JP3318001B2 - Continuous production method of fine cellulose-based solidified particles - Google Patents
Continuous production method of fine cellulose-based solidified particlesInfo
- Publication number
- JP3318001B2 JP3318001B2 JP18444492A JP18444492A JP3318001B2 JP 3318001 B2 JP3318001 B2 JP 3318001B2 JP 18444492 A JP18444492 A JP 18444492A JP 18444492 A JP18444492 A JP 18444492A JP 3318001 B2 JP3318001 B2 JP 3318001B2
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- Japan
- Prior art keywords
- cellulose
- polymer compound
- stirring
- particles
- fine powder
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、微小セルロース系凝固
粒子の製造方法に係り、更に詳しくは、微粉末（例え
ば、着色料、研磨砥粒、抗菌剤等）を含有するセルロー
ス系高分子化合物の微小液滴の分散液を生成させたの
ち、凝集のない凝固粒子を連続して製造する方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing coagulated fine cellulose particles, and more particularly, to a cellulosic polymer compound containing fine powders (eg, coloring agents, abrasive grains, antibacterial agents, etc.). The present invention relates to a method for continuously producing coagulated particles without agglomeration after generating a dispersion of fine droplets.
【０００２】[0002]
【従来の技術】従来、球状をした微小セルロース系凝固
粒子を得る方法としては、特開昭６１−２４１３３７号
公報に記載の方法が知られている。この方法は高粘度の
液体であるセルロース系溶液から球状のセルロース系微
粒子を生成させる方法であって、ビスコース（セルロー
ス系溶液）とアニオン性高分子化合物を混合し撹拌して
ビスコースの微粒子分散液となし、続いて凝固剤を加え
るか加熱するかして凝集のない微小セルロース系凝固粒
子を得る方法である。2. Description of the Related Art Conventionally, a method described in Japanese Patent Application Laid-Open No. 61-241337 is known as a method for obtaining spherical microcellulose coagulated particles. In this method, spherical cellulose-based fine particles are generated from a high-viscosity liquid cellulose-based solution, and viscose (cellulose-based solution) and an anionic polymer compound are mixed and stirred to disperse viscose fine particles. This is a method in which a liquid is formed, and then a coagulant is added or heated to obtain fine cellulosic coagulated particles without aggregation.
【０００３】また、特開平２−３００２４３号には、上
述の方法を応用して有機顔料を含有したセルロース系微
粒子を得る方法が開示され、更に特開平２−３００２４
４号には研磨砥粒を含有したセルロース複合粒子の製造
方法が開示されている。Further, Japanese Patent Application Laid-Open No. 2-300243 discloses a method for obtaining cellulose-based fine particles containing an organic pigment by applying the above-mentioned method.
No. 4 discloses a method for producing cellulose composite particles containing abrasive grains.
【０００４】しかしながら、上記公報に記載された方法
はいずれも連続法ではなく、バッチ式による製造方法で
あり、また工業的な大規模スケールでは、粒径及び粒径
分布の調整が難しく、更にバッチ間で変動しやすいとい
った問題点があった。[0004] However, all of the methods described in the above-mentioned publications are not continuous methods, but are batch-type production methods. Further, it is difficult to adjust the particle size and particle size distribution on an industrial large scale, and furthermore, the batch method is difficult. There was a problem that it fluctuated easily between the two.
【０００５】一方、球状をしたセルロース微粒子を連続
して得る方法としては、特開昭６２−１９１０３３号公
報に記載の方法が知られている。この方法は、セルロー
ス系溶液に振動を直接加えながら該溶液をノズルから噴
出させることで均一液滴を形成する方法であり、これを
凝固することでセルロース系凝固粒子を得るものであ
る。On the other hand, as a method for continuously obtaining spherical cellulose fine particles, a method described in JP-A-62-191033 is known. This method is a method in which uniform droplets are formed by ejecting the solution from a nozzle while directly applying vibration to the cellulose solution, and solidifying the cellulose droplets to obtain cellulose-based coagulated particles.
【０００６】しかしながらこの方法は、凝固粒子を連続
的に得ることができるものの、セルロース系溶液をノズ
ルから噴出させる必要があり、このため粘度の低い（例
えば５０〜２０００ｃＰ）溶液しか使用できず、粘度の
高い溶液には適用できないものであった。このため、こ
の方法で得られるセルロース系凝固粒子は、均一な構造
ではなく、表層部が密で内部が粗となった構造のものと
なり、機械的強度の弱いものしか得られないという問題
点があった。In this method, however, although coagulated particles can be obtained continuously, it is necessary to jet a cellulosic solution from a nozzle. Therefore, only a solution having a low viscosity (for example, 50 to 2000 cP) can be used. Was not applicable to solutions with high For this reason, the cellulosic coagulated particles obtained by this method do not have a uniform structure, but have a structure in which the surface layer is dense and the inside is rough, and only a material having low mechanical strength can be obtained. there were.
