JPH0146443B2 - - Google Patents
Info
- Publication number
- JPH0146443B2 JPH0146443B2 JP55060407A JP6040780A JPH0146443B2 JP H0146443 B2 JPH0146443 B2 JP H0146443B2 JP 55060407 A JP55060407 A JP 55060407A JP 6040780 A JP6040780 A JP 6040780A JP H0146443 B2 JPH0146443 B2 JP H0146443B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- concentration
- particle size
- weight
- particles
- 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.)
- Expired
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 93
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000007900 aqueous suspension Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000123 paper Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 206010024769 Local reaction Diseases 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000005540 biological transmission Effects 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
- 239000011362 coarse particle Substances 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は、柱状及び／又は紡錘形粒子からなる
分散性に優れた炭酸カルシウムの製造法に関す
る。
炭酸カルシウムの代表的な工業的製造方法は、
水酸化カルシウム濃度５〜20重量％程度の水懸濁
液に炭酸ガスを吹き込み、炭酸化反応を行なわせ
る方法である。この方法では、水酸化カルシウム
水懸濁液の濃度、温度或いは炭酸ガスの吹き込み
量等を適宜調節することにより、電子顕微鏡観察
による平均粒子径（長辺の長さ）１〜5μm程度の
紡錘形粒子及び／又は柱状粒子のカルサイト結晶
及び／又はアラゴナイト結晶からなる軽質炭酸カ
ルシウム、又は平均粒子径（立方形の一辺の長
さ）0.03〜0.3μm程度の立方形粒子のカルサイト
結晶からなる膠質炭酸カルシウムが製造されてい
る。軽質炭酸カルシウムは、炭酸化反応終了後の
懸濁液中での沈降速度がかなり大きく、その５％
水懸濁液100mlの１時間静置後の沈降体積は、40
ml／hrと小さい。また、炭酸化反応終了後の懸濁
液から乾燥及び粉末化工程を経て得られた粒子を
再び水中に懸濁させる場合にも、その沈降速度は
大きく、上記と同様条件下の沈降体積は一般に15
〜35ml／hrと極めて小さい。これは、軽質炭酸カ
ルシウム生成の炭酸化反応の過程ですでにかなり
凝集した粒子が生成され、更に乾燥及び粉末化工
程においても二次凝集を生ずる為と考えられる。
従つて、従来の軽質炭酸カルシウムを剪断力の余
りかからない液状分散系、例えば塗料、インキ、
紙の填料、塗被料、液状プラスチツク等に添加す
る場合には、その分散性は満足すべきものとは到
底言い難い。一方、膠質炭酸カルシウムは、炭酸
化反応終了後の乾燥工程において強固な二次凝集
物を形成する傾向が大きいので、乾燥前に脂肪
酸、樹脂酸等の石鹸或いは他の界面活性剤等で予
め表面処理を行ない、二次凝集物の生成防止をは
かることが多いが、やはり分散性の改善は十分で
あるとは言い難い。
そこで本発明者は、従来方法の欠点を解消若し
くは大巾に軽減すべく種々研究を重ねた結果、水
懸濁液中の水酸化カルシウム濃度を高めるととも
に、特定流速の吹き込み攪拌下に行なわれる特定
温度での炭酸化反応中に水酸化カルシウム水懸濁
液を回転翼により特定条件下に更に機械的に攪拌
することにより、凝集粒子の少ない、柱状及び／
又は紡錘形粒子からなる分散性に優れた炭酸カル
シウムが得られることを見出し、遂に本発明を完
成するに到つた。即ち、本発明は濃度15〜40重量
％、温度15〜60℃の水酸化カルシウム水懸濁液に
炭酸ガスを流速５〜30／min／Kg・Ca（OH）2
で吹き込んで撹拌を行なうとともに回転翼により
下記式(1)
Re＝ρnD2／μ
〔但し、ρは液の密度、ｎは回転翼の回転数
（rps）、Ｄは回転翼の直径（cm）及びμは液の粘
度（ポアズ）を夫々示す。〕で定義されるレイノ
ルズ数100〜50000の条件下に機械攪拌することに
より炭酸化反応を行なわせることを特徴とする柱
