JPH07223810A - Particulate precipitated silicic acid and production thereof - Google Patents
Particulate precipitated silicic acid and production thereofInfo
- Publication number
- JPH07223810A JPH07223810A JP1837594A JP1837594A JPH07223810A JP H07223810 A JPH07223810 A JP H07223810A JP 1837594 A JP1837594 A JP 1837594A JP 1837594 A JP1837594 A JP 1837594A JP H07223810 A JPH07223810 A JP H07223810A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- precipitated silicic
- suspension
- granular
- range
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Glanulating (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な顆粒状沈殿ケイ
酸に関する。特に、本発明は、ゴム、プラスチック、樹
脂、歯磨き等の充填剤に適した比較的大きな粒子径を有
し、しかも高い強度を有しており、粉化しにくい新規な
顆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 silicic acid. In particular, the present invention has a relatively large particle size suitable for a filler such as rubber, plastic, resin, toothpaste, etc., and also has high strength, and a novel granular precipitated silicic acid that is difficult to pulverize and its A manufacturing method is provided.
【０００２】[0002]
【従来の技術】ケイ酸アルカリと鉱酸を原料とするケイ
酸の製法には大きく分類すると、アルカリ性で反応させ
ケイ酸を沈殿させる沈殿法と、酸性で反応させ中間体と
してヒドロゲルを得るゲル法とがある。ゲル法により得
られるケイ酸は、一般的に硬く、乾燥剤、分離剤、塗料
の艶消し剤等として使用されている。一方、沈殿ケイ酸
は、一般的に柔らかく、表面活性を有す無味無臭で白色
度の高い粉末であり、ゴム補強充填剤をはじめ農薬、塗
料、樹脂、情報用紙、歯磨き、食品添加等様々な分野に
使用されている。2. Description of the Related Art The methods for producing silicic acid using alkali silicates and mineral acids as raw materials can be broadly classified into a precipitation method of reacting with alkali to precipitate silicic acid and a gel method of reacting with acid to obtain a hydrogel as an intermediate. There is. The silicic acid obtained by the gel method is generally hard and is used as a desiccant, a separating agent, a delustering agent for paints, and the like. On the other hand, precipitated silicic acid is generally a soft, surface-active, tasteless, odorless, and highly white powder, and is used for various purposes such as rubber-reinforcing fillers, agricultural chemicals, paints, resins, information paper, toothpaste, food additives, etc. Used in the field.
【０００３】[0003]
【発明が解決しようとする課題】ところで、用途の多様
化と新たな物性への要求から、これまでより粒子径が大
きい沈殿ケイ酸に対するニーズが出てきている。例え
ば、化粧品や歯磨き等では、これまでより粒子径が大き
い沈殿ケイ酸を用いて肌ざわりや触感等を向上させたい
という要望がある。また、ゴム、プラスチック、樹脂等
の充填剤としての分野では、これまでより粒子径が大き
い沈殿ケイ酸を用いることで、沈殿ケイ酸をゴム等へ添
加する際の作業性を改善したいという要望もある。By the way, due to diversification of applications and demands for new physical properties, there is a need for precipitated silicic acid having a larger particle diameter than ever before. For example, in cosmetics, toothpaste, etc., there is a demand to improve the texture and feel by using precipitated silicic acid having a larger particle size than ever before. Further, in the field of fillers for rubber, plastics, resins, etc., there is also a desire to improve workability when adding precipitated silicic acid to rubber etc. by using precipitated silicic acid having a larger particle size than ever before. is there.
【０００４】それに対して、これまで市販されている沈
殿ケイ酸の粒子径は、平均粒子径で、一般に１〜５０μ
ｍ程度である。しかし、粒子径がさらに大きい沈殿ケイ
酸を得ることを目的とした技術を開示する文献等も実質
的にない。但し、本来、粒子径の大きい沈殿ケイ酸を得
ることを目的とするものではないが、例えば、特公昭６
２−３２１２９号や特開昭６２−１５３１１３号に開示
されている方法によれば、比較的大きな粒子径の沈殿ケ
イ酸を製造することができることは知られている。これ
らの方法は、水和ケイ酸を濾別した湿潤ケーキを水に分
散させてスラリーとし、このスラリーに炭酸ナトリウム
又は酢酸ナトリウム等の弱アルカリ性化合物を添加し
て、噴霧乾燥して塩基性の沈殿ケイ酸を得るものであ
る。On the other hand, the particle size of the precipitated silicic acid commercially available so far is generally 1 to 50 μm in terms of average particle size.
It is about m. However, there are substantially no documents disclosing a technique aiming at obtaining precipitated silicic acid having a larger particle size. However, although it is not intended to obtain precipitated silicic acid having a large particle size, for example, Japanese Patent Publication 6
It is known that the precipitated silicic acid having a relatively large particle size can be produced by the method disclosed in JP-A-2-32129 or JP-A-62-153113. In these methods, a wet cake obtained by filtering out hydrated silicic acid is dispersed in water to form a slurry, and a weak alkaline compound such as sodium carbonate or sodium acetate is added to the slurry, followed by spray drying to form a basic precipitate. This is to obtain silicic acid.
