JPH04321515A - Production of aragonite crystal calcium carbonate having large grain diameter of needlelike shape - Google Patents
Production of aragonite crystal calcium carbonate having large grain diameter of needlelike shapeInfo
- Publication number
- JPH04321515A JPH04321515A JP11697191A JP11697191A JPH04321515A JP H04321515 A JPH04321515 A JP H04321515A JP 11697191 A JP11697191 A JP 11697191A JP 11697191 A JP11697191 A JP 11697191A JP H04321515 A JPH04321515 A JP H04321515A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- aragonite
- phosphoric acid
- acicular
- slurry
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 168
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 56
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000002002 slurry Substances 0.000 claims abstract description 44
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 34
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 34
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims abstract description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 claims abstract description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 51
- -1 phosphoric acid compound Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 239000007836 KH2PO4 Substances 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000012779 reinforcing material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 40
- 238000000034 method Methods 0.000 description 30
- 230000000704 physical effect Effects 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 229910021532 Calcite Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、針状形状をした大粒径
のアラゴナイト結晶炭酸カルシウムの製造方法に関し、
更に詳しくは、各種プラスチック配合用の補強材、ブレ
ーキライニング用の補強材、及び各種シーリング材、接
着剤、塗料等の増粘材等に好適な、大粒径、即ち長径５
〜１００μｍ、短径０．１〜４．０μｍ程度で高分散性
の針状形状アラゴナイト結晶炭酸カルシウム（以下、大
粒径の針状形状アラゴナイト炭酸カルシウムと記す）に
関する。[Industrial Application Field] The present invention relates to a method for producing aragonite crystalline calcium carbonate having a large particle size and having an acicular shape.
More specifically, it is suitable for reinforcing materials for various plastic formulations, reinforcing materials for brake linings, and thickeners for various sealants, adhesives, paints, etc.
It relates to highly dispersible acicular-shaped aragonite crystal calcium carbonate (hereinafter referred to as large-particle-diameter acicular-shaped aragonite calcium carbonate) with a diameter of 100 μm and a minor axis of about 0.1 to 4.0 μm.
【０００２】0002
【従来の技術】アラゴナイト結晶炭酸カルシウム（以下
、アラゴナイトと略記する）はカルサイト結晶炭酸カル
シウム（以下、カルサイトと略記する）に比べて粒子の
分散性が優れている。また、カルサイトにはない柱状と
いう結晶習性（Ｃｒｙｓｔａｌ ｈａｂｂｉｔ）は、カ
ルサイトでは期待できない色々の特性を発揮する。従っ
て、従来から工業的にアラゴナイトを、より効率的に生
産することが試みられて来た。しかし、これらの方法に
より得られたアラゴナイトは殆どが微細な針状形状（長
径０．５〜３．０μｍ、短径０．１〜０．７μｍ程度）
であり、塗工紙の印刷適性を向上させるために、塗工紙
表面に使用されてきた。従来、例えば、Ｃａ（ＯＨ）２
スラリーとＣＯ２ ガスとの気液反応に関する技術と
しては、炭酸化工程でＣＯ２ ガス量を各段階で調整し
て行う方法（特公昭５５−５１８５２）、Ｃａ（ＯＨ）
２ スラリーにあらかじめ結晶核形成剤を加える方法（
特開昭５９−２２３２２５）等がある。BACKGROUND OF THE INVENTION Aragonite crystalline calcium carbonate (hereinafter abbreviated as aragonite) has better particle dispersibility than calcite crystalline calcium carbonate (hereinafter abbreviated as calcite). In addition, its crystal habit of columnar shape, which calcite does not have, exhibits various properties that cannot be expected from calcite. Therefore, attempts have been made to industrially produce aragonite more efficiently. However, most of the aragonite obtained by these methods has a fine needle-like shape (long axis 0.5 to 3.0 μm, short axis 0.1 to 0.7 μm).
It has been used on the surface of coated paper to improve its printability. Conventionally, for example, Ca(OH)2
Technologies related to the gas-liquid reaction between slurry and CO2 gas include a method in which the amount of CO2 gas is adjusted at each stage in the carbonation process (Japanese Patent Publication No. 55-51852), Ca(OH)
2 Method of adding a crystal nucleating agent to the slurry in advance (
JP-A-59-223225), etc.
【０００３】一方、より大きな針状形状をしたアラゴナ
イトを生成させれば、色々な工業的用途が開けるであろ
うと期待されている。大きな針状形状をしたアラゴナイ
トを作る方法としては、特開昭６２−２７８１２３、特
開昭６２−２７３２５等により提案されているが、これ
らは水酸化カルシウムの水飽和溶液〔Ｃａ（ＯＨ）２
の溶解度は０℃、１００ｇの水に０．１８５ｇ〕から生
成させるため生産効率が極めて悪く、工業用原料の製法
としては極めて不適当である。また特開昭５８−３６９
２４には、アラゴナイトと水酸化カルシウムのモル比が
１〜５の範囲で炭酸化させ粒子を大きくする方法が開示
されている。しかし乍ら、かかる方法では得られる粒子
の大きさは精々長径１．４〜４．５μｍ、短径０．１２
〜０．６μｍ程度のアラゴナイトであり、更に粒子を大
きくせんとして上記モル比を大きくすると、殆どカルサ
イト型の炭酸カルシウムとなってしまう。On the other hand, it is expected that the production of aragonite with a larger needle-like shape will open up a variety of industrial uses. Methods for producing large needle-shaped aragonite have been proposed in JP-A-62-278123, JP-A-62-27325, etc., but these methods are based on an aqueous saturated solution of calcium hydroxide [Ca(OH)2].