状及び／又は紡錘形粒子からなる分散性に優れた
炭酸カルシウムの製造法を提供するものである。
本発明で使用する水酸化カルシウム水懸濁液の
濃度は、通常15〜40重量％、好ましくは20〜35重
量％である。濃度が15重量％未満の場合には炭酸
化反応時の凝集防止が十分に行なわれ得ず且つ微
細粒子も生成して乾燥工程における凝集を惹き起
す。これは、液の粘度が低い為、回転翼による剪
断力があまり高くならない為であろうと思われ
る。一方、濃度が40重量％を上回ると炭酸ガスと
の接触が均一に行なわれなくなり、局部反応に基
く粒度のバラツキが大きくなる。水酸化カルシウ
ム水懸濁液の温度は、15〜60℃の範囲内が適当で
ある。15℃未満では、微細粒子が一部に形成され
て乾燥時の凝集の原因となり、一方温度が60℃を
超えると粗大粒子の生成による粒度のバラツキが
大きくなる傾向が顕著となる。回転翼による機械
的攪拌機構は、懸濁液系全体が均一に攪拌出来る
ものであれば良く、プロペラ型攪拌機、高速イン
ペラー分散機、櫂型攪拌機、タービン型攪拌機等
が使用される。前記式(1)で定義されるレイノルズ
数（Re）が100未満では、懸濁液全体を均一に攪
拌することが困難であり、一方50000を上回る場
合には攪拌による効果のより一層の改善は認めら
れず且つ設備も著しく高価となる。一般に、攪拌
は液の粘度が高い程強力に行なう必要があり、ま
た液の粘度が一定の場合には、攪拌を強力に行な
う程、生成炭酸カルシウム粒子の粒径は小さくな
る。炭酸ガスの濃度は10容量％以上であることが
特に望ましい。10容量％未満の場合には、局部反
応の為、結晶生成時の凝集発生及び粒度不均一の
傾向が大となる。炭酸ガスは、石灰石焼成廃ガス
を精製した濃度30容量％程度の炭酸ガスを使用す
るのが有利である。炭酸ガス吹き込み量は、５〜
30／min／Kg・Ca（OH）2程度が適当である。
５／min／Kg・Ca（OH）2未満では、局部反応
に起因する凝集発生及び生成粒子の粒度不均一と
いう難点が生じる傾向が大となり、30／min／
Kg・Ca（OH）2を上回ると、炭酸ガスの流失が大
となつて経済上不利である。
本発明の炭酸カルシウムは、炭酸化反応終了後
の液を過脱水し、固形分濃度40％以上のペース
トとしてそのまま使用しても良く、或いは更にこ
れを乾燥及び粉砕して粉末状製品としても良い。
本発明方法により得られる炭酸カルシウムは、
柱状及び／又は紡錘形粒子であり、粒径１〜5μm
程度の範囲内で粒度が均一で凝集が少なく、液状
分散系への分散性に著しく優れている。例えば本
発明炭酸カルシウムの５％水懸濁液100mlの１時
間静置後の沈降体積は45ml以上にも達する。従つ
て、本発明の炭酸カルシウムをあまり高い剪断力
の生じない塗料、インキ、紙の填料組成物及び塗
被料、液状又は流動状のプラスチツク等に添加混
合する場合にも、被混合物中に極めて容易且つ均
一に分散され、夫々の材料の性質を大きく向上さ
せる。例えば、紙の塗被料用顔料として使用する
場合には、従来法による炭酸カルシウムを使用す
る場合に比して、塗被面が平滑となり、極めて高
い光学的特性を示す。
尚、本発明方法により得られた炭酸カルシウム
に更に公知の表面処理を施し、分散性、補強性等
を一層改善し得ることはいうまでもない。
実施例 １
攪拌機付反応容器内の濃度30重量％、温度20℃
の水酸化カルシウム水懸濁液100Kgに濃度30容量
％の炭酸ガスを流速300／minで吹き込むとと
もに機械的に攪拌し、炭酸化反応を行なわせる。
得られた炭酸カルシウム懸濁物をプレス脱水機に
より脱水し、乾燥し、解砕することにより、平均
粒子径1.5μmの紡錘−柱状粒子からなる炭酸カル
シウム40.5Kgを得る。
機械的攪拌条件を第１表に示し、又得られた炭
酸カルシウムの平均粒子径、BET比の表面積、
沈降体積及び粒度分布を第２表に示す。尚、第１
表には実施例２〜５の機械的攪拌条件を併せて示
し、又第２表には実施例２〜５及び比較例１〜２
で得られた炭酸カルシウム並びに市販軽質炭酸カ
ルシウム（Ａ）についての結果を併せて示す。
第２表に示す結果から、本発明炭酸カルシウム
の粒度の均一性及び水に対する優れた分散性が明
らかである。
実施例 ２
水酸化カルシウム水懸濁液の温度を40℃とする
以外は実施例１と同様にして、平均粒子径1.8μm
の均一な柱状粒子からなる炭酸カルシウム40.5Kg
を得る。
実施例 ３
水酸化カルシウム水懸濁液の濃度を20重量％と
し、温度を40℃とする以外は実施例１と同様にし
て、平均粒子径1.5μmの均一な柱状粒子からなる
炭酸カルシウム27Kgを得る。
実施例 ４
攪拌機付反応容器内の濃度15重量％、温度40℃
の水酸化カルシウム水懸濁液500Kgに濃度30容量
％の炭酸ガスを流速1500／minで吹き込むとと
もに機械的に攪拌し、炭酸化反応を行なわせる。
得られた炭酸カルシウム懸濁物から実施例１と同
様にして平均粒子径1μm柱状粒子−紡錘形粒子混
合の炭酸カルシウム100Kgを得る。
実施例 ５
水酸化カルシウム水懸濁液の濃度を35重量％と
し、温度を40℃とする以外は実施例１と同様にし
