JPH0431315A - Monodispersed spherical or elliptic vaterite calcium carbonate and production thereof - Google Patents
Monodispersed spherical or elliptic vaterite calcium carbonate and production thereofInfo
- Publication number
- JPH0431315A JPH0431315A JP13748290A JP13748290A JPH0431315A JP H0431315 A JPH0431315 A JP H0431315A JP 13748290 A JP13748290 A JP 13748290A JP 13748290 A JP13748290 A JP 13748290A JP H0431315 A JPH0431315 A JP H0431315A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- particle size
- carbonation reaction
- quicklime
- vaterite
- 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 239
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000292 calcium oxide Substances 0.000 claims abstract description 58
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 35
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 32
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 32
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 26
- 238000009826 distribution Methods 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 16
- 230000001186 cumulative effect Effects 0.000 claims description 11
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 4
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 4
- 239000004571 lime Substances 0.000 abstract description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 93
- 239000006185 dispersion Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005259 measurement Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910021532 Calcite Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241000347881 Kadua laxiflora Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- RNAICSBVACLLGM-GNAZCLTHSA-N pilocarpine hydrochloride Chemical compound Cl.C1OC(=O)[C@@H](CC)[C@H]1CC1=CN=CN1C RNAICSBVACLLGM-GNAZCLTHSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は二次凝集がほとんど無く、分散性の良好な球状
又は楕円球状バテライト炭酸カルシウム及びその製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to spherical or ellipsoidal vaterite calcium carbonate with almost no secondary aggregation and good dispersibility, and a method for producing the same.
現在、合成炭酸カルシウムの工業的製造方法としては、
炭酸ガス法が広く採用されている。この炭酸ガス法とは
、天然に産する石灰石を焼成することにより生石灰（Ｍ
化カルシウム）を得、この生石灰と水を反応させ石灰乳
（水酸化カルシウムの水懸濁液）を得、この石灰乳に石
灰石を焼成する際発生する炭酸ガスを導通し反応させる
ことにより炭酸カルシウムを得る方法である。Currently, the industrial manufacturing method for synthetic calcium carbonate is as follows:
The carbon dioxide method is widely used. This carbon dioxide method is a quicklime (M
This quicklime is reacted with water to obtain lime milk (an aqueous suspension of calcium hydroxide), and carbon dioxide gas generated when calcining limestone is passed through the lime milk to cause a reaction, thereby producing calcium carbonate. This is the way to obtain.
この炭酸ガス法により製造される合成炭酸カルシウムは
、その一次粒子の大きさに応じてゴム、プラスチック、
紙、塗料等の填料又は顔料として、広く大量に使用され
ている。また、これらの用途に用いられる合成炭酸カル
シウムは、その配合時の物性をさらに向上させるため、
粒子表面にその使用目的に応じた無機系又は有機系の様
々な処理剤が表面処理され一般に使用されている。Synthetic calcium carbonate produced by this carbon dioxide method can be used for rubber, plastic, etc. depending on the size of its primary particles.
It is widely used in large quantities as a filler or pigment in paper, paint, etc. In addition, in order to further improve the physical properties of synthetic calcium carbonate used in these applications,
Particle surfaces are generally treated with various inorganic or organic treatment agents depending on the purpose of use.
しかし乍ら、この炭酸ガス法で製造される合成炭酸カル
シウムは、元来一次粒子間の凝集力が非常に強いもので
あり、一次粒子が多数凝集して大きな二次粒子（一次粒
子の粗大凝集体）を形成しており、この二次粒子のスラ
リーは、長時間強力に攪拌を続けても、はぼ一次粒子に
まで分散させることは不可能であるとされている。However, synthetic calcium carbonate produced by this carbon dioxide method originally has very strong cohesive force between primary particles, and many primary particles aggregate to form large secondary particles (coarse coagulation of primary particles). It is said that it is impossible to disperse this slurry of secondary particles into primary particles even if the slurry is vigorously stirred for a long time.
このような一次粒子の凝集体を多数含有する合成炭酸カ
ルシウムを、ゴム、プラスチック、紙、塗料等の填料又
は顔料として使用した場合、二次粒子があたかも一次粒
子のような挙動を示すため、分散不良、強度の低下、光
沢の低下、流動性の悪化等、良好な物性が得られず、本
来一次粒子を配合した場合の様な配合効果が得られない
。また同様に、このように多数の凝集体を含有する合成
炭酸カルシウムに、無機系又は有機系の表面処理剤を処
理しても二次粒子表面のみが処理されるにすぎず、充分
な効果を発揮するに至らない。When synthetic calcium carbonate containing a large number of aggregates of primary particles is used as a filler or pigment for rubber, plastic, paper, paint, etc., the secondary particles behave just like primary particles, causing dispersion. Good physical properties such as defects, decreased strength, decreased gloss, and poor fluidity cannot be obtained, and the blending effect that would normally be obtained when primary particles are blended cannot be obtained. Similarly, even if synthetic calcium carbonate containing a large number of aggregates is treated with an inorganic or organic surface treatment agent, only the surface of the secondary particles will be treated, and the effect will not be sufficient. Not enough to demonstrate.
現在まで、これら一次粒子凝集体を分散させる方法は幾
多報告されているが、一般にボールミル、サンドグライ
ンダーミル等により、強力に粉砕破壊する方法が採用さ
れている。しかし乍ら、このような方法は強大なエネル
ギーを使用した摩砕粉砕であるため、凝集体の分散が行
われると同時に一次粒子の破壊も行われ、その結果、表
面状態の非常に不安定な、しかも希望する一次粒子径よ
りさらに小さな粒子と、分散が不完全な二次凝集粒子と
が混在し、粒度の分布が幅広くなってしまうため、好ま
しい方法であるといいがたい、また、このようなサンド
グラインダー等の湿式粉砕機には、通常粉砕用メディア
として微少なガラスピーズが用いられるが、炭酸カルシ
ウムの粉砕破壊工程時これらガラスピーズ表面も粉砕破
壊されるため、分散処理後の炭酸カルシウム中に２０μ
ｍ前後の粗大ガラス片が多数混入することになり、例え
ば１５μｍ前後の厚みの薄物フィルムの充填剤として使
用するような炭酸カルシウムをこのような湿式粉砕方法
を用いて分散調製することは好ましくない。To date, many methods for dispersing these primary particle aggregates have been reported, but generally a method of crushing them by forcefully using a ball mill, a sand grinder mill, etc. has been adopted. However, since this method involves grinding and grinding using a large amount of energy, the primary particles are destroyed at the same time as the aggregates are dispersed, and as a result, the surface state is extremely unstable. Moreover, it is difficult to say that this is a preferable method because particles smaller than the desired primary particle size and secondary agglomerated particles with incomplete dispersion will be mixed, resulting in a wide particle size distribution. Wet grinders such as sand grinders usually use minute glass beads as the grinding media, but since the surface of these glass beads is also crushed and broken during the crushing process of calcium carbonate, 20μ
It is not preferable to disperse and prepare calcium carbonate, which is used as a filler for a thin film having a thickness of about 15 μm, by using such a wet grinding method because a large number of coarse glass pieces of about 15 μm in size will be mixed in.
炭酸カルシウムには、同質異像として大方晶系のカルサ
イト型結晶、斜方晶系のアラブナイト結晶、および擬人
方晶系のバテライト型結晶があるが、この中で工業的に
製造され多種の用途に利用されているのは、立方体もし
くは紡錘形のカルサイト型結晶、または針状もしくは柱
状のアラゴナイト結晶が大半である。これに対して、バ
テライト型の炭酸カルシウムの場合は、その形態的な特
徴からして、他の２結晶型と比べて比較的分散性が良好
であり、大きな粗大凝集体を含有しないとされているた
め、紙、塗料、あるいはゴム、プラスチック用の顔料、
填料として用いた場合、塗工性の改善、充填性の向上等
の効果が期待でき、ひいては製品の物理強度、光沢性、
白色度、あるいは印刷特性の向上につながると考えられ
る。Calcium carbonate has allomorphic forms, including macrogonal calcite crystals, orthorhombic arabite crystals, and anthropomorphic vaterite crystals. Most of the crystals used are cubic or spindle-shaped calcite crystals, or acicular or columnar aragonite crystals. On the other hand, in the case of vaterite-type calcium carbonate, its morphological characteristics indicate that it has relatively good dispersibility compared to other two-crystalline types and does not contain large coarse aggregates. pigments for paper, paint, or rubber and plastic;
When used as a filler, it can be expected to have effects such as improving coating properties and filling properties, and in turn improving the physical strength, glossiness, etc. of the product.
It is thought that this leads to improvement in whiteness or printing characteristics.