The solubility is 0.185 g in 100 g of water at 0°C], so the production efficiency is extremely low, and this is extremely inappropriate as a method for producing industrial raw materials. Also, JP-A-58-369
No. 24 discloses a method of enlarging particles by carbonation at a molar ratio of aragonite and calcium hydroxide in a range of 1 to 5. However, with this method, the size of the particles obtained is at most 1.4 to 4.5 μm in major axis and 0.12 μm in minor axis.
It is aragonite with a size of about 0.6 μm, and if the molar ratio is increased by making the particles larger, it becomes mostly calcite-type calcium carbonate.
【０００４】本発明者らは、大粒径、即ち長径が１０〜
１００μｍ程度の針状形状アラゴナイト炭酸カルシウム
の工業的製造方法を確立し、先に特許出願した（特願平
１−１６７２６７）。この方法は大粒径の針状結晶アラ
ゴナイト炭酸カルシウムの工業的製法としては非常に効
率がよいが、生成する粒子が必ずしも充分に分散した状
態にない。従って、プラスチック、その他に使用した場
合、その効果を最大限に発揮することができない。例え
ばポリプロピレンの補強剤として使用した場合、複合材
としてのポリプロピレンの物性は、できる限りアスペク
ト比が大きく且つ針状粒子ができる限り一次粒子に近い
状態まで分散した針状形状アラゴナイト炭酸カルシウム
の方が優れている。特に曲げ弾性率でその効果は顕著で
ある。凝集粒子であるとその凝集点が強度的に弱く、プ
ラスチック成型時等において、その点から破損しアスペ
クト比が低下する。このことも凝集粒子が充分な効果を
発揮できない一因と考えられる。以上の理由より、一次
粒子に近い状態まで高分散した大粒径針状結晶アラゴナ
イト炭酸カルシウムを供給することは非常に重要なこと
である。[0004] The present inventors discovered that the large particle size, that is, the major axis is 10~
We established an industrial method for producing aragonite calcium carbonate having a needle-like shape of about 100 μm and filed a patent application (Japanese Patent Application No. 1-167267). Although this method is very efficient as an industrial method for producing large-sized acicular crystal aragonite calcium carbonate, the particles produced are not necessarily in a sufficiently dispersed state. Therefore, when used in plastics or other materials, the effect cannot be maximized. For example, when used as a reinforcing agent for polypropylene, the physical properties of polypropylene as a composite material are superior to acicular-shaped aragonite calcium carbonate, which has as large an aspect ratio as possible and has acicular particles dispersed as close to primary particles as possible. ing. The effect is particularly remarkable in bending elastic modulus. If the particles are agglomerated, their agglomeration point is weak in strength, and during plastic molding, etc., the particles break from that point and the aspect ratio decreases. This is also considered to be one of the reasons why the aggregated particles cannot exhibit sufficient effects. For the above reasons, it is very important to supply large-sized acicular crystal aragonite calcium carbonate that is highly dispersed to a state close to that of primary particles.
【０００５】大粒径の針状形状アラゴナイト炭酸カルシ
ウムの製法としては、他に特開平２−３４５１４、特開
昭６２−２７８１２３等があるが、これらの方法は生産
効率、物性の両面で充分なものではない。特開平２−３
４５１４の製法は、反応槽に水酸化カルシウム水スラリ
ーを連続的に導入しながらＣＯ２ ガスを吹き込むもの
である。このとき反応槽中のカルシウムイオン濃度を０
．００１〜０．００５ｍｏｌ ／リットルの範囲になる
ようにＣＯ２ と水酸化カルシウム水スラリーの供給量
を調整するものである。このカルシウムイオン濃度の範
囲をｐＨに換算すると約６．８〜１０．２程度である。
この範囲内で水酸化カルシウム水スラリーを反応槽に供
給すると、たとえＣＯ２ 量を増加させても供給できる
Ｃａ（ＯＨ）２ 水スラリーの量は単位時間あたり微々
たる量である。即ち、生成する針状形状アラゴナイト炭
酸カルシウムの量も単位時間あたり極端に少なく、生産
効率が非常に悪く、実用生産は不可能に近い。また、こ
の方法で生成した針状形状アラゴナイト炭酸カルシウム
は各粒子が凝集し、プラスチック等に使用しても満足し
うる物性が得られない。[0005] Other methods for producing aragonite calcium carbonate having a large particle size and acicular shape include JP-A-2-34514 and JP-A-62-278123, but these methods are insufficient in terms of both production efficiency and physical properties. It's not a thing. JP-A-2-3
The manufacturing method for No. 4514 involves blowing CO2 gas into a reaction tank while continuously introducing an aqueous calcium hydroxide slurry. At this time, the calcium ion concentration in the reaction tank was reduced to 0.
．． The amount of CO2 and calcium hydroxide aqueous slurry supplied is adjusted so that it falls within the range of 0.001 to 0.005 mol/liter. When this range of calcium ion concentration is converted into pH, it is about 6.8 to 10.2. When calcium hydroxide aqueous slurry is supplied to the reaction tank within this range, even if the amount of CO2 is increased, the amount of Ca(OH)2 aqueous slurry that can be supplied per unit time is negligible. That is, the amount of needle-shaped aragonite calcium carbonate produced is extremely small per unit time, and the production efficiency is very poor, making practical production nearly impossible. Further, the particles of the acicular aragonite calcium carbonate produced by this method aggregate, and satisfactory physical properties cannot be obtained even when used in plastics or the like.