【０００７】[0007]
【発明が解決しようとする課題】本発明者等は、上述の
事情に鑑み鋭意研究した結果本発明を完成したものであ
って、その目的とするところは、微粉末を含有し且つ粒
径の安定した微小セルロース凝固粒子を効率よく連続し
て製造する方法を提供するにある。DISCLOSURE OF THE INVENTION The present inventors have completed the present invention as a result of intensive studies in view of the above-mentioned circumstances. It is an object of the present invention to provide a method for efficiently and continuously producing stable fine cellulose coagulated particles.
【０００８】[0008]
【課題を解決するための手段】本発明の目的は、セルロ
ース系水溶性高分子化合物及びアニオン性高分子化合物
が所定量供給されこれを撹拌混合する混合槽と、該混合
槽から微小セルロース系液滴の分散液が連続的に供給さ
れると共にこれを撹拌する撹拌槽と、該撹拌槽から微小
セルロース系未凝固粒子の分散液が連続的に供給される
細管と、該細管を加熱する手段とからなる製造装置で微
粉末を含有する微小セルロース系凝固粒子を連続して製
造する方法であって、前記混合槽には前記セルロース系
水溶性化合物と共に前記微粉末を供給し且つ前記アニオ
ン性高分子化合物１重量部と共に炭酸カルシウム０．５
〜２重量部を供給し、更に前記セルロース系水溶性化合
物１重量部に対するアニオン性高分子化合物の混合割合
が３〜５重量部であることを特徴とする微粉末を含有す
る微小セルロース系凝固粒子の連続製造方法によって達
成される。SUMMARY OF THE INVENTION An object of the present invention is to provide a mixing tank in which a predetermined amount of a cellulose-based water-soluble polymer compound and an anionic polymer compound are supplied and agitated and mixed; A stirring tank for continuously supplying and stirring the dispersion of the droplets, a thin tube to which the dispersion of the microcellulose-based uncoagulated particles is continuously supplied from the stirring tank, and a means for heating the thin tube A method for continuously producing fine cellulosic coagulated particles containing fine powder with a production apparatus comprising: supplying the fine powder together with the cellulosic water-soluble compound to the mixing tank; Calcium carbonate 0.5 with 1 part by weight of compound
To 2 parts by weight, and the mixing ratio of the anionic polymer compound to 3 parts by weight of the cellulose-based water-soluble compound is 3 to 5 parts by weight. Is achieved by a continuous production method.
【０００９】本発明の装置及び方法で製造しようとする
微小セルロース系凝固粒子とは、セルロース系液滴粒子
を凝固せしめた平均粒径５００μｍ以下の球状ないし長
球状の凝固粒子である。The microcellulose-based coagulated particles to be produced by the apparatus and method of the present invention are spherical or oblong coagulated particles having an average particle diameter of 500 μm or less obtained by coagulating cellulosic droplet particles.
【００１０】本発明に用いる微粉末とは、微小セルロー
ス系凝固粒子に新たな性質や作用効果等を付与するもの
である。このようなものとしては、例えば顔料等の着色
料のほか、研磨砥粒、抗菌剤、防黴剤等を挙げることが
できる。また、本発明に用いる微粉末の粒子径は、通常
１００μｍ以下、好ましくは５０μｍ以下、更に好まし
くは２０μｍ以下である。[0010] The fine powder used in the present invention is one that imparts new properties, functions and effects to the finely divided cellulose-based coagulated particles. Such materials include, for example, colorants such as pigments, abrasive grains, antibacterial agents, and fungicides. The particle size of the fine powder used in the present invention is usually 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less.
【００１１】まず、本発明の製造方法に用いられる装置
を図面に基づいて説明する。図１は本発明に用いる装置
の一例を示す概略図である。混合槽（１）は、所定量の
セルロース系水溶性高分子化合物及びアニオン性高分子
化合物が間歇的、好ましくは連続的に供給されると共
に、混合液を撹拌するための撹拌手段（４）を備えてい
る。本発明においては、セルロース系水溶性高分子化合
物には上記微粉末が、アニオン性高分子化合物には炭酸
カルシウムがそれぞれ分散含有している。First, an apparatus used in the manufacturing method of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of an apparatus used in the present invention. The mixing tank (1) is provided with a predetermined amount of a cellulosic water-soluble polymer compound and an anionic polymer compound intermittently, preferably continuously, and has a stirring means (4) for stirring the mixed solution. Have. In the present invention, the cellulosic water-soluble polymer compound contains the fine powder, and the anionic polymer compound contains calcium carbonate.
【００１２】本発明においてセルロース系水溶性高分子
化合物としては、具体的にはビスコースのほかセルロー
スを銅アンモニア液で溶解した溶液等も挙げることがで
きるが、特にビスコースが好適である。また、本発明に
おいてアニオン性高分子化合物としては、水溶性のもの
であって、具体的にはポリスチレンスルホン酸ナトリウ
ム，ポリアクリル酸ナトリウム等を挙げることができ
る。In the present invention, specific examples of the cellulose-based water-soluble polymer compound include, in addition to viscose, a solution obtained by dissolving cellulose with a copper ammonia solution, etc., and viscose is particularly preferred. In the present invention, the anionic polymer compound is a water-soluble compound, and specific examples thereof include sodium polystyrenesulfonate and sodium polyacrylate.
