JP3634404B2 - Porous calcium carbonate compound and method for producing the same - Google Patents
Porous calcium carbonate compound and method for producing the same Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明は、多孔質炭酸カルシウム化合物及びその製造方法に関する。本発明の多孔質炭酸カルシウム化合物は、その表面が多孔質であるという特性によって、濾過助剤、増粘剤、各種徐放剤、乾燥剤、顔料や粉末の成形助剤等に広く利用され得る。
【０００２】
【従来の技術】
従来から多孔質物質は各種提案され、それぞれの特性に合った種々の分野で使用されている。これらの多孔質物質を構成する成分としては、ゼオライト、活性炭、ケイ酸カルシウム、リン酸カルシウム等がある。しかし、これらは一長一短があり、充分に満足しうるものとは云い難い。具体的には、これらは殆どが高価格であり、汎用的に大量に使用する分野では商品価値が乏しい。また品質的には、粒子の形状、空孔の大きさがほぼ固定的であり、各種用途に合った最適なスペックにする自由度が殆どないのが実情である。
【０００３】
【発明が解決しようとする課題】
本発明はかかる実情を鑑み、従来、多孔質物質の対象として検討されたことがない炭酸カルシウムを基材とし、これの表面を多孔質状にした安価で品質性能の優れた多孔質炭酸カルシウム化合物を提供するものである。
【０００４】
【課題を解決するための手段】
即ち、本発明の第１は、重質炭酸カルシウム又は合成炭酸カルシウムの表面に空孔を多数形成したリン酸カルシウム（但し、リン酸水素カルシウムを除く）を定着させてなり、原料の炭酸カルシウムに対しＢＥＴ法の比表面積が３〜１０倍であることを特徴とする多孔質炭酸カルシウム化合物を、
本発明の第２は、炭酸カルシウムの水スラリーにリン酸を投入して１５〜５０℃で反応させることを特徴とする上記多孔質炭酸カルシウム化合物の製造方法を、それぞれ内容とするものである。
【０００５】
炭酸カルシウムは他の無機物質に比べて形状制御が容易であるため、各種用途に合った形状を設定出来る。また、炭酸カルシウムは、Ca(OH)2 の水スラリーにCO2 ガスを導入してCaCO3 を析出させる方法で工業的に製造され、Ca(OH)2 とCO2 は石灰石を強熱分解させて生じるCaO とCO2 を原料として使用する。従って、製造コストは他の多孔質物質に比較して安い。即ち、一般の多孔質物質は複雑な製造方法で且つ多大な熱エネルギー等が必要なため、必然的に製造コストは高くなる。
【０００６】
以下、本発明を詳細に説明する。
本発明の多孔質炭酸カルシウム化合物は、炭酸カルシウムをリン酸と反応させることにより得られる。
本発明に使用する炭酸カルシウムは、重質炭酸カルシウム、合成炭酸カルシウムのいずれでもよい。また粒子径の大小、粒子形状、粒子の分散状態、結晶形、炭酸カルシウム中の不純物の程度等も特に限定されない。
【０００７】
リン酸の反応量は、炭酸カルシウムに対して約１〜５５重量％程度が好ましい。勿論、用途等によってはこれ以上でもよい。これは炭酸カルシウムの形状、粒子径の大小、使用分野等に応じて適宜決定すればよい。一般にリン酸の反応量が多くなる程、同一反応条件下であれば、ＢＥＴ比表面積は大きくなり、即ち、多孔質化は進行する。しかし、変曲点があり、ある量以上反応させると粒子が互に凝集し、ＢＥＴ比表面積はそれ以上大きくならない。また空孔も少々いびつなものとなる。一方、同一反応条件下では、一般にリン酸の反応量が少ない程、空孔の径は小さい。反応量が多くなる程径は大きくなり且つ花弁状化してくる。
本発明の多孔質炭酸カルシウム化合物の一般的な方法としては、炭酸カルシウムの水スラリーにリン酸を投入する方法が好ましい。
【０００８】
反応条件としては（１）系の反応温度、（２）リン酸の投入時間、（３）攪拌条件、（４）両者混合後の攪拌放置（熟成）時間、（５）反応系の濃度等が多孔質化させるための反応条件として関与する。
【０００９】
上記（１）については、１５〜３０℃の範囲で反応させるのが好ましい。これで反応が充分に進行しない時は両者を混合後、更に１５〜２０℃程度温度を上昇させればよい。最初から５０℃以上の温度で反応させると空孔がいびつな状態となり易い。
【００１０】
上記（２）については、上記したように、一般には炭酸カルシウムの水スラリーにリン酸を投入する方法がよいが、この場合、リン酸を一気に投入するのでなく、３０〜６０分以上かけて投入する方法が好ましい。一気に投入すると、粒子が凝集し且つ空孔がいびつとなり易い。
【００１１】