て、平均粒子径1.8μmの柱状粒子の炭酸カルシウ
ム47.3Kgを得る。
比較例 11
炭酸化反応進行中に攪拌機による攪拌を行なわ
ない以外は実施例３と同様にして、炭酸カルシウ
ムを製造する。生成物は、平均粒子径1.2μmの不
均一な紡錘形粒子が５〜10μmに凝集した粒子か
らなる炭酸カルシウムである。
比較例 ２
水酸化カルシウム水懸濁液の濃度を10重量％、
温度を40℃とし、炭酸ガスの送給量を200／
minとする以外は実施例１と同様にして、炭酸カ
ルシウムを得る。生成物は、平均粒子径1.0μmの
柱状−紡錘形粒子が５〜7μmに凝集した粒子から
なる炭酸カルシウムである。
The present invention relates to a method for producing calcium carbonate having excellent dispersibility and comprising columnar and/or spindle-shaped particles. The typical industrial manufacturing method for calcium carbonate is
This method involves blowing carbon dioxide gas into an aqueous suspension having a calcium hydroxide concentration of about 5 to 20% by weight to cause a carbonation reaction. In this method, spindle-shaped particles with an average particle diameter (long side length) of about 1 to 5 μm are obtained by electron microscopic observation by appropriately adjusting the concentration of calcium hydroxide aqueous suspension, the temperature, the amount of carbon dioxide gas blown, etc. and/or light calcium carbonate consisting of columnar particles of calcite crystals and/or aragonite crystals, or colloidal carbonate consisting of cubic particles of calcite crystals with an average particle diameter (length of one side of the cube) of about 0.03 to 0.3 μm Calcium is produced. Light calcium carbonate has a considerably high sedimentation rate in the suspension after the carbonation reaction, with a sedimentation rate of 5%
The sedimentation volume of 100ml of water suspension after standing for 1 hour is 40
As small as ml/hr. Furthermore, when the particles obtained from the suspension after the carbonation reaction are dried and pulverized are resuspended in water, the sedimentation rate is high, and the sedimentation volume under the same conditions as above is generally 15
~35ml/hr, which is extremely small. This is thought to be due to the fact that considerably agglomerated particles are already produced during the carbonation reaction for producing light calcium carbonate, and secondary agglomeration also occurs during the drying and powdering steps.
Therefore, conventional light calcium carbonate can be used in liquid dispersion systems that are not subject to much shearing force, such as paints, inks, etc.
