JPH01119512A - Platy basic calcium carbonate and its production - Google Patents
Platy basic calcium carbonate and its productionInfo
- Publication number
- JPH01119512A JPH01119512A JP62274671A JP27467187A JPH01119512A JP H01119512 A JPH01119512 A JP H01119512A JP 62274671 A JP62274671 A JP 62274671A JP 27467187 A JP27467187 A JP 27467187A JP H01119512 A JPH01119512 A JP H01119512A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- slaked lime
- basic calcium
- plate
- carbon dioxide
- 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 141
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 241000276425 Xiphophorus maculatus Species 0.000 title abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 67
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 67
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 64
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 56
- 235000013336 milk Nutrition 0.000 claims abstract description 51
- 239000008267 milk Substances 0.000 claims abstract description 51
- 210000004080 milk Anatomy 0.000 claims abstract description 51
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000007664 blowing Methods 0.000 claims abstract description 44
- 230000000694 effects Effects 0.000 claims abstract description 37
- 239000000292 calcium oxide Substances 0.000 claims abstract description 24
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 62
- 239000007789 gas Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000000123 paper Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000005995 Aluminium silicate Substances 0.000 description 13
- 235000012211 aluminium silicate Nutrition 0.000 description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- -1 250 μm) Chemical compound 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-IGMARMGPSA-N Calcium-40 Chemical group [40Ca] OYPRJOBELJOOCE-IGMARMGPSA-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
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- OTGAHJPFNKQGAE-UHFFFAOYSA-N cresatin Chemical compound CC(=O)OC1=CC=CC(C)=C1 OTGAHJPFNKQGAE-UHFFFAOYSA-N 0.000 description 1
- 229960000862 cresatin Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分散性の極めて良好な、多角形の板状塩基性
炭酸カルシウムおよびその製造方法に関する。さらに詳
しくは、本発明は、紙、ゴム、プラスチック、塗料など
の製造における顔料や充填剤として有用な、優れた白色
度や光沢性、平滑性およびインキ吸収性などの品質特性
と良好な作業性とを与えることのできる、分散性の極め
て良好な、多角形の板状塩基性炭酸カルシウムおよびそ
の工業的製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polygonal plate-like basic calcium carbonate having extremely good dispersibility and a method for producing the same. More specifically, the present invention is useful as a pigment or filler in the production of paper, rubber, plastics, paints, etc., with quality properties such as excellent whiteness, gloss, smoothness and ink absorption, and good workability. The present invention relates to a polygonal plate-like basic calcium carbonate having extremely good dispersibility, and an industrial method for producing the same.
わが国においては、−船釣な沈降性炭酸カルシウムとし
て、立方形、紡錘状、柱状、針状、連鎖状などの各種の
形状を有するものが市販されている。それらの用途とし
ては、製紙やゴム、プラスチック、塗料工業などの分野
があるが、当該分野で広く一般的に使用されている板状
のカオリンやタルク等に代わって、炭酸カルシウムがさ
らに多用されるためには、板状の形状を存するものの出
現が切望されている。しかし、工業的には未だ、品質面
からも、コスト面からも、確立されるに至っていないの
が現状である。In Japan, precipitated calcium carbonate is commercially available in various shapes such as cubes, spindles, columns, needles, and chains. They are used in fields such as paper manufacturing, rubber, plastics, and paint industries, but calcium carbonate is more frequently used in place of plate-shaped kaolin and talc, which are widely used in these fields. For this purpose, there is a strong desire for something that has a plate-like shape. However, the current situation is that it has not yet been established industrially from both quality and cost perspectives.
上記要求に応えるぺ（、特公昭６２−
３２１３０、特開昭６１−２１９７１５および特開昭６
２−１１３７１８において、ＸＣａＣＯ３・ＹＣａ （
ＯＨ）２ ・ＺＨ２０の組成式で示される板状の塩基性
炭酸カルシウムもしくはその複合体の製造が提案され、
その工業化が試みられている。In order to meet the above requirements, the following publications were developed:
2-113718, XCaCO3・YCa (
It has been proposed to produce a plate-shaped basic calcium carbonate or its complex represented by the composition formula OH)2 ・ZH20,
Attempts are being made to industrialize it.
しかし、これら提案の方法による塩基性炭酸カルシウム
およびその複合体は、いずれも分散性が不良な凝集品と
してしか得られず、光沢性、インキ吸収性などの特性が
十分でなく、また作業性も不満足のものとなり、従って
有効な用途開発も進まず、工業化も今−歩の段階にある
のが現状である。However, basic calcium carbonate and its complexes produced by these proposed methods can only be obtained as agglomerated products with poor dispersibility, do not have sufficient properties such as gloss and ink absorption, and have poor workability. As a result, the development of effective uses has not progressed, and industrialization is currently at an early stage.
このように、従来技術における如き、電気伝導度、ｐＨ
１あるいは炭酸化率等をもって、炭酸ガスの吹込速度を
制御して、炭酸化反応を行う方法では、得られる製品に
はいずれも分散性の不良な凝集物が多量に混在し、十分
な性能品質の製品を得ることはできなかったのである。Thus, as in the prior art, electrical conductivity, pH
However, if the carbonation reaction is carried out by controlling the blowing speed of carbon dioxide gas at a certain carbonation rate or the like, the resulting products will contain a large amount of aggregates with poor dispersibility, resulting in insufficient performance and quality. It was not possible to obtain this product.