【０００６】特開昭６２−２７８１２３は、滴下するＣ
ａ（ＯＨ）２ がスラリーでなく水溶液であるため、そ
の生産効率は甚だ悪い。また物性も充分でない。ちなみ
にＣａ（ＯＨ）２ の溶解度は０．１８５ｇ／１００ｇ
水（ａｔ０℃）であり、この溶解度の低さからも、該方
法は生産効率が悪く実用性に乏しいことが窺い知れよう
。[0006] Japanese Patent Application Laid-Open No. 62-278123 discloses that dropping C
Since a(OH)2 is not a slurry but an aqueous solution, its production efficiency is extremely poor. Also, the physical properties are not sufficient. By the way, the solubility of Ca(OH)2 is 0.185g/100g
Water (at 0° C.), and this low solubility indicates that this method has poor production efficiency and is impractical.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、粒径が大き
く、且つ高分散性の著しく改良された針状形状アラゴナ
イト炭酸カルシウムを工業的に有利に提供するものであ
る。OBJECTS OF THE INVENTION The present invention provides industrially advantageous acicular-shaped aragonite calcium carbonate having a large particle size and significantly improved high dispersibility.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記実情に
鑑み鋭意研究の結果、本発明に到達したものである。即
ち、本発明は、針状形状のアラゴナイト結晶炭酸カルシ
ウムの水スラリーに、リン酸及び可溶性リン酸化合物か
ら選択される少なくとも１種を含有するＣａ（ＯＨ）２
水スラリーを滴下し、温度を３０〜８０℃、ｐＨを１
０以上に調整してＣＯ２ を導入し炭酸化させることを
特徴とする大粒径の針状形状アラゴナイト結晶炭酸カル
シウムの製造方法を内容とするものである。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive research in view of the above circumstances. That is, the present invention provides an aqueous slurry of acicular aragonite crystal calcium carbonate containing Ca(OH)2 containing at least one selected from phosphoric acid and soluble phosphoric acid compounds.
Add the water slurry dropwise, adjust the temperature to 30-80℃, and adjust the pH to 1.
The content is a method for producing large-sized, needle-shaped aragonite crystalline calcium carbonate, which is characterized by carbonating carbonation by introducing CO2 at a temperature of 0 or more.
【０００９】本発明において、最初に反応槽に存在させ
る針状形状アラゴナイト炭酸カルシウムは、長径３〜５
０μｍ、短径０．０１〜３μｍ、より好ましくは長径５
〜２０μｍ、短径０．０５〜２μｍの粒子径のものがよ
い。この針状形状アラゴナイト炭酸カルシウムを含む水
スラリーにＣａ（ＯＨ）２ の水スラリーを滴下するの
であるが、このＣａ（ＯＨ）２ の水スラリーにはあら
かじめリン酸及び可溶性リン酸化合物から選択される少
なくとも１種を添加しておく。可溶性リン酸化合物とし
ては、リン酸のＮａ塩、Ｋ 塩、ＮＨ４ 塩等が挙げら
れる。これらリン酸の塩としては、Ｋ３ＰＯ４， ＫＨ
２ＰＯ４， Ｋ２ＨＰＯ４， Ｎａ２ＨＰＯ４，・１２
Ｈ２Ｏ， （ＮＨ４）３ＰＯ４，・３Ｈ２Ｏ等が例示さ
れる。可溶性の程度については０．１ｇ／１００ｃｃ（
２０℃の水）以上、好ましくは５．０ｇ／１００ｃｃ（
２０℃の水）以上水に溶けるものが良い。リン酸又は可
溶性リン酸化合物は単独又は２種以上組み合わせて用い
られ、その添加量はＣａ（ＯＨ）２ に対して０．１〜
１５重量％が好ましく、より好ましくは０．３〜５．０
重量％である。In the present invention, the needle-shaped aragonite calcium carbonate initially present in the reaction tank has a major axis of 3 to 5.
0 μm, minor axis 0.01 to 3 μm, more preferably major axis 5
Preferably, the particles have a particle size of ~20 μm and a short axis of 0.05 to 2 μm. A Ca(OH)2 water slurry is dropped into the water slurry containing the acicular-shaped aragonite calcium carbonate. Add at least one kind. Examples of the soluble phosphoric acid compound include Na salt, K salt, NH4 salt, etc. of phosphoric acid. These phosphoric acid salts include K3PO4, KH
2PO4, K2HPO4, Na2HPO4,・12
Examples include H2O, (NH4)3PO4, and .3H2O. Regarding the degree of solubility, 0.1g/100cc (
20℃ water) or more, preferably 5.0g/100cc (
It is best to use something that is soluble in water (20°C water) or higher. Phosphoric acid or soluble phosphoric acid compounds are used alone or in combination of two or more, and the amount added is 0.1 to 0.1 to Ca(OH)2.
15% by weight is preferred, more preferably 0.3-5.0%
Weight%.
【００１０】濃度については、最初反応槽に存在させる
針状形状アラゴナイト炭酸カルシウムと滴下するＣａ（
ＯＨ）２ スラリーが反応槽で２０〜２５０ｇ・ＣａＣ
Ｏ３ ／リットル、より好ましくは３０〜１２０ｇ・Ｃ
ａＣＯ３ ／リットルである。この場合、滴下するＣａ
（ＯＨ）２ はＣａＣＯ３ に反応したと換算して濃度
を計算する。この濃度より小さいと生産効率が悪く、実
生産の処方としては問題がある。また、この濃度より大
きいと反応系内のスラリー粘度が極端に上昇し、ＣＯ２
ガスを導入しても均一な炭酸化反応ができない場合が
ある。気液反応を充分効率的に進行させるためには、Ｃ
Ｏ２ ガスが充分分散する程度の低いスラリー粘度であ
ることが必要である。Regarding the concentration, the acicular aragonite calcium carbonate initially present in the reaction tank and the Ca(
OH)2 slurry is 20-250g・CaC in the reaction tank
O3/liter, more preferably 30-120g・C
aCO3/liter. In this case, the dripping Ca
The concentration is calculated by converting that (OH)2 has reacted with CaCO3. If the concentration is lower than this, the production efficiency will be poor and there will be problems as a prescription for actual production. In addition, if the concentration is higher than this, the viscosity of the slurry in the reaction system will increase extremely, resulting in CO2
Even if gas is introduced, a uniform carbonation reaction may not be possible. In order for the gas-liquid reaction to proceed sufficiently efficiently, C
The slurry viscosity needs to be low enough to sufficiently disperse O2 gas.