When added to paper fillers, coatings, liquid plastics, etc., its dispersibility is far from satisfactory. On the other hand, colloidal calcium carbonate has a strong tendency to form strong secondary aggregates in the drying process after the carbonation reaction, so before drying, the surface of colloidal calcium carbonate should be pretreated with soap such as fatty acids, resin acids, or other surfactants. Treatment is often carried out to prevent the formation of secondary aggregates, but it cannot be said that the improvement in dispersibility is sufficient. Therefore, as a result of repeated research in order to eliminate or significantly reduce the drawbacks of the conventional methods, the present inventors increased the concentration of calcium hydroxide in the aqueous suspension and determined that the By further mechanically stirring the calcium hydroxide aqueous suspension under specific conditions with a rotary blade during the carbonation reaction at high temperatures, columnar and/or
Alternatively, the present inventors discovered that calcium carbonate with excellent dispersibility consisting of spindle-shaped particles could be obtained, and finally completed the present invention. That is, in the present invention, carbon dioxide gas is introduced into an aqueous suspension of calcium hydroxide at a concentration of 15 to 40% by weight and a temperature of 15 to 60°C at a flow rate of 5 to 30/min/Kg・Ca(OH) 2
The following formula (1) Re = ρnD 2 /μ [where ρ is the density of the liquid, n is the rotation speed of the rotor (rps), and D is the diameter of the rotor (cm). and μ indicate the viscosity (poise) of the liquid. ] Provides a method for producing calcium carbonate with excellent dispersibility consisting of columnar and/or spindle-shaped particles, which is characterized by carrying out a carbonation reaction by mechanical stirring under conditions of a Reynolds number of 100 to 50,000 as defined by It is something to do. The concentration of the calcium hydroxide aqueous suspension used in the present invention is usually 15 to 40% by weight, preferably 20 to 35% by weight. If the concentration is less than 15% by weight, aggregation during the carbonation reaction cannot be sufficiently prevented and fine particles are also produced, causing aggregation during the drying process. This is probably because the shearing force caused by the rotor does not become too high due to the low viscosity of the liquid. On the other hand, if the concentration exceeds 40% by weight, the contact with carbon dioxide gas will not be uniform, and the variation in particle size will increase due to local reactions. The temperature of the calcium hydroxide aqueous suspension is suitably within the range of 15 to 60°C. At temperatures below 15°C, fine particles are formed in some parts, causing agglomeration during drying, while at temperatures above 60°C, there is a marked tendency for variation in particle size to increase due to the formation of coarse particles. The mechanical stirring mechanism using rotary blades may be any mechanism as long as it can uniformly stir the entire suspension system, and a propeller-type stirrer, a high-speed impeller disperser, a paddle-type stirrer, a turbine-type stirrer, etc. are used. If the Reynolds number (Re) defined by the above formula (1) is less than 100, it is difficult to stir the entire suspension uniformly, while if it exceeds 50,000, it is difficult to further improve the effect of stirring. This is not permitted and the equipment is extremely expensive. In general, the higher the viscosity of the liquid, the more powerful the stirring needs to be, and when the viscosity of the liquid is constant, the stronger the stirring, the smaller the particle size of the produced calcium carbonate particles. It is particularly desirable that the concentration of carbon dioxide gas is 10% by volume or more. If the amount is less than 10% by volume, there is a strong tendency for agglomeration to occur during crystal formation and non-uniform particle size due to local reactions. As the carbon dioxide gas, it is advantageous to use carbon dioxide gas with a concentration of about 30% by volume obtained by refining limestone calcination waste gas. The amount of carbon dioxide gas blown is 5~
Approximately 30/min/Kg・Ca(OH) 2 is appropriate.
If the rate is less than 5/min/Kg・Ca(OH) 2 , problems such as agglomeration due to local reactions and non-uniform particle size of generated particles tend to occur.
If it exceeds Kg・Ca(OH) 2 , the loss of carbon dioxide gas becomes large, which is economically disadvantageous. The calcium carbonate of the present invention may be used as it is as a paste with a solid content concentration of 40% or more by super-dehydrating the liquid after the carbonation reaction is completed, or it may be further dried and pulverized to form a powder product. . Calcium carbonate obtained by the method of the present invention is
Columnar and/or spindle-shaped particles, particle size 1-5 μm
The particle size is uniform within a certain range, there is little aggregation, and the dispersibility in liquid dispersion systems is extremely excellent. For example, after 100 ml of a 5% aqueous suspension of the calcium carbonate of the present invention is allowed to stand for one hour, the sedimentation volume reaches 45 ml or more. Therefore, even when the calcium carbonate of the present invention is added to and mixed with paints, inks, paper filler compositions, coating materials, liquid or fluid plastics, etc. that do not generate very high shear forces, extremely high shearing forces are added to the materials to be mixed. It is easily and uniformly dispersed and greatly improves the properties of each material. For example, when used as a pigment for coating paper, the coated surface becomes smoother and exhibits extremely high optical properties compared to when calcium carbonate is used by conventional methods. It goes without saying that the calcium carbonate obtained by the method of the present invention can be further subjected to a known surface treatment to further improve its dispersibility, reinforcing properties, etc. Example 1 Concentration in reaction vessel with stirrer: 30% by weight, temperature: 20°C
Carbon dioxide gas at a concentration of 30% by volume is blown into 100kg of an aqueous suspension of calcium hydroxide at a flow rate of 300/min and mechanically stirred to cause a carbonation reaction.
