JPH1059716A - Spherical aggregate of platy calcium carbonate and its production - Google Patents
Spherical aggregate of platy calcium carbonate and its productionInfo
- Publication number
- JPH1059716A JPH1059716A JP22003796A JP22003796A JPH1059716A JP H1059716 A JPH1059716 A JP H1059716A JP 22003796 A JP22003796 A JP 22003796A JP 22003796 A JP22003796 A JP 22003796A JP H1059716 A JPH1059716 A JP H1059716A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- reaction
- plate
- carbon dioxide
- carbonation
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な板状構造を
有した炭酸カルシウムの球状複合体およびその製造方法
に関するものである。TECHNICAL FIELD The present invention relates to a calcium carbonate spherical composite having a novel plate-like structure and a method for producing the same.
【０００２】[0002]
【従来の技術】従来から各種の多孔質物質が提案され、
それぞれの特性を生かして種々の分野で使用されてい
る。これらの多孔質物質のなかでも無機成分を構成成分
とするものとしては、ゼオライト、活性炭、珪酸カルシ
ウム、リン酸カルシウムなどが知られている。2. Description of the Related Art Various porous materials have been proposed.
It is used in various fields by taking advantage of its characteristics. Among these porous substances, zeolite, activated carbon, calcium silicate, calcium phosphate, and the like are known as those containing an inorganic component as a constituent component.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの多孔
質物質といわれている化合物には、それぞれ一長一短が
あり、いまだに充分に満足しうるものは得られていな
い。一般に多孔質物質は、球形に近い一次粒子をバイン
ダーなどを使用して球形に凝集させたものが殆どであっ
て、その細孔径は一次粒子径よりも小さいのが普通であ
る。また、その細孔は一次粒子の凝集間隙や製造時の
水、有機溶媒またはバインダーの蒸発に伴う空隙から形
成されたものであるので、細孔径を１μｍ以上にするこ
とは困難であった。また、これらの多孔質物質の殆ど
が、粒子の形状、細孔の大きさなどが固定されており、
それぞれの用途にみあった最適な品質にする自由度が殆
どないのが現状である。本発明者らは、先に「板状炭酸
カルシウムの製造方法」（特開平２−１８４５１）およ
び「板状塩基性炭酸カルシウムの製造方法」（特開平３
−２８５８１６）を発明したので、これらの知見をもと
に、従来多孔質物質の対象として検討されたことのない
炭酸カルシウムが、合成条件を変化させることによりそ
の形態を制御できることを見出し、多孔質物質の基材と
して採用し、製造条件により細孔径および細孔容積を変
えることのできる板状炭酸カルシウムの球状複合体を得
ようとしたものである。However, these compounds, which are said to be porous substances, have their respective advantages and disadvantages, and no satisfactory one has yet been obtained. In general, most porous materials are obtained by aggregating spherical primary particles into a spherical shape using a binder or the like, and the pore diameter is usually smaller than the primary particle size. In addition, the pores are formed from aggregation gaps of the primary particles and voids due to evaporation of water, an organic solvent or a binder at the time of production, so that it is difficult to reduce the pore diameter to 1 μm or more. In addition, most of these porous substances, the shape of the particles, the size of the pores are fixed,
At present, there is almost no freedom to make the quality optimal for each application. The present inventors have previously described "a method for producing plate-like calcium carbonate" (JP-A-2-18451) and a "method for producing plate-like basic calcium carbonate" (JP-A-3-18451).
Based on these findings, it has been found that calcium carbonate, which has not been conventionally studied as a porous substance, can control its form by changing the synthesis conditions. The purpose of the present invention is to obtain a plate-like calcium carbonate spherical composite which can be used as a base material of a substance and whose pore diameter and pore volume can be changed depending on production conditions.
【０００４】[0004]
【課題を解決するための手段】そこで前記課題を解決す
るために本発明者らは鋭意検討を行った結果、本発明を
完成するに至った。すなわち、本発明の第１は、板状構
造を有した炭酸カルシウムの一次粒子が球状に凝集した
板状炭酸カルシウムの球状複合体であって、カルシウム
以外のアルカリ土類金属およびリンを含有していてもよ
く、板状構造を有した炭酸カルシウムである一次粒子の
径が０．２〜１０μｍ、厚さが０．０２〜２μｍ、その
球状複合体の細孔容積が０．１〜３ｍｌ／ｇ以上である
板状炭酸カルシウムの球状複合体である。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the first aspect of the present invention is a spherical composite of plate-like calcium carbonate in which primary particles of calcium carbonate having a plate-like structure are aggregated in a spherical form, and contains an alkaline earth metal other than calcium and phosphorus. The primary particles which are calcium carbonate having a plate-like structure have a diameter of 0.2 to 10 μm, a thickness of 0.02 to 2 μm, and a pore volume of the spherical composite of 0.1 to 3 ml / g. The above is a spherical composite of plate-like calcium carbonate.
【０００５】本発明の第２は、板状構造を有した一次粒
子が、塩基性炭酸カルシウム、塩基性炭酸カルシウムと
炭酸カルシウムの複合物、炭酸カルシウムと水酸化カル
シウムの複合物、塩基性炭酸カルシウムと水酸化カルシ
ウムと炭酸カルシウムの複合物、炭酸カルシウムが球状
に凝集した板状炭酸カルシウムの球状複合体を二酸化炭
素と加熱下で接触させ、塩基性炭酸カルシウム、塩基性
炭酸カルシウムと炭酸カルシウムの複合物、塩基性炭酸
カルシウムと水酸化カルシウムと炭酸カルシウムの複合
物を炭酸カルシウムに変化させた板状炭酸カルシウムの
球状複合体であって、カルシウム以外のアルカリ土類金
属およびリンを含有していてもよく、塩基性炭酸カルシ
ウム、炭酸カルシウムまたは水酸化カルシウムである板
状構造を有した一次粒子の径が０．２〜１０μｍ、厚さ
が０．０２〜２μｍ、その球状複合体の細孔容積が０．
１〜３ｍｌ／ｇ以上である板状炭酸カルシウムの球状複
合体である。[0005] A second aspect of the present invention is that the primary particles having a plate-like structure are composed of basic calcium carbonate, a composite of basic calcium carbonate and calcium carbonate, a composite of calcium carbonate and calcium hydroxide, and a basic calcium carbonate. And calcium hydroxide, a composite of calcium hydroxide and calcium carbonate, and a spherical composite of plate-like calcium carbonate in which calcium carbonate is aggregated in a spherical form are brought into contact with carbon dioxide under heating to form a mixture of basic calcium carbonate, basic calcium carbonate and calcium carbonate Product, a spherical composite of plate-like calcium carbonate obtained by changing a composite of basic calcium carbonate, calcium hydroxide and calcium carbonate to calcium carbonate, even if it contains an alkaline earth metal other than calcium and phosphorus. One with a plate-like structure that is often basic calcium carbonate, calcium carbonate or calcium hydroxide 0.02~2μm diameter of the particles 0.2 to 10 [mu] m, the thickness, pore volume of the spherical composite is 0.
It is a spherical composite of plate-like calcium carbonate of 1 to 3 ml / g or more.
【０００６】本発明の第３は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物の存在下、塩基性炭酸カルシウム
が生成する反応条件で、石灰乳の電気伝導度が反応前に
対して２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を
止めることおよび炭酸化反応を終了させることにより製
する、板状炭酸カルシウムの球状複合体の製造方法であ
る。A third aspect of the present invention is to carry out a carbonation reaction of calcium hydroxide by reacting milk of lime with carbon dioxide under a reaction condition in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound. A method for producing a spherical composite of plate-like calcium carbonate, which is produced by stopping the carbonation reaction and terminating the carbonation reaction when the electrical conductivity of the milk drops by 2 to 10 mS / cm from that before the reaction. is there.
【０００７】本発明の第４は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物の存在下、塩基性炭酸カルシウム
が生成する反応条件で、石灰乳の電気伝導度が反応前に
対して２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を
止めた後、さらに縮合リン酸化合物および炭酸化率が７
０％以下の石灰乳を添加し、二酸化炭素を反応させるこ
とおよび炭酸化反応を終了させることにより製する板状
炭酸カルシウムの球状複合体の製造方法である。A fourth aspect of the present invention is to carry out a carbonation reaction of calcium hydroxide by reacting lime milk with carbon dioxide, under the reaction conditions in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound. After the carbonation reaction was stopped when the electrical conductivity of the milk dropped by 2 to 10 mS / cm from that before the reaction, the condensed phosphoric acid compound and the carbonation rate were further reduced by 7%.
This is a method for producing a spherical composite of plate-like calcium carbonate produced by adding 0% or less of lime milk to react carbon dioxide and terminating the carbonation reaction.
【０００８】本発明の第５は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物およびカルシウム以外のアルカリ
土類金属化合物の存在下、塩基性炭酸カルシウムが生成
する反応条件で、石灰乳の電気伝導度が反応前に対して
２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を止める
ことおよび炭酸化反応を終了させることにより製する板
状炭酸カルシウムの球状複合体の製造方法である。A fifth aspect of the present invention is to carry out a carbonation reaction of calcium hydroxide by reacting milk of lime with carbon dioxide, in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium. Plate-like calcium carbonate produced by stopping the carbonation reaction and terminating the carbonation reaction when the electrical conductivity of the lime milk drops by 2 to 10 mS / cm from that before the reaction under the reaction conditions for generating calcium. Is a method for producing a spherical composite.
【０００９】本発明の第６は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物およびカルシウム以外のアルカリ
土類金属化合物の存在下、塩基性炭酸カルシウムが生成
する反応条件で、石灰乳の電気伝導度が反応前に対して
２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を止めた
後、さらに縮合リン酸化合物および炭酸化率が７０％以
下の石灰乳を添加し、二酸化炭素を反応させることおよ
び炭酸化反応を終了させることにより製する板状炭酸カ
ルシウムの球状複合体の製造方法である。A sixth aspect of the present invention is to perform a carbonation reaction of calcium hydroxide by reacting milk of lime with carbon dioxide, in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium. Under the reaction conditions in which calcium is generated, the carbonation reaction is stopped when the electrical conductivity of the lime milk drops by 2 to 10 mS / cm from that before the reaction, and then the condensed phosphoric acid compound and the carbonation rate are 70% or less. Is a method for producing a spherical composite of plate-like calcium carbonate, which is produced by adding lime milk of the formula (1) to react carbon dioxide and terminating the carbonation reaction.