しかして、本発明の目的は、上記の如き従来技術の欠点
を解消して、分散性の極めて良好な、多角形の板状塩基
性炭酸カルシウムを提供することにある。即ち、本発明
は、例えば、製紙工業において塗工用顔料として用いる
場合に、カオリンクレーはおろかサチンホワイトなみの
白色度、光沢性、インキ受理性、平滑度などの品質特性
において優れ、かつ、作業性においても問題がなく、ス
トリーク、塗りむらなどの欠点を生じない板状塩基性炭
酸カルシウムを提供しようとするものである。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide polygonal plate-shaped basic calcium carbonate having extremely good dispersibility. That is, when used as a coating pigment in the paper industry, for example, the present invention has excellent quality characteristics such as whiteness, gloss, ink receptivity, and smoothness, comparable to that of Sachin White, let alone kaolin clay, and is easy to work with. The object of the present invention is to provide a plate-shaped basic calcium carbonate which has no problems in terms of properties and does not cause defects such as streaks and uneven coating.
本発明者らは、上記の目的を達成するべく、特に特公昭
６２−３２１３０に記載の方法の工業化を試みるに当た
って、上記問題点の解決について鋭意研究を重ねた結果
、種々の凝集粒子の発生のメカニズムは、反応の進行に
おいて、その結晶化過程でむらが発生し、結晶の核生成
反応と結晶の成長反応と、が同時に入りまじって行われ
ることにあり、これらを区分してやれば、分散性の良好
なものを製造し得ることを見出した。即ち、従来法では
管理されていない生石灰の活性度およびその生石灰を消
和して得られる消石灰乳中の消石灰粒子の粒子径に着目
し、これらの活性度と粒子径の両者の種々の組み合わせ
に対応して相対炭酸ガス吹込速度の最大値を一定範囲以
下に制御しながら、消石灰乳を炭酸化することによって
、上記本発明の目的を達成し得ることが見出されたので
ある。In order to achieve the above object, the present inventors have conducted extensive research into solving the above problems, especially in attempting to industrialize the method described in Japanese Patent Publication No. 62-32130. The mechanism is that as the reaction progresses, unevenness occurs during the crystallization process, and the crystal nucleation reaction and crystal growth reaction occur simultaneously and intermingled. It has been found that a good product can be manufactured. In other words, we focused on the activity of quicklime, which is not controlled by conventional methods, and the particle size of slaked lime particles in slaked lime milk obtained by slaking the quicklime, and investigated various combinations of both activity and particle size. It has been found that the above object of the present invention can be achieved by carbonating slaked lime milk while correspondingly controlling the maximum value of the relative carbon dioxide gas blowing speed within a certain range.
即ち、本発明によれば分散性良好な板状塩基性炭酸カル
シウムが提供されるのであって、この板状塩基性炭酸カ
ルシウムは、分散度が１．５以下であり、かつ板状部分
の平均径が０．２〜２．０μｍ、平均厚みが０．０５〜
０．２５μｍ、平均径／平均厚みの比（アスペクト比）
が４〜２０であることを特徴とする特
本発明にかかる板状塩基性炭酸カルシウムは、組成式Ｘ
ＣａＣＯ３・ＹＣａ（ＯＨ）２・ＺＨ２０（但し、Ｘ＝
２とした場合、Ｙ ＝ ０．５〜１．０であり、Ｚ ＝
０．７〜１．５ テあるものとする）で示されるもの
であるのが好ましく、また板状結晶粒子の平均径（Ｄａ
ｙ）に対して０．５ Ｄ ａ ｖ〜２、 ＯＤ ａ ｖ
の径を有する粒子が全体の８０％以上、特に９０％以上
を占めるものであるのが好ましい。That is, according to the present invention, plate-like basic calcium carbonate with good dispersibility is provided, and this plate-like basic calcium carbonate has a dispersion degree of 1.5 or less and an average of the plate-like portions. Diameter is 0.2~2.0μm, average thickness is 0.05~
0.25 μm, average diameter/average thickness ratio (aspect ratio)
The plate-like basic calcium carbonate according to the present invention, which is characterized in that is 4 to 20, has the composition formula
CaCO3・YCa(OH)2・ZH20 (however, X=
2, Y = 0.5 to 1.0, and Z =
0.7 to 1.5 Te), and the average diameter of the plate-like crystal grains (Da
y) 0.5 D a v ~ 2, OD a v
It is preferable that particles having a diameter of 100% account for 80% or more, particularly 90% or more of the total.
上記本発明の板状塩基性炭酸カルシウムは、本発明に従
い、生石灰の活性度が２００〜４００であり、その消和
物である消石灰乳の篩分最大粒度が４４μｍ〜２５０μ
ｍである時、これらの活性度および篩分最大粒度のそれ
ぞれの組み合わせに対応して一次降下点までの相対炭酸
ガス吹込速度の最大値を２３ｍｌ／ｓｉｎ−ｇ−Ｃａ
（ＯＨ） ２〜３ｏ＋１／ｍｉｎ−ｇ−Ｃａ （ＯＨ）
２の範囲で、消石灰乳を炭酸化することにより製造する
ことができる。According to the present invention, the plate-like basic calcium carbonate of the present invention has an activity of quicklime of 200 to 400, and a maximum sieved particle size of slaked lime milk, which is a slaked product thereof, of 44 μm to 250 μm.
m, the maximum value of the relative carbon dioxide gas blowing rate up to the primary drop point is 23 ml/sin-g-Ca corresponding to each combination of these activities and maximum sieve particle size.
(OH) 2~3o+1/min-g-Ca (OH)
2 can be produced by carbonating slaked lime milk.