上記（３）については、ある一定以上の強い攪拌力で攪拌することが望ましい。攪拌力が弱いと粒子全体に均一な空孔状態が出来ない傾向がある。
【００１２】
上記（４）については、両者を混合後、好ましくは５時間以上、より好ましくは２０時間以上攪拌しながら熟成するのが望ましい。
【００１３】
上記（５）については、炭酸カルシウムは生産効率も考慮して考えれば５０〜２００ｇ CaCO3／リットル、より好ましくは６０〜１５０ｇ CaCO3／リットル程度がよい。
【００１４】
以上（１）〜（５）については、炭酸カルシウムの水スラリーにリン酸を投入する方法を想定したものである。このようにして多孔質化したものは、最初の炭酸カルシウムに比べてＢＥＴ法の比表面積が一般に３倍〜１０倍程度となる。本発明で生じる空孔の大きさは、平均で０．０１〜１．０μｍ程度である。時間をかけてゆっくりと両者を反応させた方が一般に空孔は小さく、且つ均一に多孔質化する。しかし上述の反応温度、攪拌力等も複雑に作用する。一方、一次粒子径が１μｍ以下のコロイド炭酸カルシウムや数μｍの軽質炭酸カルシウムは上記方法で多孔質化することで凝集粒子が生じ、単一粒子はもとの炭酸カルシウムより相当大きくなる傾向にある。
しかし、例えば、特開平４−３２１５１５号、特開平４−２２４１１０号、特開平３−８８７１４号等に記載の方法で生成させるアラゴナイト系炭酸カルシウムは、一般にほぼもとの一次粒子のままでそれ程強い凝集はない。
【００１５】
本発明により炭酸カルシウムが多孔質化される理由については必ずしも明らかでないが、炭酸カルシウム表面にリン酸カルシウムが定着反応し、これが多孔質状態を形成しているものと考えられる。
【００１６】
以上のようにして得られた本発明の多孔質炭酸カルシウム化合物は、従来の炭酸カルシウムや炭酸カルシウム複合体に比べて、比表面積が数段大きく且つ多孔質となっている。このような粉体特性のため、下記のような種々の分野で使用される。
【００１７】
（１）濾過助剤
多孔質で且つ表面積が大きいため、各種の濾過助剤として有用である。各種の工業排水処理、食品、生化学等の分野である。この他、エンジンのオイルフィルター等もある。本発明の多孔質炭酸カルシウム化合物を単独で用いてもよく、また他の濾過助剤と併用してもよい。またパルプ等に配合してシート化する、他の媒体と併用する等も可能である。特にウイスカー状のものは、濾過圧が上がらないので濾過助剤として最適である。
【００１８】
（２）製紙用原料
一般的な製紙用填料として、また高級油性の特性のため新聞紙の不透明度向上、印刷時の作業性向上（すべり止め）等の目的のため、ホワイトカーボンの代替として使用できる。高吸油性のためファクシミリ等の感熱紙に配合してヘッドの汚れを防止することが出来る。
【００１９】
（３）乾燥剤
粉体のままで吸湿性が必要な分野に乾燥剤として使用出来、また空孔の中に吸湿物質を注入して使用してもよい。
【００２０】
（４）粉末の成形助剤及び吸液用成形体等
各種液体の吸収性且つ保持性を必要とする分野である。
また、粉末の成型助剤として、それ自体では成型が難しい粉末に成型性を付与し、且つ場合によっては成型可能な粉末でもその成型強度を向上させるために用いられる。また各種顔料、染料等の着色剤を本発明の多孔質炭酸カルシウム化合物に担持させてプラスチック等の分野に着色剤として使用することが出来る。
【００２１】
（５）潤滑油用キャリヤー
潤滑油等の油を使用する分野において、直接油を投入すると環境衛生上の汚染、熱分解等の劣化等で問題がある場合は、本発明の多孔質炭酸カルシウム化合物に油を担持させて使用すれば上述の問題は解決する。
【００２２】
（６）徐放剤
各種徐放剤として、本発明の多孔質炭酸カルシウム化合物は有用である。例えば、香料、消臭剤等の各種揮発性物質を本発明の多孔質炭酸カルシウム化合物に担持させることで持続性のある香料、消臭剤として使用出来る。また銀等の抗菌剤を担持させることで防カビ剤等の抗菌体として使用出来る。例えば、特開平４−３２１５１５号等の方法で作られるウイスカー状炭酸カルシウムは、それ自体で空気フィルター等のフィルターの素材として有用であるが、本発明のように多孔質化し、且つ抗菌処理をすれば産業上の効果は、より一層向上する。
【００２３】
（７）各種物質の担持体
直接その物質を使用すると問題がある場合、また気体等を徐々に放出し持続性をもたせるための担持体として有用である。例えば、農薬を本発明の多孔質炭酸カルシウム化合物に担持させることで飛散を防ぐ目的も兼ねている。
更に、本発明の多孔質炭酸カルシウム化合物は空孔の大きさを調整出来るので、所望する持続期間を各農薬に応じて設定出来、且つ残留農薬が空孔に残らないように出来る。このような考えは、各種薬剤の担持体として広く応用出来る。
【００２４】
（８）増粘剤等
塗料、シーラント、接着剤、塩ビペースト等の増粘剤として使用出来る。また塗料の艶消し剤としても有用である。