【００１０】本発明の第７は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物の存在下、塩基性炭酸カルシウム
が生成する反応条件で、石灰乳の電気伝導度が反応前に
対して２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を
止めた後、さらに縮合リン酸化合物および炭酸化率が７
０％以下の石灰乳を添加し、二酸化炭素を反応させるこ
とを２回以上繰り返すことおよび炭酸化反応を終了させ
ることにより製する板状炭酸カルシウムの球状複合体の
製造方法である。[0010] A seventh aspect of the present invention is to perform a carbonation reaction of calcium hydroxide by reacting lime milk with carbon dioxide under the reaction conditions in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound. After the carbonation reaction was stopped when the electrical conductivity of the milk dropped by 2 to 10 mS / cm from that before the reaction, the condensed phosphoric acid compound and the carbonation rate were further reduced by 7%.
This is a method for producing a spherical composite of plate-like calcium carbonate, which is produced by adding 0% or less of lime milk and reacting carbon dioxide at least twice, and terminating the carbonation reaction.
【００１１】本発明の第８は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物およびカルシウム以外のアルカリ
土類金属化合物の存在下、塩基性炭酸カルシウムが生成
する反応条件で、石灰乳の電気伝導度が反応前に対して
２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を止めた
後、さらに縮合リン酸化合物および炭酸化率が７０％以
下の石灰乳を添加し、二酸化炭素を反応させることを２
回以上繰り返すことおよび炭酸化反応を終了させること
により製する板状炭酸カルシウムの球状複合体の製造方
法である。An eighth aspect of the present invention is to carry out a carbonation reaction of calcium hydroxide by reacting milk of lime with carbon dioxide in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium. Under the reaction conditions in which calcium is generated, the carbonation reaction is stopped when the electrical conductivity of the lime milk drops by 2 to 10 mS / cm from that before the reaction, and then the condensed phosphoric acid compound and the carbonation rate are 70% or less. 2 of adding lime milk and reacting carbon dioxide
This is a method for producing a spherical composite of plate-like calcium carbonate, which is produced by repeating at least two times and terminating the carbonation reaction.
【００１２】本発明の第９は、石灰乳と二酸化炭素を反
応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物およびカルシウム以外のアルカリ
土類金属化合物の存在下、塩基性炭酸カルシウムが生成
する反応条件で、石灰乳の電気伝導度が反応前に対して
２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を止めた
後、さらに縮合リン酸化合物およびカルシウム以外のア
ルカリ土類金属化合物を含む炭酸化率が７０％以下の石
灰乳を添加し、二酸化炭素を反応させることを２回以上
繰り返し、炭酸化反応を止めることおよび炭酸化反応を
終了させることにより製する板状炭酸カルシウムの球状
複合体の製造方法である。A ninth aspect of the present invention relates to the reaction of lime milk with carbon dioxide to carry out a carbonation reaction of calcium hydroxide. In the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium, basic carbonate is used. Under the reaction conditions in which calcium is generated, the carbonation reaction is stopped when the electrical conductivity of the lime milk drops by 2 to 10 mS / cm from that before the reaction, and then the condensed phosphate compound and an alkaline earth metal other than calcium A plate-like calcium carbonate produced by adding lime milk containing a compound having a carbonation ratio of 70% or less and reacting carbon dioxide twice or more, stopping the carbonation reaction and terminating the carbonation reaction. Is a method for producing a spherical composite.
【００１３】本発明の第１０は、板状構造を有した一次
粒子が、塩基性炭酸カルシウム、塩基性炭酸カルシウム
と炭酸カルシウムの複合物、炭酸カルシウムと水酸化カ
ルシウムの複合物、塩基性炭酸カルシウムと水酸化カル
シウムと炭酸カルシウムの複合物、炭酸カルシウムが球
状に凝集した板状炭酸カルシウムの球状複合体を二酸化
炭素と加熱下で接触させ、塩基性炭酸カルシウム、塩基
性炭酸カルシウムと炭酸カルシウムの複合物、塩基性炭
酸カルシウムと水酸化カルシウムと炭酸カルシウムの複
合物を炭酸カルシウムに変化させた板状炭酸カルシウム
の球状複合体であって、板状構造を有した一次粒子の径
が０．２〜１０μｍ、厚さが０．０２〜２μｍ、その球
状複合体の細孔容積が０．１〜３ｍｌ／ｇ以上である板
状炭酸カルシウムの球状複合体を加熱下で、二酸化炭素
と接触させることおよび炭酸化反応を終了させることに
より製する板状炭酸カルシウムの球状複合体の製造方法
である。A tenth aspect of the present invention is that the primary particles having a plate-like structure are basic calcium carbonate, a composite of basic calcium carbonate and calcium carbonate, a composite of calcium carbonate and calcium hydroxide, and a basic calcium carbonate. And calcium hydroxide, a composite of calcium hydroxide and calcium carbonate, and a spherical composite of plate-like calcium carbonate in which calcium carbonate is aggregated in a spherical form are brought into contact with carbon dioxide under heating to form a mixture of basic calcium carbonate, basic calcium carbonate and calcium carbonate Product, a spherical composite of plate-like calcium carbonate obtained by changing a composite of basic calcium carbonate, calcium hydroxide and calcium carbonate to calcium carbonate, wherein the diameter of primary particles having a plate-like structure is 0.2 to 10 μm, 0.02 μm to 2 μm in thickness, and the pore volume of the spherical composite is 0.1 to 3 ml / g or more. This is a method for producing a spherical composite of plate-like calcium carbonate produced by bringing a spherical composite into contact with carbon dioxide under heating and terminating a carbonation reaction.
【００１４】本発明の第１１は、石灰乳と二酸化炭素を
反応させて水酸化カルシウムの炭酸化反応を行うにあた
り、縮合リン酸化合物の存在下、塩基性炭酸カルシウム
が生成する反応条件で、石灰乳の電気伝導度が反応前に
対して２〜１０ｍＳ／ｃｍ降下したときに炭酸化反応を
止めた後、または縮合リン酸化合物の存在下、塩基性炭
酸カルシウムが生成する反応条件で、石灰乳の電気伝導
度が反応前に対して２〜１０ｍＳ／ｃｍ降下したときに
炭酸化反応を止めた後、または二酸化炭素を反応させた
後に、その生成物を加熱下で二酸化炭素と接触させるこ
とにより炭酸化反応を終了させる板状炭酸カルシウムの
球状複合体の製造方法である。An eleventh aspect of the present invention is to perform a carbonation reaction of calcium hydroxide by reacting lime milk with carbon dioxide under the reaction conditions in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound. After the carbonation reaction is stopped when the electrical conductivity of the milk drops by 2 to 10 mS / cm from that before the reaction, or under the reaction conditions in which basic calcium carbonate is generated in the presence of the condensed phosphoric acid compound, the lime milk By stopping the carbonation reaction when the electric conductivity of the mixture falls by 2 to 10 mS / cm from that before the reaction, or after reacting carbon dioxide, by contacting the product with carbon dioxide under heating. This is a method for producing a spherical composite of plate-like calcium carbonate for terminating the carbonation reaction.
【００１５】[0015]
【発明の実施の形態】本発明の板状炭酸カルシウムの球
状複合体は、図１に示したような板状構造を有した炭酸
カルシウムの単一結晶が一次粒子を形成し、図２に示す
ように層状に凝集して球状複合体を形成したり、または
図３に示すように放射状に凝集して球状複合体を形成し
て、表面に細孔を多数形成させた板状炭酸カルシウムの
球状複合体であって、その粒径は凡そ１〜１００μｍで
あって、３〜５０μｍのものが、使用上扱いやすく好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION In the spherical composite of plate-like calcium carbonate of the present invention, a single crystal of calcium carbonate having a plate-like structure as shown in FIG. 1 forms primary particles and is shown in FIG. As shown in FIG. 3, a spherical composite is formed by agglomerating in layers to form a spherical composite, or a spherical composite is formed by radially aggregating to form a spherical composite as shown in FIG. The composite has a particle size of about 1 to 100 μm, and preferably 3 to 50 μm because it is easy to handle in use.
【００１６】本発明でいうカルシウム以外のアルカリ土
類金属とは、マグネシウム、ストロンチウム、バリウ
ム、ラジウムをいい、これらはその１種が含有されてい
てもよいし、または２種以上含有されていてもよい。板
状炭酸カルシウムの球状複合体に含まれるアルカリ土類
金属の含有量は、アルカリ土類金属の種類によって異な
るが、ストロンチウムの場合、０．１〜７重量％であ
り、好ましくは０．２〜４重量％である。また、板状炭
酸カルシウムの球状複合体に含まれるリンの含有量は、
０．０１〜１０重量％であり、好ましくは０．１〜５重
量％である。In the present invention, the alkaline earth metal other than calcium refers to magnesium, strontium, barium, and radium, which may contain one kind or two or more kinds. Good. The content of the alkaline earth metal contained in the plate-like calcium carbonate spherical composite varies depending on the type of the alkaline earth metal. In the case of strontium, the content is 0.1 to 7% by weight, preferably 0.2 to 7% by weight. 4% by weight. Further, the content of phosphorus contained in the spherical composite of plate-like calcium carbonate,
It is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.
【００１７】本発明の細孔とは、板状炭酸カルシウムの
球状複合体における板状構造を有した炭酸カルシウムな
どの一次粒子間の間隙をいい、その細孔容積は水銀圧入
法により測定される。この場合、細孔容積が０．１ｍｌ
／ｇ未満であれば、粉体の粒子間隙であって細孔ではな
い。また、３ｍｌ／ｇを越えると板状炭酸カルシウムの
球状複合体の強度を保つことができず実用的ではない。
従って、水銀圧入法による細孔容積が０．１〜３ｍｌ／
ｇであることが好ましい。The pores of the present invention refer to gaps between primary particles such as calcium carbonate having a plate-like structure in a spherical composite of plate-like calcium carbonate, and the pore volume is measured by a mercury intrusion method. . In this case, the pore volume is 0.1 ml
/ G is less than the pores, not the pores of the powder. On the other hand, if it exceeds 3 ml / g, the strength of the spherical composite of plate-like calcium carbonate cannot be maintained, which is not practical.
Therefore, the pore volume by the mercury intrusion method is 0.1 to 3 ml /
g is preferable.
【００１８】本発明でいう複合物は、その複合形態や割
合によって物性が変わるものであって、例えば、Ｘ線回
折における解析や解析強度比によって異なり、示差熱分
析にあっては、複合形態や割合によってそれぞれの分解
温度により減量と熱量が示され、その値は複合割合によ
り決まる。The properties of the composite according to the present invention vary depending on the form and ratio of the compound. For example, the properties vary depending on the analysis in X-ray diffraction and the analysis intensity ratio. The ratio indicates the weight loss and calorific value at each decomposition temperature, and the value is determined by the composite ratio.