【０００５】そこで、本発明者は、粒子径の大きい沈殿
ケイ酸を得ることを目的として、上記特公昭６２−３２
１２９号や特開昭６２−１５３１１３号に開示された方
法について検討した。その結果、上記方法により、ある
程度大きい粒子径を有する沈殿ケイ酸が得られることが
分かった。ところが、得られた沈殿ケイ酸を、例えばゴ
ム等に添加しようとする場合、ハンドリングの最中に粒
子が破壊されて粉化してしまう傾向があることが判明し
た。また、化粧品や歯磨き等の分野で使用する場合、肌
触りや触感が不十分であることも分かった。さらに、こ
れらの沈殿ケイ酸中には、炭酸ナトリウムや酢酸ナトリ
ウム等の不純物が混在することも、用途によっては問題
となることも判明した。Therefore, the present inventor has aimed to obtain precipitated silicic acid having a large particle size, and the above Japanese Patent Publication No. 62-32 has been proposed.
The methods disclosed in JP-A No. 129 and JP-A No. 62-153113 were examined. As a result, it was found that precipitated silica having a particle size to some extent can be obtained by the above method. However, when it was attempted to add the obtained precipitated silicic acid to rubber or the like, it was found that particles tend to be broken and pulverized during handling. It was also found that when used in the fields of cosmetics and toothpaste, the touch and feel were insufficient. Furthermore, it has been found that impurities such as sodium carbonate and sodium acetate are mixed in these precipitated silicic acids, which poses a problem depending on the application.
【０００６】そこで本発明の目的は、比較的大きな粒子
径を有し、かつ取扱い中に粉化せず、また適当な肌触り
や触感を有する顆粒状沈殿ケイ酸及びその製造方法を提
供することにある。[0006] Therefore, an object of the present invention is to provide a granular precipitated silicic acid having a relatively large particle size, which does not powder during handling, and which has an appropriate texture and feel, and a method for producing the same. is there.
【０００７】[0007]
【課題を解決するための手段】本発明は、重量換算で６
０％以上の粒子の粒子径が７５〜２５０μｍの範囲にあ
り、かつ粒子強度が０．１〜０．３ｋｇｆ／ｍｍ2 の範
囲であることを特徴とする顆粒状沈殿ケイ酸に関する。The present invention has a weight conversion of 6
The present invention relates to a granular precipitated silicic acid characterized in that 0% or more of particles have a particle diameter in the range of 75 to 250 μm and a particle strength of 0.1 to 0.3 kgf / mm 2 .
【０００８】さらに本発明は、沈殿ケイ酸の懸濁液に水
酸化ナトリウム又はケイ酸ナトリウムを添加して、前記
懸濁液のｐＨを８．５〜１１．５の範囲に調整し、得ら
れた懸濁液を噴霧乾燥することを特徴とする前記の顆粒
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 obtained by adding sodium hydroxide or sodium silicate to a suspension of precipitated silicic acid to adjust the pH of the suspension to a range of 8.5 to 11.5. The above-mentioned method for producing granular precipitated silicic acid, which comprises spray-drying the suspension. Hereinafter, the present invention will be described in more detail.
【０００９】本発明の沈殿ケイ酸は、重量換算で６０％
以上の粒子の粒子径が７５〜２５０μｍの範囲にある。
粒子径が７５μｍ以下の沈殿ケイ酸は、これまでも、塗
料、特殊紙、フィルム等の表面の状態が比較的なめらか
であることが求められるような分野で使用されている。
それに対して、本発明では、粒子径が小さくとも７５μ
ｍである粒子が６０％以上である沈殿ケイ酸は、これま
でに知られていないことであるが、例えば、化粧品や歯
磨きに新たな肌ざわりや触感等を提供することができ、
或いはゴム、プラスチック、樹脂等の充填剤としての作
業性を改善するものであることを見出した。特に、粒子
径が小さくとも７５μｍである粒子が７０％以上である
沈殿ケイ酸は、上記のような効果を得るのに適してい
る。一方、粒子径が２５０μｍを超える粒子が６０％以
上である沈殿ケイ酸では、ザラ付きが酷くなるという問
題がある。尚、本発明において粒子径は、後述のように
ロータップ式標準ふるい振とう機を用いて、２５０、２
００、１５０、１０５、７５μｍ網目の篩をセットし、
試料５０ｇを入れ１０分間振動した後、各篩上の試料重
量を測定することで求められる。The precipitated silicic acid of the present invention has a weight conversion of 60%.
The particle diameter of the above particles is in the range of 75 to 250 μm.
Precipitated silicic acid having a particle size of 75 μm or less has been used in the field where paints, special papers, films and the like are required to have comparatively smooth surfaces.
On the other hand, in the present invention, even if the particle size is small,
Precipitated silicic acid having particles of m of 60% or more is not known so far, but for example, it can provide a new feel and touch to cosmetics and toothpaste,
It has also been found that it improves workability as a filler for rubber, plastics, resins and the like. In particular, precipitated silicic acid having 70% or more of particles having a particle size of 75 μm at the smallest is suitable for obtaining the above effects. On the other hand, precipitated silica having 60% or more of particles having a particle diameter of more than 250 μm has a problem of roughening. In the present invention, the particle size is 250, 2 using a low-tap standard sieve shaker as described below.
Set a sieve of 00, 150, 105, 75 μm mesh,
It is determined by adding 50 g of a sample and shaking for 10 minutes, and then measuring the sample weight on each sieve.