以上のような各種の分野での使用が考えられるが、本発明の多孔質炭酸カルシウム化合物は、炭酸カルシウムを基材としているため人体に対しては非常に安全性が高いという特徴を有する。
【００２５】
【実施例】
以下実施例及び応用例に基づいて本発明を更に詳細に説明するが、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
一次粒子径が０．０７μｍの立方形炭酸カルシウムの固形分濃度が１０重量％で２０℃の水スラリーに、炭酸カルシウムに対して３０重量％のリン酸を投入して反応させた後、２４時間攪拌して熟成させ、単一粒子が２〜３μｍの多孔質炭酸カルシウム化合物を生成させた。
【００２６】
実施例２
０．０７μｍの立方体炭酸カルシウムを２〜３μｍの紡鐘形炭酸カルシウムに変更した以外は全て実施例１と同様に操作した。
【００２７】
実施例３
０．０７μｍの立方体炭酸カルシウムを長径３０μｍ、短径１μｍのウイスカー状炭酸カルシウムに変更した以外は全て実施例１と同様に操作した。
【００２８】
比較例１〜３
実施例１、２、３において、リン酸と反応させる前の炭酸カルシウムをそれぞれ比較例１、２、３のサンプルとした。
【００２９】
実施例１〜３の多孔質炭酸カルシウム化合物及び比較例１〜３の炭酸カルシウムの各サンプルの特性を測定した結果は表１のとおりである。
【００３０】
【表１】
応用例１
塩ビペーストに実施例１、２で得た多孔質炭酸カルシウム化合物、比較例１、２の炭酸カルシウム、及びＰＶＣペースト分野で増粘剤として広く用いられているコロイド状炭酸カルシウム「カルファイン２００」（丸尾カルシウム工業株式会社製）の各サンプルをそれぞれ増粘剤として用い、下記の配合にてＢ型粘度計により、粘度（２rpm 、20rpm)を測定した。結果を表２に示す。
（塩ビペースト配合）
ＰＶＣ樹脂（ゼオン１２１） ３０ｇ
ＤＯＰ ９０ｇ
サンプル ５ｇ
【００３２】
【表２】
比較例１、２の試料及び「カルファイン」を用いた場合は、上記配合では値が低すぎ測定不能であった。以上から、本発明の多孔質炭酸カルシウム化合物は、増粘剤として優れていることが分かる。
【００３４】
応用例２
エンジンオイルのオイルフィルター用として実施例３及び比較例２のサンプルを配合してオイルフィルター用濾紙を作成し、オイル中のカーボンの除去効率をテストした。結果を表３に示す。
【００３５】
【表３】
表３の結果から、本発明の多孔質炭酸カルシウム化合物は、濾過助剤として優れていることが分かる。
【００３７】
【発明の効果】
叙上のとおり、本発明の多孔質炭酸カルシウム化合物は、表面が多孔質という特性を利用し、濾過助剤、増粘剤、徐放剤、乾燥剤、顔料や粉末の成型助剤等の各種分野に有用である。[0001]
[Industrial application fields]
The present invention relates to a porous calcium carbonate compound and a method for producing the same. The porous calcium carbonate compound of the present invention can be widely used for filter aids, thickeners, various sustained-release agents, drying agents, pigments and powder molding aids, etc., due to the property that the surface is porous. .
[0002]
[Prior art]
Conventionally, various porous materials have been proposed and used in various fields suitable for each characteristic. Examples of components constituting these porous substances include zeolite, activated carbon, calcium silicate, calcium phosphate, and the like. However, these have merits and demerits, and it cannot be said that they are sufficiently satisfactory. Specifically, most of these are high-priced, and the commercial value is poor in a field where they are used in large quantities for general purposes. In terms of quality, the shape of the particles and the size of the pores are almost fixed, and there is almost no degree of freedom in making the optimum specifications suitable for various applications.