【００１９】本発明でいう板状炭酸カルシウムの球状複
合体の製造方法において、水酸化カルシウム水懸濁液す
なわち石灰乳の濃度は１〜１５重量％、好ましくは３〜
１０重量％が望ましい。石灰乳の濃度が１重量％未満で
は基本構造である板状構造が生成でき難くなり、さらに
１５重量％を越えると均一な板状炭酸カルシウムの球状
複合体の生成が困難になる。In the method of the present invention for producing a spherical composite of plate-like calcium carbonate, the concentration of the aqueous solution of calcium hydroxide, ie, lime milk, is 1 to 15% by weight, preferably 3 to 15% by weight.
10% by weight is desirable. When the concentration of milk of lime is less than 1% by weight, it is difficult to form a plate-like structure as a basic structure, and when it exceeds 15% by weight, it is difficult to form a uniform spherical composite of plate-like calcium carbonate.
【００２０】本発明でいう縮合リン酸化合物とは、通常
ポリリン酸化合物といわれる化合物で、ピロリン酸、ト
リポリリン酸、テトラポリリン酸、ヘキサメタリン酸、
ウルトラリン酸などを例示できるが、それらのナトリウ
ム、カリウムなどのアルカリ金属塩またはアンモニウム
塩であってもよい。これらは１種類で使用してもよい
し、また２種類以上併用してもよい。縮合リン酸化合物
の添加量は、水酸化カルシウムに対して０．０１〜１０
重量％、好ましくは０．１〜５重量％である。一般に縮
合リン酸化合物の添加量が水酸化カルシウムに対して１
０重量％を越えると、層状体または放射状体の板状炭酸
カルシウムの間隙幅が小さくなり、細孔容積も小さくな
り、本発明の目的を達成することはできない。一方、縮
合リン酸化合物の添加量が水酸化カルシウムに対して
０．０１重量％未満であると、板状炭酸カルシウムを層
状体または放射状体に凝集させることができず、本発明
の板状炭酸カルシウムの球状複合体の製造は困難とな
る。The condensed phosphoric acid compound referred to in the present invention is a compound usually referred to as a polyphosphoric acid compound, such as pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid,
Examples thereof include ultraphosphoric acid, and alkali metal salts such as sodium and potassium or ammonium salts thereof may be used. These may be used alone or in combination of two or more. The addition amount of the condensed phosphoric acid compound is 0.01 to 10 with respect to calcium hydroxide.
%, Preferably 0.1 to 5% by weight. Generally, the addition amount of the condensed phosphoric acid compound is 1 to calcium hydroxide.
If the content exceeds 0% by weight, the gap width of the plate-like calcium carbonate of the layered or radial body becomes small and the pore volume becomes small, so that the object of the present invention cannot be achieved. On the other hand, if the amount of the condensed phosphoric acid compound is less than 0.01% by weight based on the calcium hydroxide, the plate-like calcium carbonate cannot be aggregated into a layered or radial body, and the plate-like carbonate of the present invention cannot be aggregated. Production of a spherical composite of calcium becomes difficult.
【００２１】本発明でいう板状炭酸カルシウムの球状複
合体の製造方法においては、縮合リン酸化合物の存在
下、塩基性炭酸カルシウムが生成する反応条件で水酸化
カルシウムの炭酸化を行うことによって、基本構造であ
る板状構造を有する炭酸カルシウムを生成することがで
きる。生成した炭酸カルシウムの粒子の形状と電気伝導
度とは密接な関係があるので、電気伝導度を測定するこ
とにより炭酸カルシウムの生成を制御することができ
る。すなわち、電気伝導度の降下が２ｍＳ／ｃｍ未満で
あると、一次粒子である板状構造が充分に成長していな
い状態にあり、炭酸化率６０％以下であると、生成球状
複合体の均一性が損なわれる。また、電気伝導度の降下
が１０ｍＳ／ｃｍを越えると、一次粒子である板状構造
の間隙が少なく、細孔容積も少なくなり、炭酸化率も６
６．７％を越えることになる。In the method for producing a spherical composite of plate-like calcium carbonate according to the present invention, calcium hydroxide is subjected to carbonation in the presence of a condensed phosphoric acid compound under reaction conditions under which basic calcium carbonate is produced. Calcium carbonate having a plate-like structure as a basic structure can be produced. Since there is a close relationship between the shape of the generated calcium carbonate particles and the electrical conductivity, the generation of calcium carbonate can be controlled by measuring the electrical conductivity. That is, if the drop in electric conductivity is less than 2 mS / cm, the plate-like structure as the primary particles is not sufficiently grown, and if the carbonation rate is 60% or less, the uniformity of the resulting spherical composite is reduced. Sex is impaired. If the drop in electric conductivity exceeds 10 mS / cm, the gap of the plate-like structure as primary particles is small, the pore volume is small, and the carbonation ratio is 6%.
It will exceed 6.7%.
【００２２】板状炭酸カルシウムの球状複合体の粒子径
を大きくし、複合体の粒度分布の幅が狭くなるように、
炭酸化反応を止めたのち、縮合リン酸化合物および炭酸
化率７０％以下の石灰乳を添加する。ここで炭酸化率と
は、乳液中の炭酸カルシウムのモル（ｍｏｌ）数と石灰
乳中のカルシウムのモル（ｍｏｌ）数の百分率であっ
て、数１で示される式によって計算された値である。In order to increase the particle size of the spherical composite of plate-like calcium carbonate and narrow the width of the particle size distribution of the composite,
After stopping the carbonation reaction, a condensed phosphoric acid compound and lime milk having a carbonation rate of 70% or less are added. Here, the carbonation rate is a percentage of the number of moles (mol) of calcium carbonate in the emulsion and the number of moles (mol) of calcium in the lime milk, and is a value calculated by the equation shown in Expression 1. .
【００２３】[0023]
【数１】 (Equation 1)
【００２４】本発明でいう板状炭酸カルシウムの球状複
合体の製造方法において、縮合リン酸化合物およびカル
シウム以外のアルカリ土類金属化合物の存在下で水酸化
カルシウムの炭酸化反応を行う場合、縮合リン酸化合物
としては上述の化合物を１種で使用してもよいが、２種
以上併用してもよい。その添加量は、添加する化合物に
よっても異なり、ヘキサメタリン酸ナトリウムの場合、
０．１〜１０重量％、好ましくは０．５〜５重量％であ
る。また、カルシウム以外のアルカリ土類金属として
は、マグネシウム、ストロンチウム、バリウム、ラジウ
ムをいい、これらの水酸化物、塩化物、硝酸塩、硫酸
塩、などの可溶性塩を例示することができる。その添加
量は、添加する化合物によっても異なり、１種で使用し
てもよいが、２種以上併用してもよく、塩化ストロンチ
ウムの場合、０．２〜１０重量％、好ましくは０．３〜
５重量％である。In the method for producing a spherical composite of plate-like calcium carbonate according to the present invention, when a carbonation reaction of calcium hydroxide is carried out in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium, As the acid compound, one of the above compounds may be used, or two or more may be used in combination. The amount of addition depends on the compound to be added. In the case of sodium hexametaphosphate,
It is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Examples of the alkaline earth metal other than calcium include magnesium, strontium, barium, and radium, and examples thereof include soluble salts such as hydroxides, chlorides, nitrates, and sulfates. The amount of addition varies depending on the compound to be added, and may be used alone or in combination of two or more. In the case of strontium chloride, 0.2 to 10% by weight, preferably 0.3 to 10% by weight.
5% by weight.
【００２５】本発明でいう板状炭酸カルシウムの球状複
合体の製造方法において、縮合リン酸化合物の存在下で
水酸化カルシウムの炭酸化反応を行う場合、炭酸化反応
を止めた後、さらに縮合リン酸化合物および炭酸化率が
７０％以下の石灰乳を添加し、二酸化炭素を反応させる
ことを２回以上繰り返すことにより、板状炭酸カルシウ
ムの球状複合体の粒子径を大きく制御できると同時に粒
子径分布が狭くそろった板状炭酸カルシウムの複合体を
得ることができる。ここで炭酸化率は通常１０％未満で
あって、７０％を越えると板状炭酸カルシウムの球状複
合体の結晶成長に使用できる水酸化カルシウムの量が少
なくなり、球状複合体を成長させての粒子径制御ができ
難くなると同時に、成長した球状複合体の粒子径が不揃
いとなるので、好ましくない。繰り返し回数は通常２〜
１０回であるが、好ましくは２〜５回である。このとき
の反応温度は、１０〜４０℃程度の範囲、好ましくは２
０〜４０℃の範囲である。この反応温度を越えると、基
本構造である板状構造とならず本発明の目的を達成しな
い。縮合リン酸化合物の添加時期については、炭酸化前
から炭酸化率３０％、好ましくは炭酸化前から炭酸化率
２０％までに添加することが望ましい。これらの添加時
期を過ぎると、基本構造である板状構造の放射状または
層状の球状凝集体とならず本発明の目的を達成しない。
繰り返して炭酸化を行う場合、添加する石灰乳の混合割
合は、生成している炭酸カルシウムに対し、１０：１〜
１：１０、好ましくは４：１〜１：４が望ましい。生成
している炭酸カルシウムの混合割合が増加すると基本構
造の板状構造が均一に成長せず、放射状または層状の球
状凝集体と成り難く、さらに添加する石灰乳の混合割合
が増加すると基本構造の成長が大きく成りすぎるため
に、放射状または層状の球状凝集体の均一性がなくなり
本発明の目的を達成できない。In the method for producing a spherical composite of plate-like calcium carbonate according to the present invention, when the carbonation reaction of calcium hydroxide is carried out in the presence of a condensed phosphoric acid compound, after the carbonation reaction is stopped, the condensed phosphorus is further added. The acid compound and the lime milk having a carbonation ratio of 70% or less are added and the reaction of carbon dioxide is repeated twice or more, whereby the particle size of the spherical composite of plate-like calcium carbonate can be largely controlled, and at the same time, the particle size can be controlled. A composite of plate-like calcium carbonate having a narrow distribution can be obtained. Here, the carbonation rate is usually less than 10%, and if it exceeds 70%, the amount of calcium hydroxide that can be used for crystal growth of the spherical composite of plate-like calcium carbonate is reduced, and the amount of the calcium composite is increased. It is not preferable because it becomes difficult to control the particle diameter and the particle diameter of the grown spherical composite becomes irregular. The number of repetitions is usually 2
It is 10 times, but preferably 2-5 times. The reaction temperature at this time is in the range of about 10 to 40 ° C., preferably 2 to 40 ° C.