以上の観点から従来より、バテライト炭酸カルシウムを
工業的に製造するための方法が種々検討されて来ている
。From the above viewpoint, various methods for industrially producing vaterite calcium carbonate have been studied.
例えば特開昭６０−９０８２２には、マグネシウム化合
物を含む水酸化カルシウム水懸濁液に二酸化炭素含有気
体を導入し、ある一定の炭酸化率に達した時点で縮合リ
ン酸アルカリ又はそのアルカリ金属塩を添加することに
よって、バテライト炭酸カルシウムを得る方法が、また
特開昭５４−１５０３９７には塩化カルシウムと炭酸水
素カルシウムの反応において反応終了時のスラリーのｐ
ｎが６．８になるように予めアンモニアを共存させるこ
とによってバテライト型炭酸カルシウムを得る方法が記
載されている。For example, in JP-A-60-90822, a carbon dioxide-containing gas is introduced into an aqueous suspension of calcium hydroxide containing a magnesium compound, and when a certain carbonation rate is reached, a condensed alkali phosphate or an alkali metal salt thereof is introduced. There is also a method of obtaining vaterite calcium carbonate by adding
A method for obtaining vaterite-type calcium carbonate by coexisting ammonia in advance so that n is 6.8 is described.
しかし乍ら、これらの方法はいずれも、従来の立法体や
紡錘形の炭酸カルシウム結晶の製造方法に比べて、製造
方法が非常に複雑であるばかりではなく、得られＺ・バ
テライト炭酸カルシウムの一次粒子径が不均一であり、
分散性も良好でない。However, all of these methods are not only much more complex to produce than conventional methods for producing cube-shaped or spindle-shaped calcium carbonate crystals, but also produce primary particles of Z-vaterite calcium carbonate. The diameter is uneven,
Dispersibility is also not good.
また最近、有機溶媒中に含まれる水酸化カルシウムを炭
酸化させることによりバテライト炭酸カルシウムを製造
する方法が多種提案されている。Recently, various methods have been proposed for producing vaterite calcium carbonate by carbonating calcium hydroxide contained in an organic solvent.
例えば、特開昭５９−６４５２７の比較例１には、水酸
化カルシウム水懸濁液とメタノールの混合溶液に炭酸ガ
スを導通し、バテライト炭酸カルシウムを得る方法が、
また特開昭６１−７７６２２には、水酸化カルシウム＋
水子アルコール類の懸濁液系に炭酸ガスを吹き込んで非
晶質又はバテライト等の結晶質炭酸カルシウムを生成さ
せる方法が記載されている。For example, Comparative Example 1 of JP-A No. 59-64527 describes a method for obtaining vaterite calcium carbonate by introducing carbon dioxide gas into a mixed solution of calcium hydroxide aqueous suspension and methanol.
Moreover, in JP-A-61-77622, calcium hydroxide +
A method is described in which amorphous or crystalline calcium carbonate such as vaterite is produced by blowing carbon dioxide gas into a suspension system of water alcohols.
しかし乍ら、これらはいずれの方法でも、バテライト炭
酸カルシウムは高い収率で得ることは可能であるが、−
成粒子が均一で、しかも単分散した分散良好な球状又は
楕円球状バテライト炭酸カルシウムを安定して製造する
ことはできない。従って、従来の方法によって調製され
たバテライト型炭酸カルシウムを、高度な分散性と粒子
の均一性が不可欠とされる様な工業用途、例えば５μｍ
以下のフィルム、特に８閣ビデオデツキ等に使用される
８閣ビデオテープに使用されるポリエステルのベースフ
ィルム、コンデンサー用フィルム等のポリエステルフィ
ルムのブロッキング防止剤として使用することはできず
、分散性と粒子の均−性等の物性が高度に改善された炭
酸カルシウムが各方面から熱望されていた。However, although it is possible to obtain vaterite calcium carbonate in high yield with any of these methods, -
It is not possible to stably produce spherical or elliptic spherical vaterite calcium carbonate with uniform particle size, monodisperse, and good dispersion. Therefore, vaterite-type calcium carbonate prepared by the conventional method can be used in industrial applications where high dispersibility and particle uniformity are essential, e.g.
It cannot be used as an anti-blocking agent for the following films, especially the polyester base films used in the 8-kaku video tapes used in the 8-kaku video decks, polyester films such as condenser films, etc. Calcium carbonate, which has highly improved physical properties such as uniformity, has been eagerly desired from all quarters.
本発明者らは上記問題点を解決し、前述した様なポリエ
ステルのベースフィルム等の高度な分散性、粒子の均一
性が要求される分野にも充分使用可能な炭酸カルシウム
について鋭意研究の結果、特定量の生石灰及び／又は消
石灰と特定量の水を含有するメタノール懸濁液に炭酸ガ
スを導通し、炭酸化反応途中の特定時点で反応系内の温
度を特定の温度に調整し、炭酸化反応開始から反応系内
の導電率が特定の値に到達する時間を特定化して炭酸化
反応を行うことにより１．所望の球状又は楕円球状バテ
ライト炭酸カルシウムが容易かつ安定に製造でき、得ら
れる球状又は楕円球状バテライト炭酸カルシウムが、特
有の一次粒子の均−性及び分散性を有していることを見
出した０本発明は、これらの新しい知見に基づいて完成
されたものである。The present inventors solved the above problems and as a result of intensive research into calcium carbonate, which can be used in fields such as polyester base films that require high dispersibility and particle uniformity, Carbon dioxide is introduced into a methanol suspension containing a specific amount of quicklime and/or slaked lime and a specific amount of water, and the temperature within the reaction system is adjusted to a specific temperature at a specific point in the middle of the carbonation reaction. By carrying out the carbonation reaction by specifying the time from the start of the reaction until the conductivity within the reaction system reaches a specific value, 1. It has been found that the desired spherical or ellipsoidal vaterite calcium carbonate can be produced easily and stably, and that the obtained spherical or ellipsoidal vaterite calcium carbonate has unique primary particle uniformity and dispersibility. The invention was completed based on these new findings.
即ち、本発明の第１は、下記（ア）、（イ）、（つ）、
（１）、（オ）及び（力）の要件を共に具備してなる、
球状又は楕円球状バテライト炭酸カルシウムを内容とす
るものである。That is, the first aspect of the present invention is the following (a), (b), (t),
(1), (E) and (Power) are all met.
It contains spherical or ellipsoidal vaterite calcium carbonate.