[0003]
[Problems to be solved by the invention]
In view of such circumstances, the present invention is a porous calcium carbonate compound having a low cost and excellent quality performance, which is based on calcium carbonate, which has not been studied as an object of porous materials, and has a porous surface. Is to provide.
[0004]
[Means for Solving the Problems]
That is, the first present invention, the calcium phosphate formed a large number of pores on the surface of the heavy calcium carbonate or synthetic calcium carbonate (excluding calcium hydrogen phosphate) to fix the result by, BET to calcium carbonate material A porous calcium carbonate compound characterized in that the specific surface area of the method is 3 to 10 times ,
The second aspect of the present invention includes the above-described methods for producing porous calcium carbonate compounds, wherein phosphoric acid is added to a water slurry of calcium carbonate and reacted at 15 to 50 ° C.
[0005]
Since calcium carbonate is easier to control the shape than other inorganic substances, it is possible to set a shape suitable for various applications. Moreover, calcium carbonate is industrially produced by introducing CO 2 gas into Ca (OH) 2 water slurry in a manner to precipitate CaCO 3, Ca (OH) 2 and CO 2 is allowed to strongly pyrolysis limestone The resulting CaO and CO 2 are used as raw materials. Therefore, the manufacturing cost is low compared to other porous materials. That is, since a general porous material is a complicated manufacturing method and requires a large amount of heat energy, the manufacturing cost inevitably increases.
[0006]
Hereinafter, the present invention will be described in detail.
The porous calcium carbonate compound of the present invention can be obtained by reacting calcium carbonate with phosphoric acid.