本発明の方法および従来方法により得られた塩基性炭酸
カルシウムの代表例につき、走査型電子顕微鏡（ＳＥＭ
）写真および光透過型粒度測定器（島津製５Ａ−ＣＰ３
）により行った測定の結果を下記表１に示す。Representative examples of basic calcium carbonate obtained by the method of the present invention and conventional methods were examined using a scanning electron microscope (SEM).
) Photo and light transmission type particle size analyzer (Shimadzu 5A-CP3
) are shown in Table 1 below.
以下余白
本発明方法により得られる板状塩基性炭酸カルシウムは
、そのＳＥＭ写真（第１図）に見られる如く、四角形乃
至六角形程度の多角形を示し、かつ、板状部分の粒子径
がよく揃っており、個々の粒子にまで極めてよく分散し
ていることが観察される。一方、従来法による場合には
、個々の粒子が数十個程度集合して、大きな凝集塊を構
成していることが観察される（第２図）。As seen in the SEM photograph (Fig. 1), the plate-shaped basic calcium carbonate obtained by the method of the present invention exhibits a polygonal shape ranging from a square to a hexagon, and the particle size of the plate-shaped portion is good. It is observed that the particles are uniform and are extremely well dispersed even into individual particles. On the other hand, in the case of the conventional method, it is observed that about several dozen individual particles aggregate to form a large aggregate (FIG. 2).
ここで、分散性の良否を、分散度即ち光透過型粒度測定
器（ＳＡ−ＣＦ２）による５０％平均径（Ｄｓ。）μｍ
／走査型電子顕微鏡（ＳＥＭ）による平均径μｍの比を
もって定義すると、上記表１に見られるように、本発明
方法の場合は分散度＝０．３２１０．３＝１．０７と、
はとんど理論値即ち１に近い値を示すが、一方従来法の
場合には分散度＝３．７４１０．４＝９．３５と甚だ高
い値を示していることが判る。一般に、光透過型粒度測
定器による測定においては、超音波分散を行うので、単
なる物理的結合による集合体であれば、比較的容易に個
々の粒子までに分散する筈であるが、従来法の場合には
り、。−３，７４μｍを示し、ＳＥＭ観察の板状部分の
平均径０．４μｍに比して極めて大きい値を示し、強固
な化学的結合力による凝集物となっていることがわかる
。しかるに、本発明方法の場合には、ＳＥＭ測定による
平均径０．３μｍに対し、Ｄ、。＝０．３２μｍとほと
んど一致しており、極めて良好な分散状態を示している
ことがわかる。Here, the quality of dispersibility is determined by the degree of dispersion, that is, the 50% average diameter (Ds.) μm measured by a light transmission type particle size analyzer (SA-CF2).
/ average diameter μm measured by a scanning electron microscope (SEM), as shown in Table 1 above, in the case of the method of the present invention, the degree of dispersion = 0.3210.3 = 1.07,
It can be seen that the value is almost the theoretical value, that is, a value close to 1, but on the other hand, in the case of the conventional method, the degree of dispersion is extremely high at 3.7410.4=9.35. Generally, when measuring with a light transmission type particle size analyzer, ultrasonic dispersion is performed, so if it is an aggregate due to mere physical bonding, it should be relatively easy to disperse into individual particles, but conventional methods In case,. -3.74 μm, which is extremely large compared to the average diameter of the plate-shaped portion observed by SEM, which is 0.4 μm, and it can be seen that it is an aggregate due to strong chemical bonding force. However, in the case of the method of the present invention, D. = 0.32 μm, which shows an extremely good dispersion state.
一方、かかる凝集品は、良好な分散品と比較すると、例
えば、製紙塗工試験を行った場合、光沢性、平滑性、イ
ンキ受理性等において明らかに劣ったものになるという
欠点を有している。また、かかる凝集品は超音波分散処
理では容易に分散し難い。そこで、仮に、凝集品を振動
ミルで約３０分開運式破砕を行い、ＳＥＭ観察および５
Ａ−ＣＦ２で粒度をみると、凝集物は細分化されてしま
い、板状形状が失われ、粒状物に変化する（第１３およ
び１４図）。このものを用いて製紙塗工テストを行った
ところ、白紙光沢、印刷光沢、平滑性等が低下すること
が確認された（表４）。On the other hand, such agglomerated products have the disadvantage that they are clearly inferior in gloss, smoothness, ink receptivity, etc. when, for example, a paper coating test is performed, when compared with a good dispersion product. There is. In addition, such aggregated products are difficult to be easily dispersed by ultrasonic dispersion treatment. Therefore, we temporarily crushed the agglomerated product in a vibrating mill for about 30 minutes, observed it by SEM, and
Looking at the particle size in A-CF2, the aggregates are fragmented, lose their plate-like shape, and turn into granules (Figures 13 and 14). When a paper coating test was conducted using this product, it was confirmed that white paper gloss, printing gloss, smoothness, etc. were reduced (Table 4).
一方、本発明に係る、平均粒径０．３μｍと０．７μｍ
の板状塩基性炭酸カルシウムを使用してサチンホワイト
、市販の軽質炭酸カルシウム等との比較塗工試験を行っ
た（実施例８）ところ、本発明品は市販軽質炭酸カルシ
ウムに比して、光沢性、インキ受理性および平滑性にお
いて数段優っており、高品質の結果を示すサテンホワイ
トに比しても優るとも劣らぬ値を示している。更に、サ
テンホワイトに比して、強度のみならず、顔料粘度、ス
トリーク、塗りむら等作業性上の性能においても格段に
優れた結果を与えることが判明した（表４および５）。On the other hand, according to the present invention, average particle diameters of 0.3 μm and 0.7 μm
A comparative coating test was conducted using plate-like basic calcium carbonate with Sachin White, commercially available light calcium carbonate, etc. (Example 8). It is several orders of magnitude superior in properties, ink receptivity, and smoothness, and shows values that are comparable to those of Satin White, which shows high quality results. Furthermore, it was found that compared to Satin White, it gave significantly superior results not only in strength but also in terms of workability such as pigment viscosity, streaks, and uneven coating (Tables 4 and 5).
