
While adding 637 ml and stirring, 5,970 ml of No. 3 sodium silicate solution (same concentration as above) and about 1,200 ml of 48% sulfuric acid were simultaneously injected for 60 minutes so as to keep the pH of the reaction solution at 9-11. Added Further, 48% sulfuric acid was added to acidify the reaction solution. The pH at the end of acidification was about 3.0. The obtained precipitated silicic acid slurry was filtered by a filter press and sufficiently washed with warm water to obtain a wet filter cake. The water content of the cake at this time was 80%. An attempt was made to shape this filter cake into particles using a disk pelleter (F-5 type) manufactured by Fuji Paudal Co., Ltd. using an extrusion granulator. However, it became a paste or a slurry during molding. If it is dried as it is, it becomes a particle having a non-uniform diameter or one lump, and it is difficult to form a particle having a good shape.
【0024】そこで、前記方法で得られた水分80%の
フィルターケークを、熱風循環式乾燥機に入れて水分を
70%まで乾燥した。得られたケークを取り出して、不
二パウダル社製ディスクペレッター(F−5型)押出し
造粒機を用いて粒状に形成した後、再度、熱風循環式乾
燥機で水分約5%まで乾燥を行い本発明の粒状沈殿ケイ
酸を得た。Therefore, the filter cake having a water content of 80% obtained by the above method was put into a hot air circulation dryer to dry the water content to 70%. The cake thus obtained was taken out and formed into granules by using a disk pelleter (F-5 type) manufactured by Fuji Paudal Co., Ltd. and granulated, and then dried again with a hot air circulation dryer to a water content of about 5%. Then, granular precipitated silica of the present invention was obtained.
【0025】上記本発明の粒状沈殿ケイ酸50部と固体
状有機ゴムとしてスチレン−ブタジエン共重合体ゴム
(SBR1502:日本合成ゴム社製)100部を配合
し、更に加硫剤として硫黄2.0部、加硫促進剤として
ジフェニルグアニジン(大内新興化学製ノックセラー
D)1.2部、ジベンゾチアジルジスルフィド(大内新
興化学製ノックセラーDM)0.8部、及び加硫助剤と
して酸化亜鉛3部とステアリン酸1部を添加した。更
に、活性剤としてPEG(ポリエチレングリコール)#
4000(第一工業製薬製)2部を添加した。これらを
8インチロールを用いて、練り温度30℃にて混練し
て、ゴム組成物を得た。該ゴム組成物を150℃で10
分間加硫したものについて、ゴム物性試験を行った。こ
の時の製品の物性及びゴム配合試験結果を表1に示す。50 parts of the above-mentioned granular precipitated silicic acid of the present invention and 100 parts of styrene-butadiene copolymer rubber (SBR1502: manufactured by Nippon Synthetic Rubber Co., Ltd.) as a solid organic rubber are compounded, and sulfur of 2.0 is used as a vulcanizing agent. Part, 1.2 parts of diphenylguanidine (Knockceller D manufactured by Ouchi Shinko Chemical Co., Ltd.) as a vulcanization accelerator, 0.8 part of dibenzothiazyl disulfide (Knockceller DM manufactured by Ouchi Shinko Chemical Co., Ltd.), and oxidation as a vulcanization aid 3 parts zinc and 1 part stearic acid were added. Furthermore, as an activator, PEG (polyethylene glycol) #
2 parts of 4000 (Daiichi Kogyo Seiyaku) were added. These were kneaded using an 8-inch roll at a kneading temperature of 30 ° C. to obtain a rubber composition. The rubber composition was heated at 150 ° C for 10
A rubber physical property test was conducted on the vulcanized product for a minute. The physical properties of the product and the results of the rubber compounding test at this time are shown in Table 1.