【００１３】混合槽（１）で得られた前記微粉末を含有
する微小セルロース系液滴（以下、「微粉末含有微小液
滴」と略記する）の分散液は移液ポンプ（７）で連続的
に撹拌槽（２）に送液される。撹拌槽（２）には撹拌手
段（５）が備えられている。撹拌手段（４），（５）と
しては、例えば回転羽根によるものやスタティックミキ
サー等を使用することができる。A dispersion of microcellulose-based droplets containing the fine powder obtained in the mixing tank (1) (hereinafter abbreviated as "fine powder-containing microdroplets") is continuously fed by a liquid transfer pump (7). The liquid is sent to the stirring tank (2). The stirring tank (2) is provided with stirring means (5). As the stirring means (4) and (5), for example, a means using a rotating blade or a static mixer can be used.
【００１４】撹拌槽（２）で得られた微粉末を含有する
微小セルロース系未凝固粒子（以下、「微粉末含有未凝
固粒子」と略記する）の分散液は、移液ポンプ（８）で
連続的に細管（３）に送液される。細管（３）には、細
管（３）を加熱する手段が備えられている。加熱する手
段は、細管（３）を加熱し必要とする温度に保つもので
あればよく、例えば、細管（３）を恒温槽（６）の中に
浸漬する方法が一定の温度に調節しやすい点で好適であ
る。The dispersion liquid of the fine cellulose-containing non-coagulated particles containing fine powder obtained in the stirring tank (2) (hereinafter abbreviated as “non-coagulated particles containing fine powder”) is transferred by the liquid transfer pump (8). The liquid is continuously sent to the thin tube (3). The thin tube (3) is provided with a means for heating the thin tube (3). The heating means may be any as long as it heats the thin tube (3) and keeps it at a required temperature. For example, a method of immersing the thin tube (3) in the thermostatic bath (6) is easy to adjust to a constant temperature. It is suitable in this respect.
【００１５】細管に供給された未凝固粒子は、細管内で
加熱されることにより、徐々に凝固粒子となる。細管に
よる加熱は、細管出口付近の分散液の温度が７０℃以上
となるよう設定することが好ましい。The uncoagulated particles supplied to the thin tube gradually become solidified particles by being heated in the thin tube. The heating by the thin tube is preferably set so that the temperature of the dispersion near the outlet of the thin tube is 70 ° C. or higher.
【００１６】上記細管は、温度分布が少なく、中を通過
する微小セルロース系粒子の分散液が滞留することのな
い構造であって、例えば内径５〜２０ｍｍ，長さ５０〜
１００ｍのパイプを挙げることができる。細管の内径が
大き過ぎるものは分散液の中に温度分布が生じ凝固速度
が均一とならない。長さは、微粉末含有未凝固粒子が凝
固するに必要な通過時間を確保できる長さであればよ
い。細管の材料は通過する分散液に腐食されないもので
ある必要があり、例えばガラス，ステンレス，テフロ
ン，ナイロン等を挙げることができ、中でもテフロン，
ナイロンが好ましいものである。The above-mentioned thin tube has a structure in which the temperature distribution is small and the dispersion liquid of the fine cellulose-based particles passing therethrough does not stay. For example, the inside diameter is 5 to 20 mm, and the length is 50 to 50 mm.
One example is a 100 m pipe. If the inside diameter of the thin tube is too large, a temperature distribution will occur in the dispersion and the solidification rate will not be uniform. The length may be any length as long as the passage time required for the uncoagulated particles containing fine powder to coagulate can be secured. The material of the thin tube must be one that does not corrode by the passing dispersion liquid, and examples thereof include glass, stainless steel, Teflon, and nylon.
Nylon is the preferred one.
【００１７】尚、上述の装置に適用される移液ポンプ
（７），（８）は、均一な粒径の微粉末含有微小液滴あ
るいは微粉末含有未凝固粒子が細分割されない構造のも
のが好ましく、プランジャーポンプ式あるいはモノポン
プ式の構造のポンプが好適である。The liquid transfer pumps (7) and (8) applied to the above-mentioned apparatus have a structure in which fine droplets containing fine powder having a uniform particle size or unsolidified particles containing fine powder are not subdivided. Preferably, a pump having a plunger pump type or a monopump type structure is suitable.
【００１８】本発明の製造方法は、混合槽（１）で大ま
かに粒径が調整された微粉末含有微小液滴を撹拌槽
（２）で粒径の微調整し、凝集のない粒径のより均一な
微粉末含有未凝固粒子となすものである。尚、この微粉
末含有未凝固粒子は、粒径がより均一である点を除けば
その内容は微粉末含有微小液滴と同じものである。According to the production method of the present invention, fine particles containing fine powder whose particle diameter is roughly adjusted in the mixing tank (1) are finely adjusted in the stirring tank (2), and the particle diameter is adjusted to a particle diameter without agglomeration. This results in more uniform fine powder-containing unsolidified particles. The content of the non-solidified particles containing fine powder is the same as that of the fine droplet containing fine powder except that the particle diameter is more uniform.