【００１０】さらに、本発明の沈殿ケイ酸は、粒子強度
が０．１〜０．３ｋｇｆ／ｍｍ2 の範囲である。粒子強
度は０．１ｋｇｆ／ｍｍ2 以上であれば、実質的に、取
扱い中に粉化することがない。また、粒子強度が０．３
ｋｇｆ／ｍｍ2 を超える沈殿ケイ酸は、より粉化しにく
くなるが、石粉やシリカゲルのように硬くなり過ぎて、
本発明の目的とする用途分野では使用できない。さら
に、上記範囲であれば、これまでに知られていないこと
であるが、例えば、化粧品や歯磨きに新たな肌ざわりや
触感等を提供することもできる。尚、本発明における沈
殿ケイ酸の粒子強度の測定は、微小圧縮試験機（例え
ば、島津製作所社製／ＭＣＴＭ−２型）を用いて粒子強
度を測定することにより行われる。Further, the precipitated silica of the present invention has a particle strength in the range of 0.1 to 0.3 kgf / mm 2 . When the particle strength is 0.1 kgf / mm 2 or more, there is substantially no pulverization during handling. Also, the particle strength is 0.3
Precipitated silicic acid exceeding kgf / mm 2 is more difficult to pulverize, but it becomes too hard like stone powder and silica gel,
It cannot be used in the field of application for which the invention is intended. Further, within the above range, although not known so far, for example, it is possible to provide a new texture and feel to cosmetics and toothpaste. The particle strength of the precipitated silicic acid in the present invention is measured by measuring the particle strength with a micro compression tester (for example, Shimadzu Corporation / MCTM-2 type).
【００１１】本発明の沈殿ケイ酸は、粒子径が７５〜２
５０μｍの範囲にある粒子が全体の６０％以下で、かつ
嵩比重が１５０〜３００ｇ／ｌの範囲のものがより好ま
しい。嵩比重は、粒子径が７５〜２５０μｍの範囲外に
ある粒子の量をある程度規定するものである。嵩比重を
１５０ｇ／ｌ以上とすることで、粒子径小さな粒子の含
有量を抑え、粒子径を大きくしたことの効果をより発揮
し易いものとなる。また、嵩比重が３００ｇ／ｌを超え
る沈殿ケイ酸は、２５０μｍを超える粒子の含有量が多
くなり過ぎて、ザラ付きがひどくなるので、上記の用途
での使用には適さなくなる傾向がある。The precipitated silicic acid of the present invention has a particle size of 75 to 2
It is more preferable that the particles in the range of 50 μm account for 60% or less of the whole and the bulk specific gravity is in the range of 150 to 300 g / l. The bulk specific gravity defines the amount of particles having a particle diameter outside the range of 75 to 250 μm to some extent. By setting the bulk specific gravity to 150 g / l or more, the content of particles having a small particle size can be suppressed and the effect of increasing the particle size can be more easily exhibited. Further, precipitated silicic acid having a bulk specific gravity of more than 300 g / l has an excessively large content of particles having a bulk density of more than 250 μm, resulting in severe graininess, and thus tends to be unsuitable for use in the above applications.
【００１２】本発明の沈殿ケイ酸は、水酸化ナトリウム
又はケイ酸ナトリウムを添加することで、粒子の強度を
向上させたものである。従って、一定量以上の水酸化ナ
トリウム又はケイ酸ナトリウムが沈殿ケイ酸中に存在す
る。その目安として、４％懸濁液としたときのｐＨを用
いることができ、このｐＨが８．５以上のものであれ
ば、上記範囲の粒子強度を得ることができる。また、水
酸化ナトリウム又はケイ酸ナトリウムの添加量が多くな
り過ぎると、沈殿ケイ酸の溶解が起こり、沈殿ケイ酸の
物性を著しく変化させる原因ともなる。そこで、４％懸
濁液としたときのｐＨは１１．５以下であることが好ま
しい。The precipitated silicic acid of the present invention has improved particle strength by adding sodium hydroxide or sodium silicate. Therefore, a certain amount or more of sodium hydroxide or sodium silicate is present in the precipitated silicic acid. As a guideline, the pH of a 4% suspension can be used, and if the pH is 8.5 or more, the particle strength in the above range can be obtained. Further, if the amount of sodium hydroxide or sodium silicate added is too large, the precipitated silicic acid will be dissolved, which may cause a significant change in the physical properties of the precipitated silicic acid. Therefore, the pH of a 4% suspension is preferably 11.5 or less.
【００１３】以下、本発明の顆粒状沈殿ケイ酸の製造方
法について説明する。本発明の顆粒状沈殿ケイ酸は、沈
殿ケイ酸の懸濁液に水酸化ナトリウム又はケイ酸ナトリ
ウムを添加して、前記懸濁液のｐＨを８．５〜１１．５
の範囲に調整し、得られた懸濁液を噴霧乾燥することで
製造できる。原料として用いる沈殿ケイ酸には特に制限
はない。以下に一般的な沈殿ケイ酸の製造方法について
説明する。反応原料であるケイ酸アルカリとしては、一
般にケイ酸ナトリウムが使用され、該ケイ酸ナトリウム
はＳｉＯ2 ／Ｎａ2 Ｏのモル比が２．０〜４．０を用い
るのが好適である。また鉱酸としては硫酸又は塩酸を用
いるのが好適である。反応槽に温水とケイ酸ナトリウム
溶液を入れ、続いて該反応槽内の温度とｐＨが一定にな
るようにコントロールを行ないながら硫酸とケイ酸ナト
リウム溶液を所定時間で加える方法により水和沈殿ケイ
酸スラリーを得る。該水和沈殿ケイ酸スラリーを濾過及
び水洗を行ない湿潤ケーキとする。The method for producing the granular precipitated silica of the present invention will be described below. The granular precipitated silicic acid of the present invention is prepared by adding sodium hydroxide or sodium silicate to a suspension of precipitated silicic acid to adjust the pH of the suspension to 8.5 to 11.5.