The range is from 0 to 40 ° C. If the reaction temperature is exceeded, a plate-like structure as a basic structure is not obtained, and the object of the present invention is not achieved. Regarding the addition time of the condensed phosphoric acid compound, it is desirable to add the carbonation rate from before the carbonation to 30%, preferably from before the carbonation to a carbonation rate of 20%. After these addition times, the plate-like structure, which is the basic structure, does not become a radial or layered spherical aggregate, and the object of the present invention is not achieved.
When carbonation is repeatedly performed, the mixing ratio of the lime milk to be added is 10: 1 to 10% with respect to the generated calcium carbonate.
1:10, preferably 4: 1 to 1: 4. When the mixing ratio of the generated calcium carbonate increases, the plate-like structure of the basic structure does not grow uniformly, and it is difficult to form radial or layered spherical aggregates, and when the mixing ratio of the added lime milk increases, the basic structure increases. Since the growth is too large, the uniformity of the radial or layered spherical aggregates is lost, and the object of the present invention cannot be achieved.
【００２６】本発明でいう板状炭酸カルシウムの球状複
合体の製造方法において、縮合リン酸化合物およびカル
シウム以外のアルカリ土類金属化合物の存在下で水酸化
カルシウムの炭酸化反応を行う場合、炭酸化反応を止め
た後、さらに縮合リン酸化合物、カルシウム以外のアル
カリ土類金属化合物および炭酸化率が７０％以下の石灰
乳を添加し、二酸化炭素を反応させることを２回以上繰
り返すことにより、板状炭酸カルシウムの球状複合体の
粒子径を大きく制御できると同時に粒子分布が狭くそろ
った板状炭酸カルシウムの複合体を得ることができる。
ここで炭酸化率は通常１０％未満であって、７０％を越
えると板状炭酸カルシウムの球状複合体の結晶成長に使
用できる水酸化カルシウムの量が少なくなり、球状複合
体を成長させての粒径制御ができ難くなると同時に、成
長した球状複合体の粒子径が不揃いとなるので、好まし
くない。繰り返し回数は通常２〜１０回であるが、好ま
しくは２〜５回である。このときの反応温度は、１０〜
４０℃程度の範囲、好ましくは２０〜４０℃の範囲であ
る。この反応温度を越えると、基本構造である板状構造
とならず本発明の目的を達成しない。縮合リン酸化合物
の添加時期については、炭酸化前から炭酸化率３０％、
好ましくは炭酸化前から炭酸化率２０％までに添加する
ことが望ましい。これらの添加時期を過ぎると、基本構
造である板状構造の放射状または層状の球状凝集体とな
らず本発明の目的を達成しない。繰り返して炭酸化を行
う場合、添加する石灰乳の混合割合は、生成している炭
酸カルシウムに対し、１０：１〜１：１０、好ましくは
４：１〜１：４が望ましい。生成している炭酸カルシウ
ムの混合割合が増加すると基本構造の板状構造が均一に
成長せず、放射状または層状の球状凝集体と成り難く、
さらに添加する石灰乳の混合割合が増加すると基本構造
の成長が大きく成りすぎるために、放射状または層状の
球状凝集体の均一性がなくなり本発明の目的を達成でき
ない。In the process for producing a spherical composite of plate-like calcium carbonate according to the present invention, when carbonation of calcium hydroxide is carried out in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium, After stopping the reaction, a condensed phosphoric acid compound, an alkaline earth metal compound other than calcium and a lime milk having a carbonation rate of 70% or less are added, and the reaction of carbon dioxide is repeated twice or more. The particle size of the spherical composite of calcium carbonate can be controlled to be large, and a composite of plate-like calcium carbonate having a narrow particle distribution can be obtained.
Here, the carbonation rate is usually less than 10%, and if it exceeds 70%, the amount of calcium hydroxide that can be used for crystal growth of the spherical composite of plate-like calcium carbonate is reduced, and the amount of the calcium composite is increased. It is not preferable because it is difficult to control the particle diameter and the particle diameter of the grown spherical composite becomes irregular. The number of repetitions is usually 2 to 10 times, but preferably 2 to 5 times. The reaction temperature at this time is 10 to
The temperature is in the range of about 40 ° C, preferably in the range of 20 to 40 ° C. If the reaction temperature is exceeded, a plate-like structure as a basic structure is not obtained, and the object of the present invention is not achieved. Regarding the time of addition of the condensed phosphoric acid compound, the carbonation rate was 30% before carbonation,
It is desirable to add the carbonation before the carbonation until the carbonation ratio reaches 20%. After these addition times, the plate-like structure, which is the basic structure, does not become a radial or layered spherical aggregate, and the object of the present invention is not achieved. When carbonation is repeatedly performed, the mixing ratio of lime milk to be added is preferably 10: 1 to 1:10, and more preferably 4: 1 to 1: 4, based on the generated calcium carbonate. When the mixing ratio of the generated calcium carbonate increases, the plate-like structure of the basic structure does not grow uniformly, and it is difficult to form a radial or layered spherical aggregate,
Further, when the mixing ratio of the added lime milk increases, the growth of the basic structure becomes too large, so that the uniformity of the radial or layered spherical aggregates is lost and the object of the present invention cannot be achieved.
【００２７】板状構造を有した一次粒子が、塩基性炭酸
カルシウム、塩基性炭酸カルシウムと炭酸カルシウムの
複合物、炭酸カルシウムと水酸化カルシウムの複合物、
塩基性炭酸カルシウムと水酸化カルシウムと炭酸カルシ
ウムの複合物、炭酸カルシウムが球状に凝集した板状炭
酸カルシウムの球状複合体を二酸化炭素と加熱下で接触
させ、塩基性炭酸カルシウム、塩基性炭酸カルシウムと
炭酸カルシウムの複合物、塩基性炭酸カルシウムと水酸
化カルシウムと炭酸カルシウムの複合物を炭酸カルシウ
ムに変化させて板状炭酸カルシウムの球状複合体にする
場合、この炭酸化速度は、炭酸化温度、二酸化炭素濃度
と反応時間により異なるが、固体と気体の直接反応は通
常反応速度が遅いので、塩基性炭酸カルシウムの分解温
度以上または水酸化カルシウムの分解温度以上で炭酸カ
ルシウムの分解温度以下で行うのが望ましい。すなわ
ち、その温度は３００〜８００℃、好ましくは４００〜
７００℃である。また、二酸化炭素の濃度は、１０〜１
００容量％、好ましくは５０〜１００容量％である。The primary particles having a plate-like structure include basic calcium carbonate, a composite of basic calcium carbonate and calcium carbonate, a composite of calcium carbonate and calcium hydroxide,
A complex of basic calcium carbonate, calcium hydroxide, and calcium carbonate, and a spherical composite of plate-like calcium carbonate in which calcium carbonate is aggregated in a spherical form are brought into contact with carbon dioxide under heating to form a mixture of basic calcium carbonate and basic calcium carbonate. When a complex of calcium carbonate and a complex of basic calcium carbonate, calcium hydroxide and calcium carbonate are converted into calcium carbonate to form a spherical composite of plate-like calcium carbonate, the carbonation rate is determined by the carbonation temperature, Depending on the carbon concentration and the reaction time, the direct reaction between the solid and the gas is usually slow, so it is recommended that the reaction be performed at a temperature above the decomposition temperature of basic calcium carbonate or above the decomposition temperature of calcium hydroxide and below the decomposition temperature of calcium carbonate. desirable. That is, the temperature is 300-800 ° C., preferably 400-800 ° C.
700 ° C. The concentration of carbon dioxide is 10 to 1
00% by volume, preferably 50 to 100% by volume.
【００２８】上述のごとくして、得られた板状炭酸カル
シウムの球状複合体は、従来の炭酸カルシウムや炭酸カ
ルシウム系複合体に比べて、比表面積が大きく、かつ粒
子表面が、図２および図３にみられるように、多孔質と
なっているので、その特性を利用した種々の用途を有し
ている。直接その物質を使用すると毒性など問題がある
場合、すなわち農薬などを本発明の板状炭酸カルシウム
の球状複合体に担持させることにより、任意の濃度に調
整し、かつ飛散を防ぐことができる。また、香料、消臭
剤などの揮発性の物質を担持させることにより、持続性
のある徐放剤として利用できる。例えば、触媒、医薬、
化粧料、農薬、微生物、過酸化物、植物成長剤、オレフ
ィン吸収剤、紫外線吸収剤、香料、芳香剤、消臭剤など
の各種物質の担持体として、利用することができ、この
とき吸着された物質をすみやかに放出することがないの
で、その徐放性を利用し、担持された物質の徐放剤とし
ての用途がある。さらに、物質の吸着性を利用して、乾
燥剤、吸液剤、防臭剤としての用途並びに塗料、シーラ
ント、接着剤、塩化ビニールペーストなどの増粘剤とし
ての用途がある。その他、濾過助剤、粉体の成形助剤お
よび吸液用成形体、潤滑油用キャリヤー、製紙用原料と
しても利用できる。As described above, the obtained spherical composite of plate-like calcium carbonate has a larger specific surface area and a particle surface as shown in FIG. 2 and FIG. As shown in No. 3, since it is porous, it has various uses utilizing its characteristics. When there is a problem such as toxicity when the substance is directly used, that is, when the pesticide or the like is supported on the spherical composite of plate-like calcium carbonate of the present invention, the concentration can be adjusted to an arbitrary concentration and scattering can be prevented. Also, by supporting volatile substances such as fragrances and deodorants, it can be used as a sustained sustained release agent. For example, catalysts, pharmaceuticals,
It can be used as a carrier for various substances such as cosmetics, pesticides, microorganisms, peroxides, plant growth agents, olefin absorbers, ultraviolet absorbers, fragrances, fragrances, deodorants, etc. Since the released substance is not released immediately, there is a use of the carried substance as a sustained release agent utilizing its sustained release property. Further, there is a use as a desiccant, a liquid absorbing agent, a deodorant and a use as a thickener such as a paint, a sealant, an adhesive, a vinyl chloride paste, etc. by utilizing the adsorptivity of the substance. In addition, it can be used as a filter aid, a powder molding aid, a molded article for absorbing liquid, a carrier for lubricating oil, and a raw material for papermaking.