【００１９】本発明の方法は、まずセルロース系水溶性
高分子化合物と前記微粉末との混合液を準備する。セル
ロース系水溶性高分子化合物と微粉末との混合割合は、
微粉末の種類と所望する効果等によって適宜設定すれば
よいが、セルロース系水溶性高分子化合物１重量部に対
し微粉末を、好ましくは０．１〜１０重量部、更に好ま
しくは０．５〜５重量部の割合である。混合は、通常、
攪拌翼例えばニーダー等の高粘度用攪拌装置によって行
われる。In the method of the present invention, first, a mixed solution of the cellulose-based water-soluble polymer compound and the fine powder is prepared. The mixing ratio of the cellulosic water-soluble polymer compound and the fine powder,
It may be appropriately set depending on the type of the fine powder, the desired effect, and the like. 5 parts by weight. Mixing is usually
The stirring is performed by a high-viscosity stirring device such as a stirring blade such as a kneader.
【００２０】次いで、混合槽（１）で微粉末を含有する
セルロース系水溶性高分子化合物と炭酸カルシウムを含
有するアニオン性高分子化合物とを撹拌混合し、微粉末
含有微小液滴の分散液となす。この分散液中の平均粒径
は通常６００μｍ以下であるが、粒径分布としては極め
て微細なものを多く含むものである。Next, a cellulose-based water-soluble polymer compound containing fine powder and an anionic polymer compound containing calcium carbonate are stirred and mixed in a mixing tank (1) to form a dispersion of fine droplets containing fine powder. Eggplant The average particle size in this dispersion is usually 600 μm or less, but the particle size distribution contains many very fine particles.
【００２１】ここで使用するアニオン性高分子化合物
は、通常は水溶液として、好ましくは濃度５〜１５重量
％の水溶液として用いられる。この水溶液には、微粉末
状の炭酸カルシウムがアニオン性高分子化合物１重量部
に対して０．５〜２重量部の割合で混合される。炭酸カ
ルシウムが０．５重量部未満の場合は、良好な微小液滴
が得られない。炭酸カルシウムが２重量部を超えた場合
は、後述するところの細管（３）の中を通過する際に、
細管を閉塞させる虞がある。The anionic polymer compound used here is usually used as an aqueous solution, preferably an aqueous solution having a concentration of 5 to 15% by weight. In this aqueous solution, fine powdered calcium carbonate is mixed at a ratio of 0.5 to 2 parts by weight with respect to 1 part by weight of the anionic polymer compound. If the content of calcium carbonate is less than 0.5 parts by weight, good fine droplets cannot be obtained. When the calcium carbonate exceeds 2 parts by weight, when passing through a thin tube (3) described later,
There is a possibility that the thin tube may be closed.
【００２２】続いて、撹拌槽（２）で上記微粉末含有微
小液滴は更に撹拌され、分割と凝集を繰り返すが、この
工程においては極めて微細な液滴が他の液滴と凝集する
傾向が強く、微細な液滴は少なくなり、粒径はより均一
化される。その結果、次工程の細管（３）に移液される
微粉末含有未凝固粒子の平均粒径は、混合槽（１）から
移液される微粉末含有微小液滴の平均粒径よりも若干大
きいものとなるが、その粒径分布は狭く均一性のよいも
のである。Subsequently, the fine droplets containing fine powder are further stirred in the stirring tank (2), and division and aggregation are repeated. In this step, there is a tendency that extremely fine droplets aggregate with other droplets. Strong, fine droplets are reduced and the particle size is more uniform. As a result, the average particle size of the fine powder-containing uncoagulated particles transferred to the capillary (3) in the next step is slightly smaller than the average particle size of the fine powder-containing microdroplets transferred from the mixing tank (1). Although it is large, its particle size distribution is narrow and has good uniformity.
【００２３】上述の混合槽（１）と撹拌槽（２）の容量
及び撹拌条件は、目的とする粒径のものが得られるよう
適宜設定すればよいが、本発明においては混合槽（１）
と撹拌槽（２）の容量及び撹拌条件を同一とすること
が、安定した粒径のものが得られる点で好ましい。ま
た、混合槽（１）と撹拌槽（２）の温度は、好ましくは
３０℃以下、更に好ましくは２５℃以下であって、通常
室温である。温度が高過ぎると液滴が凝固しやすくなり
好ましくない。The volumes and stirring conditions of the mixing tank (1) and the stirring tank (2) may be appropriately set so as to obtain a target particle diameter. In the present invention, the mixing tank (1)
It is preferable that the capacity and stirring conditions of the stirring tank (2) and the stirring tank (2) are the same in that a stable particle diameter can be obtained. The temperature of the mixing tank (1) and the stirring tank (2) is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and is usually room temperature. If the temperature is too high, the droplets tend to solidify, which is not preferable.