（ア）０．１μｍ≦ＤＳ≦２． Ｏｕ ｍ（イ）ＤＰ３
／ＤＳ≦１．２５
（つ）１．０≦ＤＰ２／ＤＰ４≦１．４（１）１．０≦
ＤＰＩ／ＤＰ５≦２．５（オ’）（ＤＰ２−ＤＰ４）／
ＤＰ３≦０．３５（力）Ｓ≧４０
但し、
ＤＳ＝走査電子顕微鏡（ＳＥＭ）により調べた平均粒子
径（μｍ）であり、一次粒子を同一体積を有する球に換
算し、核球の粒子径の平均値を計１し夏出したもの
ｐｐｉ：光透過式粒度分布測定ＩＩ（１津製作所製ＳＡ
−ＣＰ３）を用いて測定した粒
度分布において、大きな粒子径側から
起算した重量累計１０％の時の粒子径
（μｍ）
ＤＰ２ ：上記測定機を用いて測定した粒度分布におい
て、大きな粒子径側から起算し
た重量累計２５％の時の粒子径（μ
ｍ）
ＤＰ３ ：上記測定機を用いて測定した粒度分布におい
て、大きな粒子径側から起算し
た重量累計５０％の時の粒子径Ｃμ
ｍ）
ＤＰ４：上記測定機を用いて測定した粒度分布において
、大きな粒子径側から起算し
た重量累計７５％の時の粒子径（μ
ｍ）
ＤＰ５ ：上記測定機を用いて測定した粒度分布におい
て、大きな粒子径側から起算し
た重量累計９０％の時の粒子径（μ
ｍ）
Ｓ：パテライト粒子の投影図に外接する円の面積に対す
る粒子の投影面積割合
Ｓ−（粒子の投影断面積／粒子に外接する円の面積）Ｘ
１００
更に、上記バテライト炭酸カルシウムを得るための本発
明の第２は、生石灰換算濃度が０．５〜１２重量％であ
る生石灰及び／又は消石灰のメタノール懸濁液に、生石
灰（消石灰の場合は同一モルの生石灰に換ｙｔ＞に対し
５〜２０倍モル相当量の水を加え、メタノールと生石灰
及び／又は消石灰と水との混合系を調製後、該混合系に
炭酸ガスを導通し、炭酸化反応系内の導電率変化曲線に
おいて、炭酸化反応系内の導電率が極大点Ｂに到達する
以前に系内温度を３０℃以上に調整し、炭酸化反応開始
点Ａから炭酸化反応系内導電率が１００μＳ／ｃｍであ
る点りに到達するまでの時間を１２０分未満になるよう
調整して炭酸化反応を行うことを特徴とする、単分散球
状又は楕円球状バテライト炭酸カルシウムの製造方法を
内容とするものである。(a) 0.1μm≦DS≦2. Ou m(ii) DP3
/DS≦1.25 (T) 1.0≦DP2/DP4≦1.4 (1) 1.0≦
DPI/DP5≦2.5(O')(DP2-DP4)/
DP3≦0.35 (force) S≧40 However, DS = average particle diameter (μm) examined by scanning electron microscope (SEM), converting the primary particle into a sphere with the same volume, and the particle diameter of the nuclear sphere. Total average value of 1 and summer value ppi: Light transmission type particle size distribution measurement II (SA made by Itsu Seisakusho)
-Particle size (μm) when the cumulative weight is 10% starting from the larger particle size side in the particle size distribution measured using the above measuring device DP2: In the particle size distribution measured using the above measuring device, starting from the larger particle size side Particle diameter (μ m) when the cumulative weight is 25% DP3: Particle diameter Cμ m when the cumulative weight is 50% from the larger particle size side in the particle size distribution measured using the above measuring device DP4: In the particle size distribution measured using the above measuring device, the particle diameter (μm) when the cumulative weight is 75% starting from the large particle size side DP5: In the particle size distribution measured using the above measuring device, the particle size on the large particle size side Particle diameter (μm) when the cumulative weight is 90% calculated from S: Ratio of the projected area of the particle to the area of the circle circumscribing the projected diagram of the puterite particle area)
100 Furthermore, the second aspect of the present invention for obtaining the above-mentioned vaterite calcium carbonate is to add quicklime (in the case of slaked lime, the same After adding water in an amount equivalent to 5 to 20 times the mole of quicklime (yt) to prepare a mixed system of methanol and quicklime and/or slaked lime and water, carbon dioxide gas is passed through the mixed system to carbonate it. In the electrical conductivity change curve in the reaction system, before the electrical conductivity in the carbonation reaction system reaches the maximum point B, the temperature in the system is adjusted to 30°C or higher, and the temperature in the carbonation reaction system is adjusted from the carbonation reaction starting point A to A method for producing monodisperse spherical or elliptic spherical vaterite calcium carbonate, characterized in that the carbonation reaction is carried out by adjusting the time until reaching a point where the conductivity is 100 μS/cm to be less than 120 minutes. The content shall be as follows.
本発明における光透過式粒度分布測定機による粒子径の
計測は、下記の要領で測定計夏されたものである。In the present invention, the particle diameter is measured using a light transmission type particle size distribution analyzer in the following manner.
測定機種：１津製作所製ＳＡ−ＣＰ３
測定方法：
溶媒：イオン交換水にポリアクリル酸ソーダ０、 ＯＯ
４重量％溶解させた水溶液
予備分散：超音波分散１００秒
測定温度＝２５．０℃±２．５℃
計測方法：以下の計夏例の通りとする。Measuring model: SA-CP3 made by Ichitsu Seisakusho Measuring method: Solvent: Sodium polyacrylate 0, OO in ion exchange water
Preliminary dispersion of an aqueous solution containing 4% by weight: Ultrasonic dispersion for 100 seconds Measurement temperature = 25.0°C ± 2.5°C Measurement method: Follow the measurement example below.
粒度分布測定結果（−例）
上記粒度分布測定結果から計夏したＤＰＩ３．４．５は
以下の通りとなる
Ｄ Ｐ Ｉ ＝２．００＋ （ｉｌ、ｏ−１０，０）
Ｘ （３，００−２，００）÷（１１，０−６，０）
＝２．２０
Ｄ Ｐ ２−０．８０＋ （２８，０−２５，０） ｘ
（１，００−０，８０）＋ （２８，０−１８，０）
＝０．８６Ｄ Ｐ ３−０．５０＋ （５８，０−５
０，０） ｘ （０，６０−０，５０）÷（５８，０−
４２，０） ＝０．５５２゜
Ｄ Ｐ ４−０．３０＋ （８２，０−７５，０） ｘ
（０，４０−０，３０）÷（８２，０−７２，０）
−０，３７Ｄ Ｐ ５ ＝０．１５＋ （９４，０−９
０，０） Ｘ （０，２０−０，１５）＋（９４，０−
８９，０）＝０．１９
本発明のＤＳの測定には、日立製作所製走査型電子顕微
鏡を使用し、倍率２００００倍で観察した。Particle size distribution measurement results (-example) DPI3.4.5 calculated from the above particle size distribution measurement results is as followsD P I =2.00+ (il, o-10,0)
X (3,00-2,00)÷(11,0-6,0)
=2.20 D P 2-0.80+ (28,0-25,0) x
(1,00-0,80)+ (28,0-18,0)
=0.86D P 3-0.50+ (58,0-5
0,0) x (0,60-0,50)÷(58,0-
42,0) =0.552゜D P 4-0.30+ (82,0-75,0) x
(0,40-0,30)÷(82,0-72,0)
-0,37D P5 =0.15+ (94,0-9
0,0) X (0,20-0,15)+(94,0-
89,0)=0.19 A scanning electron microscope manufactured by Hitachi, Ltd. was used to measure the DS of the present invention, and observation was performed at a magnification of 20,000 times.
以下、本発明の球状又は楕円球状バテライト炭酸カルシ
ウムの製造方法につき記述する。The method for producing the spherical or ellipsoidal vaterite calcium carbonate of the present invention will be described below.
本発明の球状又は楕円球状バテライト炭酸カルシウムは
、特定量の生石灰及び／又は消石灰と特定量の水を含有
するメタノール懸濁液に炭酸ガスを導通し、炭酸化反応
途中の特定時点で反応系内の温度を特定の温度に調整し
、炭酸化反応開始から反応系内の導電率が特定の値に到
達する時間を特定化して炭酸化反応を行うことにより製
造される。The spherical or elliptic spherical vaterite calcium carbonate of the present invention is produced by introducing carbon dioxide gas into a methanol suspension containing a specific amount of quicklime and/or slaked lime and a specific amount of water, and then entering the reaction system at a specific point in the middle of the carbonation reaction. The carbonation reaction is produced by adjusting the temperature to a specific temperature and specifying the time from the start of the carbonation reaction until the conductivity within the reaction system reaches a specific value.
まず、生石灰粉体及び／又は消石灰粉体をメタノール中
に投入し、生石灰及び／又は消石灰のメタノール懸濁液
を調製する。生石灰及び／又は消石灰の濃度は、生石灰
換算濃度（消石灰の場合は同一モルの生石灰に換算した
濃度、以下生石灰濃度と略称する）としてメタノールに
対し０．５〜１２重量％、好ましくは１〜８重量％であ
ればよい。First, quicklime powder and/or slaked lime powder is poured into methanol to prepare a methanol suspension of quicklime and/or slaked lime. The concentration of quicklime and/or slaked lime is 0.5 to 12% by weight, preferably 1 to 8% by weight of methanol, in terms of quicklime conversion concentration (in the case of slaked lime, the concentration converted to the same mole of quicklime, hereinafter referred to as quicklime concentration). It suffices if it is % by weight.
生石灰濃度が０．５重量％未溝の場合、単位メタノール
必要量が増大し不経済であるばかりではなく、以降の炭
酸化反応工程における反応条件のコントロールが困難に
なるため、本発明のバテライト炭酸カルシウムの収率が
非常に悪くなる。また、生石灰濃度が１２重量％を越え
た場合、以降の炭酸化反応工程において系内がゲル化し
やすく、さらに得られる炭酸カルシウムの粒子の形状、
大きさが不均一となり、さらに粒子の分散状態も良好で
ない炭酸カルシウムしか得られない。If the quicklime concentration is 0.5% by weight, the amount of methanol required per unit increases, which is not only uneconomical, but also makes it difficult to control the reaction conditions in the subsequent carbonation reaction step. Calcium yield becomes very poor. In addition, if the quicklime concentration exceeds 12% by weight, the system tends to gel in the subsequent carbonation reaction process, and the shape of the resulting calcium carbonate particles also changes.
Calcium carbonate can only be obtained with non-uniform size and poor particle dispersion.