【００１１】反応系内のスラリー温度は３０〜８０℃、
好ましくは４０〜７５℃である。これより温度が低くて
も高くても結晶が針状方向に充分成長せず、新たに小さ
い針状形状の結晶核や立方体形状のカルサイトが生成す
る。[0011] The slurry temperature in the reaction system is 30 to 80°C,
Preferably it is 40-75°C. Even if the temperature is lower or higher than this, the crystals do not grow sufficiently in the needle-like direction, and new small needle-shaped crystal nuclei and cubic-shaped calcite are generated.
【００１２】反応槽内のスラリーｐＨは１０．０以上、
好ましくは１０．５以上になるように、滴下するＣａ（
ＯＨ）２ スラリーとＣＯ２ ガスを調整する。前記特
開平２−３４５１４、特開昭６２−２７８１２３の方法
とは、この点が根本的に異なる。即ち、これらの方法で
は生産効果を上げるためにＣａ（ＯＨ）２ の滴下量を
増すと大粒径の針状形状アラゴナイト炭酸カルサイトは
生成しなくなるのである。そのために特開平２−３４５
１４ではＣａイオン濃度を０．００１〜０．００５ｍｏ
ｌ ／リットルの範囲にせねばならず、滴下するＣａ（
ＯＨ）２ の滴下量は極力抑えなければならない。一方
、特開昭６２−２７８１２３では、スラリーではなくＣ
ａ（ＯＨ）２ の水溶液を滴下して初めて大粒径のもの
を生成させるのが可能となる。Ｃａ（ＯＨ）２ の溶解
度は前述のとおりであり微々たる量である。これに対し
、本発明の場合はこれらの方法に比べ単位時間あたり数
１０倍から数１００倍の量を滴下することができる。
従って、生産効率もこれらの方法に比べて数段優れてい
る。滴下するＣａ（ＯＨ）２ スラリーの濃度は、Ｃａ
ＣＯ３ に換算して最初に存在する針状形状アラゴナイ
ト炭酸カルシウムの濃度と大巾に異ならない方がよい。[0012] The slurry pH in the reaction tank is 10.0 or more,
The Ca(
Adjust the OH)2 slurry and CO2 gas. This point is fundamentally different from the methods of JP-A-2-34514 and JP-A-62-278123. That is, in these methods, if the amount of Ca(OH)2 added dropwise is increased in order to increase the production efficiency, large-sized needle-shaped aragonite carbonate calcite is no longer produced. For that purpose, JP-A-2-345
In No. 14, the Ca ion concentration was set to 0.001 to 0.005 mo.
1 / liter, and the amount of Ca (
The amount of OH)2 dripped must be suppressed as much as possible. On the other hand, in JP-A No. 62-278123, C was used instead of slurry.
It is only by dropping an aqueous solution of a(OH)2 that large particles can be produced. The solubility of Ca(OH)2 is as described above and is insignificant. On the other hand, in the case of the present invention, it is possible to drop several tens to hundreds of times the amount per unit time compared to these methods. Therefore, the production efficiency is also much better than these methods. The concentration of the Ca(OH)2 slurry dropped is Ca
It is better that the concentration in terms of CO3 is not significantly different from the concentration of the initially existing acicular aragonite calcium carbonate.
【００１３】最初、反応槽に存在させる針状形状アラゴ
ナイト炭酸カルシウムと滴下するＣａ（ＯＨ）２ スラ
リーの比率は特に制限されないが、好ましくは一回の滴
下反応においては、針状形状アラゴナイト炭酸カルシウ
ム／Ｃａ（ＯＨ）２ スラリー＝１／１０以内がよい。
これ以上の倍率で反応させたい場合は、この滴下反応で
生成した針状形状アラゴナイト炭酸カルシウムを別の反
応槽に入れ替えて再度針状形状アラゴナイト炭酸カルシ
ウム／Ｃａ（ＯＨ）２ スラリー＝１／１０以内の倍率
で滴下反応させることが好ましい。必要に応じ、３回又
はそれ以上同様の滴下反応を繰り返すこともできる。こ
の場合、あらかじめ存在させる針状形状アラゴナイト炭
酸カルシウムは炭酸化途中のものでも、炭酸化を終了さ
せたものでもよい。本発明の大粒径針状形状アラゴナイ
ト炭酸カルシウムを各分野で使用する場合は、勿論Ｃａ
（ＯＨ）２ 滴下を止めた後ＣＯ２ を導入して炭酸化
を終了させたものを使用する方が好ましい。また反応槽
にＣＯ２ を導入しながらＣａ（ＯＨ）２ スラリーを
滴下し、一方で生成した大粒径針状形状アラゴナイト炭
酸カルシウムをオーバーフロー形式で連続的に生成させ
てもよい。この場合も反応槽内の条件は前記した範囲に
設定すればよい。そして炭酸化途中のものは最後に炭酸
化を終了させればよい。Initially, the ratio of the acicular aragonite calcium carbonate present in the reaction tank and the Ca(OH)2 slurry to be dropped is not particularly limited, but preferably in one dropping reaction, the acicular aragonite calcium carbonate/acicular aragonite calcium carbonate/ Ca(OH)2 slurry is preferably within 1/10. If you want to react at a higher magnification, transfer the acicular aragonite calcium carbonate produced in this dropping reaction to another reaction tank and try again acicular aragonite calcium carbonate/Ca(OH)2 slurry = within 1/10. It is preferable to carry out the dropwise reaction at a magnification of . If necessary, the same dropping reaction can be repeated three or more times. In this case, the acicular aragonite calcium carbonate pre-existing may be in the middle of carbonation or may be carbonated. When using the large particle size needle-shaped aragonite calcium carbonate of the present invention in various fields, of course, Ca
It is preferable to use one in which carbonation is completed by introducing CO2 after stopping the dropping of (OH)2. Alternatively, the Ca(OH)2 slurry may be dropped while introducing CO2 into the reaction tank, and on the other hand, large-sized, needle-shaped aragonite calcium carbonate may be continuously produced in an overflow format. In this case as well, the conditions within the reaction tank may be set within the ranges described above. For those in the process of carbonation, carbonation may be completed at the end.