【００２４】従来、微粉末含有未凝固粒子を加熱により
凝固させるに際しては、粒径を揃える必要性から、撹拌
しながら加熱をしていたが、本発明においては凝固のた
めの加熱を細管（３）内で施し、特に撹拌することなく
凝固せしめるのが本発明の特長のひとつでもある。即
ち、撹拌槽（２）から送液された微粉末含有未凝固粒子
は、細管（３）内を通過しながら加熱され、撹拌と静置
の中間的な状態において凝固していくのである。Conventionally, when coagulating non-coagulated particles containing fine powder by heating, heating was performed with stirring because of the necessity of uniforming the particle size. However, in the present invention, heating for coagulation is performed by a thin tube (3). It is also one of the features of the present invention that the composition is applied in the step (1) and solidified without stirring. That is, the non-coagulated particles containing fine powder sent from the stirring tank (2) are heated while passing through the narrow tube (3), and solidify in an intermediate state between stirring and standing.
【００２５】本発明者等は、微粉末含有未凝固粒子を撹
拌と静置の中間的な状態（即ち、細管を通過する状態）
で加熱し凝固せしめた場合においても、安定した粒径の
凝固粒子が得られる条件のあることを見出し、本発明の
方法を完成したものである。即ち、本発明者等は混合槽
（１）で混合されるセルロース系水溶性高分子化合物と
アニオン性高分子化合物との混合割合及びアニオン性高
分子化合物と炭酸カルシウムとの混合割合が、加熱凝固
する際の粒径に与える影響について、撹拌した場合と静
置状態の場合とについて数多くの実験を繰り返し、極め
て興味深い結果を得たのである。The present inventors have considered that the uncoagulated particles containing fine powder are in a state intermediate between stirring and standing (ie, a state passing through a capillary).
The present inventors have found that there is a condition under which solidified particles having a stable particle size can be obtained even when the mixture is heated and coagulated, and the method of the present invention has been completed. That is, the inventors have found that the mixing ratio of the cellulose-based water-soluble polymer compound and the anionic polymer compound and the mixing ratio of the anionic polymer compound and calcium carbonate mixed in the mixing tank (1) are determined by heat coagulation. A number of experiments were repeated with respect to the effect on the particle size during the stirring and the case of the stationary state, and extremely interesting results were obtained.
【００２６】図２は、セルロース系水溶性高分子化合物
としてのビスコースと、アニオン性高分子化合物として
の分子量５万のポリアクリル酸ナトリウム水溶液とを混
合し撹拌して得た微小セルロース系凝固粒子の分散液
を、一方は撹拌しながら加熱した場合、他方は静置状態
で加熱した場合に得られる凝固粒子の平均粒径の大きさ
を表わしたグラフである。横軸は、セルロース系高分子
化合物とポリアクリル酸ナトリウムとのポリマーの混合
割合を表わす。なお、上記ポリアクリル酸ナトリウム水
溶液には炭酸カルシウム微粉末１重量部を添加混合し
た。FIG. 2 shows fine cellulose-based coagulated particles obtained by mixing and stirring viscose as a cellulose-based water-soluble polymer compound and an aqueous solution of sodium polyacrylate having a molecular weight of 50,000 as an anionic polymer compound. Is a graph showing the average particle size of the coagulated particles obtained when one of the dispersions is heated with stirring and the other is heated in a stationary state. The horizontal axis represents the mixing ratio of the polymer of the cellulosic polymer compound and sodium polyacrylate. In addition, 1 part by weight of calcium carbonate fine powder was added to the aqueous solution of sodium polyacrylate and mixed.
【００２７】図２のグラフより極めて特徴的な傾向が明
らかとなった。即ち、撹拌しながら加熱した場合には、
ポリアクリル酸ナトリウムの割合が増えるに従って平均
粒径も大きくなるが、静置状態で加熱した場合には、ポ
リアクリル酸ナトリウムの割合が増えるに従って平均粒
径は逆に小さくなっていくのである。そして、セルロー
ス系高分子化合物１重量部に対しポリアクリル酸ナトリ
ウムが約４重量部の割合で混合された場合に、撹拌しな
がら加熱したときと静置状態で加熱したときに得られる
凝固粒子の粒径がほぼ同じ大きさとなるのである。この
傾向はポリアクリル酸ナトリウムの分子量が異なる場合
でも同様であった。An extremely characteristic tendency became apparent from the graph of FIG. That is, when heating with stirring,
The average particle size increases as the ratio of sodium polyacrylate increases, but when heated in a stationary state, the average particle size decreases as the ratio of sodium polyacrylate increases. Then, when sodium polyacrylate is mixed at a ratio of about 4 parts by weight with respect to 1 part by weight of the cellulosic polymer compound, the coagulated particles obtained when heated while stirring and when heated in a stationary state are obtained. The particle size is almost the same size. This tendency was the same even when the molecular weight of sodium polyacrylate was different.