【００２９】[0029]
【実施例】以下実施例にもとづいて、本発明を詳細に説
明するが、本発明はこれらのみに限定されるものではな
い。 （実施例１）６重量％で１５℃の石灰乳８００ｍｌを攪
拌しながら２５容量％の二酸化炭素ガス（以下単に「炭
酸ガス」という）を１２００ｍｌ／分で導入し、炭酸化
を行った。炭酸ガス導入開始と同時にヘキサメタリン酸
ナトリウム０．４８ｇを水２５ｍｌに溶解した液を石灰
乳に添加した。反応開始より５０分後に電気伝導度が反
応前より６．０ｍＳ／ｃｍ降下したので炭酸ガスの導入
を停止した。この時の石灰乳の炭酸化率は６１％であっ
た。この石灰乳から固形物を通常の方法で濾過し、アル
コール洗浄した後、１１０℃で１２時間乾燥した。この
乾燥固形物を粉末Ｘ線回折の結果、図４に示すとおりカ
ルサイトと塩基性炭酸カルシウムであり、走査型電子顕
微鏡観察の結果、厚さ０．２μｍ、粒子径３μｍの板状
構造をしたものが放射状に凝集し１０μｍの球状粒子を
形成していた。この乾燥品１００ｇを１０４μｍの篩を
通過させ、円筒形容器に充填し、５５０℃に加熱した縦
型電気炉に装着し、下部から１００％炭酸ガスを５０ｍ
ｌ／分で２０時間炭酸化を行った。炭酸化反応終了後の
Ｘ線回折の結果、図５に示すとおりカルサイトのみであ
り、他の結晶構造は認められなかった。走査型電子顕微
鏡観察の結果、厚さ０．２μｍ、粒子径３μｍの板状構
造をしたものが放射状に凝集し、約１０μｍの球状粒子
を形成していた。このものは水銀圧入法（以下同じ）に
よる細孔容積は０．８４ｍｌ／ｇであった。また、ＢＥ
Ｔ法による比表面積（以下同じ）は７ｍ2 ／ｇ、ＪＩＳ
Ｋ−６２２３によるＤＯＰ（フタル酸ジオクチル、以
下同じ）の吸油量（以下同じ）は９０ｍｌ／１００ｇで
あった。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 Carbon dioxide gas (hereinafter simply referred to as “carbon dioxide gas”) of 25% by volume was introduced at 1200 ml / min while stirring 800 ml of lime milk at 15 ° C. at 6% by weight to carry out carbonation. Simultaneously with the introduction of carbon dioxide gas, a solution prepared by dissolving 0.48 g of sodium hexametaphosphate in 25 ml of water was added to lime milk. 50 minutes after the start of the reaction, the introduction of carbon dioxide gas was stopped because the electric conductivity dropped by 6.0 mS / cm from that before the reaction. At this time, the carbonation ratio of the lime milk was 61%. The solid matter was filtered from the milk of lime by an ordinary method, washed with alcohol, and dried at 110 ° C. for 12 hours. As a result of powder X-ray diffraction, the dried solid was calcite and basic calcium carbonate as shown in FIG. 4, and had a plate-like structure having a thickness of 0.2 μm and a particle diameter of 3 μm as observed by a scanning electron microscope. The particles radially aggregated to form 10 μm spherical particles. 100 g of the dried product was passed through a 104 μm sieve, filled in a cylindrical container, and mounted in a vertical electric furnace heated to 550 ° C., and 100% carbon dioxide gas was supplied from the lower part for 50 m.
Carbonation was performed at 1 / min for 20 hours. As a result of X-ray diffraction after completion of the carbonation reaction, as shown in FIG. 5, there was only calcite, and no other crystal structure was observed. As a result of observation with a scanning electron microscope, a plate-like structure having a thickness of 0.2 μm and a particle diameter of 3 μm was radially aggregated to form spherical particles of about 10 μm. This had a pore volume of 0.84 ml / g by a mercury intrusion method (the same applies hereinafter). Also, BE
The specific surface area by the T method (the same applies hereinafter) is 7 m 2 / g, JIS
The oil absorption (hereinafter the same) of DOP (dioctyl phthalate, hereinafter the same) by K-6223 was 90 ml / 100 g.
【００３０】（実施例２）６重量％で１５℃の石灰乳８
００ｍｌを攪拌しながら炭酸ガスを１２００ｍｌ／分で
導入し、炭酸化を行った。炭酸ガス導入開始１分前にヘ
キサメタリン酸ナトリウム０．４８ｇを水２５ｍｌに溶
解した液を石灰乳に添加した。反応開始より５０分後に
電気伝導度が反応前より４．３ｍＳ／ｃｍ降下したので
炭酸ガスの導入を停止した。この時の石灰乳の炭酸化率
は６５％でＡ液とした。６重量％で２０℃の石灰乳８０
０ｍｌを攪拌しながら炭酸ガスを１２００ｍｌ／分で導
入し、炭酸化を行った。炭酸ガス導入開始２分後にヘキ
サメタリン酸ナトリウム０．４８ｇを水２５ｍｌに溶解
した液を石灰乳に添加した。反応開始より３０分後に炭
酸ガスの導入を停止した。この石灰乳の炭酸化率は３４
％でＢ液とした。Ａ液８００ｍｌとＢ液８００ｍｌを混
合し、石灰乳温度を２５℃とし、攪拌しながら炭酸ガス
を２４００ｍｌ／分で導入した。反応開始より２０分後
に電気伝導度が反応前より６．５ｍＳ／ｃｍ降下したの
で、炭酸ガスの導入を停止し、石灰乳を濾過、アルコー
ル洗浄した後、１１０℃で１２時間乾燥した。この乾燥
品は、Ｘ線回折の結果、塩基性炭酸カルシウムと炭酸カ
ルシウムであり、走査型電子顕微鏡観察の結果、厚さ
０．２５μｍ、大きさ３μｍの板状構造をしたものが放
射状に凝集し、約１５μｍの球状粒子を形成していた。
この乾燥品１００ｇを１０４μｍの篩を通過させ、円筒
形容器に充填し、５５０℃に加熱した縦型電気炉に装着
し、下部から１００％炭酸ガスを５０ｍｌ／分で２０時
間炭酸化を行った。炭酸化反応終了後のＸ線回折の結果
は、カルサイトのみであり、他の結晶構造は認められな
かった。走査型電子顕微鏡の写真を図２に示した。観察
の結果、厚さ０．２５μｍ、粒子径３μｍの板状構造を
したものが放射状に凝集し、約１５μｍの球状粒子を形
成していた。このものの細孔容積は０．６７ｍｌ／ｇで
あった。また、比表面積は６ｍ2 ／ｇ、ＤＯＰの吸油量
は１１０ｍｌ／１００ｇであった。Example 2 Lime milk 8 at 6% by weight and 15 ° C.
While stirring 00 ml, carbon dioxide was introduced at 1200 ml / min to carry out carbonation. One minute before the start of the introduction of carbon dioxide, a solution of 0.48 g of sodium hexametaphosphate dissolved in 25 ml of water was added to the lime milk. 50 minutes after the start of the reaction, the electric conductivity dropped 4.3 mS / cm from that before the reaction, so the introduction of carbon dioxide gas was stopped. At this time, the ratio of carbonation of the lime milk was 65%, and the solution A was used. 80% lime milk at 20 ° C at 6% by weight
Carbon dioxide was introduced at 1200 ml / min while stirring 0 ml to carry out carbonation. Two minutes after the start of the introduction of carbon dioxide, a solution of 0.48 g of sodium hexametaphosphate dissolved in 25 ml of water was added to the lime milk. Thirty minutes after the start of the reaction, the introduction of carbon dioxide was stopped. The carbonation rate of this lime milk is 34
% Of solution B. 800 ml of solution A and 800 ml of solution B were mixed, the lime milk temperature was adjusted to 25 ° C., and carbon dioxide gas was introduced at 2400 ml / min while stirring. After 20 minutes from the start of the reaction, the electric conductivity dropped by 6.5 mS / cm from that before the reaction. Therefore, the introduction of carbon dioxide gas was stopped, the lime milk was filtered, the residue was washed with alcohol, and then dried at 110 ° C. for 12 hours. This dried product was found to be basic calcium carbonate and calcium carbonate as a result of X-ray diffraction. As a result of observation with a scanning electron microscope, a plate-like structure having a thickness of 0.25 μm and a size of 3 μm was radially aggregated. , About 15 μm.
100 g of the dried product was passed through a 104 μm sieve, filled in a cylindrical container, and mounted in a vertical electric furnace heated to 550 ° C., and carbonized from the lower part with 100% carbon dioxide at 50 ml / min for 20 hours. . The result of X-ray diffraction after completion of the carbonation reaction was only calcite, and no other crystal structure was observed. FIG. 2 shows a photograph of the scanning electron microscope. As a result of the observation, a plate-like structure having a thickness of 0.25 μm and a particle diameter of 3 μm was radially aggregated to form spherical particles of about 15 μm. Its pore volume was 0.67 ml / g. The specific surface area was 6 m 2 / g, and the oil absorption of DOP was 110 ml / 100 g.
【００３１】（実施例３）６重量％で２０℃の石灰乳８
００ｍｌを攪拌しながら炭酸ガスを１２００ｍｌ／分で
導入し、炭酸化を行った。炭酸ガス導入と同時にピロリ
ン酸ナトリウム０．５６ｇを水２５ｍｌに溶解した液を
石灰乳に添加した。反応開始より８５分で石灰乳のｐＨ
が７．０になったので炭酸ガスの導入を停止し、石灰乳
を濾過し、アルコール洗浄した後、１１０℃で１２時間
乾燥した。この乾燥品は、粉末Ｘ線回折の結果、すべて
がカルサイトであり、走査型電子顕微鏡観察の結果、厚
さ０．２μｍ、粒子径３μｍの板状構造をしたものが放
射状に凝集し、約１０μｍの球状粒子を形成していた。
このものの細孔容積は０．７９ｍｌ／ｇ、比表面積は約
１０ｍ2 ／ｇ、ＤＯＰの吸油量は６０ｍｌ／１００ｇで
あった。EXAMPLE 3 Milk of lime 8 at 6% by weight and 20 ° C.
While stirring 00 ml, carbon dioxide was introduced at 1200 ml / min to carry out carbonation. Simultaneously with the introduction of carbon dioxide, a solution of 0.56 g of sodium pyrophosphate dissolved in 25 ml of water was added to the lime milk. 85 minutes after the start of the reaction
Was 7.0, the introduction of carbon dioxide gas was stopped, the lime milk was filtered, washed with alcohol, and dried at 110 ° C. for 12 hours. As a result of powder X-ray diffraction, all of the dried product was calcite, and as a result of observation by a scanning electron microscope, a plate-like structure having a thickness of 0.2 μm and a particle size of 3 μm was radially aggregated. 10 μm spherical particles were formed.