生石灰の代わりに生石灰と同一モル重量の消石灰を用い
ても本発明の炭酸カルシウムは得られるが、生石灰を原
料とする場合と比較し、炭酸化反応工程における反応条
件が非常に幅の狭いものとなるため、生石灰を使用する
のが好ましい、また、生石灰の好ましい活性度は８０以
上であり、以下の方法で測定される。Although the calcium carbonate of the present invention can be obtained by using slaked lime with the same molar weight as quicklime instead of quicklime, the reaction conditions in the carbonation reaction step are very narrow compared to when quicklime is used as a raw material. Therefore, it is preferable to use quicklime, and the preferable activity of quicklime is 80 or more, which is measured by the following method.
活性度：
１０００ｃｃのビーカーに４０℃の脱イオン水５００ｍ
を入れ、攪拌機で攪拌しながらフェノールフタレイン２
〜３滴を加えた後、生石灰１０ｇを一挙に投入すると同
時に、ストップウォッチで計時を始める。１分経過後か
ら、溶液がわずかに赤味を呈するのを持続するよう、４
Ｎ−Ｈ（ｌを継続して滴下する。１分ごとにそれまでの
４Ｎ−ＨＣｌの滴下量を記録し、２０分間この作業を続
ける。活性度は１０分経過後の累積滴下量（ａｌりをも
って表示する。Activity: 500m of deionized water at 40℃ in a 1000cc beaker
Add phenolphthalein 2 while stirring with a stirrer.
After adding ~3 drops, add 10g of quicklime all at once and start timing with a stopwatch. After 1 minute, add 4 ml to keep the solution slightly reddish.
Continuously drop N-HCl (l). Record the amount of 4N-HCl dropped every minute and continue this process for 20 minutes. The activity is calculated by the cumulative amount of dropped 10 minutes (al Displayed with.
本発明で使用される生石灰及び消石灰は、一定の粒度に
調整するため、乾式粉砕機を用いての乾式粉砕、または
湿式粉砕機を用いた生石灰、消石灰のメタノール懸濁液
の湿式解砕を行った後使用するのが好ましい。In order to adjust the quicklime and slaked lime to a constant particle size, the quicklime and slaked lime used in the present invention are dry-pulverized using a dry-type pulverizer, or wet-pulverized using a wet-type pulverizer to wet a methanol suspension of quicklime and slaked lime. It is preferable to use it after washing.
次に、この生石灰及び／又は消石灰のメタノール懸濁液
に、生石灰に対して５〜２０倍モル相当量の水、好まし
くは５〜１５倍モル相当量の水を加え、（メタノール＋
生石灰または消石灰）土水の混合系を調製する。加える
水の量が５倍モル未満の場合は、以降の炭酸化反応工程
においてゲル化しやすく、また２０倍モルを越える場合
は、本発明のバテライト炭酸カルシウム以外にカルサイ
ト、アラブナイト等の結晶型の炭酸カルシウムが多数混
在する炭酸カルシウムが得られることになり好ましくな
い。Next, to this methanol suspension of quicklime and/or slaked lime, water is added in an amount equivalent to 5 to 20 times the molar amount of quicklime, preferably 5 to 15 times the molar amount of water, and (methanol +
(quicklime or slaked lime) Prepare a soil/water mixture system. If the amount of water added is less than 5 times the molar amount, gelation tends to occur in the subsequent carbonation reaction step, and if it exceeds 20 times the molar amount, crystal forms such as calcite, arabite, etc. are added in addition to the vaterite calcium carbonate of the present invention. This is not preferable since calcium carbonate containing a large amount of calcium carbonate is obtained.
次に、このメタノールと生石灰及び／又は消石灰と水と
の混合系に炭酸ガス（炭酸ガスを含有するガスでもよい
）を導通し、炭酸化反応を行う。Next, carbon dioxide gas (a gas containing carbon dioxide gas may be used) is passed through the mixed system of methanol, quicklime and/or slaked lime, and water to carry out a carbonation reaction.
炭酸ガスの単位供給量は、第１図に示された炭酸化反応
系内の導電率変化曲線において、炭酸化反応開始点Ａか
ら炭酸化反応系内導電率が１００μＳ／ＣＩＩである点
りに到達するまでの時間が１２０分未満、好ましくは１
００分未満になるよう調整される。従って、例えば炭酸
ガスの反応効率が１００％の場合、通常反応系内の生石
灰１モル当り０、２２４ ｊ！ ／ｓｉｎ以上の炭酸ガ
ス単位供給量で炭酸化を開始し、反応系内ｐＨが６．５
付近になるまで炭酸ガスの導通を継続し、反応系内導電
率が１００μＳ／ｅ１ｍ（第１図の点Ｄ）に達した場合
、確実に本発明のバテライト炭酸カルシウムは製造され
る。また、前記反応例において、反応系内ｐＨを１０．
０で炭酸ガスの導通を停止したとしても、メタノール中
に残存していた炭酸ガス等の影響で反応系のｐＨが自然
に低下し、反応系内導電率が１００μＳ／ｃｍ（第１図
の点Ｄ）に達した場合、炭酸化反応開始から炭酸化反応
系内導電率が点りに到達するまでの時間が１２０分未満
であれば本発明の目的は達成される。The unit supply amount of carbon dioxide gas is calculated from the carbonation reaction starting point A to the point where the conductivity in the carbonation reaction system is 100 μS/CII on the conductivity change curve in the carbonation reaction system shown in Figure 1. Time to reach less than 120 minutes, preferably 1
Adjusted to be less than 00 minutes. Therefore, for example, if the reaction efficiency of carbon dioxide gas is 100%, usually 0.224 j! per mole of quicklime in the reaction system! Carbonation starts with a unit supply of carbon dioxide of /sin or more, and the pH in the reaction system is 6.5.
When the conductivity of carbon dioxide gas is continued until the conductivity within the reaction system reaches 100 μS/e1m (point D in FIG. 1), the vaterite calcium carbonate of the present invention is reliably produced. In addition, in the reaction example, the pH within the reaction system was set to 10.
Even if the conduction of carbon dioxide gas is stopped at 0, the pH of the reaction system will naturally decrease due to the influence of carbon dioxide gas remaining in methanol, and the conductivity in the reaction system will decrease to 100 μS/cm (point in Figure 1). When D) is reached, the object of the present invention can be achieved if the time from the start of the carbonation reaction until the electrical conductivity within the carbonation reaction system reaches a point is less than 120 minutes.
しかし乍ら、前記反応例と同様に反応系内の生石灰１モ
ル当り０．２２４１ ／＋ｍｉｎ以上の炭酸ガス単位供
給量で炭酸化を開始し、反応系内ｐＨを１０゜５で炭酸
ガスの導通を停止したとしても、系内に残存していたア
ルカリの影響でｐｔ＋が上昇し、系内導電率が点りに到
達しないまま上昇した場合、板状炭酸カルシウムが多数
混在した不揃いの炭酸カルシウムが得られることになり
、また、これらの炭酸カルシウムの分散性は良好とは言
えず、本発明の目的は達成されない。However, as in the reaction example above, carbonation was started with a unit supply of carbon dioxide of 0.2241/+min per mole of quicklime in the reaction system, and the pH in the reaction system was set at 10°5 to conduct carbon dioxide. Even if the system is stopped, pt+ increases due to the influence of the alkali remaining in the system, and if the conductivity in the system increases without reaching the point, irregular calcium carbonate containing many plate-shaped calcium carbonate Moreover, the dispersibility of these calcium carbonates cannot be said to be good, and the object of the present invention cannot be achieved.