【００２８】本発明の製造方法において、細管（３）の
中を通過する微粉末含有未凝固粒子の分散液は、撹拌と
静置の中間の状態と考えられ、上記実験結果より安定し
た粒径の凝固粒子を得るには、炭酸カルシウムを混合し
たアニオン性高分子化合物とセルロース系水溶性高分子
化合物の水溶液とを混合するに際し、混合槽（１）で混
合されるセルロース系水溶性高分子化合物を１重量部に
対しアニオン性高分子化合物を好ましくは３〜５重量
部、更に好ましくは３．５〜４．５重量部の割合で混合
すればよいのである。尚、得られる凝固粒子の粒径を決
定する大きな要因はアニオン性高分子化合物の種類であ
って、例えばポリアクリル酸ナトリウムではその分子量
を挙げることができ、分子量が大きいもの程凝固粒子の
平均粒径が小さいものとなるのである。In the production method of the present invention, the dispersion of the non-coagulated particles containing fine powder passing through the thin tube (3) is considered to be in an intermediate state between stirring and standing, and a stable particle size is obtained from the above experimental results. In order to obtain the coagulated particles, the cellulose-based water-soluble polymer compound mixed in the mixing tank (1) when the anionic polymer compound mixed with calcium carbonate is mixed with the aqueous solution of the cellulose-based water-soluble polymer compound Is mixed with 1 part by weight of the anionic polymer compound in an amount of preferably 3 to 5 parts by weight, more preferably 3.5 to 4.5 parts by weight. The major factor that determines the particle size of the obtained coagulated particles is the type of anionic polymer compound. For example, in the case of sodium polyacrylate, the molecular weight can be mentioned. The diameter is small.
【００２９】尚、上述の製造方法において、炭酸カルシ
ウムを添加混合しない場合は、安定した粒径の未凝固粒
子を得ることができなかった。In the above-mentioned production method, when calcium carbonate was not added and mixed, uncoagulated particles having a stable particle size could not be obtained.
【００３０】[0030]
【実施例】以下、実施例により本発明を具体的に説明す
る。尚、以下の実施例に用いた製造装置は図１に示す様
な概略図のものであった。混合槽（１）と撹拌槽（２）
は容量５０ lのタンクであって、それぞれのタンクには
撹拌手段（４），（５）として、７ｃｍの回転羽根を有
する撹拌機（ヤマト科学社製，ＭＯＤＥＬ ＬＲ−５１
Ｂ）が取りつけられていた。The present invention will be described below in detail with reference to examples. The manufacturing apparatus used in the following examples had a schematic view as shown in FIG. Mixing tank (1) and stirring tank (2)
Is a tank having a capacity of 50 l, and each tank is provided with a stirrer having 7 cm of rotating blades (Model LR-51, manufactured by Yamato Scientific Co., Ltd.) as stirring means (4) and (5).
B) was installed.
【００３１】細管（３）は、内径１０ｍｍ，長さ１００
ｍのテフロン製のパイプであって、細管（３）は９５℃
に温調された熱水よりなる恒温槽（６）に浸漬させた。The thin tube (3) has an inner diameter of 10 mm and a length of 100 mm.
m Teflon pipe, and the thin tube (3) is 95 ° C.
Immersed in a thermostat (6) made of hot water whose temperature had been adjusted.
【００３２】実施例１ セルロース系水溶性高分子化合物として、セルロースザ
ンテートを水酸化ナトリウム溶液で溶解し、これに微粉
末状の顔料を添加し分散せしめて、セルロース濃度１
０．５重量％，顔料濃度０．２重量％，水酸化ナトリウ
ム濃度６．４重量％に調整したビスコースを用意した。
また、アニオン性高分子化合物として、炭酸カルシウム
微粉末を１重量％分散したポリアクリル酸ナトリウム水
溶液（高分子濃度１０．５重量％，分子量５万）を用意
した。Example 1 As a cellulose-based water-soluble polymer compound, cellulose xanthate was dissolved in a sodium hydroxide solution, and a fine powder pigment was added thereto and dispersed.
Viscose adjusted to 0.5% by weight, pigment concentration 0.2% by weight, and sodium hydroxide concentration 6.4% by weight was prepared.
Further, as an anionic polymer compound, an aqueous solution of sodium polyacrylate (polymer concentration: 10.5% by weight, molecular weight: 50,000) in which 1% by weight of calcium carbonate fine powder was dispersed was prepared.
【００３３】混合槽（１）に上記ビスコースを０．２ｋ
ｇ／分，上記ポリアクリル酸ナトリウム水溶液を０．８
ｋｇ／分で供給した。混合槽（１）の液量は５０．４ｋ
ｇで、撹拌機で撹拌混合して、顔料を含有する微小液滴
の分散液となした。撹拌条件は２５℃，３００ｒｐｍで
あった。得られた顔料を含有する微小液滴の分散液は移
液ポンプ（７）により１．０ｋｇ／分で撹拌槽（２）に
連続的に送液し、混合槽（１）の液量は常に５０．４ｋ
ｇに保持した。Add the above viscose to the mixing tank (1) in an amount of 0.2 k
g / min, 0.8 g of the above aqueous solution of sodium polyacrylate.
kg / min. The liquid volume in the mixing tank (1) is 50.4k
g, and stirred and mixed with a stirrer to form a dispersion of fine droplets containing the pigment. The stirring conditions were 25 ° C. and 300 rpm. The obtained dispersion liquid of the fine droplets containing the pigment is continuously fed to the stirring tank (2) at 1.0 kg / min by the transfer pump (7), and the amount of the liquid in the mixing tank (1) is always constant. 50.4k
g.