【００１４】導入するＣＯ２ ガス量は特に制約はない
が、反応槽内のｐＨを１０以上に設定しようとすれば、
Ｃａ（ＯＨ）２ スラリーの滴下量も考慮してＣＯ２
１００％として、４リットル／ｍｉｎ ／ｋｇ・Ｃａ（
ＯＨ）２ 以下が好ましく、より好ましくは２リットル
／ｍｉｎ ／ｋｇ・Ｃａ（ＯＨ）２ 以下がよい。
本発明において最初に存在させる針状形状アラゴナイト
炭酸カルシウムは、特願平１−１６７２６７、特開昭６
３−２５６５１４、特開昭６３−２６０８１５等の方法
で生成させたものを使用すればよいが、特に制限されな
い。[0014] There are no particular restrictions on the amount of CO2 gas introduced, but if you want to set the pH in the reaction tank to 10 or more,
Considering the amount of Ca(OH)2 slurry dropped, CO2
As 100%, 4 liters/min/kg・Ca(
OH)2 or less is preferable, and more preferably 2 liters/min/kg·Ca(OH)2 or less. In the present invention, the acicular-shaped aragonite calcium carbonate initially present is disclosed in Japanese Patent Application No. 1-167267,
3-256514, JP-A-63-260815, etc. may be used, but there is no particular limitation.
【００１５】本発明において、分散性を一層向上させる
ために、状況に応じ次の２方法を採用してもよい。第１
は、あらかじめ反応槽に存在させる針状形状アラゴナイ
ト炭酸カルシウム水スラリーをガラスビーズ等を使用し
た湿式粉砕機で分散させ、該炭酸カルシウム粒子間の軽
い凝集をほぐしてからＣａ（ＯＨ）２水スラリーを滴下
させる。こうすれば良く分散した状態で針状方向に結晶
成長し、より高分散性の針状アラゴナイト炭酸カルシウ
ムが得られる。第２は、Ｃａ（ＯＨ）２ 水スラリーを
滴下させながら、その反応槽に超音波を照射させる。針
状形状アラゴナイト炭酸カルシウムの結晶成長過程にお
いては、各粒子間の軽い凝集が生じやすい。ところが超
音波を照射することによって、常に粒子が分散した状態
で結晶の成長が進む。従って、最終的に生成する粒子も
非常に高分散性のものが得られる。更に分散性を向上さ
せるために、上記第１、第２の２つの方法を併用しても
よいことは勿論である。上記の如き方法により、大粒径
、即ち長径５〜１００μｍ、短径０．１〜４．０μｍ程
度の高分散性の針状結晶アラゴナイト炭酸カルシウムを
得ることができる。In the present invention, in order to further improve the dispersibility, the following two methods may be adopted depending on the situation. 1st
In this method, an aqueous slurry of acicular aragonite calcium carbonate, which is pre-existing in a reaction tank, is dispersed using a wet grinder using glass beads, etc., and light agglomerations between the calcium carbonate particles are loosened, and then the Ca(OH)2 aqueous slurry is dispersed. Let it drip. In this way, the crystals grow in the acicular direction in a well-dispersed state, and acicular aragonite calcium carbonate with higher dispersion can be obtained. The second method is to irradiate the reaction tank with ultrasonic waves while dropping the Ca(OH) 2 water slurry. During the crystal growth process of needle-shaped aragonite calcium carbonate, light aggregation between particles tends to occur. However, by applying ultrasonic waves, crystal growth progresses while particles are always dispersed. Therefore, the particles finally produced have very high dispersion. Of course, in order to further improve the dispersibility, the first and second methods described above may be used in combination. By the method described above, it is possible to obtain highly dispersible acicular crystal aragonite calcium carbonate having a large particle size, that is, a major axis of about 5 to 100 μm and a short axis of about 0.1 to 4.0 μm.
【００１６】粒子径の調整については、最初に存在させ
る針状形状アラゴナイト炭酸カルシウムに対してＣａ（
ＯＨ）２ のモル比が大きくなればなるほど、生成粒子
は大きくなる。特に短径に比べて長径の成長が大きい。Regarding the adjustment of the particle size, Ca(
The larger the molar ratio of OH)2, the larger the particles produced. In particular, the growth of the long axis is larger than that of the short axis.