【0026】実施例2 実施例1と同様な方法で得られた水分80%のフィルタ
ーケークを、熱風循環式乾燥機に入れて水分を52%ま
で乾燥した。得られたケークを取り出して、実施例1と
同様の押出し造粒機を用いて粒状に形成した後、再度熱
風循環式乾燥機で水分約5%まで乾燥を行い本発明の粒
状沈殿ケイ酸を得た。得られた粒状沈殿ケイ酸を用い
て、実施例1と同様にしてゴム組成物を得た。この時の
製品の物性及びゴム配合試験結果を表1に示す。Example 2 A filter cake having a water content of 80% obtained in the same manner as in Example 1 was placed in a hot air circulation dryer to dry the water content to 52%. The cake obtained was taken out and formed into granules using the same extrusion granulator as in Example 1, and then dried again to a moisture content of about 5% with a hot air circulation dryer to obtain the granular precipitated silicic acid of the present invention. Obtained. A rubber composition was obtained in the same manner as in Example 1 using the obtained granular precipitated silicic acid. The physical properties of the product and the results of the rubber compounding test at this time are shown in Table 1.
【0027】比較例1 実施例1と同様な方法で得られた水分80%のフィルタ
ーケークを、軽く解砕した後、熱風循環式乾燥機に入れ
て水分が約5%になるまで乾燥を行い粒状沈殿ケイ酸を
得た。得られた粒状沈殿ケイ酸を用いて、実施例1と同
様にしてゴム組成物を得た。この時の製品の物性及びゴ
ム配合試験結果を表1に示す。Comparative Example 1 A filter cake having a water content of 80% obtained in the same manner as in Example 1 was lightly crushed and then placed in a hot air circulation dryer to dry it until the water content became about 5%. A granular precipitated silicic acid was obtained. A rubber composition was obtained in the same manner as in Example 1 using the obtained granular precipitated silicic acid. The physical properties of the product and the results of the rubber compounding test at this time are shown in Table 1.
【0028】比較例2 実施例1と同様な方法で得られた水分80%のフィルタ
ーケークを、熱風循環式乾燥機で水分40%まで乾燥し
た後、実施例1と同様の押出し造粒機を用いて粒状に形
成した後、再度熱風循環式乾燥機で水分約5%まで乾燥
を行い粒状沈殿ケイ酸を得た。得られた粒状沈殿ケイ酸
を用いて、実施例1と同様にしてゴム組成物を得た。こ
の時の製品の物性及びゴム配合試験結果を表1に示す。Comparative Example 2 A filter cake having a moisture content of 80% obtained in the same manner as in Example 1 was dried to a moisture content of 40% with a hot air circulation dryer, and then the same extrusion granulator as in Example 1 was used. After being used to form particles, it was dried again with a hot air circulation dryer to a water content of about 5% to obtain granular precipitated silicic acid. A rubber composition was obtained in the same manner as in Example 1 using the obtained granular precipitated silicic acid. The physical properties of the product and the results of the rubber compounding test at this time are shown in Table 1.
【0029】[0029]
【表1】 [Table 1]
Claims (4)
る粒子の占める割合が80重量%以上であり、且つ粒子
硬度が10〜30gfであることを特徴とする粒状沈殿
ケイ酸。1. A granular precipitated silicic acid characterized in that the proportion of particles having a particle diameter in the range of 500 μm to 5 mm is 80% by weight or more and the particle hardness is 10 to 30 gf.
範囲である請求項1記載の粒状沈殿ケイ酸。2. The granular precipitated silicic acid according to claim 1, having a bulk specific gravity in the range of 250 to 500 g / liter.
gの範囲である請求項1又は請求項2記載の粒状沈殿ケ
イ酸。3. A BET specific surface area of 100 to 300 m 2 /
The granular precipitated silicic acid according to claim 1 or 2, which is in the range of g.
水分が50〜75%の範囲になるように乾燥し、次いで
得られた沈殿ケイ酸ケークを造粒することを特徴とす
る、請求項1記載の粒状沈殿ケイ酸の製造方法。4. The wet precipitated silicic acid filter cake is dried so that the water content is in the range of 50 to 75%, and the obtained precipitated silicic acid cake is then granulated. A method for producing the granular precipitated silicic acid described.
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