Its pore volume was 0.79 ml / g, the specific surface area was about 10 m 2 / g, and the oil absorption of DOP was 60 ml / 100 g.
【００３２】（実施例４）塩化ストロンチウム２水和物
０．４５ｇを含む６重量％、１５℃の石灰乳４００ｍｌ
を攪拌しながら炭酸ガスを６００ｍｌ／分で導入し、炭
酸化を行った。炭酸ガス導入開始と同時にヘキサメタリ
ン酸ナトリウム０．２４ｇを水１５ｍｌに溶解した液を
石灰乳に添加した。炭酸ガス導入より６０分で石灰乳の
ｐＨが７．０になったので炭酸ガスの導入を停止し、石
灰乳を濾過し、アルコール洗浄した後、１１０℃で１２
時間乾燥した。この乾燥品は、Ｘ線回折の結果、カルサ
イト型炭酸カルシウムであり、走査型電子顕微鏡観察の
結果、厚さ０．１μｍ、粒子径２．５μｍの板状構造を
したものが放射状に凝集し、約２０μｍの球状粒子を形
成していた。このものの細孔容積は０．９４ｍｌ／ｇ、
比表面積は約３．６ｍ 2 ／ｇ、ＤＯＰの吸油量は１２０
ｍｌ／１００ｇであった。Example 4 Strontium chloride dihydrate
400 ml of 6% by weight, 15 ° C. lime milk containing 0.45 g
While stirring, carbon dioxide gas was introduced at 600 ml / min.
Oxidation was performed. Hexametallic at the same time as the introduction of carbon dioxide
A solution prepared by dissolving 0.24 g of sodium phosphate in 15 ml of water
Added to lime milk. 60 minutes from the introduction of carbon dioxide,
When the pH reached 7.0, the introduction of carbon dioxide gas was stopped,
After filtering off the ashes and washing with alcohol,
Dried for hours. As a result of X-ray diffraction,
Calcium carbonate
As a result, a plate-like structure with a thickness of 0.1 μm and a particle diameter of 2.5 μm was formed.
Are aggregated radially to form spherical particles of about 20 μm.
Had been done. Its pore volume is 0.94 ml / g,
The specific surface area is about 3.6m Two/ G, DOP oil absorption is 120
ml / 100 g.
【００３３】（実施例５）塩化ストロンチウム２水和物
０．４５ｇを含む６重量％、１３℃の石灰乳８００ｍｌ
を攪拌しながら炭酸ガスを１２００ｍｌ／分で導入し、
炭酸化を行った。炭酸ガス導入開始１分後にヘキサメタ
リン酸ナトリウム０．４８ｇを水１５ｍｌに溶解した液
を石灰乳に添加した。反応開始より５０分後に電気伝導
度が反応前より３．２ｍＳ／ｃｍ降下したので炭酸ガス
の導入を停止した。この時の石灰乳の炭酸化率は６５％
であった。この石灰乳を濾過し、アルコール洗浄した
後、１１０℃で１２時間乾燥した。この乾燥品を粉末Ｘ
線回折の結果、カルサイトと塩基性炭酸カルシウムであ
り、走査型電子顕微鏡観察の結果、厚さ０．１５μｍ、
粒子径３μｍの板状構造をしたものが放射状に凝集し、
約１５μｍの球状粒子を形成していた。この乾燥品１０
０ｇを１０４μｍの篩を通過させ、円筒形容器に充填
し、５５０℃に加熱した縦型電気炉に装着し、下部から
１００％炭酸ガスを１００ｍｌ／分で２０時間炭酸化を
行った。炭酸化反応終了後のＸ線回折の結果、カルサイ
トのみであり、他の結晶構造は認められなかった。走査
型電子顕微鏡の写真を図３に示した。観察の結果、厚さ
０．１５μｍ、大きさ３μｍの板状構造をしたものが放
射状に凝集し、約１５μｍの球状粒子を形成していた。
このものの細孔容積は１．２２ｍｌ／ｇ、比表面積は８
ｍ2 ／ｇ、ＤＯＰの吸油量は１５０ｍｌ／１００ｇであ
った。Example 5 800 ml of lime milk at 13 ° C. containing 6% by weight containing 0.45 g of strontium chloride dihydrate
While stirring, carbon dioxide gas was introduced at 1200 ml / min,
Carbonation was performed. One minute after the start of carbon dioxide gas introduction, a solution of 0.48 g of sodium hexametaphosphate dissolved in 15 ml of water was added to the lime milk. 50 minutes after the start of the reaction, the electric conductivity dropped 3.2 mS / cm from that before the reaction, so the introduction of carbon dioxide gas was stopped. The carbonation rate of the lime milk at this time is 65%
Met. The lime milk was filtered, washed with alcohol, and dried at 110 ° C. for 12 hours. This dried product is powder X
As a result of line diffraction, it was calcite and basic calcium carbonate, and as a result of observation by a scanning electron microscope, the thickness was 0.15 μm,
Those having a plate-like structure with a particle diameter of 3 μm aggregate radially,
Approximately 15 μm spherical particles were formed. This dried product 10
0 g was passed through a 104 μm sieve, filled in a cylindrical container, and mounted in a vertical electric furnace heated to 550 ° C., and carbonized from the bottom with 100% carbon dioxide at 100 ml / min for 20 hours. As a result of X-ray diffraction after completion of the carbonation reaction, it was only calcite, and no other crystal structure was observed. A photograph of the scanning electron microscope is shown in FIG. As a result of observation, a plate-like structure having a thickness of 0.15 μm and a size of 3 μm was radially aggregated to form spherical particles of about 15 μm.
It has a pore volume of 1.22 ml / g and a specific surface area of 8
m 2 / g, and the oil absorption of DOP was 150 ml / 100 g.
【００３４】（実施例６）実施例２のＡ液４００ｍｌに
ヘキサメタリン酸ナトリウム０．１８ｇを含む６重量％
の石灰乳（以下「Ｃ液」という）４００ｍｌを注加し、
石灰乳温度２０℃に調整後、炭酸ガスを６００ｍｌ／分
で導入し、４５分後に電気伝導度が反応前より７．０ｍ
Ｓ／ｃｍ降下したので、炭酸ガスの導入を停止した。こ
の石灰乳４００ｍｌに新たにＣ液４００ｍｌを注加し、
上記の条件下で炭酸化を行い、同様に電気伝導度が反応
前より７．０ｍＳ／ｃｍ降下した時点で炭酸ガスの導入
を停止した。このような反応を５回繰り返したところ、
この石灰乳の炭酸化率は６９％であり、この石灰乳を濾
過し、アルコール洗浄した後、１１０℃で１２時間乾燥
した。この乾燥品は、粉末Ｘ線回折の結果、図６に示す
とおりカルサイト、塩基性炭酸カルシウムおよび消石灰
であり、走査型電子顕微鏡観察の結果、厚さ０．３μ
ｍ、粒子径３．５μｍの板状構造をしたものが放射状に
凝集し、約２７μｍの球状粒子を形成していた。この乾
燥品１００ｇを１０４μｍの篩を通過させ、円筒形容器
に充填し、５５０℃に加熱した縦型電気炉に装着し、下
部から１００％炭酸ガスを１００ｍｌ／分で２０時間炭
酸化を行った。炭酸化反応終了後のＸ線回折の結果、カ
ルサイトのみであり、他の結晶構造は認められなかっ
た。走査型電子顕微鏡観察の結果、厚さ０．３μｍ、粒
子径３．５μｍの板状構造をしたものが放射状に凝集
し、約２７μｍの球状粒子を形成していた。Example 6 6% by weight of 0.1 ml of sodium hexametaphosphate in 400 ml of solution A of Example 2
400 ml of lime milk (hereinafter referred to as "liquid C")
After adjusting the lime milk temperature to 20 ° C., carbon dioxide gas was introduced at 600 ml / min, and after 45 minutes, the electric conductivity was 7.0 m higher than before the reaction.
Since the pressure dropped by S / cm, the introduction of carbon dioxide gas was stopped. 400 ml of liquid C is newly added to 400 ml of this lime milk,
Carbonation was carried out under the above conditions, and the introduction of carbon dioxide gas was stopped when the electric conductivity dropped by 7.0 mS / cm from that before the reaction. When such a reaction was repeated five times,
This lime milk had a carbonation rate of 69%. The lime milk was filtered, washed with alcohol, and then dried at 110 ° C. for 12 hours. The dried product was calcite, basic calcium carbonate and slaked lime as shown in FIG. 6 as a result of powder X-ray diffraction.
The plate-like structure having a particle diameter of 3.5 μm and a particle diameter of 3.5 μm aggregated radially to form spherical particles of about 27 μm. 100 g of the dried product was passed through a 104 μm sieve, filled in a cylindrical container, and mounted in a vertical electric furnace heated to 550 ° C., and carbonized from the lower part with 100% carbon dioxide at 100 ml / min for 20 hours. . As a result of X-ray diffraction after completion of the carbonation reaction, it was only calcite, and no other crystal structure was observed. As a result of observation with a scanning electron microscope, a plate-like structure having a thickness of 0.3 μm and a particle diameter of 3.5 μm was radially aggregated to form spherical particles of about 27 μm.
【００３５】（実施例７）６重量％で１５℃の石灰乳１
６００ｍｌを攪拌しながら、２５容量％の炭酸ガス（以
下炭酸ガスという）を３６００ｍｌ／分で導入し、炭酸
化を行った。炭酸ガス導入開始と同時にヘキサメタリン
酸ナトリウム０．９６ｇを水５０ｍｌに溶解した液を添
加した。反応開始より４０分後に電気伝導度が反応前よ
り４．１ｍＳ／ｃｍ降下したので、炭酸ガスの導入を停
止した。このときの乳液の炭酸化率は６５％であった。
この乳液から固形物を通常の方法で濾過し、アルコール
洗浄した後、１１０℃で１２時間乾燥した。この乾燥固
形物を粉末Ｘ線回折の結果、カルサイトと塩基性炭酸カ
ルシウムであり、走査型電子顕微鏡観察の結果、厚さ
０．１５μｍ、粒子径１μｍの板状構造をしたものが、
放射状に凝集し、５μｍの球状粒子を形成していた。こ
の乾燥品１００ｇを１０４μｍの篩を通過させ、円筒形
容器に充填し、５５０℃に加熱した縦型電気炉に装着
し、下部から１００％炭酸ガスを１００ｍｌ／分で２０
時間炭酸化を行った。炭酸化反応終了後のＸ線回折の結
果、カルサイトのみであり、他の結晶構造は認められな
かった。走査型電子顕微鏡観察の結果、厚さ０．１５μ
ｍ、粒子径１μｍの板状構造をしたものが、放射状に凝
集し、約５μｍの球状粒子を形成していた。このもの
は、細孔容積０．６ｍｌ／ｇであった。また、ＢＥＴ法
による比表面積は、５ｍ2 ／ｇ、ＤＯＰも吸油量は６０
ｍｌ／１００ｇであった。Example 7 Milk of Lime 1 at 6 ° C. and 15 ° C.