The obtained calcium carbonate suspension is dehydrated using a press dehydrator, dried, and crushed to obtain 40.5 kg of calcium carbonate consisting of spindle-columnar particles with an average particle size of 1.5 μm. The mechanical stirring conditions are shown in Table 1, and the average particle diameter of the obtained calcium carbonate, the surface area of the BET ratio,
The sedimentation volume and particle size distribution are shown in Table 2. Furthermore, the first
The table also shows the mechanical stirring conditions of Examples 2 to 5, and Table 2 also shows the mechanical stirring conditions of Examples 2 to 5 and Comparative Examples 1 to 2.
The results for the calcium carbonate obtained in and the commercially available light calcium carbonate (A) are also shown. From the results shown in Table 2, it is clear that the calcium carbonate of the present invention has uniform particle size and excellent dispersibility in water. Example 2 Same as Example 1 except that the temperature of the calcium hydroxide aqueous suspension was 40°C, and the average particle size was 1.8 μm.
40.5 kg of calcium carbonate consisting of uniform columnar particles
get. Example 3 In the same manner as in Example 1 except that the concentration of the calcium hydroxide aqueous suspension was 20% by weight and the temperature was 40°C, 27 kg of calcium carbonate consisting of uniform columnar particles with an average particle size of 1.5 μm was prepared. obtain. Example 4 Concentration in reaction vessel with stirrer: 15% by weight, temperature: 40°C
Carbon dioxide gas at a concentration of 30% by volume is blown into 500kg of an aqueous suspension of calcium hydroxide at a flow rate of 1500/min and mechanically stirred to cause a carbonation reaction.
From the obtained calcium carbonate suspension, 100 kg of calcium carbonate containing a mixture of columnar particles and spindle-shaped particles having an average particle diameter of 1 μm is obtained in the same manner as in Example 1. Example 5 47.3 kg of columnar particles of calcium carbonate having an average particle diameter of 1.8 μm are obtained in the same manner as in Example 1, except that the concentration of the aqueous calcium hydroxide suspension is 35% by weight and the temperature is 40° C. Comparative Example 11 Calcium carbonate is produced in the same manner as in Example 3, except that stirring with a stirrer is not performed during the carbonation reaction. The product is calcium carbonate consisting of non-uniform spindle-shaped particles with an average particle size of 1.2 μm aggregated to 5-10 μm. Comparative Example 2 The concentration of calcium hydroxide aqueous suspension was 10% by weight,
The temperature is 40℃, and the amount of carbon dioxide gas supplied is 200/
Calcium carbonate is obtained in the same manner as in Example 1 except that the amount is set to min. The product is calcium carbonate consisting of columnar-spindle-shaped particles with an average particle size of 1.0 μm aggregated to 5-7 μm.
【表】【table】
【表】
尚、第２表及び後記第４表に示す各物理的性質
の測定法は以下の通りである。
平均粒子径；電子顕微鏡による観察
比表面積；N2を使用するBET法
沈降体積；炭酸カルシウム濃度５％の水懸濁液
100mlをメスシリンダーに入れ、
20秒間振とうした後、１時間静置
後の沈降した部分の体積を測定
粒度分布；光透過式粒度分布測定器による測定
比較例 ３〜８
実施例２における種々の反応パラメータを第３
表に示す様に変更する以外は実施例２と同様にし
て炭酸カルシウムを得る。尚、第３表には、実施
例２のパラメータをも併せて示す。
得られた炭酸カルシウムの生成量及び物性を実
施例２の結果とともに第４表に示す。[Table] The methods for measuring each physical property shown in Table 2 and Table 4 below are as follows. Average particle size: Observation using an electron microscope Specific surface area: BET method using N 2 Sedimentation volume: Aqueous suspension with calcium carbonate concentration of 5%
Put 100ml into a graduated cylinder,
After shaking for 20 seconds and standing still for 1 hour, the volume of the settled part was measured Particle size distribution: Measurement using a light transmission particle size distribution analyzer Comparative examples 3 to 8 Various reaction parameters in Example 2 were
Calcium carbonate was obtained in the same manner as in Example 2 except for the changes shown in the table. Note that Table 3 also shows the parameters of Example 2. The production amount and physical properties of the obtained calcium carbonate are shown in Table 4 together with the results of Example 2.