更に、本発明に係る板状塩基性炭酸カルシウムは、驚く
べきことに、単味顔料の三者配合即ち本発明品とカオリ
ンクレーとの配合および市販の軽質炭酸カルシウムとカ
オリンクレーとの配合における比較において、各単味顔
料の特性を維持しつつ、しかも相乗的効果を発揮して、
光沢性の面で従来の定説を覆すが如き優れた結果を与え
ることがわかった（表６）。Furthermore, the plate-shaped basic calcium carbonate according to the present invention surprisingly shows a comparison between three-way blending of simple pigments, that is, a blending of the product of the present invention and kaolin clay, and a blending of commercially available light calcium carbonate and kaolin clay. , while maintaining the characteristics of each single pigment, and also exhibiting a synergistic effect,
It was found that excellent results were obtained in terms of glossiness, overturning conventional wisdom (Table 6).
本発明に係る板状塩基性炭酸カルシウムの水性スラリー
を加熱熟成（５０℃×３日間）すると、製紙塗工テスト
の白紙光沢および印刷光沢において優れた結果を示し、
測定値において２％程度の上昇となった（表７）。When the aqueous slurry of plate-like basic calcium carbonate according to the present invention is heated and aged (50°C x 3 days), it shows excellent results in white paper gloss and printing gloss in paper coating tests,
The measured values increased by about 2% (Table 7).
本発明の板状塩基性炭酸カルシウムの水性スラリーから
、例えば、噴霧乾燥を行って得た乾燥製品は、デイシル
バーなどによって容易に水に再分散する。このようにし
て、その６０重量％濃度のスラリーを作り、これをＳＥ
Ｍで観察すると、はとんどもとの分散状態を示している
ことが認められた。これを用いて製紙塗工テストを行っ
たところ、処理前の製品を用いた場合に比較して、品質
に差はほとんど認められなかった（表８）。A dried product obtained by, for example, spray drying from the aqueous slurry of the plate-like basic calcium carbonate of the present invention is easily redispersed in water using a daysilver or the like. In this way, a slurry with a concentration of 60% by weight is made, and this is used for SE
When observed with M, it was found that the particles were mostly in the same dispersed state as before. When a paper coating test was conducted using this product, there was almost no difference in quality compared to when the product before treatment was used (Table 8).
本発明に係る板状塩基性炭酸カルシウムの組成式は、第
５および１１図に示す熱重量分析（７０曲線）およびガ
ス分析の結果から、ＸＣａＣＯ３・ＹＣａ （ＯＨ）２
・ＺＨ２０で示され、第６および１２図のＸ線回折図
には、塩基性炭酸カルシウムのピークのみで、カルサイ
トおよび消石灰のピークはほとんど見当たらない。熱重
量分析の結果から、本発明の塩基性炭酸カルシウムの組
成式は、Ｘ＝２とした場合、Ｙ ＝ ０．５〜１．０、
Ｚ ＝ ０．７〜１．５の範囲で示される多角形の板状
塩基性炭酸カルシウムであると認められる。The composition formula of the plate-like basic calcium carbonate according to the present invention is determined from the results of thermogravimetric analysis (70 curve) and gas analysis shown in Figures 5 and 11.
- In the X-ray diffraction diagrams shown by ZH20 and shown in Figures 6 and 12, only the peak of basic calcium carbonate is found, and the peaks of calcite and slaked lime are almost absent. From the results of thermogravimetric analysis, the compositional formula of basic calcium carbonate of the present invention is, when X = 2, Y = 0.5 to 1.0,
It is recognized that it is polygonal plate-like basic calcium carbonate with Z = 0.7 to 1.5.
本発明の分散性良好な板状塩基性炭酸カルシウムは、例
えば、次のようにして製造することができる。The plate-shaped basic calcium carbonate with good dispersibility of the present invention can be produced, for example, as follows.
本発明の方法においては、生石灰の活性度とその消和物
である消石灰乳の篩分最大粒度との種々の組み合わせに
対応して、−吹降下点までの相対炭酸ガス吹込速度の最
大値の所定範囲で消石灰乳を炭酸化するものである。ま
ず、生石灰の反応性の評価目安となる活性度として、本
発明者らは、これを粗粒滴定法（４Ｎ−ＨＣＩ、１〜４
．７６ｍｍ粒度、５０ｇ法）の５分値でもって区分した
。In the method of the present invention, the maximum value of the relative carbon dioxide gas blowing speed up to the blowdown point is adjusted in accordance with various combinations of the activity of quicklime and the maximum sieve particle size of milk of slaked lime, which is its slaked product. It carbonates slaked lime milk within a predetermined range. First, the present inventors used the coarse particle titration method (4N-HCI, 1 to 4
．． The particles were classified according to the 5-minute value (76 mm particle size, 50 g method).