また、炭酸ガスの単位供給量の不足、あるいは反応装置
の攪拌力不足等による炭酸ガスの反応効率の低下等の理
由により、炭酸化反応開始から炭酸化反応系内導電率が
点りに到達するまでの時間が１２０分を超えた場合、例
えば点りに到達するまでの時間が２００分の場合は、板
状炭酸カルシウムが得られることになり、本発明の目的
が達成されないことは言うまでもない。また、炭酸化反
応の開始時点の混合系の温度は、炭酸化反応工程中にお
けるゲル化防止のため、好ましくは２０℃以上、より好
ましくは３０℃以上に設定したほうがよいが、第１図に
示された炭酸化反応系内の導電率変化曲線において、炭
酸化反応系内の導電率が極大点Ｂに到達する以前に系内
温度を３０℃以上、好ましくは４０℃以上に調整しさえ
すれば、炭酸化反応の開始時点の混合系の温度に関係な
く本発明の目的は達成される。炭酸化反応系内の導電率
が極大点Ｂに到達する以前の系内の温度が３０゛Ｃ未満
の場合、炭酸化反応系内の導電率が極大点Ｂに到達した
時点以降、炭酸化反応系の粘度が急上昇しゲル化しやす
く、炭酸化反応を継続出来ない状態になりやすい。また
、炭酸化反応系の粘度が急上昇した場合、強力な攪拌等
を行うことにより炭酸化反応を継続しえたとしても、系
内の炭酸化反応が不均一な反応となるため、得られる炭
酸カルシウムの粒子の均一性が悪く、良好な分散性を有
するバテライト炭酸カルシウムは得られない。In addition, the electrical conductivity within the carbonation reaction system may reach a point from the start of the carbonation reaction due to reasons such as a decrease in the reaction efficiency of carbon dioxide gas due to insufficient unit supply of carbon dioxide gas or insufficient stirring power of the reaction device. It goes without saying that if the time to reach the point of burning exceeds 120 minutes, for example if the time to reach the point of lightness is 200 minutes, plate-shaped calcium carbonate will be obtained and the object of the present invention will not be achieved. In addition, the temperature of the mixing system at the start of the carbonation reaction should preferably be set at 20°C or higher, more preferably 30°C or higher, in order to prevent gelation during the carbonation reaction process. In the shown conductivity change curve within the carbonation reaction system, the temperature within the system must be adjusted to 30°C or higher, preferably 40°C or higher before the conductivity within the carbonation reaction system reaches maximum point B. For example, the object of the present invention is achieved regardless of the temperature of the mixing system at the beginning of the carbonation reaction. If the temperature in the system before the electrical conductivity in the carbonation reaction system reaches the maximum point B is less than 30°C, the carbonation reaction will start after the electrical conductivity in the carbonation reaction system reaches the maximum point B. The viscosity of the system increases rapidly and tends to gel, making it difficult to continue the carbonation reaction. In addition, if the viscosity of the carbonation reaction system increases rapidly, even if the carbonation reaction can be continued by performing strong stirring, etc., the carbonation reaction within the system becomes a non-uniform reaction, and the calcium carbonate obtained The uniformity of the particles is poor, and vaterite calcium carbonate with good dispersibility cannot be obtained.
このようにして得られる球状又は楕円球状バテライト炭
酸カルシウムは、電子顕微鏡により測定される平均粒子
径と粒度分布測定機により計測される平均粒子径がほと
んど近似であるばかりでなく、粒度分布もきわめてシャ
ープであり、分散媒中に凝集せずに単分散されている。The spherical or ellipsoidal vaterite calcium carbonate obtained in this way not only has an average particle diameter measured by an electron microscope and an average particle diameter measured by a particle size distribution analyzer, but also has an extremely sharp particle size distribution. It is monodispersed in the dispersion medium without agglomeration.
本発明において、得られたバテライト炭酸カルシウムが
単分散された分散液を濃縮、脱水等の方法で固液分離を
行ない、固液分離により得られるメタノールを再度炭酸
カルシウムの合成に用いることができる。また、本発明
により得られたノ飄テライト炭酸カルシウムの分散液に
、単分散された粒子の安定性をさらに高めるために、得
られた分散液中に、カルボン酸又はそのアルカリ塩等を
添加することにより、長期間安定な分散性を有するバテ
ライト炭酸カルシウムの分散体を得ることが可能となる
。また、分散液中のメタノールを別の有機溶媒に置換す
ることも容易であり、例えば単分散した球状又は楕円球
状バテライト炭酸カルシウムのエチレングリコールスラ
リーは、ポリエステル繊維、ポリエステルフィルム等へ
応用され、良好なブロッキング防止性を発揮する。さら
にまた、本発明によって得られたバテライト炭酸カルシ
ウムが単分散された分散液に脂肪酸、樹脂酸又はそのア
ルカリ塩等を添加した後乾燥すれば、分散性のよいバテ
ライト炭酸カルシウム粉体が調製され、従来公知の用途
、即ち塗料、インクの体質顔料、ゴム、プラスチックの
充填剤、製紙用の顔料として良好な光学的特性、力学的
特性、良好な流動性や充填性を有する炭酸カルシウムが
調製される。In the present invention, the obtained dispersion in which vaterite calcium carbonate is monodispersed is subjected to solid-liquid separation by methods such as concentration and dehydration, and methanol obtained by solid-liquid separation can be used again for the synthesis of calcium carbonate. Further, in order to further increase the stability of the monodispersed particles in the dispersion of nototerite calcium carbonate obtained according to the present invention, a carboxylic acid or an alkali salt thereof is added to the dispersion obtained. This makes it possible to obtain a dispersion of vaterite calcium carbonate that has stable dispersibility over a long period of time. In addition, it is easy to replace methanol in the dispersion with another organic solvent. For example, an ethylene glycol slurry of monodispersed spherical or ellipsoidal vaterite calcium carbonate can be applied to polyester fibers, polyester films, etc., and has good properties. Demonstrates anti-blocking properties. Furthermore, if a fatty acid, a resin acid, or an alkali salt thereof, etc. are added to a monodispersed dispersion of vaterite calcium carbonate obtained by the present invention and then dried, a vaterite calcium carbonate powder with good dispersibility can be prepared. Calcium carbonate is prepared with good optical properties, mechanical properties, and good fluidity and filling properties for use in conventionally known applications, such as extender pigments in paints and inks, fillers in rubber and plastics, and pigments for paper manufacturing. .
以下、本発明を実施例及び比較例により説明するが、本
発明はこれらにより何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.
導電率の測定：東亜電波工業型ＣＭ−４０Ｓ電導度計を
使用した。ただし、基準部
度を２５℃とした値。Measurement of conductivity: A Toa Denpa Kogyo model CM-40S conductivity meter was used. However, the value is based on the standard temperature of 25°C.
ｐｎの測定：横河電気製パーソナルｐｉ（メーターＰＨ
８１−１１−Ｊを使用した。Measurement of pn: Yokogawa Electric personal pi (meter PH
81-11-J was used.
調製例：実施例及び比較例に使用するメタノール懸濁液
分散体の調製
活性度が８２の粒状生石灰（試薬特級）、及び消石灰（
試薬特級）を乾式粉砕機（コロブレックス、アルピネ社
製）で粉砕し、得られた生石灰粉体をメタノール中に投
入し、２００メツシユの篩を用いて粗粒を除去した後、
生石灰としての固形分濃度２０％の、生石灰のメタノー
ル懸濁液及び消石灰のメタノール懸濁液を調製した。該
メタノール懸濁液を湿式粉砕機（ダイノーミルＰＩＬＯ
Ｔ型、ＷＡＢ社製）により解砕処理し、生石灰のメタノ
ール懸濁液分散体及び消石灰のメタノール懸濁液分散体
をそれぞれ調製した。Preparation example: Preparation of methanol suspension dispersion used in Examples and Comparative Examples Granular quicklime (reagent special grade) with an activity of 82 and slaked lime (
Reagent grade) was crushed using a dry crusher (Colorbrex, manufactured by Alpine), the resulting quicklime powder was poured into methanol, and coarse particles were removed using a 200-mesh sieve.
A methanol suspension of quicklime and a methanol suspension of slaked lime were prepared, each having a solid concentration of 20% as quicklime. The methanol suspension was processed using a wet pulverizer (Dyno Mill PILO).
Type T, manufactured by WAB Corporation) to prepare a methanol suspension dispersion of quicklime and a methanol suspension dispersion of slaked lime, respectively.
実施例１
前記調製例で得られた生石灰のメタノール懸濁液分散体
にメタノールを追加添加し、生石灰濃度が３．０重量％
となるように希釈し、さらに生石灰に対し１１倍相当モ
ルの水を添加し、メタノールと生石灰と水の混合系を調
製した。２００ｇの生石灰を含有する該混合系を４２℃
に調整した後、攪拌条件下該混合系中に炭酸ガスを生石
灰１モル当り０．０８２モル／ Ｉｌｌ ｎの導通速度
で導通し、炭酸化反応を開始した。炭酸化反応開始５分
後に系内の導電率が極大点（第１図の点Ｂに相当する点
）に達し、該極大点における系内温度は４５℃になるよ
う調節した。その後も炭酸化反応を継続し、炭酸化反応
開始１９分後に系内の導電率が１００μＳ ／ Ｃ１ｌ
に達した点（第１図の点りに相当する点）で炭酸ガスの
供給を停止し、炭酸化反応を停止した。Example 1 Methanol was additionally added to the methanol suspension dispersion of quicklime obtained in the above preparation example, and the quicklime concentration was 3.0% by weight.
The mixture of methanol, quicklime, and water was prepared by diluting the mixture and adding water in an amount equivalent to 11 times the molar amount of quicklime. The mixed system containing 200g of quicklime was heated to 42°C.