It can be manufactured by adjusting the range to, and spray-drying the obtained suspension. The precipitated silicic acid used as a raw material is not particularly limited. Hereinafter, a general method for producing precipitated silicic acid will be described. Sodium silicate is generally used as the alkali silicate which is a reaction raw material, and it is preferable that the sodium silicate has a SiO 2 / Na 2 O molar ratio of 2.0 to 4.0. It is preferable to use sulfuric acid or hydrochloric acid as the mineral acid. A hydrated precipitated silicic acid is prepared by adding warm water and a sodium silicate solution to a reaction tank, and then adding sulfuric acid and a sodium silicate solution for a predetermined time while controlling the temperature and pH in the reaction tank to be constant. Obtain a slurry. The hydrated precipitated silicic acid slurry is filtered and washed with water to obtain a wet cake.
【００１４】上記で得られた湿潤ケーキを水に分散させ
てスラリー化することで、沈殿ケイ酸の懸濁液を得るこ
とができる。本発明では、この懸濁液にケイ酸ナトリウ
ム又は水酸化ナトリウムを加えて懸濁液のｐＨを８．５
〜１１．５の範囲に調整する。ｐＨ調整前の懸濁液のｐ
Ｈは、前記の水和沈殿ケイ酸の反応時の鉱酸の使用量等
により異なり、従って、一般に、一定量のケイ酸ナトリ
ウム又は水酸化ナトリウムを添加することで、所望のｐ
Ｈに調整することは難しい。従って、沈殿ケイ酸の懸濁
液を十分に攪拌しながら、懸濁液のｐＨをモニターしな
がら、ケイ酸ナトリウム又は水酸化ナトリウムを添加し
て、所望のｐＨの懸濁液を得る。尚、ケイ酸ナトリウム
又は水酸化ナトリウムの代わりに、炭酸ナトリウムや酢
酸ナトリウムを用いることでも懸濁液のｐＨを上記の範
囲に調整することはできる。しかし、炭酸ナトリウムや
酢酸ナトリウムを用いて、所定の範囲に設定した懸濁液
を用いたのでは、本発明の顆粒状沈殿ケイ酸を得ること
はできない。A suspension of precipitated silicic acid can be obtained by dispersing the wet cake obtained above in water to form a slurry. In the present invention, sodium silicate or sodium hydroxide is added to this suspension to adjust the pH of the suspension to 8.5.
Adjust to a range of ~ 11.5. p of the suspension before pH adjustment
H varies depending on the amount of mineral acid used during the reaction of the hydrated precipitated silicic acid, etc., and therefore, in general, the addition of a fixed amount of sodium silicate or sodium hydroxide will reduce the desired p
It is difficult to adjust to H. Therefore, sodium silicate or sodium hydroxide is added with sufficient stirring of the suspension of precipitated silicic acid while monitoring the pH of the suspension to obtain a suspension of the desired pH. The pH of the suspension can be adjusted within the above range by using sodium carbonate or sodium acetate instead of sodium silicate or sodium hydroxide. However, if a suspension in which sodium carbonate or sodium acetate is set in a predetermined range is used, the granular precipitated silicic acid of the present invention cannot be obtained.
【００１５】水酸化ナトリウム又はケイ酸ナトリウムの
添加による懸濁液のｐＨが８．５未満の場合、所望の粒
子強度を有する顆粒状沈殿ケイ酸を得ることはできな
い。また、添加量が多くなりすぎてｐＨが１１．５を超
えるような場合は、沈殿ケイ酸の溶解が始まり、本発明
の顆粒状沈殿ケイ酸を得ることはできない。尚、水和沈
殿ケイ酸スラリーを得る際に、反応用の鉱酸の量を少な
くし、反応終了時にスラリー液のｐＨを高く維持するこ
とで、沈殿ケイ酸の懸濁液のｐＨを８．５以上とするこ
も可能ではある。しかるに、このようにして得られる所
定範囲のｐＨを示す沈殿ケイ酸懸濁液を本発明と同様に
乾燥しても、本発明の顆粒状沈殿ケイ酸と同様の粒子強
度を有するものは得られない。If the pH of the suspension by addition of sodium hydroxide or sodium silicate is below 8.5, it is not possible to obtain granular precipitated silicic acid with the desired particle strength. Further, when the amount added is too large and the pH exceeds 11.5, the precipitated silicic acid begins to dissolve and the granular precipitated silicic acid of the present invention cannot be obtained. When the hydrated precipitated silicic acid slurry is obtained, the amount of the mineral acid for reaction is reduced and the pH of the slurry liquid is maintained high at the end of the reaction so that the pH of the suspension of precipitated silicic acid is 8. It is possible to set it to 5 or more. However, even if the thus-obtained precipitated silicic acid suspension having a pH within a predetermined range is dried in the same manner as in the present invention, a suspension having the same particle strength as the granular precipitated silicic acid of the present invention can be obtained. Absent.