While stirring 600 ml, carbon dioxide was introduced by introducing 25% by volume of carbon dioxide gas (hereinafter referred to as carbon dioxide gas) at 3600 ml / min. At the same time as the introduction of carbon dioxide gas, a solution prepared by dissolving 0.96 g of sodium hexametaphosphate in 50 ml of water was added. Forty minutes after the start of the reaction, the electric conductivity dropped by 4.1 mS / cm from that before the reaction, so the introduction of carbon dioxide gas was stopped. At this time, the carbonation ratio of the emulsion was 65%.
The solid was filtered from the emulsion by a conventional method, washed with alcohol, and dried at 110 ° C. for 12 hours. As a result of powder X-ray diffraction, the dried solid was calcite and basic calcium carbonate. As a result of observation by a scanning electron microscope, a plate-like structure having a thickness of 0.15 μm and a particle diameter of 1 μm was obtained.
The particles aggregated radially to form 5 μm spherical particles. 100 g of the dried product was passed through a 104 μm sieve, filled in a cylindrical container, and mounted in a vertical electric furnace heated to 550 ° C., and 100% carbon dioxide gas was supplied from the bottom at 100 ml / min.
Carbonation was performed for hours. As a result of X-ray diffraction after completion of the carbonation reaction, it was only calcite, and no other crystal structure was observed. As a result of observation by a scanning electron microscope, the thickness was 0.15 μm.
m, a plate-like structure having a particle diameter of 1 μm was radially aggregated to form spherical particles of about 5 μm. This had a pore volume of 0.6 ml / g. The specific surface area by the BET method is 5 m 2 / g, and the oil absorption of DOP is 60
ml / 100 g.
【００３６】[0036]
【発明の効果】本発明の製造条件によって、石灰乳と二
酸化炭素の反応により生成される炭酸カルシウムは、板
状構造を有した炭酸カルシウムの一次粒子が球状に凝集
した比表面積が大きく、多孔質である板状炭酸カルシウ
ムの球状複合体であって、一次粒子間に間隙を有するた
め、直接その物質を使用すると問題がある場合、すなわ
ち農薬などを本発明の板状炭酸カルシウムの球状複合体
に担持させることにより、任意の濃度に調整し、かつ飛
散を防ぐことができる。また、香料、消臭剤などの揮発
性の物質を担持させることにより、持続性のある徐放剤
として利用できる。さらに、物質の吸着性を利用して、
乾燥剤、吸液剤、防臭剤としての用途並びに塗料、シー
ラント、接着剤、塩化ビニールペーストなどの増粘剤と
しての用途があり、その他、濾過助剤、粉体の成形助剤
および吸液用成形体、潤滑油用キャリヤー、製紙用原料
としても利用できる。According to the production conditions of the present invention, calcium carbonate produced by the reaction between milk of lime and carbon dioxide has a large specific surface area in which primary particles of calcium carbonate having a plate-like structure are aggregated in a spherical form, and have a large specific surface area. It is a spherical composite of plate-like calcium carbonate, which has a gap between the primary particles, if there is a problem when using the substance directly, that is, the pesticide etc. into the spherical composite of plate-like calcium carbonate of the present invention By supporting it, the concentration can be adjusted to an arbitrary value and scattering can be prevented. Also, by supporting volatile substances such as fragrances and deodorants, it can be used as a sustained sustained release agent. Furthermore, utilizing the adsorptivity of the substance,
Used as a desiccant, liquid absorbing agent, deodorant, and as a thickener for paints, sealants, adhesives, vinyl chloride paste, etc. In addition, filter aids, powder molding aids, and liquid absorption molding It can also be used as a body, a carrier for lubricating oil, and a raw material for papermaking.
【図１】板状構造をした炭酸カルシウムFIG. 1 Calcium carbonate having a plate-like structure
【図２】層状に凝集した球状複合体FIG. 2 is a spherical composite agglomerated in layers.
【図３】放射状に凝集した球状複合体FIG. 3 is a radially aggregated spherical composite.
【図４】実施例１におけるカルサイトと塩基性炭酸カル
シウムのＸ線回折FIG. 4 is an X-ray diffraction of calcite and basic calcium carbonate in Example 1.
【図５】実施例１におけるカルサイトのＸ線回折FIG. 5 is an X-ray diffraction of calcite in Example 1.
【図６】実施例６におけるカルサイト、塩基性炭酸カル
シウムおよび水酸化カルシウムのＸ線回折FIG. 6: X-ray diffraction of calcite, basic calcium carbonate and calcium hydroxide in Example 6
Ａ．板状構造を有した炭酸カルシウムの一次粒子 １．板状構造を有した炭酸カルシウムの単一結晶 A. Primary particles of calcium carbonate having a plate-like structure Single crystal of calcium carbonate with plate-like structure
───────────────────────────────────────────────────── フロントページの続き (72)発明者 薬師寺 良行 大分県臼杵市大字井村2052番地の３ (72)発明者 森 一晃 大分県津久見市上宮本町10番21号 (72)発明者 水口 正昭 大阪府大阪市東淀川区井高野２丁目１番37 号 鈴木油脂工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Yakushiji 3rd, 2052 Imura, Oaza, Usuki City, Oita Prefecture (72) Inventor Kazuaki Mori 10-21 Kamimiyahonmachi, Tsukumi City, Oita Prefecture (72) Inventor Masaaki Mizuguchi Osaka Suzuki Yushi Kogyo Co., Ltd. 2-137 Idano, Higashiyodogawa-ku, Osaka
Claims (17)
子が球状に凝集した板状炭酸カルシウムの球状複合体。A spherical composite of plate-like calcium carbonate in which primary particles of calcium carbonate having a plate-like structure are aggregated in a spherical shape.
リンを含有した請求項１記載の板状炭酸カルシウムの球
状複合体。2. The spherical composite of plate-like calcium carbonate according to claim 1, which contains an alkaline earth metal other than calcium and phosphorus.
次粒子の径が０．２〜１０μｍ、厚さが０．０２〜２μ
ｍである請求項１または２記載の板状炭酸カルシウムの
球状複合体。3. The primary particles of calcium carbonate having a plate-like structure have a diameter of 0.2 to 10 μm and a thickness of 0.02 to 2 μm.
The spherical composite of plate-like calcium carbonate according to claim 1 or 2, wherein m is m.
請求項１から３のいずれか１項に記載の板状炭酸カルシ
ウムの球状複合体。4. The spherical composite of plate-like calcium carbonate according to any one of claims 1 to 3, wherein the pore volume is 0.1 to 3 ml / g or more.
カルシウム、塩基性炭酸カルシウムと炭酸カルシウムの
複合物、炭酸カルシウムと水酸化カルシウムの複合物、
塩基性炭酸カルシウムと水酸化カルシウムと炭酸カルシ
ウムの複合物、炭酸カルシウムが球状に凝集した板状炭
酸カルシウムの球状複合体を二酸化炭素と加熱下で接触
させ、塩基性炭酸カルシウム、塩基性炭酸カルシウムと
炭酸カルシウムの複合物、塩基性炭酸カルシウムと水酸
化カルシウムと炭酸カルシウムの複合物を炭酸カルシウ
ムに変化させた板状炭酸カルシウムの球状複合体。5. The primary particles having a plate-like structure are basic calcium carbonate, a composite of basic calcium carbonate and calcium carbonate, a composite of calcium carbonate and calcium hydroxide,
A complex of basic calcium carbonate, calcium hydroxide, and calcium carbonate, and a spherical composite of plate-like calcium carbonate in which calcium carbonate is aggregated in a spherical form are brought into contact with carbon dioxide under heating to form a mixture of basic calcium carbonate and basic calcium carbonate. A spherical composite of plate-like calcium carbonate obtained by converting a composite of calcium carbonate and a composite of basic calcium carbonate, calcium hydroxide and calcium carbonate into calcium carbonate.
リンを含有した請求項５記載の板状炭酸カルシウムの球
状複合体。6. The spherical composite of plate-like calcium carbonate according to claim 5, which contains an alkaline earth metal other than calcium and phosphorus.
１０μｍ、厚さが０．０２〜２μｍである、塩基性炭酸
カルシウム、炭酸カルシウムまたは水酸化カルシウムで
ある請求項５または６記載の板状炭酸カルシウムの球状
複合体。7. The particle size of the primary particles having a plate-like structure is 0.2 to 0.2.
The spherical composite of plate-like calcium carbonate according to claim 5 or 6, which is basic calcium carbonate, calcium carbonate or calcium hydroxide having a thickness of 10 µm and a thickness of 0.02 to 2 µm.
請求項５から７のいずれか１項に記載の板状炭酸カルシ
ウムの球状複合体。8. The spherical composite of plate-like calcium carbonate according to claim 5, which has a pore volume of 0.1 to 3 ml / g or more.
乳」という）と二酸化炭素を反応させて水酸化カルシウ
ムの炭酸化反応を行うにあたり、縮合リン酸化合物の存
在下、塩基性炭酸カルシウムが生成する反応条件で、石
灰乳の電気伝導度が反応前に対して２〜１０ｍＳ／ｃｍ
降下したときに炭酸化反応を止めることおよび炭酸化反
応を終了させることを特徴とする板状炭酸カルシウムの
球状複合体の製造方法。9. A method of reacting carbon dioxide with an aqueous suspension of calcium hydroxide (hereinafter referred to as "lime milk") to carry out a carbonation reaction of calcium hydroxide, wherein a basic calcium carbonate is present in the presence of a condensed phosphoric acid compound. Under the reaction conditions in which the electrical conductivity of the lime milk is 2 to 10 mS / cm with respect to that before the reaction.