After adjusting the temperature, carbon dioxide gas was introduced into the mixed system under stirring conditions at a rate of 0.082 mol/Illn per mol of quicklime to start the carbonation reaction. Five minutes after the start of the carbonation reaction, the electrical conductivity in the system reached a maximum point (corresponding to point B in FIG. 1), and the temperature in the system at this maximum point was adjusted to 45°C. After that, the carbonation reaction continued, and 19 minutes after the start of the carbonation reaction, the conductivity in the system reached 100μS/C1l.
At the point where the temperature reached (corresponding to the point in Figure 1), the supply of carbon dioxide gas was stopped, and the carbonation reaction was stopped.
点りにおける系内ｐＨは７．０であった。本実施例１の
炭酸化反応中の系内の導電率測定結果及びｐｔｉの測定
結果を第２図に示す。また、本実施例】の炭酸化反応条
件を第１表に示す。更に、本実施例１によって調製され
た炭酸カルシウムはＸ線回折測定の結果、１００％バテ
ライト構造を有する炭酸カルシウムであり、該バテライ
ト炭酸カルシウムの物性を第３表に、走査型電子顕微鏡
による写真を第３図に示す。The pH in the system at the time of lighting was 7.0. FIG. 2 shows the results of measuring the electrical conductivity and Pti in the system during the carbonation reaction of Example 1. Further, the carbonation reaction conditions of this example are shown in Table 1. Further, as a result of X-ray diffraction measurement, the calcium carbonate prepared in Example 1 was found to be calcium carbonate having a 100% vaterite structure, and the physical properties of the vaterite calcium carbonate are shown in Table 3, and a photograph taken with a scanning electron microscope is It is shown in Figure 3.
第３表及び第３図の結果から、実施例１により調製され
た炭酸カルシウムは、二次凝集がほとんどない分散性良
好なバテライト炭酸カルシウムであることがわかる。From the results shown in Table 3 and FIG. 3, it can be seen that the calcium carbonate prepared in Example 1 is vaterite calcium carbonate with good dispersibility and almost no secondary aggregation.
実施例２、実施例３
第１表に示されている実施例工の製造方法の特定値を、
同表に示す特定値に変更することを除き、実施例１と同
じ手順で炭酸カルシウムを合成した。Example 2, Example 3 The specific values of the manufacturing method of the example work shown in Table 1 are as follows:
Calcium carbonate was synthesized using the same procedure as in Example 1, except for changing the specific values shown in the table.
本実施例２．３によって調製された炭酸カルシウムはＸ
線回折の結果、１００％バテライト構造を有する炭酸カ
ルシウムであり、該バテライト炭酸カルシウムの物性を
第３表に示す。Calcium carbonate prepared according to this Example 2.3 was
As a result of line diffraction, it was found that the calcium carbonate had a 100% vaterite structure, and the physical properties of the vaterite calcium carbonate are shown in Table 3.
第３表の結果から、実施例２．３により調製された炭酸
カルシウムは、二次凝集がほとんどない分散性良好なバ
テライト炭酸カルシウムであることがわかる。From the results in Table 3, it can be seen that the calcium carbonate prepared in Example 2.3 is vaterite calcium carbonate with good dispersibility and almost no secondary aggregation.
実施例４
実施例１と同様の方法で炭酸化反応を開始した後、炭酸
化反応開始１３分後に、系内ｐｉが１０．０になった時
点で炭酸ガスの供給を停止した。炭酸ガス供給停止後も
系内の攪拌を継続し、炭酸化反応開始２０分後に系内の
導電率が１００μＳ／Ｃ１ｍに達した。Example 4 After starting a carbonation reaction in the same manner as in Example 1, the supply of carbon dioxide gas was stopped when the pi in the system reached 10.0, 13 minutes after the start of the carbonation reaction. Stirring in the system was continued even after the carbon dioxide gas supply was stopped, and the electrical conductivity in the system reached 100 μS/C1m 20 minutes after the start of the carbonation reaction.
点りにおける系内ｐＮは９．７であった。本実施例４の
炭酸化反応中の系内の導電率測定結果及びｐＨの測定結
果を第４図に示す。また本実施例４の炭酸化反応条件を
第１表に示す。更に、本実施例４によって調製された炭
酸カルシウムはＸ線回折の結果、１００％バテライト構
造を有する炭酸カルシウムであり、該へテライト炭酸カ
ルシウムの物性を第３表に、走査型電子顕微鏡による写
真を第５図に示す。The in-system pN in the test was 9.7. FIG. 4 shows the results of measuring the electrical conductivity and pH within the system during the carbonation reaction of Example 4. Further, the carbonation reaction conditions of Example 4 are shown in Table 1. Furthermore, as a result of X-ray diffraction, the calcium carbonate prepared in Example 4 was found to be calcium carbonate having a 100% vaterite structure. The physical properties of the heterite calcium carbonate are shown in Table 3, and a photograph taken with a scanning electron microscope It is shown in FIG.
第３表及び第５図の結果から、実施例４により調製され
た炭酸カルシウムは、二次凝集がほとんどない分散性良
好なバテライト炭酸カルシウムであることがわかる。From the results shown in Table 3 and FIG. 5, it can be seen that the calcium carbonate prepared in Example 4 is vaterite calcium carbonate with good dispersibility and almost no secondary aggregation.
実施例５
実施例１に使用した生石灰のメタノール懸濁液分散体を
前記調製例で得られた消石灰のメタノール懸濁液分散体
に変更し、更に第１表に示されている実施例１の製造方
法の特定値を同表に示す特定値に変更することを診き、
実施例１と同じ手順で炭酸カルシウムを合成した０本実
施例５によって調製された炭酸カルシウムはＸ線回折の
結果、１００％バテライト構造を有する炭酸カルシウム
であり、該バテライト炭酸カルシウムの物性を第３表に
示す。Example 5 The methanol suspension dispersion of quicklime used in Example 1 was changed to the methanol suspension dispersion of slaked lime obtained in the above preparation example, and the dispersion of Example 1 shown in Table 1 was further changed. Examining the need to change the specific value of the manufacturing method to the specific value shown in the same table,
Calcium carbonate was synthesized using the same procedure as in Example 1. As a result of X-ray diffraction, the calcium carbonate prepared in Example 5 was found to be calcium carbonate having a 100% vaterite structure. Shown in the table.
第３表の結果から、実施例５により調製された炭酸カル
シウムは、二次凝集がほとんどない分散性良好なバテラ
イト炭酸カルシウムであることがわかる。From the results in Table 3, it can be seen that the calcium carbonate prepared in Example 5 is vaterite calcium carbonate with good dispersibility and almost no secondary aggregation.
比較例工
第１表に示されている実施例１の製造方法の特定値を第
２表に示す特数値に変更することを除き、実施例１と同
じ手順で炭酸化反応を行った。しかし炭酸化反応途中に
系内が著しく増粘し系内がシャーベット状となり、炭酸
化反応の継続が困難になったため、炭酸化反応を中止し
た。Comparative Example A carbonation reaction was carried out in the same manner as in Example 1, except that the specific values of the manufacturing method of Example 1 shown in Table 1 were changed to the special values shown in Table 2. However, during the carbonation reaction, the viscosity in the system increased significantly and the system became sherbet-like, making it difficult to continue the carbonation reaction, so the carbonation reaction was discontinued.
比較例２〜５
第１表に示されている実施例１の製造方法の特定値を第
２表に示す特数値に変更することを除き、実施例１と同
じ手順で炭酸カルシウムを合成した。Comparative Examples 2 to 5 Calcium carbonate was synthesized using the same procedure as in Example 1, except that the specific values of the manufacturing method of Example 1 shown in Table 1 were changed to the special values shown in Table 2.
比較例２〜５によって調製された炭酸カルシウムの物性
を第４表に示す、比較例５の炭酸化反応中の系内の導電
率測定結果及びｐｉの測定結果を第６図に示す。The physical properties of the calcium carbonates prepared in Comparative Examples 2 to 5 are shown in Table 4, and the results of measuring the electrical conductivity and pi in the system during the carbonation reaction of Comparative Example 5 are shown in FIG.
第４表から、比較例２．４により調製されたバテライト
炭酸カルシウムは、極めて分散性の悪い炭酸カルシウム
であることがわかる。また、比較例３により調製された
炭酸カルシウムには、カルサイト炭酸カルシウムやアラ
ブナイト炭酸カルシウムが多数混在しており、その粒度
分布がブロードで不良であることがわかる。また、比較
例５により調製された炭酸カルシウムは、走査型電子顕
微鏡写真で確認した結果、板状の形態を有する炭酸カル
シウムであった。Table 4 shows that the vaterite calcium carbonate prepared in Comparative Example 2.4 is calcium carbonate with extremely poor dispersibility. Further, it can be seen that the calcium carbonate prepared in Comparative Example 3 contained a large amount of calcite calcium carbonate and arabite calcium carbonate, and its particle size distribution was broad and poor. Further, the calcium carbonate prepared in Comparative Example 5 was found to have a plate-like shape as confirmed by scanning electron micrograph.