【００１６】本発明の製造方法において、使用する沈殿
ケイ酸は、ＢＥＴ比表面積を１５０〜４００ｍ2 ／ｇの
範囲になるように反応段階で調整することが好ましい。
ＢＥＴ比表面積を１５０ｍ2 ／ｇ以上とすることで、比
較的少ない水酸化ナトリウム又はケイ酸ナトリウムの添
加量で、所望の粒子強度を有する顆粒状沈殿ケイ酸を得
ることができる。一方、ＢＥＴ比表面積が大きくなると
高濃度の沈殿ケイ酸懸濁液を得ることが難しくなる傾向
がある。そこで、ＢＥＴ比表面積は４００ｍ2／ｇ以下
とすることが好ましい。In the production method of the present invention, the precipitated silicic acid used is preferably adjusted in the reaction stage so that the BET specific surface area is in the range of 150 to 400 m 2 / g.
By setting the BET specific surface area to 150 m 2 / g or more, a granular precipitated silicic acid having a desired particle strength can be obtained with a relatively small amount of sodium hydroxide or sodium silicate added. On the other hand, when the BET specific surface area becomes large, it tends to be difficult to obtain a highly concentrated precipitated silica suspension. Therefore, the BET specific surface area is preferably 400 m 2 / g or less.
【００１７】上記のｐＨに調整した沈殿ケイ酸懸濁液を
噴霧乾燥することで、顆粒状沈殿ケイ酸を得る。顆粒状
沈殿ケイ酸を得るためには、静置乾燥のようにゆっくり
乾燥する方法よりも噴霧乾燥する方法が適している。噴
霧乾燥には、公知の噴霧乾燥機を用いることができ、噴
霧としては、ノズル式、ディスク式等を挙げることがで
き、特に、ノズル式の噴霧乾燥機を用いることが好まし
い。ノズル式の噴霧乾燥機の場合、噴霧ノズル径をコン
トロールすることにより、粒子径をコントロールするこ
とができる。従って、本発明の顆粒状沈殿ケイ酸を得る
にはノズル径の比較的大きなものを使用することが望ま
しい。また、顆粒状沈殿ケイ酸は、噴霧乾燥する懸濁液
のスラリー濃度により、粒子径を変化させることもでき
る。所望の粒子径の顆粒状沈殿ケイ酸を得るには、例え
ば１５０〜２５０ｇ／ｌのスラリー濃度とすることが適
当である。特に、ＢＥＴ比表面積が１５０〜４００ｍ2
／ｇの沈殿ケイ酸の懸濁液を用い、かつスラリー濃度を
１５０〜２５０ｇ／ｌに調整した懸濁液を噴霧乾燥する
ことで、所望の粒子径を有する顆粒状沈殿ケイ酸を得る
ことができる。The precipitated silicic acid suspension adjusted to the above pH is spray-dried to obtain granular precipitated silicic acid. In order to obtain granular precipitated silicic acid, a spray drying method is more suitable than a slow drying method such as static drying. A well-known spray dryer can be used for the spray drying, and examples of the spray include a nozzle type and a disk type, and it is particularly preferable to use a nozzle type spray dryer. In the case of a nozzle type spray dryer, the particle size can be controlled by controlling the spray nozzle diameter. Therefore, in order to obtain the granular precipitated silicic acid of the present invention, it is desirable to use one having a relatively large nozzle diameter. Further, the particle size of the granular precipitated silicic acid can be changed depending on the slurry concentration of the suspension to be dried by spraying. In order to obtain granular precipitated silicic acid having a desired particle size, it is suitable to have a slurry concentration of, for example, 150 to 250 g / l. Particularly, the BET specific surface area is 150 to 400 m 2.
A granular precipitated silica having a desired particle size can be obtained by using a suspension of precipitated silica / g / g and spray-drying the suspension having a slurry concentration adjusted to 150 to 250 g / l. it can.
【００１８】[0018]
【実施例】以下、本発明を実施例及び比較例を挙げてさ
らに説明する。なお、実施例及び比較例における嵩比
重、粒子径、ｐＨ、粒子強度の測定は次の方法で行っ
た。EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples. The bulk specific gravity, particle size, pH, and particle strength in Examples and Comparative Examples were measured by the following methods.
【００１９】（Ｉ）嵩比重の測定 ＪＩＳＫ５１０１（顔料試験法）の１８に規定するカサ
試験法に準じ測定した。 （II）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、２５０、２００、１５０、１０
５、７５μｍ網目の篩をセットし、試料５０ｇを入れ１
０分間振動した後、各篩上の試料重量を測定し、７５〜
２５０μｍ範囲の割合を表した。(I) Measurement of Bulk Specific Gravity The bulk specific gravity was measured according to the bulk test method specified in 18 of JIS K5101 (pigment test method). (II) Measurement of particle size 250, 200, 150, 10 using a low-tap standard sieve shaker (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.)
Set the sieve of 5,75μm mesh, put 50g of sample and put 1
After oscillating for 0 minutes, the sample weight on each sieve was measured,
The ratio in the 250 μm range is shown.