【００３４】撹拌槽（２）は、液量を５０．４ｋｇに保
持し、送液された顔料を含有する微小液滴の分散液を撹
拌機によって２５℃，３００ｒｐｍで撹拌し、顔料を含
有し凝集のない未凝固粒子の分散液となした。得られた
顔料を含有する未凝固粒子の分散液は、撹拌槽（２）に
供給したのと同量を、移液ポンプ（８）によって細管
（３）へ連続的に送液した。The stirring tank (2) holds the liquid volume at 50.4 kg, stirs the dispersion of the fine droplets containing the supplied pigment with a stirrer at 25 ° C. and 300 rpm to contain the pigment. A dispersion of unagglomerated particles without agglomeration was obtained. The same amount of the obtained non-coagulated particle-containing dispersion liquid containing pigment was supplied to the capillary (3) by the liquid transfer pump (8) in the same amount as that supplied to the stirring tank (2).
【００３５】細管（３）に供給した顔料を含有する未凝
固粒子の分散液は、細管中で加熱され細管出口付近では
約８０℃であった。加熱されることにより顔料を含有す
る未凝固粒子は徐々に凝固し、細管出口付近では完全に
凝固し、平均粒径１２０μｍの球状の顔料を含有した凝
固粒子が得られた。得られた凝固粒子は、凝集もなく粒
径の均一性の良いものであった。この凝固粒子を希酸で
中和したところ、発色性に優れた着色セルロース粒子が
得られた。The dispersion of uncoagulated particles containing the pigment supplied to the capillary (3) was heated in the capillary and was at about 80 ° C. near the exit of the capillary. The uncoagulated particles containing the pigment were gradually solidified by heating, and were completely solidified in the vicinity of the outlet of the thin tube to obtain solidified particles containing a spherical pigment having an average particle diameter of 120 μm. The obtained coagulated particles had good uniformity of particle size without aggregation. When the coagulated particles were neutralized with a dilute acid, colored cellulose particles having excellent coloring properties were obtained.
【００３６】実施例２ 実施例１で用いた分子量５万のポリアクリル酸ナトリウ
ムに代えて、分子量５０万のポリアクリル酸ナトリウム
を用いた以外は実施例１と同様にして顔料を含有する凝
固粒子を得た。得られた凝固粒子は、凝集もなく、これ
を希酸で中和したところ、平均粒径１０μｍの着色セル
ロース球状体が得られた。Example 2 Coagulated particles containing a pigment in the same manner as in Example 1 except that sodium polyacrylate having a molecular weight of 500,000 was used in place of sodium polyacrylate having a molecular weight of 50,000 used in Example 1. I got The obtained coagulated particles did not agglomerate and were neutralized with a dilute acid to obtain a colored cellulose sphere having an average particle size of 10 μm.
【００３７】実施例３ 実施例１で用いた顔料に代えて、平均粒径３μｍの砥粒
（酸化セリウム）をビスコース中の濃度が３重量％にな
るように添加し分散せしめた。それ以外は、実施例１と
同様にして凝固粒子を得た。これを希酸で中和したとこ
ろ、砥粒を３０重量％含有し、平均粒径１２０μｍのセ
ルロース球状体が得られた。Example 3 Instead of the pigment used in Example 1, abrasive grains (cerium oxide) having an average particle size of 3 μm were added and dispersed so that the concentration in viscose was 3% by weight. Except for this, coagulated particles were obtained in the same manner as in Example 1. When this was neutralized with a dilute acid, a cellulose spherical body containing 30% by weight of abrasive grains and having an average particle diameter of 120 μm was obtained.
【００３８】[0038]
【発明の効果】本発明の方法は上述のような製造装置を
用いたため、微粉末を含有するセルロース系溶液から凝
固粒子を効率よく連続して製造することができる。ま
た、高粘度のセルロース系溶液を使用することが可能な
ため、均一な内部構造の微小セルロース系凝固粒子を得
ることができる。According to the method of the present invention, since the above-described production apparatus is used, coagulated particles can be efficiently and continuously produced from a cellulose-based solution containing fine powder. In addition, since a high-viscosity cellulose-based solution can be used, fine cellulose-based solidified particles having a uniform internal structure can be obtained.