次いで、上記生石灰を消和して得られた消石灰乳を区分
に従い、篩分けする。篩分けして得た消石灰乳に水を添
加して、消石灰濃度を区分に従い、調整する。炭酸化反
応を開始する時の消石灰乳の温度を区分に従い、調節す
る。Next, the slaked lime milk obtained by slaking the quicklime is sieved according to the classification. Water is added to the slaked lime milk obtained by sieving to adjust the slaked lime concentration according to the classification. Adjust the temperature of slaked lime milk when starting the carbonation reaction according to the classification.
次いで、炭酸ガスを消石灰乳中に導入して、炭酸化反応
を行うが、相対炭酸ガス吹込速度を次式で表し、区分に
従い、炭酸化を実施する。Next, carbon dioxide gas is introduced into the slaked lime milk to perform a carbonation reaction.The relative carbon dioxide gas blowing rate is expressed by the following formula, and carbonation is performed according to the classification.
相対炭酸ガス吹込速度＝炭酸ガス導入！（ガス導入量×
００２容量％、標準状ａ） ： ｍｌ／１ｌｉｎ／消
石灰乳中のＣａ （ＯＨ）２量：ｇ
炭酸化反応の間の電気伝導度を連続して測定し、−吹降
下点の電気伝導度を７以上に保持し、反応の終了点は二
次降下における電気伝導度が４〜５の範囲とする。Relative carbon dioxide gas blowing speed = carbon dioxide gas introduction! (Gas introduction amount ×
002% by volume, standard a): ml/1 lin/amount of Ca (OH)2 in slaked lime milk: g The electrical conductivity during the carbonation reaction was continuously measured, and the electrical conductivity at the -blowing point was measured. 7 or more, and the end point of the reaction is when the electrical conductivity in the secondary drop is in the range of 4 to 5.
以上を総合して、製造条件を一覧表として示すと、例え
ば、下記表２の通りとなる。If the above is summarized and the manufacturing conditions are shown as a list, for example, it will be as shown in Table 2 below.
以下余日
表 ２
尚、本発明者の検討によれば、このとき、生石灰の活性
度が２００〜４００の範囲で相対炭酸ガス吹込速度は、
２３〜３ｍｌ／ｗｉｎ−ｇ−Ｃａ （ＯＨ） ２となる
ことが認められた。The following table shows the remaining days. 2 According to the inventor's study, when the activity of quicklime is in the range of 200 to 400, the relative carbon dioxide gas blowing speed is:
23-3 ml/win-g-Ca(OH)2.
望ましい分散生良好な板状塩基性炭酸カルシウムの製造
条件としては、生石灰の活性度が高い場合（例えば３５
０）には相対炭酸ガス吹込速度は大きく （例えば１０
〜１９醜ｌ／ＩＩＩｉｎ−ｇ）、活性度が低い場合（例
えば２５０）には相対炭酸ガス吹込速度を小さく （例
えば５〜１１ｍｌ／ｍｉｎ・ｇ ）する必要がある。Desirable conditions for producing plate-like basic calcium carbonate with good dispersion are when the activity of quicklime is high (for example, 35
0), the relative carbon dioxide gas blowing speed is large (for example, 10
~19 ml/IIIin-g), and when the activity is low (for example, 250), the relative carbon dioxide gas blowing speed must be reduced (for example, 5 to 11 ml/min.g).
同一の活性度、（例えば３５０）の生石灰では、消石灰
乳の篩分最大粒度が粗い程（例えば２５０μｍ）、相対
炭酸ガス吹込速度は小さく （例えば１０ＩＩＩｌ／ｍ
ｉｎ−ｇ）、細かい程（例えば４４μｍ）相対炭酸ガス
吹込速度は大きくできる（例えば１９ｍｌ／ｓｉｎ−ｇ
）。同一の消石灰乳の篩分最大粒度では（例えば７４
μｍ）生石灰の活性度が高い程（例えば３５０）相対炭
酸ガス吹込速度は大きく （例えば１８輪ｌ／ｌｌｉｎ
−ｇ）、生石灰の活性度が低い程（例えば２５０）相対
炭酸ガス吹込速度を小さくする必要がある（例えば１０
ｍｌ／ｍ＋ｉｎ−ｇ ）。For quicklime with the same activity (e.g. 350), the coarser the maximum sieve particle size of the milk of slaked lime (e.g. 250 μm), the lower the relative carbon dioxide gas blowing speed (e.g. 10IIIl/m
in-g), the finer it is (e.g. 44 μm), the higher the relative carbon dioxide gas blowing speed can be (e.g. 19 ml/sin-g).
). For the maximum sieve particle size of the same slaked lime milk (for example, 74
μm) The higher the activity of quicklime (e.g. 350), the higher the relative carbon dioxide gas blowing speed (e.g. 18 l/llin).
-g), the lower the activity of quicklime (e.g. 250), the smaller the relative carbon dioxide gas blowing speed needs to be (e.g. 10
ml/m+in-g).
相対炭酸ガス吹込速度について、この制限範囲を超える
と、塩基性炭酸カルシウムは得られ難く、たとえ得られ
たとしても、分散性の良好なものを得ることはできない
、また、あまりにも極端に低い相対炭酸ガス吹込速度で
は生産性が低く、実用上好ましくない。If the relative carbon dioxide gas blowing speed exceeds this limit range, it will be difficult to obtain basic calcium carbonate, and even if it is obtained, it will not be possible to obtain one with good dispersibility; The productivity is low at a carbon dioxide gas blowing speed, which is not practical.