【００２０】（III)ｐＨの測定 ａ）スラリー液のｐＨ スラリー１００ｍｌをビーカーに採り、その濃度でガラ
ス電極ｐＨメーターで測定した。 ｂ）製品のｐＨ ｐＨ７の調整水５０ｍｌに試料２ｇを加え、５分間混合
後ガラス電極ｐＨメーターで測定した。 （IV) 粒子強度の測定 微小圧縮試験機（島津製作所社製／ＭＣＴＭ−２型）を
用いて粒子強度を測定した。 （Ｖ) 粉化の程度 沈殿ケイ酸試料を親指と人指し指との間でこすりつけ、
以下の基準に従って粉化の程度を評価した。 ◎：ころがり性が持続し、粉化されない。 ○：一部の粒子だ壊れるが、顆粒状と感じる。 ×：粒子が破壊され、粒子が認められなくなる。(III) Measurement of pH a) pH of slurry liquid 100 ml of the slurry was placed in a beaker and the concentration was measured with a glass electrode pH meter. b) pH of the product 2 g of the sample was added to 50 ml of adjusted pH 7 water, mixed for 5 minutes, and measured with a glass electrode pH meter. (IV) Measurement of particle strength The particle strength was measured using a micro compression tester (manufactured by Shimadzu Corporation / MCTM-2 type). (V) Degree of pulverization Rub the precipitated silicic acid sample between your thumb and forefinger,
The degree of pulverization was evaluated according to the following criteria. ⊚: Rolling property continues and is not pulverized. ◯: Some particles are broken but feel like granules. X: The particles are destroyed and the particles are no longer recognized.
【００２１】実施例１〜３及び比較例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（前記濃度と同じ）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。得られた沈殿物を濾別し、温水で充分
洗浄を行ない湿潤ケーキを得た。該湿潤ケーキを水に分
散させ、スラリー液濃度が約１８０ｇ／ｌになるように
スラリー液を作った。次に該スラリー液へ３号ケイ酸ナ
トリウム溶液（Ｎａ2 Ｏ約４％、ＳｉＯ2 約１３％）を
注加した。注加量はスラリー液中の固形分に対して、ケ
イ酸ナトリウム溶液中のＮａ2 Ｏ量で１．３％、１．６
％、１．９％を各々注加し２時間攪拌後スラリー液のｐ
Ｈを測定した後、ノズル式噴霧乾燥機を用いて乾燥を行
ない顆粒状沈殿ケイ酸を得た。比較例１はケイ酸ナトリ
ウム未添加のものである。この製品の測定結果を表１に
示した。Examples 1 to 3 and Comparative Example 1 Sodium No. 3 silicate solution (about 7% Na 2 O and about 22% SiO 2 ) was added to 17,200 ml of warm water heated to 90 ° C.
Add 637 ml and stir, then add 5,970 ml of No. 3 sodium silicate solution (same as the above concentration) and 48%.
About 1,200 ml of sulfuric acid was co-injected for 60 minutes so that the pH of the reaction solution was kept at 9-11. Further, 48% sulfuric acid was added to acidify the reaction solution. The pH at the end of acidification was about 3.0. The obtained precipitate was separated by filtration and sufficiently washed with warm water to obtain a wet cake. The wet cake was dispersed in water to prepare a slurry liquid having a slurry liquid concentration of about 180 g / l. Next, a No. 3 sodium silicate solution (Na 2 O about 4%, SiO 2 about 13%) was added to the slurry liquid. The amount added was 1.3% or 1.6% of Na 2 O in the sodium silicate solution with respect to the solid content in the slurry liquid.
% And 1.9% were added and stirred for 2 hours, then p
After measuring H, it was dried using a nozzle type spray dryer to obtain granular precipitated silicic acid. Comparative Example 1 is one in which sodium silicate was not added. The measurement results of this product are shown in Table 1.
【００２２】実施例４〜６及び比較例２ ６０℃に加熱した温水１７，９００ｍｌに、３号ケイ酸
ナトリウム溶液（Ｎａ2 Ｏ約７％、ＳｉＯ2 約２２％）
１３０ｍｌを加え攪拌しながら、次いで３号ケイ酸ナト
リウム溶液（前記濃度と同じ）５，７７０ｍｌ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。得られた沈殿物を濾別し、温水で充分
洗浄を行ない湿潤ケーキを得た。該湿潤ケーキを水に分
散させ、スラリー液濃度が約１５０ｇ／ｌになるように
スラリー液を作った。次に該スラリー液中へ水酸化ナト
リウム水溶液を注加した。注加量はスラリー液中の固形
分に対して、水酸化ナトリウム溶液中のＮａ2 Ｏ量で
０．６％、１．１％、１．６％を各々注加し２時間攪拌
後スラリー液のｐＨを測定した後、ノズル式噴霧乾燥機
を用いて乾燥を行ない顆粒状沈殿ケイ酸を得た。比較例
２はケイ酸ナトリウム未添加のものである。この製品の
測定結果を表１に示した。Examples 4 to 6 and Comparative Example 2 Sodium silicate solution No. 3 (Na 2 O about 7%, SiO 2 about 22%) was added to 17,900 ml of warm water heated to 60 ° C.
While adding 130 ml and stirring, No. 3 sodium silicate solution (same as the above concentration) 5,770 ml and 48%
About 1,200 ml of sulfuric acid was co-injected for 60 minutes so that the pH of the reaction solution was kept at 9-11. Further, 48% sulfuric acid was added to acidify the reaction solution. The pH at the end of acidification was about 3.0. The obtained precipitate was separated by filtration and sufficiently washed with warm water to obtain a wet cake. The wet cake was dispersed in water to prepare a slurry liquid having a slurry liquid concentration of about 150 g / l. Next, an aqueous sodium hydroxide solution was poured into the slurry liquid. The amount of Na 2 O in the sodium hydroxide solution was 0.6%, 1.1% and 1.6%, respectively, relative to the solid content in the slurry liquid, and the slurry liquid was stirred for 2 hours. After the pH was measured, it was dried using a nozzle type spray dryer to obtain granular precipitated silicic acid. Comparative Example 2 is one in which sodium silicate was not added. The measurement results of this product are shown in Table 1.