【００３９】更に本発明の方法によれば、原料を特定の
配合割合で混合するため、微粉末を含有する凝固粒子
を、安定した粒子径で凝集することなく、容易に得るこ
とができる。従って、従来のバッチ式の製造方法で生じ
ていたロット間のバラツキやスケールアップの困難さを
解消することができ、産業上極めて有用である。Further, according to the method of the present invention, since the raw materials are mixed at a specific blending ratio, solidified particles containing fine powder can be easily obtained without agglomerating with a stable particle diameter. Therefore, it is possible to eliminate the lot-to-lot variation and the difficulty of scale-up caused by the conventional batch-type manufacturing method, which is extremely useful in industry.
【図１】本発明の方法に使用する製造装置の一例を示す
概略図である。FIG. 1 is a schematic view showing an example of a manufacturing apparatus used in the method of the present invention.
【図２】セルロース系水溶性高分子化合物とポリアクリ
ル酸ナトリウムの混合割合と凝固粒子の平均粒径との関
係を表わすグラフである。FIG. 2 is a graph showing the relationship between the mixing ratio of a cellulose-based water-soluble polymer compound and sodium polyacrylate and the average particle size of coagulated particles.
１ 混合槽 ２ 撹拌槽 ３ 細管 ４，５ 撹拌手段 ６ 恒温槽 ７，８，９，１０ 移液ポンプ １１ 微粉末を含有したセルロース系水溶性高分子化合
物溶液 １２ 炭酸カルシウムを含有したアニオン性高分子化合
物溶液DESCRIPTION OF SYMBOLS 1 Mixing tank 2 Stirring tank 3 Capillary tube 4,5 Stirrer 6 Constant temperature bath 7,8,9,10 Liquid transfer pump 11 Cellulose-based water-soluble polymer compound solution containing fine powder 12 Anionic polymer containing calcium carbonate Compound solution
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 2/06 C08J 3/16 C08L 1/08 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) B01J 2/06 C08J 3/16 C08L 1/08
Claims (1)
ニオン性高分子化合物が所定量供給されこれを撹拌混合
する混合槽と、該混合槽から微小セルロース系液滴の分
散液が連続的に供給されると共にこれを撹拌する撹拌槽
と、該撹拌槽から微小セルロース系未凝固粒子の分散液
が連続的に供給される細管と、該細管を加熱する手段と
からなる製造装置で微粉末を含有する微小セルロース系
凝固粒子を連続して製造する方法であって、前記混合槽
には前記セルロース系水溶性化合物と共に前記微粉末を
供給し且つ前記アニオン性高分子化合物１重量部と共に
炭酸カルシウム０．５〜２重量部を供給し、更に前記セ
ルロース系水溶性化合物１重量部に対するアニオン性高
分子化合物の混合割合が３〜５重量部であることを特徴
とする微粉末を含有する微小セルロース系凝固粒子の連
続製造方法。1. A mixing tank in which predetermined amounts of a cellulose-based water-soluble polymer compound and an anionic polymer compound are supplied and agitated and mixed, and a dispersion of fine cellulose droplets is continuously supplied from the mixing tank. The fine powder is contained in a production apparatus comprising a stirring tank for stirring and stirring this, a thin tube to which a dispersion liquid of microcellulose uncoagulated particles is continuously supplied from the stirring tank, and a means for heating the thin tube. A method for continuously producing fine cellulose-based coagulated particles, wherein the mixing tank is supplied with the fine powder together with the cellulose-based water-soluble compound and 0.5 parts of calcium carbonate together with 1 part by weight of the anionic polymer compound. To 2 parts by weight, and further contains a fine powder characterized in that the mixing ratio of the anionic polymer compound to 1 part by weight of the water-soluble cellulose compound is 3 to 5 parts by weight. Continuous production method of microcellular coagulated particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18444492A JP3318001B2 (en) | 1992-06-17 | 1992-06-17 | Continuous production method of fine cellulose-based solidified particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18444492A JP3318001B2 (en) | 1992-06-17 | 1992-06-17 | Continuous production method of fine cellulose-based solidified particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06355A JPH06355A (en) | 1994-01-11 |
| JP3318001B2 true JP3318001B2 (en) | 2002-08-26 |
Family
ID=16153258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18444492A Expired - Fee Related JP3318001B2 (en) | 1992-06-17 | 1992-06-17 | Continuous production method of fine cellulose-based solidified particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3318001B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500276A (en) * | 2011-10-17 | 2012-06-20 | 中国科学院微生物研究所 | Automatic microsphere production device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0824106A3 (en) * | 1996-08-12 | 1998-04-22 | Lenzing Aktiengesellschaft | Cellulose particles |
| JP5110782B2 (en) * | 2005-08-23 | 2012-12-26 | 大東化成工業株式会社 | Pigment-encapsulated cellulose powder and cosmetics, resins and paints containing the same |
| FI20105744A (en) * | 2010-06-29 | 2011-12-30 | Waertsilae Finland Oy | REGULATION METHOD AND ARRANGEMENT FOR SELECTIVE CATALYTIC REDUCTION |
-
1992
- 1992-06-17 JP JP18444492A patent/JP3318001B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500276A (en) * | 2011-10-17 | 2012-06-20 | 中国科学院微生物研究所 | Automatic microsphere production device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06355A (en) | 1994-01-11 |
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