同一の活性度（例えば３５０）の生石灰を乾式消和して
得られた消石灰を原料として、上記製造条件の下で作製
したものは、形が不揃いで、凝集物が多く、結晶形に関
しても板状の外に粒状、糸状など各種のものが混在して
いた。Products produced under the above production conditions using slaked lime obtained by dry slaking lime of the same activity level (e.g. 350) are irregular in shape, have many aggregates, and have an irregular crystal shape. In addition to the shape, there were various types of particles such as granular and thread-like.
篩分は後に炭酸化されるＣａ （ＯＨ）２の濃度は、活
性度の高い程（例えば３５０）、上限が低くなる（例え
ば１２重量％以下、好ましくは１０重量％以下）。逆に
活性度が低い程（例えば２５０）、上限濃度は高くなる
（例えば１５重景％以下、好ましくは１３重景％以下）
。一方、下Ｉ＠濃度としては、５重量％以上、好ましく
は８重量％以上であるのがよく、これ以下では生産性が
低くなるので好ましくない。The higher the activity level (for example, 350), the lower the upper limit of the concentration of Ca (OH)2, which is subsequently carbonated in the sieve fraction (for example, 12% by weight or less, preferably 10% by weight or less). Conversely, the lower the activity level (for example, 250), the higher the upper limit concentration (for example, 15% or less, preferably 13% or less)
. On the other hand, the lower I@ concentration is preferably 5% by weight or more, preferably 8% by weight or more, and if it is less than this, the productivity decreases, which is not preferable.
次に、反応開始時点の消石灰乳の温度は、生石灰の活性
度が高い程（例えば３５０）、上限は低くなる（例えば
１３℃以下、好ましくは１０”Ｃ以下）。この上限温度
（例えば１３℃）以上では良好な分散性の塩基性炭酸カ
ルシウムは得られない。Next, as for the temperature of slaked lime milk at the time of starting the reaction, the higher the activity of quicklime (e.g. 350), the lower the upper limit (e.g. 13°C or less, preferably 10"C or less). This upper limit temperature (e.g. 13°C or less) ) or above, basic calcium carbonate with good dispersibility cannot be obtained.
一方、下限温度は５℃以上（好ましくは８℃以上）であ
り、これ以下では反応速度が遅く、生産性が低くなるの
で好ましくない。On the other hand, the lower limit temperature is 5° C. or higher (preferably 8° C. or higher); lower temperature is not preferred because the reaction rate is slow and the productivity is low.
いかなる場合にも、−吹降下点での温度は１８℃以下に
保持する必要がある。１８℃以上では、分散性の良好な
る板状塩基性炭酸カルシウムは得られない。必要の場合
には冷却を行ってもよい。In any case, the temperature at the -down point must be kept below 18°C. If the temperature is 18° C. or higher, plate-like basic calcium carbonate with good dispersibility cannot be obtained. Cooling may be performed if necessary.
導入する炭酸ガスは、単独ガスであっても、空気等の混
合ガスであってもよい。また石灰石の焼成時の排出炉ガ
ス（Ｃ０２濃度約３０％）を用いることもできる。The carbon dioxide gas introduced may be a single gas or a mixed gas such as air. It is also possible to use exhaust furnace gas (C02 concentration of about 30%) during limestone firing.
製紙用、ゴム用、プラスチック用等の各用途に応じて所
要最適粒径を得たい場合には、使用する生石灰の活性度
、その生石灰を消和した消石灰乳の篩分は最大粒度に従
い、反応開始温度および消石灰乳のＣａ （ＯＨ）２濃
度を調節し、相対炭酸ガス吹込速度を制御することによ
って、望ましい粒径のものを得ることができる。また、
その粒度分布も任意に調節することができ、この点も本
発明の１つの特長である。If you want to obtain the required optimum particle size according to each application such as paper making, rubber use, plastic use, etc., the activity of the quicklime used and the sieve content of the slaked lime milk that has slaked the quicklime should be determined according to the maximum particle size. By adjusting the starting temperature and Ca(OH)2 concentration of the slaked lime milk and controlling the relative carbon dioxide gas blowing rate, the desired particle size can be obtained. Also,
The particle size distribution can also be adjusted arbitrarily, and this point is also one of the features of the present invention.
次いで、反応過程における炭酸化度の調節は、電気伝導
度を測定しつつ、相対炭酸ガス吹込速度を制御し、前述
の制限範囲以下で行うことが望ましい。初期には（即ち
一次降下点に達するまでは）吹込速度を抑えれば、後に
吹込速度を増大することは可能である。Next, the degree of carbonation during the reaction process is desirably adjusted by controlling the relative carbon dioxide gas blowing rate while measuring the electrical conductivity, and keeping it within the above-mentioned limit range. If the blowing speed is suppressed initially (that is, until the primary drop point is reached), it is possible to increase the blowing speed later.
一次降下点での電気伝導度が７より下がると、塩基性炭
酸カルシウムの生成は全く困難となる。When the electrical conductivity at the primary drop point falls below 7, it becomes very difficult to form basic calcium carbonate.
さらに、反応の終点は二次降下の中間点即ち電気伝導度
として４〜５の範囲、実際上は４．５でもって行うこと
が大切である。降下速度は非常に速いので、終点時には
注意が肝要である。５以上では未反応の消石灰が残存し
て（るので好ましくない。Furthermore, it is important that the end point of the reaction is the midpoint of the quadratic descent, that is, the electrical conductivity is in the range of 4 to 5, in practice 4.5. The descent speed is very fast, so it is important to be careful at the final point. If it is 5 or more, unreacted slaked lime remains, which is not preferable.
一方、４以下ではカルサイトの生成が始まり、これが生
成物中に混入してくるので好ましくない。On the other hand, if it is less than 4, calcite will start to form and this will be mixed into the product, which is not preferable.