【００２３】比較例３〜４ 実施例１〜３と同様な反応方法で得た湿潤ケーキを水に
分散させ、スラリー液濃度が約１８０ｇ／ｌになるよう
にスラリー液を作った。該スラリー液中へ１０％炭酸ナ
トリウム水溶液をスラリー液中の固形分に対して、Ｎａ
2 ＣＯ3 量で２％、６％各々注加し、２時間攪拌後スラ
リー液ｐＨを測定し、ノズル式噴霧乾燥機を用いて乾燥
を行ない顆粒状沈殿ケイ酸を得た。この製品の測定結果
を表１に示した。Comparative Examples 3 to 4 The wet cake obtained by the same reaction method as in Examples 1 to 3 was dispersed in water to prepare a slurry liquid having a slurry liquid concentration of about 180 g / l. An aqueous solution of 10% sodium carbonate was added to the slurry liquid with respect to the solid content in the slurry liquid.
2 % and 6% of 2 CO 3 respectively were added, and after stirring for 2 hours, the pH of the slurry liquid was measured and dried using a nozzle type spray dryer to obtain granular precipitated silicic acid. The measurement results of this product are shown in Table 1.
【００２４】比較例５ ９０℃に加熱した温水１６，０００ｍｌに、３号ケイ酸
ナトリウム溶液（Ｎａ2 Ｏ約７％、ＳｉＯ2 約２２％）
３５５ｍｌを加え攪拌しながら、次いで３号ケイ酸ナト
リウム溶液（前記濃度と同じ）７，１００ｍｌと４８％
硫酸約１，４００ｍｌ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。同時注加終了後、硫
酸の添加を行わずに沈殿物を濾別し、温水で充分洗浄を
行ない湿潤ケーキを得た。該湿潤ケーキを水に分散さ
せ、スラリー液濃度が約１５０ｇ／ｌになるようにスラ
リー液を作った。スラリー液のｐＨを測定した後、ノズ
ル式噴霧乾燥機を用いて乾燥を行ない顆粒状沈殿ケイ酸
を得た。この製品の測定結果を表１に示した。Comparative Example 5 No. 3 sodium silicate solution (Na 2 O about 7%, SiO 2 about 22%) was added to 16,000 ml of warm water heated to 90 ° C.
355 ml was added and stirred, and then No. 3 sodium silicate solution (same as the above concentration) 7,100 ml and 48%
About 1,400 ml of sulfuric acid was co-injected for 60 minutes so that the pH of the reaction solution was kept at 9-11. After completion of the simultaneous injection, the precipitate was filtered off without adding sulfuric acid and sufficiently washed with warm water to obtain a wet cake. The wet cake was dispersed in water to prepare a slurry liquid having a slurry liquid concentration of about 150 g / l. After measuring the pH of the slurry liquid, it was dried using a nozzle type spray dryer to obtain granular precipitated silicic acid. The measurement results of this product are shown in Table 1.
【００２５】比較例６ ６０℃に熱した温水１９，６００ｍｌに、４８％硫酸を
加えｐＨ約３．０とし、次いで３号ケイ酸ナトリウム溶
液（Ｎａ2 Ｏ約７％、ＳｉＯ2 約２２％）４，４６０ｍ
ｌと４８％硫酸約９４０ｍｌを、反応液のｐＨが２．５
〜３．５を保つように６０分間で同時注加した。次に２
３％水酸化ナトリウム水溶液を反応液ｐＨが約９．０に
なるまで加え、反応液温度９０℃まで昇温し４時間熱成
を行なった後、再度４８％硫酸を加えて反応液ｐＨを約
３．０にした。得られた沈殿物を濾過・水洗して湿潤ケ
ーキを得た。該湿潤ケーキを水に分散させスラリー液濃
度が約１００ｇ／ｌになるようにスラリー液を作り、該
スラリーをノズル式噴霧乾燥機を用いて乾燥を行ない顆
粒状沈殿ケイ酸を得た。この製品の測定結果を表１に示
した。Comparative Example 6 To 19,600 ml of warm water heated to 60 ° C., 48% sulfuric acid was added to adjust the pH to about 3.0, and then a No. 3 sodium silicate solution (Na 2 O about 7%, SiO 2 about 22%). 4,460m
1 and 48% sulfuric acid about 940 ml, the reaction solution pH is 2.5
Co-injection over 60 minutes to keep ~ 3.5. Then 2
A 3% aqueous solution of sodium hydroxide was added until the pH of the reaction solution reached about 9.0, the temperature of the reaction solution was raised to 90 ° C., and the mixture was heat-treated for 4 hours. It was set to 3.0. The obtained precipitate was filtered and washed with water to obtain a wet cake. The wet cake was dispersed in water to prepare a slurry liquid having a slurry liquid concentration of about 100 g / l, and the slurry was dried using a nozzle type spray dryer to obtain granular precipitated silicic acid. The measurement results of this product are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明によれば、比較的大きな粒子径を
有し、かつ取扱い中に粉化せず、また適当な肌触りや触
感を有する顆粒状沈殿ケイ酸を得ることができる。本発
明の製造方法によれば、顆粒状沈殿ケイ酸の粒子強度
を、容易にかつ自由にコントロールして、所望の粒子強
度を有する顆粒状沈殿ケイ酸を得ることができる。本発
明の顆粒状沈殿ケイ酸は、流動性が良く、取扱い中に粉
化することが少ないので多量に取り扱う産業では特に有
効的である。ゴムの充填剤として使用する場合は、練り
込み時の食い込みが良く作業時間の短縮に顕著な効果を
発揮する。勿論、プラスチック、樹脂等の充填剤として
も有効である。また歯磨きの充填剤として使用する場合
は、歯磨き製造時や保存中に顆粒物が破壊すること無
く、口中での触感を損なうことなく、使用時まで適度な
粘性を維持することができる。According to the present invention, it is possible to obtain a granular precipitated silicic acid which has a relatively large particle size, does not powder during handling, and has an appropriate texture and feel. According to the production method of the present invention, it is possible to easily and freely control the particle strength of granular precipitated silicic acid to obtain granular precipitated silicic acid having a desired particle strength. The granular precipitated silicic acid of the present invention has good fluidity and is less likely to be powdered during handling, and is therefore particularly effective in the industry where a large amount is handled. When it is used as a filler for rubber, it bites well during kneading and exerts a remarkable effect in shortening the working time. Of course, it is also effective as a filler for plastics, resins and the like. When used as a filler for toothpaste, the granules are not destroyed during toothpaste production or storage, and the feel in the mouth is not impaired, and an appropriate viscosity can be maintained until the time of use.