【表】【table】
【表】
第３表及び第４表に示す結果から、本発明の要
件のいずれかが充足されない場合には、粒度の均
一性、水に対する優れた分散性等の本発明所望の
効果が達成されないことが明らかである。
参考例 １
実施例１で得られた炭酸カルシウム100重量部、
酸化デンプン（商標名“MS＃3800”、日本食品
加工(株)製）10重量部、ラテツクス（商標名“SN
＃307”、住友ノーガタツク(株)製、濃度48重量％）
21重量部及び水169重量部を均一に混練し、紙塗
工用塗料とする。これをアプリケーターバーによ
り塗工原紙（市販上質紙）の片面に20ｇ／m2の割
合で塗布し、風乾後24時間にわたり20℃、60％
RHにおいて調湿し、更にスーパーカレンダー処
理を行う。次いで、塗工面にRIテスターにより
インキ（商標名“Fine Ink Ｆグロス85墨”、大
日本インキ化学工業(株)製）をべた刷りする。塗工
紙の白紙面と印刷面につき光学的性質を測定した
結果は、第５表に示す通りである。第５表には、
実施例２〜５及び比較例１〜２で得られた炭酸カ
ルシウム並びに前出市販炭酸カルシウム（Ａ）を
同様にして紙塗工用塗料に使用した場合の結果を
併せて示す。[Table] From the results shown in Tables 3 and 4, if any of the requirements of the present invention are not met, the desired effects of the present invention, such as uniform particle size and excellent dispersibility in water, will not be achieved. That is clear. Reference example 1 100 parts by weight of calcium carbonate obtained in Example 1,
10 parts by weight of oxidized starch (trade name "MS#3800", manufactured by Nihon Shokuhin Kako Co., Ltd.), latex (trade name "SN")
#307”, manufactured by Sumitomo Nogatatsuku Co., Ltd., concentration 48% by weight)
21 parts by weight and 169 parts by weight of water are uniformly kneaded to make a paint for paper coating. This was applied to one side of coating base paper (commercially available high-quality paper) at a rate of 20 g/m 2 using an applicator bar, and after air-drying, the mixture was heated at 20°C for 24 hours at 60%
Humidity is controlled at RH and super calender treatment is performed. Next, ink (trade name "Fine Ink F Gloss 85 Sumi", manufactured by Dainippon Ink and Chemicals Co., Ltd.) is printed all over the coated surface using an RI tester. The optical properties of the blank surface and printed surface of the coated paper were measured and the results are shown in Table 5. In Table 5,
The results are also shown when the calcium carbonate obtained in Examples 2 to 5 and Comparative Examples 1 to 2 and the commercially available calcium carbonate (A) mentioned above were used in a paper coating paint in the same manner.
【表】
第５表に示す結果から明らかな如く、本発明方
法による炭酸カルシウムは、塗被料用顔料として
不透明度、白紙面光沢及び印刷面光沢を改善する
効果を有し、特に白紙面光沢及び印刷面光沢を著
るしく向上させることが明らかである。
参考例 ２
参考例１で得られた実施例１の炭酸カルシウム
を塗布した塗被紙の表面状態を走査電子顕微鏡写
真（1000倍）により示すと、第１図の通りであ
る。
同様に、参考例１で得られた市販軽質炭酸カル
シウム（Ａ）を使用する塗被紙の表面状態を第２
図として示す。
両図を対比すれば、本発明炭酸カルシウムが、
市販炭酸カルシウムに比して水へ分散性に優れ且
つ凝集粒子が少ない為、塗被面が極めて平滑とな
つていることが明らかである。[Table] As is clear from the results shown in Table 5, the calcium carbonate produced by the method of the present invention has the effect of improving opacity, white paper surface gloss, and printed surface gloss as a pigment for coating materials, and is particularly effective in improving white paper surface gloss. It is clear that the printed surface gloss is significantly improved. Reference Example 2 The surface condition of the coated paper coated with the calcium carbonate of Example 1 obtained in Reference Example 1 is shown in FIG. 1 by a scanning electron micrograph (1000x magnification). Similarly, the surface condition of coated paper using commercially available light calcium carbonate (A) obtained in Reference Example 1 was
Shown as a diagram. Comparing both figures, it can be seen that the calcium carbonate of the present invention
It is clear that the coated surface is extremely smooth because it has better dispersibility in water and fewer aggregated particles than commercially available calcium carbonate.