【００１７】[0017]
【発明の効果】本発明は上述のごとく、従来の針状形状
アラゴナイト炭酸カルシウムを成長させ大粒径とし、且
つ高分散性とする方法である特開昭６２−２７８１２３
、特開平２−３４５１４と同じ滴下反応であるが、生産
効率が飛躍的に異なるのである。また物性、特に粒子の
分散性については、特願平１−１６７２６７に比べても
充分に改良されている。このことは電子顕微鏡写真で両
方の粒子を比較しただけでも判る。Effects of the Invention As mentioned above, the present invention is a method of growing conventional acicular-shaped aragonite calcium carbonate to a large particle size and high dispersibility.
, is the same dropping reaction as in JP-A-2-34514, but the production efficiency is dramatically different. Furthermore, the physical properties, particularly the dispersibility of particles, are sufficiently improved compared to Japanese Patent Application No. 1-167267. This can be seen by comparing both types of particles in electron micrographs.
【００１８】本発明の大粒径の針状形状アラゴナイト炭
酸カルシウムはプラスチック、製紙、摩擦材、断熱材等
に特に好適に利用される。プラスチックでは特にポリプ
ロピレンの充填剤として剛性を付与する効果が著しい。
従来、ポリプロピレンに剛性を付与する充填剤としては
タルク、ウォラストナイト、ガラス繊維等があるが、タ
ルク、ウォラストナイトは天然物のための白度が悪く、
また粒子径が不揃いで粗大粒子が混在するため衝撃強度
が劣る。ガラス繊維は剛性は良いが表面平滑性が悪く、
作業性、労働衛生上の問題、価格等に問題がある。本発
明品はこれらの問題を解決した新しい素材である。製紙
用としては、このような大きな針状粒子を填材として使
用することによって、パルプに対して無機物を多く混合
（パルプ／無機物＝１／９程度）した無機質紙を作るこ
とができる。従来のような粒子の小さい針状形状炭酸カ
ルシウムであると、抄紙時にパルプに充分滞まらず無機
物の比率を上げることができないが、本発明品のような
大きな粒子径により、初めて無機物を多く配合できるの
である。このような無機質紙は不燃紙として室内インテ
リア等に使用できる。本発明品はその特異な針状形状の
ために粒子間に充分な空隙が生じ、そのため、断熱材、
濾過材等の用途にも好適に使用できる。また各種ペース
ト、シーリング材、塗料等に増粘剤や補強材として使用
できる。針状形状のためにこれらの分野でチキソ性が発
揮できると考えられる。The large particle size, needle-shaped aragonite calcium carbonate of the present invention is particularly suitable for use in plastics, paper manufacturing, friction materials, heat insulating materials, and the like. In plastics, it is particularly effective as a filler for polypropylene in imparting rigidity. Traditionally, fillers that impart rigidity to polypropylene include talc, wollastonite, and glass fiber, but talc and wollastonite are natural products and have poor whiteness.
In addition, the impact strength is poor because the particle diameter is uneven and coarse particles are mixed. Glass fiber has good rigidity but poor surface smoothness.
There are problems with workability, occupational health issues, price, etc. The product of the present invention is a new material that solves these problems. For paper manufacturing, by using such large acicular particles as a filler, it is possible to produce inorganic paper in which a large amount of inorganic material is mixed with pulp (pulp/inorganic material = about 1/9). With conventional calcium carbonate particles having a small acicular shape, they do not sufficiently accumulate in the pulp during paper making, making it impossible to increase the ratio of inorganic substances. It can be mixed. Such inorganic paper can be used as a noncombustible paper for indoor interior decoration. Due to the unique acicular shape of the product of the present invention, sufficient voids are created between the particles, and therefore, the insulating material,
It can also be suitably used for applications such as filter media. It can also be used as a thickener or reinforcing material in various pastes, sealants, paints, etc. It is thought that thixotropic properties can be exhibited in these fields due to the needle-like shape.
【００１９】ポリプロピレン等のプラスチックにおいて
は、補強材として、針状の無機物を使用することが多い
。特に剛性を付与する目的で針状無機物を使用するが、
この場合、針状品のアスペクト比が大きく、各々の粒子
が充分分散していることが不可欠である。本発明品はア
スペクト比が大きく、各粒子が充分、分散したものであ
るため、ポリプロピレン等に配合した場合に優れた剛性
を発揮する。In plastics such as polypropylene, acicular inorganic materials are often used as reinforcing materials. Acicular inorganic substances are used especially for the purpose of imparting rigidity,
In this case, it is essential that the needle-shaped article has a large aspect ratio and that each particle is sufficiently dispersed. Since the product of the present invention has a large aspect ratio and each particle is sufficiently dispersed, it exhibits excellent rigidity when blended with polypropylene or the like.