Claims (6)
７５〜２５０μｍの範囲にあり、かつ粒子強度が０．１
〜０．３ｋｇｆ／ｍｍ2 の範囲であることを特徴とする
顆粒状沈殿ケイ酸。1. 60% or more by weight of particles have a particle size in the range of 75 to 250 μm and a particle strength of 0.1.
Granular precipitated silicic acid in the range of ~ 0.3 kgf / mm 2 .
が８．５〜１１．５である請求項１記載の顆粒状沈殿ケ
イ酸。2. The pH of the suspension when a 4% suspension is prepared.
Is 8.5 to 11.5, and the granular precipitated silicic acid according to claim 1.
範囲である請求項１又は２記載の顆粒状沈殿ケイ酸。3. The granular precipitated silicic acid according to claim 1, which has a bulk specific gravity in the range of 150 to 300 g / liter.
又はケイ酸ナトリウムを添加して、前記懸濁液のｐＨを
８．５〜１１．５の範囲に調整し、得られた懸濁液を噴
霧乾燥することを特徴とする請求項１記載の顆粒状沈殿
ケイ酸の製造方法。4. A suspension obtained by adding sodium hydroxide or sodium silicate to a suspension of precipitated silicic acid to adjust the pH of the suspension to a range of 8.5 to 11.5. The method for producing a granular precipitated silicic acid according to claim 1, wherein the liquid is spray-dried.
ｇの範囲にある沈殿ケイ酸を用いる請求項４記載の製造
方法。5. A BET specific surface area of 150 to 400 m 2 /
The method according to claim 4, wherein the precipitated silicic acid in the range of g is used.
リー濃度を１５０〜２５０にする請求項４又は５記載の
製造方法。6. The production method according to claim 4, wherein the slurry concentration of the suspension of precipitated silicic acid to be spray-dried is set to 150 to 250.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01837594A JP3153698B2 (en) | 1994-02-15 | 1994-02-15 | Granular precipitated silicic acid and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01837594A JP3153698B2 (en) | 1994-02-15 | 1994-02-15 | Granular precipitated silicic acid and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH07223810A true JPH07223810A (en) | 1995-08-22 |
| JP3153698B2 JP3153698B2 (en) | 2001-04-09 |
Family
ID=11969973
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007366A1 (en) * | 2002-07-10 | 2004-01-22 | Tokuyama Corporation | Cake of easily dispersible precipitated silica and process for producing the same |
| JP2004091313A (en) * | 2002-07-10 | 2004-03-25 | Tokuyama Corp | Easily dispersible precipitated silica cake and manufacturing method therefor |
| JP2011529842A (en) * | 2008-08-01 | 2011-12-15 | エボニック デグサ ゲーエムベーハー | A new class of precipitated silica for support applications. |
| JP2012131736A (en) * | 2010-12-21 | 2012-07-12 | Kao Corp | Method for producing dentifrice granule |
-
1994
- 1994-02-15 JP JP01837594A patent/JP3153698B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007366A1 (en) * | 2002-07-10 | 2004-01-22 | Tokuyama Corporation | Cake of easily dispersible precipitated silica and process for producing the same |
| JP2004091313A (en) * | 2002-07-10 | 2004-03-25 | Tokuyama Corp | Easily dispersible precipitated silica cake and manufacturing method therefor |
| CN100422080C (en) * | 2002-07-10 | 2008-10-01 | 株式会社德山 | Cake of easily dispersible precipitated silica and process for producing the same |
| US7985392B2 (en) | 2002-07-10 | 2011-07-26 | Tokuyama Corporation | Cake of easily dispersible precipitated silica |
| JP2011529842A (en) * | 2008-08-01 | 2011-12-15 | エボニック デグサ ゲーエムベーハー | A new class of precipitated silica for support applications. |
| US8962519B2 (en) | 2008-08-01 | 2015-02-24 | Evonik Degussa Gmbh | Precipitated silicic acids for support applications |
| JP2012131736A (en) * | 2010-12-21 | 2012-07-12 | Kao Corp | Method for producing dentifrice granule |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3153698B2 (en) | 2001-04-09 |
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