第１図は、本発明方法による炭酸カルシウムを
塗布した紙の表面状態を示す走査電子顕微鏡写
真、第２図は、市販炭酸カルシウムを塗布した紙
の表面状態を示す走査電子顕微鏡写真を夫々示
す。
FIG. 1 shows a scanning electron micrograph showing the surface condition of paper coated with calcium carbonate according to the method of the present invention, and FIG. 2 shows a scanning electron micrograph showing the surface condition of paper coated with commercially available calcium carbonate.
Claims (1)
ルシウム水懸濁液に炭酸ガスを流速５〜30／
min／Kg・Ca（OH）2で吹き込んで攪拌を行なう
とともに回転翼により Re＝ρnD2／μ 〔但し、ρは液の密度、ｎは回転翼の回転数
（rps）、Ｄは回転翼の直径（cm）及びμは液の粘
度（ポアズ）を夫々示す。〕 で定義されるレイノルズ数100〜50000の条件下に
機械攪拌することにより炭酸化反応を行なわせる
ことを特徴とする柱状及び／又は紡錘形粒子から
なる分散性に優れた炭酸カルシウムの製造法。[Claims] 1. Carbon dioxide gas is introduced into an aqueous suspension of calcium hydroxide at a concentration of 15 to 40% by weight and a temperature of 15 to 60°C at a flow rate of 5 to 30%.
Min/Kg・Ca(OH) 2 is blown in and stirred using a rotor, and Re=ρnD 2 /μ [where ρ is the density of the liquid, n is the rotational speed of the rotor (rps), and D is the rotation speed of the rotor. The diameter (cm) and μ indicate the viscosity (poise) of the liquid, respectively. ] A method for producing calcium carbonate having excellent dispersibility and comprising columnar and/or spindle-shaped particles, the method comprising carrying out a carbonation reaction by mechanical stirring under conditions of a Reynolds number of 100 to 50,000 defined by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6040780A JPS56160322A (en) | 1980-05-06 | 1980-05-06 | Manufacture of calcium carbonate with superior dispersibility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6040780A JPS56160322A (en) | 1980-05-06 | 1980-05-06 | Manufacture of calcium carbonate with superior dispersibility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56160322A JPS56160322A (en) | 1981-12-10 |
| JPH0146443B2 true JPH0146443B2 (en) | 1989-10-09 |
Family
ID=13141286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6040780A Granted JPS56160322A (en) | 1980-05-06 | 1980-05-06 | Manufacture of calcium carbonate with superior dispersibility |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56160322A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3316949C3 (en) * | 1983-05-09 | 1995-03-23 | Pluss Stauffer Ag | calcium carbonate |
| JPH01119512A (en) * | 1987-10-31 | 1989-05-11 | Agency Of Ind Science & Technol | Platy basic calcium carbonate and its production |
| JP2590508B2 (en) * | 1988-01-25 | 1997-03-12 | トヨタ自動車株式会社 | Universal joint |
| US5342600A (en) * | 1990-09-27 | 1994-08-30 | Ecc International Limited | Precipitated calcium carbonate |
| US5846500A (en) * | 1995-10-10 | 1998-12-08 | James W. Bunger And Associates, Inc. | Process for purifying highly impure calcium hydroxide and for producing high-value precipitated calcium carbonate and other calcium products |
| EP0857160B1 (en) * | 1995-10-26 | 1999-07-28 | SOLVAY BARIUM STRONTIUM GmbH | Micronized alkaline earth metal carbonate |
| JP2003040617A (en) * | 2001-07-31 | 2003-02-13 | Yahashi Kogyo Kk | Method for producing high dispersibility spindle-shaped calcium carbonate |
| JP7809239B1 (en) * | 2025-04-10 | 2026-01-30 | 神島化学工業株式会社 | Calcium-based carbonate compound, composition, molded plate, inorganic molded body, and method for producing calcium-based carbonate compound |
-
1980
- 1980-05-06 JP JP6040780A patent/JPS56160322A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56160322A (en) | 1981-12-10 |
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