【００２０】[0020]
【実施例】以下、本発明を実施例及び比較例を挙げて更
に詳細に説明するが、本発明はこれらにより何ら制限さ
れるものではない。
実施例１
容量３０リットル反応槽に平均粒径が長径１０μｍ、短
径０．２μｍの針状形状アラゴナイト炭酸カルシウムを
７０ｇ／リットルの濃度に調整して５リットル入れ、こ
れに重量比で３．０重量％〔Ｃａ（ＯＨ）２ の固形分
に対し〕のリン酸を添加したＣａ（ＯＨ）２ の水スラ
リーを５２ｇ・Ｃａ（ＯＨ）２ ／リットルの濃度に調
整して、この反応槽に連続的に滴下した。この反応槽に
は下部から濃度３０％のＣＯ２ ガスを導入し反応系内
のｐＨは常に１１．５になるようにＣａ（ＯＨ）２ 水
スラリーとＣＯ２ ガス量を調整した。また反応系内の
温度は７０℃になるように反応槽を調節した。
このような条件下でＣａ（ＯＨ）２ 水スラリーを２５
リットル反応槽に滴下させ全体のスラリーの量を３０リ
ットルとした。この後Ｃａ（ＯＨ）２ 水スラリーの滴
下を止め、ＣＯ２ ガスだけを反応槽に導入してｐＨを
７．０とした。EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way. Example 1 5 liters of acicular-shaped aragonite calcium carbonate with an average particle size of 10 μm in major axis and 0.2 μm in minor axis was adjusted to a concentration of 70 g/liter and put into a 30-liter reaction tank, and a weight ratio of 3.0 An aqueous slurry of Ca(OH)2 to which phosphoric acid of % by weight [based on the solid content of Ca(OH)2] was adjusted to a concentration of 52 g Ca(OH)2/liter was continuously added to this reaction tank. dripped onto the target. CO2 gas with a concentration of 30% was introduced into the reaction tank from the bottom, and the amounts of the Ca(OH)2 water slurry and CO2 gas were adjusted so that the pH in the reaction system was always 11.5. Further, the reaction tank was adjusted so that the temperature inside the reaction system was 70°C. Under these conditions, the Ca(OH)2 water slurry was
The slurry was dropped into a liter reaction tank to make the total amount of slurry 30 liters. Thereafter, the dropping of the Ca(OH)2 water slurry was stopped, and only CO2 gas was introduced into the reaction tank to adjust the pH to 7.0.
【００２１】実施例２
実施例１で最初に反応槽に入れる針状結晶アラゴナイト
炭酸カルシウムの量を２リットルにする以外は実施例１
と同様とした。Example 2 Example 1 except that the amount of acicular crystal aragonite calcium carbonate initially added to the reaction tank was changed to 2 liters.
The same is true.
【００２２】実施例３
実施例１で滴下するＣａ（ＯＨ）２ の濃度を３０ｇ・
Ｃａ（ＯＨ）２ ／リットルにする以外は実施例１と同
様とした。Example 3 The concentration of Ca(OH)2 dropped in Example 1 was changed to 30 g.
The procedure was the same as in Example 1 except that the amount of Ca(OH)2/liter was changed.
【００２３】比較例１
実施例１で滴下するＣａ（ＯＨ）２ スラリーにリン酸
を滴下しない以外は実施例１と同様とした。Comparative Example 1 The same procedure as in Example 1 was carried out except that phosphoric acid was not added dropwise to the Ca(OH)2 slurry added dropwise in Example 1.
【００２４】比較例２
実施例１で反応槽内の温度を２０℃にする以外は実施例
１と同様とした。Comparative Example 2 The same procedure as in Example 1 was carried out except that the temperature inside the reaction tank was changed to 20°C.
【００２５】比較例３
実施例１で反応槽内の温度を９０℃にする以外は実施例
１と同様とした。上記の実施例、比較例で生成したアラ
ゴナイト炭酸カルシウムの粒子形状を表１に示した。形
状等は電子顕微鏡写真、Ｘ線で確認した。Comparative Example 3 The same procedure as in Example 1 was carried out except that the temperature inside the reaction tank was changed to 90°C. Table 1 shows the particle shapes of the aragonite calcium carbonate produced in the above Examples and Comparative Examples. The shape etc. were confirmed using electron micrographs and X-rays.
【００２６】実施例１でリン酸を添加したＣａ（ＯＨ）
２ スラリーを反応槽に逐次連続的に滴下するのではな
く、最初から一括投入する以外は実施例１と同様とした
。Ca(OH) to which phosphoric acid was added in Example 1
2 The procedure was the same as in Example 1 except that the slurry was added all at once from the beginning instead of being dropped into the reaction tank one after another.
【００２７】[0027]
【表１】[Table 1]
【００２８】応用例
実施例１で生成した大粒径の針状形状アラゴナイト炭酸
カルシウムを用いて、下記の要領でポリプロピレンに配
合し強度物性を測定した。
（１）試験法
配合：
ポリプロピレン樹脂 １０
０重量部（商品名ＭＡ−３、三菱油化製）
アラゴナイト炭酸カルシウム ３０重量
部この配合比で混練してペレット化した後、射出成型し
て試験片を作り強度物性を測定した。比較として、一般
にポリプロピレン樹脂用フィラーとして広く使用されて
いるタルク（富士タルク製、ＰＫＳ−１００）と重質炭
酸カルシウム（丸尾カルシウム株式会社製、スーパー３
Ｓ）、及び比較例４で得られた針状形状アラゴナイト炭
酸カルシウムを用いて同一の操作を行った。結果を第２
表に示した。Application Example The large particle size, needle-shaped aragonite calcium carbonate produced in Example 1 was blended with polypropylene in the following manner, and its strength and physical properties were measured. (1) Test method formulation: Polypropylene resin 10
0 parts by weight (trade name: MA-3, manufactured by Mitsubishi Yuka) Aragonite calcium carbonate 30 parts by weight After kneading and pelletizing at this blending ratio, injection molding was performed to make test pieces, and strength and physical properties were measured. For comparison, talc (manufactured by Fuji Talc, PKS-100) and heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd., Super 3) are used as fillers for polypropylene resin.
The same operation was performed using the acicular-shaped aragonite calcium carbonate obtained in Comparative Example 4. Second result
Shown in the table.