Calcium carbonate used in the present invention, heavy calcium carbonate may be either synthetic calcium carbonate. Further, the size of the particle size, the particle shape, the dispersed state of the particles, the crystal shape, the degree of impurities in the calcium carbonate, etc. are not particularly limited.
[0007]
The reaction amount of phosphoric acid is preferably about 1 to 55% by weight with respect to calcium carbonate. Of course, it may be more than that depending on the application. This may be appropriately determined according to the shape of calcium carbonate, the size of the particle diameter, the field of use, and the like. In general, the larger the reaction amount of phosphoric acid, the larger the BET specific surface area under the same reaction conditions, that is, the porous formation proceeds. However, there is an inflection point, and if the reaction is carried out for a certain amount or more, the particles aggregate with each other and the BET specific surface area does not increase any more. Also, the vacancies are a little distorted. On the other hand, under the same reaction conditions, generally, the smaller the reaction amount of phosphoric acid, the smaller the pore diameter. The larger the reaction amount, the larger the diameter and petals.
As a general method of the porous calcium carbonate compound of the present invention, a method of adding phosphoric acid to an aqueous slurry of calcium carbonate is preferable.
[0008]
The reaction conditions include (1) reaction temperature of the system, (2) phosphoric acid charging time, (3) stirring conditions, (4) stirring standing (aging) after mixing both, (5) reaction system concentration, etc. It is involved as a reaction condition for making it porous.
[0009]
About said (1), it is preferable to make it react in 15-30 degreeC. If the reaction does not proceed sufficiently, the temperature may be further increased by about 15 to 20 ° C. after mixing the two. When the reaction is carried out at a temperature of 50 ° C. or higher from the beginning, the pores tend to be distorted.
[0010]
As for the above (2), as described above, it is generally preferable to add phosphoric acid to an aqueous slurry of calcium carbonate. In this case, phosphoric acid is not charged all at once, but is charged over 30 to 60 minutes or more. Is preferred. When charged at once, the particles tend to agglomerate and the pores tend to be distorted.
[0011]
About said (3), it is desirable to stir with the strong stirring force more than a certain fixed value. If the stirring force is weak, there is a tendency that a uniform pore state cannot be formed in the entire particle.
[0012]
About (4), after mixing both, it is desirable to age with stirring for 5 hours or longer, more preferably 20 hours or longer.
[0013]
The above (5), calcium carbonate 50 to 200 g CaCO 3 / l when considered in consideration of production efficiency, more preferably from about 60 to 150 g CaCO 3 / l.
[0014]
About (1)-(5) above, the method of throwing phosphoric acid into the water slurry of calcium carbonate is assumed. The porous material thus obtained generally has a BET specific surface area of about 3 to 10 times that of the first calcium carbonate. The size of the holes generated in the present invention is about 0.01 to 1.0 μm on average. When the two are reacted slowly over time, the pores are generally smaller and become uniformly porous. However, the above reaction temperature, stirring force and the like also act in a complicated manner. On the other hand, colloidal calcium carbonate with a primary particle size of 1 μm or less and light calcium carbonate with several μm are made porous by the above-mentioned method to produce agglomerated particles, and single particles tend to be considerably larger than the original calcium carbonate. .
However, for example, aragonite-based calcium carbonate produced by the methods described in JP-A-4-321515, JP-A-4-224110, JP-A-3-88714 and the like is generally as strong as the primary particles. There is no aggregation.
[0015]
Although the reason why the calcium carbonate is made porous by the present invention is not necessarily clear, it is considered that calcium phosphate is fixed on the surface of the calcium carbonate to form a porous state.
[0016]
The porous calcium carbonate compound of the present invention obtained as described above has a specific surface area that is several steps larger and porous than conventional calcium carbonate and calcium carbonate composites. Due to such powder characteristics, it is used in various fields as described below.