上記の他に反応に影響を与える装置的要因として、反応
層の寸法、攪拌翼の形状と回転速度、炭酸ガス吹込手段
等があり、これらを適宜適切に選択することが肝要であ
る。In addition to the above, equipment factors that influence the reaction include the dimensions of the reaction layer, the shape and rotational speed of the stirring blade, the carbon dioxide gas blowing means, etc., and it is important to appropriately select these factors.
本発明に係る板状塩基性炭酸カルシウムは、極めて良好
な分散性を有し、粒径を任意に調節することが可能であ
り、かつ、粒度分布中も極めて小さい、また、純度的に
も極めて高品質のものである。The plate-like basic calcium carbonate according to the present invention has extremely good dispersibility, the particle size can be arbitrarily adjusted, and the particle size distribution is also extremely small, and the purity is also extremely high. It is of high quality.
製紙用の塗工剤として用いた場合、本発明の板状塩基性
炭酸カルシウムは、白色度、光沢性、インク受理性、平
滑性などについては、従来のカオリンクレーや市販の軽
質炭酸カルシウムに比して数段価れた効果を示し、サテ
ンホワイトに比して同等の効果となり、作業性や経済面
ではこれらよりもはるかに優れた効果が期待できる。尚
、製紙塗工用の他にも、ゴムおよびプラスチックの充填
剤や塗料用顔料として有効に利用し得る。When used as a coating agent for paper manufacturing, the plate-like basic calcium carbonate of the present invention is superior to conventional kaolin clay and commercially available light calcium carbonate in terms of whiteness, gloss, ink receptivity, smoothness, etc. The effect is much higher than that of Satin White, and the effect is comparable to that of Satin White, and it can be expected to have far superior effects in terms of workability and economy. In addition to being used as a coating for paper manufacturing, it can also be effectively used as a filler for rubber and plastics and as a pigment for paints.
次に、本発明の板状塩基性炭酸カルシウムおよびその製
造方法について、実施例によりさらに説明する。Next, the plate-shaped basic calcium carbonate of the present invention and the method for producing the same will be further explained with reference to Examples.
実施例１：本発明（活性度３５０）
活性度３５０の工業用生石灰２．４ ｋ ｇを４０℃の
水１７．６ ｋ ｇの中に投入し、攪拌しながら、１５
分間消和を行う。その後分級機で篩分けし、７４μｍ通
過の消石灰乳を取り出し、これに水を加えて消石灰濃度
１０重量％の消石灰乳２０ｋｇを得た。これを反応容器
（内径３４５×高さ３６０ｍｍ、内容積４０１）に入れ
、攪拌しながら（かい型羽根、径１００ｍｍ、５００ｒ
ｐｍ）１０℃に冷却後、１００％濃度の炭酸ガスを２５
１／ｍｉｎの速度で導入する。この時の相対炭酸ガス吹
込速度は１２．５ｍｌ／ｗｉｎ−ｇ−Ｃａ （ＯＨ）
２である。Example 1: The present invention (activity 350) 2.4 kg of industrial quicklime with an activity of 350 was put into 17.6 kg of water at 40°C, and while stirring,
Do a minute of decontamination. Thereafter, the mixture was sieved using a classifier to take out the slaked lime milk that passed 74 μm, and water was added thereto to obtain 20 kg of slaked lime milk with a slaked lime concentration of 10% by weight. This was placed in a reaction container (inner diameter 345 x height 360 mm, inner volume 401 mm), and while stirring (paddle-shaped impeller, diameter 100 mm, 500 r
pm) After cooling to 10℃, add 100% carbon dioxide gas to 25℃.
Introduce at a rate of 1/min. The relative carbon dioxide gas blowing rate at this time was 12.5ml/win-g-Ca (OH)
It is 2.
反応開始から少なくとも１５分間は冷却を続け、１５℃
以下に液温を保持した後電気伝導度を４．５ｍＳ／Ｃｍ
で炭酸ガスの吹込を停止した。Continue cooling for at least 15 minutes from the start of the reaction to 15°C.
After maintaining the liquid temperature below, the electrical conductivity is 4.5mS/Cm.
The injection of carbon dioxide gas was stopped.
反応条件および結果を後記の表３に示す。The reaction conditions and results are shown in Table 3 below.
反応生成物を走査型電子顕微鏡（ＳＥＭ）で観察したと
ころ、平均粒径０．３μｍ１厚み０．０８μｍの板状の
形状を有していた（第１図）。凝集部分は皆無で、個々
の粒子にまでよく分散されている。When the reaction product was observed with a scanning electron microscope (SEM), it had a plate-like shape with an average particle size of 0.3 μm and a thickness of 0.08 μm (FIG. 1). There are no agglomerated parts, and the individual particles are well dispersed.
一方、光透過型粒度測定器（島津製、５Ａ−ＣＦ２）で
求めた平均粒径（５０％値：Ｄ５゜）は、０．３２μｍ
であって（第３図）、これはＳＥＭから求めた値０．３
とよ（一致している。このときの分散度は０．３２１０
．３−１．０７である。このことからも、本発明による
と凝集部分がほとんど皆無で、極めて良好な分散状態の
板状塩基性炭酸カルシウムが得られることがわかる。On the other hand, the average particle diameter (50% value: D5°) determined with a light transmission particle size analyzer (manufactured by Shimadzu, 5A-CF2) was 0.32 μm.
(Figure 3), which is the value 0.3 obtained from SEM.