【００２９】[0029]
【表２】[Table 2]
【００３０】以上の結果より、本発明品はポリプロピレ
ン樹脂に配合した場合、優れた強度物性を発揮すること
が判る。従来のフィラー、例えばタルクであれば曲げ弾
性率は良いが、衝撃強度が悪く、両方の物性を維持でき
ないのに対し、本発明品は両方の物性をバランス良く付
与するものである。特に曲げ弾性率における改良効果が
顕著である。また、比較例４の炭酸カルシウムに比べて
も改良効果が認められる。上記物性から、本発明品は従
来の大粒径針状形状アラゴナイト炭酸カルシウムに比べ
てアスペクト比が大きく、均一な形状で各粒子が良く分
散していることが理解される。また本発明品は、ポリプ
ロピレン樹脂になじみの良い物質で表面処理をすれば、
一層物性が向上することが期待される。From the above results, it is clear that the product of the present invention exhibits excellent strength and physical properties when blended with polypropylene resin. Conventional fillers such as talc have good flexural modulus but poor impact strength and cannot maintain both physical properties, whereas the product of the present invention provides both physical properties in a well-balanced manner. In particular, the improvement effect on flexural modulus is remarkable. Moreover, an improvement effect is also recognized compared to calcium carbonate of Comparative Example 4. From the above physical properties, it is understood that the product of the present invention has a larger aspect ratio than the conventional large-particle, acicular-shaped aragonite calcium carbonate, has a uniform shape, and has well-dispersed particles. In addition, if the product of the present invention is surface treated with a substance that is compatible with polypropylene resin,
It is expected that the physical properties will further improve.
Claims (5)
シウムの水スラリーに、リン酸及び可溶性リン酸化合物
から選択される少なくとも１種を含有するＣａ（ＯＨ）
２ 水スラリーを滴下し、温度を３０〜８０℃、ｐＨを
１０以上に調整してＣＯ２ を導入し炭酸化させること
を特徴とする、大粒径の針状形状アラゴナイト結晶炭酸
カルシウムの製造方法。1. Ca(OH) containing at least one selected from phosphoric acid and soluble phosphoric acid compounds in an aqueous slurry of acicular-shaped aragonite crystal calcium carbonate.
2. A method for producing large acicular aragonite crystalline calcium carbonate, which comprises dropping a water slurry, adjusting the temperature to 30 to 80°C and the pH to 10 or higher, and introducing CO2 for carbonation.
ゴナイト結晶炭酸カルシウム及び滴下するＣａ（ＯＨ）
２ 水スラリーの濃度〔ＣａＣＯ３ に反応した後の濃
度に換算〕が２０〜２５０ｇ／リットルである請求項１
記載の製造方法。[Claim 2] Pre-existing acicular-shaped aragonite crystal calcium carbonate and dripping Ca(OH)
2.Claim 1, wherein the concentration of the water slurry (converted to the concentration after reacting with CaCO3) is 20 to 250 g/liter.
Manufacturing method described.
として４リットル／ｍｉｎ／ｋｇ．Ｃａ（ＯＨ）２ 以
下である請求項１記載の製造方法。[Claim 3] The amount of CO2 introduced is 100% CO2
as 4 liters/min/kg. The manufacturing method according to claim 1, wherein the content is less than or equal to Ca(OH)2.
択される少なくとも１種の添加量が、水酸化カルシウム
に対して０．１〜１５重量％である請求項１記載の製造
方法。4. The production method according to claim 1, wherein the amount of at least one selected from phosphoric acid and soluble phosphoric acid compounds added is 0.1 to 15% by weight based on calcium hydroxide.
，ＫＨ２ＰＯ４，Ｋ２ＨＰＯ４，Ｎａ２ＨＰＯ４．１２
Ｈ２Ｏ ，（ＮＨ４）３ＰＯ４ から選択される請求項
１記載の製造方法。5. The soluble phosphoric acid compound is K3PO4
,KH2PO4,K2HPO4,Na2HPO4.12
The manufacturing method according to claim 1, wherein the material is selected from H2O, (NH4)3PO4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3116971A JP2787622B2 (en) | 1991-04-19 | 1991-04-19 | Method for producing needle-shaped large-diameter aragonite crystalline calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3116971A JP2787622B2 (en) | 1991-04-19 | 1991-04-19 | Method for producing needle-shaped large-diameter aragonite crystalline calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04321515A true JPH04321515A (en) | 1992-11-11 |
| JP2787622B2 JP2787622B2 (en) | 1998-08-20 |
Family
ID=14700290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3116971A Expired - Lifetime JP2787622B2 (en) | 1991-04-19 | 1991-04-19 | Method for producing needle-shaped large-diameter aragonite crystalline calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2787622B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156286A (en) * | 1997-05-21 | 2000-12-05 | Imerys Pigments, Inc. | Seeding of aragonite calcium carbonate and the product thereof |
| US6685908B1 (en) * | 2000-03-06 | 2004-02-03 | 3P Technologies Ltd. | Precipitated aragonite and a process for producing it |
| EP2552835B1 (en) * | 2010-04-01 | 2016-08-31 | Omya International AG | Process for obtaining precipitated calcium carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388714A (en) * | 1989-06-29 | 1991-04-15 | Maruo Calcium Co Ltd | Production of acicular aragonite crystal type calcium carbonate |
-
1991
- 1991-04-19 JP JP3116971A patent/JP2787622B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388714A (en) * | 1989-06-29 | 1991-04-15 | Maruo Calcium Co Ltd | Production of acicular aragonite crystal type calcium carbonate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156286A (en) * | 1997-05-21 | 2000-12-05 | Imerys Pigments, Inc. | Seeding of aragonite calcium carbonate and the product thereof |
| US6685908B1 (en) * | 2000-03-06 | 2004-02-03 | 3P Technologies Ltd. | Precipitated aragonite and a process for producing it |
| EP2552835B1 (en) * | 2010-04-01 | 2016-08-31 | Omya International AG | Process for obtaining precipitated calcium carbonate |
| US9725329B2 (en) | 2010-04-01 | 2017-08-08 | Omya International Ag | Process for obtaining precipitated calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2787622B2 (en) | 1998-08-20 |
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