[0017]
(1) Filter aid Since it is porous and has a large surface area, it is useful as various filter aids. Various industrial wastewater treatment, food, biochemistry and other fields. In addition, there are engine oil filters and the like. The porous calcium carbonate compound of the present invention may be used alone or in combination with other filter aids. It can also be blended with pulp or the like to form a sheet, or used in combination with other media. In particular, whisker-shaped ones are optimal as filter aids because the filtration pressure does not increase.
[0018]
(2) Raw material for papermaking Can be used as a substitute for white carbon for general papermaking fillers and for purposes such as improving the opacity of newspapers and improving workability during printing (slip prevention) due to its high-grade oil characteristics. . Due to its high oil absorbency, it can be blended into thermal paper such as facsimiles to prevent head contamination.
[0019]
(3) The desiccant powder can be used as a desiccant in a field where moisture absorption is required, or a hygroscopic substance may be injected into the pores.
[0020]
(4) It is a field that requires the absorbability and retention of various liquids such as powder molding aids and molded bodies for liquid absorption.
Further, as a powder molding aid, it is used to impart moldability to a powder that is difficult to mold by itself, and in some cases, even a moldable powder is used to improve its molding strength. Further, colorants such as various pigments and dyes can be supported on the porous calcium carbonate compound of the present invention and used as colorants in the field of plastics and the like.
[0021]
(5) Carriers for lubricating oils In the field of using oils such as lubricating oils, if there are problems due to environmental hygiene contamination, thermal decomposition, etc., when direct oil is added, the porous calcium carbonate compound of the present invention If the oil is supported on the above, the above-mentioned problems are solved.
[0022]
(6) Sustained release agent The porous calcium carbonate compound of the present invention is useful as various sustained release agents. For example, by supporting various volatile substances such as fragrances and deodorants on the porous calcium carbonate compound of the present invention, they can be used as persistent fragrances and deodorants. Moreover, it can be used as an antibacterial agent such as a fungicide by supporting an antibacterial agent such as silver. For example, whisker-like calcium carbonate produced by a method such as JP-A-4-321515 is useful as a material for a filter such as an air filter by itself, but is made porous as in the present invention and subjected to antibacterial treatment. Industrial effects will be further improved.
[0023]
(7) Carriers of various substances Useful when the substance is used directly, or as a carrier for gradually releasing gas or the like to provide sustainability. For example, the pesticide is supported on the porous calcium carbonate compound of the present invention to prevent scattering.
Furthermore, since the porous calcium carbonate compound of the present invention can adjust the size of the pores, a desired duration can be set according to each agricultural chemical, and the residual agricultural chemical can be prevented from remaining in the pores. Such an idea can be widely applied as a carrier for various drugs.
[0024]
(8) It can be used as a thickener such as a paint such as a thickener, a sealant, an adhesive, or a vinyl chloride paste. It is also useful as a matting agent for paints.
Although it can be used in various fields as described above, the porous calcium carbonate compound of the present invention is characterized by being extremely safe for the human body because it is based on calcium carbonate.
[0025]
【Example】
Hereinafter, the present invention will be described in more detail based on examples and application examples, but the present invention is not limited to these examples.
Example 1
After adding and reacting 30% by weight of phosphoric acid with respect to calcium carbonate in a water slurry at 20 ° C. with a solid content concentration of 10% by weight of cubic calcium carbonate having a primary particle size of 0.07 μm, 24 hours The mixture was aged with stirring to produce a porous calcium carbonate compound having a single particle of 2 to 3 μm.
[0026]
Example 2
All operations were performed in the same manner as in Example 1 except that the 0.07 μm cubic calcium carbonate was changed to a 2-3 μm bell-shaped calcium carbonate.
[0027]
Example 3
All operations were performed in the same manner as in Example 1 except that 0.07 μm cubic calcium carbonate was changed to whisker-like calcium carbonate having a major axis of 30 μm and a minor axis of 1 μm.
[0028]
Comparative Examples 1-3
In Examples 1, 2, and 3, calcium carbonate before being reacted with phosphoric acid was used as samples of Comparative Examples 1, 2, and 3, respectively.