比較例６
生石灰に水を加え調製された石灰乳を、比重１゜０７０
、温度１０℃に調製し、該石灰乳７．２イ中に炭酸ガス
濃度２５重量％の炉ガスを２０ｒｒｒ／＊ｉｎの導通速
度で供給し炭酸化反応を行ない、ｐＨ６゜５で炭酸化反
応を終了した。該炭酸化反応の終了した炭酸カルシウム
の水懸濁液の液温を５０℃に調製し、２４時間攪拌した
。このようにしてｌｌ＆！された炭酸カルシウムは、カ
ルサイト型の炭酸カルシウムであり、走査型電子顕微鏡
写真による１次粒子径は０．２μｍであった。この炭酸
カルシウムの水懸濁液を常法に従い脱水し、得られた脱
水ケーキにポリアクリル酸ソーダを炭酸力ルソウム固形
分に対し１．５重量％添加し、強力にＷＩ拌することに
より、固形分濃度３５重量％の炭酸カルシウムの水スラ
リーを得た。該水スラリーを、６０ｃｃ／＋ｗｉｎの流
量で繰り返し１０回、湿式粉砕機（ダイノーミルＰｉ
ｌｏｔ型、ＷＡＢ社製、メディア充填率８０％、メディ
ア０．６〜０．９ ｍ、回転数１５０Ｏｒｐｍ）を通過
せしめ湿式粉砕を行ない、凝集体の分散を行った。Comparative Example 6 Milk of lime prepared by adding water to quicklime had a specific gravity of 1°070.
The temperature was adjusted to 10°C, and a furnace gas with a carbon dioxide concentration of 25% by weight was supplied into the milk of lime at a conduction rate of 20rrr/*in to carry out a carbonation reaction, and the carbonation reaction was carried out at a pH of 6°5. has ended. The temperature of the aqueous suspension of calcium carbonate after the carbonation reaction was adjusted to 50° C., and the suspension was stirred for 24 hours. In this way ll&! The obtained calcium carbonate was calcite-type calcium carbonate, and the primary particle diameter according to a scanning electron micrograph was 0.2 μm. This aqueous suspension of calcium carbonate was dehydrated according to a conventional method, and 1.5% by weight of sodium polyacrylate was added to the resulting dehydrated cake based on the solid content of russoum carbonate. An aqueous slurry of calcium carbonate with a concentration of 35% by weight was obtained. The water slurry was repeatedly processed 10 times at a flow rate of 60cc/+win using a wet grinder (Dyno Mill Pi).
The agglomerates were dispersed by passing through a lot type (manufactured by WAB Co., Ltd., media filling rate 80%, media 0.6 to 0.9 m, rotation speed 150 rpm) for wet pulverization.
本比較例６によって調製された炭酸カルシウムの物性を
第４表に、走査型電子顕微鏡による写真を第７図に示す
。The physical properties of calcium carbonate prepared in Comparative Example 6 are shown in Table 4, and a photograph taken with a scanning electron microscope is shown in FIG.
第４表及び第７図の結果から、比較例６により調製され
た炭酸カルシウムは、強力な湿式粉砕を繰り返し行って
調製されているにもかかわらず、その粒度分布はブロー
ドであり、
均一であることがわかる。From the results in Table 4 and Figure 7, the particle size distribution of the calcium carbonate prepared in Comparative Example 6 is broad and uniform, even though it was prepared by repeated intensive wet grinding. I understand that.
また粒子形が不
生石灰換ＸＮａ度：炭酸化反応前のメタノール懸濁液分
散体中の生石灰換算濃度
（重量％）
水添加量：炭酸化反応前のメタノール懸濁液分散体中の
生石灰１モルに対し添加される
水の添加量（モル）
温度１：炭酸化反応開始時点の系内温度（”Ｃ）速度１
：炭酸化反応前のメタノール懸濁液分散体中の生石灰１
モルに対し供給される炭酸ガスの供給速度（モル７分）
温度２：系内の導電率の極大点Ｂの系内温度（’Ｃ）ゲ
ル化の有無：炭酸化反応途中の増粘・ゲル化の有無
ｐＨ１：炭酸ガス供給途中停止時の系内ｐＨ時間１：炭
酸化反応開始時点から炭酸ガス供給途中停止時までの経
過時間（分）
時間３：最初の炭酸化反応開始後から系内の導電率が１
００μＳ ／ Ｃ１ｌに達した点りに到達するまでの経
過時間（分）
ｐＨ２：炭酸ガス供給最終停止時の系内ｐＨ第
表
第
表
〔作用・効果〕
軟土の通り、本発明によれば、二次凝集がほとんど無く
、分散性に優れた球状又は楕円球状バテライト炭酸カル
シウムが提供される。In addition, the particle form is inert lime equivalent to Amount of water added to (mol) Temperature 1: Temperature inside the system at the start of carbonation reaction ("C) Rate 1
: Quicklime 1 in methanol suspension dispersion before carbonation reaction
Supply rate of carbon dioxide gas supplied per mole (7 minutes per mole) Temperature 2: Temperature within the system at the maximum point B of electrical conductivity within the system ('C) Presence or absence of gelation: Thickening and gelation during the carbonation reaction Presence or absence of carbonation pH 1: pH within the system when carbon dioxide gas supply is stopped midway Time 1: Elapsed time (minutes) from the start of carbonation reaction to when carbon dioxide gas supply is stopped midway Time 3: Inside system after the start of the first carbonation reaction conductivity is 1
Elapsed time (minutes) until reaching the point at which 00μS/C1l is reached pH2: System pH at final stop of carbon dioxide gas supply Table Table 1 [Function/Effect] According to the present invention, as in soft soil, Spherical or ellipsoidal vaterite calcium carbonate with almost no secondary aggregation and excellent dispersibility is provided.
第１図は炭酸化反応系内の導電率変化曲線である。第２
図は実施例１の炭酸化反応系内の導電率測定結果及びｐ
Ｈ測定結果を示し、第３図は実施例１で得られたバテラ
イト炭酸カルシウムの粒子構造を示す電子顕微鏡写真、
第４図は実施例４の炭酸化反応系内の導電率測定結果及
びｐＨ測定結果を示し１、第５図は実施例４で得られた
バテライト炭酸カルシウムの粒子構造を示す電子顕微鏡
写真、第６図は比較例５の炭酸化反応系内の導電率測定
結果及びｐＨ測定結果を示し、第７図は比較例６で得ら
れた戻酸カルシウムの粒子構造を示す電子顕微鏡写真で
ある。
Ａ・・・炭酸化反応開始点
Ｂ・・・炭酸化反応系内の導電率の極大点Ｃ・・・炭酸
化反応系内の導電率の膝下開始点Ｄ・・・炭酸化反応系
内の導電率が１００μＳ／１である点
第３図
第１図
糞り叫閘（句
ガ）
第２図
第４図
経過時間（ｍｉｎ）
経過時間＜ｍｉｎ＞
第５図
第６図
経過時間（ｍｉｎ）
第７図FIG. 1 is a conductivity change curve within the carbonation reaction system. Second
The figure shows the conductivity measurement results in the carbonation reaction system of Example 1 and p
H measurement results are shown, and FIG. 3 is an electron micrograph showing the particle structure of vaterite calcium carbonate obtained in Example 1.