A method of producing a spherical composite of plate-like calcium carbonate, wherein the carbonation reaction is stopped and the carbonation reaction is terminated when the mixture falls.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物の存在下、塩基性炭酸カルシウムが生成する反応条
件で、石灰乳の電気伝導度が反応前に対して２〜１０ｍ
Ｓ／ｃｍ降下したときに炭酸化反応を止めた後、さらに
縮合リン酸化合物および炭酸化率が７０％以下の石灰乳
を添加し、二酸化炭素を反応させることおよび炭酸化反
応を終了させることを特徴とする板状炭酸カルシウムの
球状複合体の製造方法。10. The reaction of lime milk with carbon dioxide by reacting lime milk with carbon dioxide under a reaction condition in which basic calcium carbonate is generated in the presence of a condensed phosphoric acid compound. Is 2 to 10 m before the reaction
After stopping the carbonation reaction when the S / cm has dropped, it is further added that a condensed phosphoric acid compound and lime milk having a carbonation rate of 70% or less are added to react carbon dioxide and terminate the carbonation reaction. A method for producing a spherical composite of plate-like calcium carbonate.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物およびカルシウム以外のアルカリ土類金属化合物の
存在下、塩基性炭酸カルシウムが生成する反応条件で、
石灰乳の電気伝導度が反応前に対して２〜１０ｍＳ／ｃ
ｍ降下したときに炭酸化反応を止めることおよび炭酸化
反応を終了させることを特徴とする板状炭酸カルシウム
の球状複合体の製造方法。11. A reaction in which a basic calcium carbonate is formed in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium when carbon dioxide is reacted by reacting lime milk with carbon dioxide. By condition,
The electrical conductivity of the lime milk is 2 to 10 mS / c before the reaction.
A method for producing a spherical composite of plate-like calcium carbonate, wherein the carbonation reaction is stopped and the carbonation reaction is terminated when the temperature falls by m.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物およびカルシウム以外のアルカリ土類金属化合物の
存在下、塩基性炭酸カルシウムが生成する反応条件で、
石灰乳の電気伝導度が反応前に対して２〜１０ｍＳ／ｃ
ｍ降下したときに炭酸化反応を止めた後、さらに縮合リ
ン酸化合物および炭酸化率が７０％以下の石灰乳を添加
し、二酸化炭素を反応させることおよび炭酸化反応を終
了させることを特徴とする板状炭酸カルシウムの球状複
合体の製造方法。12. A reaction in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium in the reaction of calcium carbonate by reacting milk of lime and carbon dioxide. By condition,
The electrical conductivity of the lime milk is 2 to 10 mS / c before the reaction.
m, after the carbonation reaction is stopped, a condensed phosphoric acid compound and a lime milk having a carbonation rate of 70% or less are further added to react carbon dioxide and terminate the carbonation reaction. For producing a spherical composite of plate-like calcium carbonate.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物の存在下、塩基性炭酸カルシウムが生成する反応条
件で、石灰乳の電気伝導度が反応前に対して２〜１０ｍ
Ｓ／ｃｍ降下したときに炭酸化反応を止めた後、さらに
縮合リン酸化合物および炭酸化率が７０％以下の石灰乳
を添加し、二酸化炭素を反応させることを２回以上繰り
返すことおよび炭酸化反応を終了させることを特徴とす
る板状炭酸カルシウムの球状複合体の製造方法。13. The reaction of lime milk with carbon dioxide by reacting lime milk with carbon dioxide under a reaction condition in which basic calcium carbonate is produced in the presence of a condensed phosphoric acid compound. Is 2 to 10 m before the reaction
After the carbonation reaction is stopped when the S / cm drops, the condensed phosphoric acid compound and lime milk having a carbonation rate of 70% or less are further added, and the reaction of carbon dioxide is repeated twice or more. A method for producing a spherical composite of plate-like calcium carbonate, which comprises terminating the reaction.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物およびカルシウム以外のアルカリ土類金属化合物の
存在下、塩基性炭酸カルシウムが生成する反応条件で、
石灰乳の電気伝導度が反応前に対して２〜１０ｍＳ／ｃ
ｍ降下したときに炭酸化反応を止めた後、さらに縮合リ
ン酸化合物および炭酸化率が７０％以下の石灰乳を添加
し、二酸化炭素を反応させることを２回以上繰り返すこ
とおよび炭酸化反応を終了させることを特徴とする板状
炭酸カルシウムの球状複合体の製造方法。14. A reaction in which basic calcium carbonate is formed in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium in the reaction of calcium carbonate by reacting milk of lime and carbon dioxide. By condition,
The electrical conductivity of the lime milk is 2 to 10 mS / c before the reaction.
m, the carbonation reaction is stopped, and then a condensed phosphoric acid compound and a lime milk having a carbonation rate of 70% or less are added, and the reaction of carbon dioxide is repeated twice or more. A method for producing a spherical composite of plate-like calcium carbonate, which is terminated.
カルシウムの炭酸化反応を行うにあたり、縮合リン酸化
合物およびカルシウム以外のアルカリ土類金属化合物の
存在下、塩基性炭酸カルシウムが生成する反応条件で、
石灰乳の電気伝導度が反応前に対して２〜１０ｍＳ／ｃ
ｍ降下したときに炭酸化反応を止めた後、さらに縮合リ
ン酸化合物およびカルシウム以外のアルカリ土類金属化
合物を含む炭酸化率が７０％以下の石灰乳を添加し、二
酸化炭素を反応させることを２回以上繰り返し、炭酸化
反応を止めることおよび炭酸化反応を終了させることを
特徴とする板状炭酸カルシウムの球状複合体の製造方
法。15. A reaction in which basic calcium carbonate is formed in the presence of a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium in the reaction of lime milk and carbon dioxide to cause carbonation of calcium hydroxide. By condition,
The electrical conductivity of the lime milk is 2 to 10 mS / c before the reaction.
m, the carbonation reaction is stopped, and then a lime milk containing a condensed phosphoric acid compound and an alkaline earth metal compound other than calcium and having a carbonation rate of 70% or less is added to react carbon dioxide. A method for producing a spherical composite of plate-like calcium carbonate, wherein the carbonation reaction is stopped and the carbonation reaction is terminated at least twice.
板状炭酸カルシウムの球状複合体を加熱下で、二酸化炭
素と接触させることおよび炭酸化反応を終了させること
を特徴とする板状炭酸カルシウムの球状複合体の製造方
法。16. A plate characterized in that the plate-like spherical composite of calcium carbonate according to any one of claims 5 to 8 is brought into contact with carbon dioxide under heating and the carbonation reaction is terminated. A method for producing a spherical composite of glassy calcium carbonate.
石灰乳と二酸化炭素を反応させて水酸化カルシウムの炭
酸化反応を行うにあたり、炭酸化反応を止めた後、また
は二酸化炭素を反応させた後に、その生成物を加熱下で
二酸化炭素と接触させることにより炭酸化反応を終了さ
せることを特徴とする板状炭酸カルシウムの球状複合体
の製造方法。17. The reaction of the lime milk according to claim 9 with carbon dioxide to carry out a carbonation reaction of calcium hydroxide, after the carbonation reaction is stopped, or when carbon dioxide is removed. A method for producing a spherical composite of plate-like calcium carbonate, wherein the carbonation reaction is terminated by bringing the product into contact with carbon dioxide under heating after the reaction.
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| JP2002087815A (en) * | 2000-09-12 | 2002-03-27 | Hokkaido Kyodo Sekkai Kk | Calcium carbonate powder and its manufacturing method |
| WO2003104311A1 (en) * | 2002-06-06 | 2003-12-18 | 丸尾カルシウム株式会社 | Foam stabilizer and foam molding containing the same |
| WO2004076352A1 (en) * | 2003-02-27 | 2004-09-10 | Okutama Kogyo Co., Ltd. | Spherical calcium carbonate and method for production thereof |
| WO2004108597A1 (en) * | 2003-06-05 | 2004-12-16 | Okutama Kogyo Co., Ltd. | Light calcium carbonate, method for production thereof and loading material for loading into paper |
| WO2006011661A1 (en) * | 2004-07-29 | 2006-02-02 | New Lime Kenkyusha Co Inc. | Cosmetic composition |
| JP2007500672A (en) * | 2003-05-29 | 2007-01-18 | スペシャルティ ミネラルズ （ミシガン） インク． | Synthesis of plate-like precipitated calcium carbonate |
| CN115057461A (en) * | 2022-06-13 | 2022-09-16 | 北京晨晰环保工程有限公司 | Ultra-small-size calcium hydroxide composite material, and preparation method and application thereof |
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1996
- 1996-08-21 JP JP22003796A patent/JP3376826B2/en not_active Expired - Lifetime
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| JP2002087815A (en) * | 2000-09-12 | 2002-03-27 | Hokkaido Kyodo Sekkai Kk | Calcium carbonate powder and its manufacturing method |
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| US7754176B2 (en) | 2003-02-27 | 2010-07-13 | Okutama Kogyo Co., Ltd. | Spherical calcium carbonate and method for producing thereof |
| WO2004076352A1 (en) * | 2003-02-27 | 2004-09-10 | Okutama Kogyo Co., Ltd. | Spherical calcium carbonate and method for production thereof |
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| JPWO2004076352A1 (en) * | 2003-02-27 | 2006-06-01 | 奥多摩工業株式会社 | Spherical calcium carbonate and method for producing the same |
| JP2007500672A (en) * | 2003-05-29 | 2007-01-18 | スペシャルティ ミネラルズ （ミシガン） インク． | Synthesis of plate-like precipitated calcium carbonate |
| JPWO2004108597A1 (en) * | 2003-06-05 | 2006-07-20 | 奥多摩工業株式会社 | LIGHT CALCIUM CARBONATE, PROCESS FOR PRODUCING THE SAME, AND PAPER MATERIAL INFLATING |
| CN100379683C (en) * | 2003-06-05 | 2008-04-09 | 奥多摩工业株式会社 | Light calcium carbonate, method for production thereof and loading material for loading into paper |
| JP4571583B2 (en) * | 2003-06-05 | 2010-10-27 | 奥多摩工業株式会社 | LIGHT CALCIUM CARBONATE, PROCESS FOR PRODUCING THE SAME, AND PAPER MATERIAL INFLATING |
| WO2004108597A1 (en) * | 2003-06-05 | 2004-12-16 | Okutama Kogyo Co., Ltd. | Light calcium carbonate, method for production thereof and loading material for loading into paper |
| JP2006063062A (en) * | 2004-07-29 | 2006-03-09 | New Raimu Kenkyusha:Kk | Cosmetic composition |
| WO2006011661A1 (en) * | 2004-07-29 | 2006-02-02 | New Lime Kenkyusha Co Inc. | Cosmetic composition |
| CN115057461A (en) * | 2022-06-13 | 2022-09-16 | 北京晨晰环保工程有限公司 | Ultra-small-size calcium hydroxide composite material, and preparation method and application thereof |
| CN115057461B (en) * | 2022-06-13 | 2023-10-27 | 北京晨晰环保工程有限公司 | Ultra-small-size calcium hydroxide composite material and preparation method and application thereof |
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