[0029]
Table 1 shows the results of measuring the characteristics of the samples of the porous calcium carbonate compounds of Examples 1 to 3 and the calcium carbonate of Comparative Examples 1 to 3.
[0030]
[Table 1]
Application example 1
The porous calcium carbonate compound obtained in Examples 1 and 2, the calcium carbonate of Comparative Examples 1 and 2 and the colloidal calcium carbonate “Calfine 200” widely used as a thickener in the PVC paste field. Each sample of Maruo Calcium Industry Co., Ltd. was used as a thickener, and the viscosity (2 rpm, 20 rpm) was measured with a B-type viscometer with the following composition. The results are shown in Table 2.
(Contains vinyl chloride paste)
PVC resin (Zeon 121) 30g
DOP 90g
Sample 5g
[0032]
[Table 2]
When the samples of Comparative Examples 1 and 2 and “Calfine” were used, the values were too low for the above formulation to be measured. From the above, it can be seen that the porous calcium carbonate compound of the present invention is excellent as a thickener.
[0034]
Application example 2
Samples of Example 3 and Comparative Example 2 were blended for use as an oil filter for engine oil to prepare an oil filter filter paper, and the removal efficiency of carbon in the oil was tested. The results are shown in Table 3.
[0035]
[Table 3]
From the results in Table 3, it can be seen that the porous calcium carbonate compound of the present invention is excellent as a filter aid.
[0037]
【The invention's effect】
As mentioned above, the porous calcium carbonate compound of the present invention utilizes the property that the surface is porous, and various kinds of filter aids, thickeners, sustained-release agents, desiccants, pigments and powder molding aids, etc. Useful in the field.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12958394A JP3634404B2 (en) | 1993-12-14 | 1994-05-18 | Porous calcium carbonate compound and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-343124 | 1993-12-14 | ||
| JP34312493 | 1993-12-14 | ||
| JP12958394A JP3634404B2 (en) | 1993-12-14 | 1994-05-18 | Porous calcium carbonate compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07223813A JPH07223813A (en) | 1995-08-22 |
| JP3634404B2 true JP3634404B2 (en) | 2005-03-30 |
Family
ID=26464934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12958394A Expired - Fee Related JP3634404B2 (en) | 1993-12-14 | 1994-05-18 | Porous calcium carbonate compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3634404B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013043786A (en) * | 2011-08-22 | 2013-03-04 | Ehime Prefecture | Calcium compound, method for producing the same and enamel paper |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129310A (en) * | 1997-07-11 | 1999-02-02 | Maruo Calcium Co Ltd | Material for heat-sensitive recording paper and heat-sensitive recording paper |
| JP2002338896A (en) * | 2001-05-21 | 2002-11-27 | Maruo Calcium Co Ltd | Matting agent for coating material and coating material composition containing the same |
| EP2168572A1 (en) | 2008-09-30 | 2010-03-31 | Omya Development Ag | New controlled release active agent carrier |
| PL2421508T3 (en) * | 2009-04-24 | 2017-06-30 | Omya International Ag | Particulate material for controlled release of active ingredients |
| ES2384017T3 (en) * | 2009-06-15 | 2012-06-28 | Omya Development Ag | Process to prepare calcium carbonate that reacts on the surface and its use |
| EP3216510A1 (en) | 2016-03-07 | 2017-09-13 | Omya International AG | A particulate earth alkali carbonate-comprising material for nox uptake |
| EP4274952A1 (en) | 2021-01-11 | 2023-11-15 | Omya International AG | A particulate magnesium ion-comprising material for nox uptake |
-
1994
- 1994-05-18 JP JP12958394A patent/JP3634404B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013043786A (en) * | 2011-08-22 | 2013-03-04 | Ehime Prefecture | Calcium compound, method for producing the same and enamel paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07223813A (en) | 1995-08-22 |
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