FIG. 4 shows the conductivity measurement results and pH measurement results in the carbonation reaction system of Example 41, and FIG. 5 shows an electron micrograph showing the particle structure of vaterite calcium carbonate obtained in Example 4. FIG. 6 shows the conductivity measurement results and pH measurement results in the carbonation reaction system of Comparative Example 5, and FIG. 7 is an electron micrograph showing the particle structure of the returned calcium oxide obtained in Comparative Example 6. A...Carbonation reaction starting point B...Maximum point of electrical conductivity in the carbonation reaction system C...Below the knee starting point of electrical conductivity in the carbonation reaction system D...In the carbonation reaction system The point where the conductivity is 100 μS/1 Fig. 3 Fig. 1 Elapsed time (min) Fig. 2 Fig. 4 Elapsed time (min) Fig. 5 Fig. 6 Elapsed time (min) Figure 7
Claims (1)
（カ）の要件を共に具備してなる、球状又は楕円球状バ
テライト炭酸カルシウム。 （ア）０．１μｍ≦ＤＳ≦２．０μｍ （イ）ＤＰ３／ＤＳ≦１．２５ （ウ）１．０≦ＤＰ２／ＤＰ４≦１．４ （エ）１．０≦ＤＰ１／ＤＰ５≦２．５ （オ）（ＤＰ２−ＤＰ４）／ＤＰ３≦０．３５（カ）Ｓ
≧４０ 但し、 ＤＳ：走査電子顕微鏡（ＳＥＭ）により調べた平均粒子
径（μｍ）であり、一次粒子を 同一体積を有する球に換算し、該球の粒 子径の平均値を計算し算出したもの ＤＰ１：光透過式粒度分布測定機（島津製作所製ＳＡ−
ＣＰ３）を用いて測定した粒 度分布において、大きな粒子径側から 起算した重量累計１０％の時の粒子径 （μｍ） ＤＰ２：上記測定機を用いて測定した粒度分布において
、大きな粒子径側から起算し た重量累計２５％の時の粒子径（μ ｍ） ＤＰ３：上記測定機を用いて測定した粒度分布において
、大きな粒子径側から起算し た重量累計５０％の時の粒子径（μ ｍ） ＤＰ４：上記測定機を用いて測定した粒度分布において
、大きな粒子径側から起算し た重量累計７５％の時の粒子径（μ ｍ） ＤＰ５：上記測定機を用いて測定した粒度分布において
、大きな粒子径側から起算し た重量累計９０％の時の粒子径（μ ｍ） Ｓ：バテライト粒子の投影図に外接する円の面積に対す
る粒子の投影面積割合 Ｓ＝（粒子の投影断面積／粒子に外接する 円の面積）×１００ ２、生石灰換算濃度が０．５〜１２重量％である生石灰
及び／又は消石灰のメタノール懸濁液に、生石灰（消石
灰の場合は同一モルの生石灰に換算）に対し５〜２０倍
モル相当量の水を加え、メタノールと生石灰及び／又は
消石灰と水との混合系を調製した後、該混合系に炭酸ガ
スを導通し、炭酸化反応系内の導電率変化曲線において
、炭酸化反応系内の導電率が極大点に到達する以前に系
内温度を３０℃以上に調整し、炭酸化反応開始点から炭
酸化反応系内導電率が１００μＳ／ｃｍである点に到達
するまでの時間を１２０分未満になるよう調整して炭酸
化反応を行うことを特徴とする、単分散球状又は楕円球
状バテライト炭酸カルシウムの製造方法。 ３、メタノール懸濁液中の生石灰換算濃度が、１〜８重
量％である請求項２記載の製造方法。 ４、生石灰に対し加えられる水の量が、５〜１５倍モル
相当量である請求項２記載の製造方法。 ５、導電率が極大点に到達する以前に調整される系内温
度が、４０℃以上である請求項２記載の製造方法。 ６、炭酸化反応開始から炭酸化反応系内導電率が１００
μＳ／ｃｍである点に到達するまでの時間が、１００分
未満である請求項２記載の製造方法。[Scope of Claims] 1. A spherical or ellipsoidal vaterite calcium carbonate that satisfies the following requirements (a), (b), (c), (d), (e), and (f). (a) 0.1μm≦DS≦2.0μm (b) DP3/DS≦1.25 (c) 1.0≦DP2/DP4≦1.4 (d) 1.0≦DP1/DP5≦2.5 (E) (DP2-DP4)/DP3≦0.35 (F)S
≧40 However, DS: Average particle diameter (μm) examined by scanning electron microscope (SEM), calculated by converting the primary particle into a sphere having the same volume and calculating the average value of the particle diameter of the sphere. DP1: Light transmission type particle size distribution analyzer (SA- manufactured by Shimadzu Corporation)
In the particle size distribution measured using CP3), the particle diameter (μm) when the cumulative weight is 10% starting from the larger particle size side DP2: In the particle size distribution measured using the above measuring device, starting from the larger particle size side Particle diameter (μ m) when the cumulative weight is 25% DP3: Particle diameter (μ m) when the cumulative weight is 50% starting from the larger particle size side in the particle size distribution measured using the above measuring device DP4: In the particle size distribution measured using the above measuring device, the particle diameter (μm) when the cumulative weight is 75% starting from the large particle size side DP5: In the particle size distribution measured using the above measuring device, the particle size on the large particle size side Particle diameter (μm) when the cumulative weight is 90% calculated from S: Projected area ratio of the particle to the area of the circle circumscribing the projected diagram of the vaterite particle area) x 100 2. Add 5 to 20 times more quicklime (in the case of slaked lime, to the same mole of quicklime) to a methanol suspension of quicklime and/or slaked lime with a quicklime equivalent concentration of 0.5 to 12% by weight. After adding a molar equivalent amount of water to prepare a mixed system of methanol and quicklime and/or slaked lime and water, carbon dioxide gas is introduced into the mixed system, and the carbonation Before the electrical conductivity in the reaction system reaches the maximum point, the temperature in the system is adjusted to 30°C or higher, and the temperature from the carbonation reaction start point to the point where the electrical conductivity in the carbonation reaction system reaches a point of 100 μS/cm is A method for producing monodisperse spherical or ellipsoidal vaterite calcium carbonate, the method comprising performing a carbonation reaction for a time of less than 120 minutes. 3. The manufacturing method according to claim 2, wherein the concentration of quicklime in the methanol suspension is 1 to 8% by weight. 4. The manufacturing method according to claim 2, wherein the amount of water added to the quicklime is 5 to 15 times the molar equivalent. 5. The manufacturing method according to claim 2, wherein the temperature within the system that is adjusted before the electrical conductivity reaches the maximum point is 40° C. or higher. 6. The conductivity within the carbonation reaction system is 100 from the start of the carbonation reaction.
3. The manufacturing method according to claim 2, wherein the time required to reach a certain μS/cm point is less than 100 minutes.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13748290A JP2956041B2 (en) | 1990-05-28 | 1990-05-28 | Spherical or elliptical spherical vaterite calcium carbonate to prevent film blocking |
| DE69103472T DE69103472T2 (en) | 1990-05-28 | 1991-05-28 | Monodisperse fatherite type calcium carbonate, process for producing the same and process for controlling particle growth and shape. |
| KR1019910008739A KR0176250B1 (en) | 1990-05-28 | 1991-05-28 | Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof |
| US07/706,423 US5275651A (en) | 1990-05-28 | 1991-05-28 | Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof |
| EP91108695A EP0459399B1 (en) | 1990-05-28 | 1991-05-28 | Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof |
| TW080104299A TW198000B (en) | 1990-05-28 | 1991-06-01 | |
| US08/138,048 US5494651A (en) | 1990-05-28 | 1993-10-19 | Method for manufacturing monodisperse vaterite type calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13748290A JP2956041B2 (en) | 1990-05-28 | 1990-05-28 | Spherical or elliptical spherical vaterite calcium carbonate to prevent film blocking |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03539699A Division JP3258290B2 (en) | 1999-02-15 | 1999-02-15 | Method for producing spherical or elliptical spherical vaterite calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0431315A true JPH0431315A (en) | 1992-02-03 |
| JP2956041B2 JP2956041B2 (en) | 1999-10-04 |
Family
ID=15199666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13748290A Expired - Fee Related JP2956041B2 (en) | 1990-05-28 | 1990-05-28 | Spherical or elliptical spherical vaterite calcium carbonate to prevent film blocking |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2956041B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222161A (en) * | 2009-03-23 | 2010-10-07 | Taiheiyo Cement Corp | Vaterite-type spherical calcium carbonate and method for producing the same |
| JP2018502042A (en) * | 2015-01-14 | 2018-01-25 | アイメリーズ ユーエスエー，インコーポレーテッド | Controlled process for precipitating precipitated calcium carbonate and vaterite precipitated calcium carbonate composition formed by the process |
| CN113201459A (en) * | 2021-06-17 | 2021-08-03 | 浙江海洋大学 | Method for quick freeze-drying preservation of microorganisms |
-
1990
- 1990-05-28 JP JP13748290A patent/JP2956041B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222161A (en) * | 2009-03-23 | 2010-10-07 | Taiheiyo Cement Corp | Vaterite-type spherical calcium carbonate and method for producing the same |
| JP2018502042A (en) * | 2015-01-14 | 2018-01-25 | アイメリーズ ユーエスエー，インコーポレーテッド | Controlled process for precipitating precipitated calcium carbonate and vaterite precipitated calcium carbonate composition formed by the process |
| CN113201459A (en) * | 2021-06-17 | 2021-08-03 | 浙江海洋大学 | Method for quick freeze-drying preservation of microorganisms |
| CN113201459B (en) * | 2021-06-17 | 2023-06-16 | 浙江海洋大学 | Method for quick-freezing, drying and preserving microorganisms |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2956041B2 (en) | 1999-10-04 |
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