Toyo (they match. The degree of dispersion at this time is 0.3210
．． 3-1.07. This also shows that according to the present invention, plate-like basic calcium carbonate with almost no agglomerated portions and an extremely well dispersed state can be obtained.
結晶粒径も０．２〜０．８μｍの範囲にあり、その巾も
小さいことがわかる。一方、厚みは０．０８であり、従
ってアスペクト比は４である。また、この生成物の熱重
量分析（ＴＯ曲線）（第５図）およびＸ線回折（第６図
）を行った結果からは、カルサイト、消石灰のピークは
ほとんど認められず、２ＣａＣＯｓ ・０．６３Ｃａ
（ＯＨ）２ ・０．８６Ｈ２０の組成式を有する塩基
性炭酸カルシウムであることが確認された。It can be seen that the crystal grain size is also in the range of 0.2 to 0.8 μm, and the width is also small. On the other hand, the thickness is 0.08, so the aspect ratio is 4. Furthermore, from the results of thermogravimetric analysis (TO curve) (Fig. 5) and X-ray diffraction (Fig. 6) of this product, almost no peaks of calcite or slaked lime were observed, and 2CaCOs.0. 63Ca
It was confirmed that it was basic calcium carbonate having the composition formula of (OH)2.0.86H20.
比較例１−１：凝集品
実施例１と同じく消和して、篩分けを行うことなく、・
消石灰濃度１１重量％の消石灰乳を２０ｋｇ調製した。Comparative Example 1-1: Agglomerated product Same as Example 1, slaked and without sieving.
20 kg of slaked lime milk with a slaked lime concentration of 11% by weight was prepared.
この消石灰乳を１０℃に冷却した後、１００％濃度の炭
酸ガスを２０１／ｌｌｌ１ｎ （相対炭酸ガス吹込速度
−９，１ｍｌ／ｍｉｎ−ｇ−Ｃａ （ＯＨ） ２）で吹
き込み、炭酸化し、電気伝導度が４．５ ｍｓ／ｃｎ＋
になったときに反応を停止した。反応条件および結果を
表３に示す。反応生成物をＳＥＭで観察すると（第２図
）、０．３〜０．７μｍの一次粒子（平均０．４μｍ）
が凝集して、約３．０〜４．０ ｐ ｍ大の二次粗大凝
集粒子を形成していた。After cooling the slaked lime milk to 10°C, 100% carbon dioxide gas was blown into it at a rate of 201/lll1n (relative carbon dioxide gas blowing rate -9.1 ml/min-g-Ca (OH) 2) to carbonate it and conduct electricity. degree is 4.5 ms/cn+
The reaction stopped when The reaction conditions and results are shown in Table 3. When observing the reaction product with SEM (Fig. 2), primary particles of 0.3 to 0.7 μm (average 0.4 μm)
were aggregated to form secondary coarse agglomerated particles with a size of approximately 3.0 to 4.0 pm.
第４図に５Ａ−ＣＦ２の結果を示す。分散度を求めると
、３．７４１０．４〜９．３５と甚だ大きい値を示して
いる。相対炭酸ガス吹込速度は１０ｍ１／Ｉｌｉｎ−ｇ
以下であり、本発明に規定の条件内であるが、消石灰乳
の篩分けを実施していないために凝集品となった。Figure 4 shows the results for 5A-CF2. When the degree of dispersion is calculated, it shows an extremely large value of 3.7410.4 to 9.35. Relative carbon dioxide gas blowing speed is 10 m1/Ilin-g
Although it was within the conditions specified in the present invention, the slaked lime milk was not sieved, resulting in an agglomerated product.
比較例１−２：粒状炭酸カルシウム
実施例１と同じく消和して、７４μｍで消石灰乳の篩分
けを行って、消石灰濃度１０重量％の消石灰乳を２０ｋ
ｇ調製した。この消石灰乳を１０℃に冷却後１００％濃
度の炭酸ガスを３７ ｆｆｉ／ｗｉｎ（相対炭酸ガス吹
込速度＝ １８．５ａ＋ｌ／ｓｉｎ−ｇ−Ｃａ（ＯＨ）
２）で吹き込んだ。反応を開始して約１０分後に電気伝
導度が２ ａｓ／ｃｍまで低下し、同時に反応液の粘度
も増加して、ゲル化した。引き続き炭酸ガスの吹き込み
を続けると電気伝導度は再び上昇して粘度は元の状態に
戻った。更に炭酸ガスの吹き込みを続けると電気伝導度
が再び低下してくるが、電気伝導度が４．５ ｍｓ／ｃ
ｍになったときに反応を停止した。反応条件および結果
を表３に示す。Comparative Example 1-2: Granular calcium carbonate was slaked in the same manner as in Example 1, and the slaked lime milk was sieved at 74 μm to obtain 20 kg of slaked lime milk with a slaked lime concentration of 10% by weight.
g was prepared. After cooling this slaked lime milk to 10°C, 100% carbon dioxide gas was added at 37 ffi/win (relative carbon dioxide gas blowing rate = 18.5a+l/sin-g-Ca(OH)
2). About 10 minutes after starting the reaction, the electrical conductivity decreased to 2 as/cm, and at the same time the viscosity of the reaction solution increased and gelled. When carbon dioxide gas was continued to be blown into the solution, the electrical conductivity increased again and the viscosity returned to its original state. If the blowing of carbon dioxide gas continues, the electrical conductivity decreases again, but the electrical conductivity is 4.5 ms/c.
The reaction was stopped when m. The reaction conditions and results are shown in Table 3.
反応生成物をＳＥＭで観察すると、０．１μｍ以下の微
細な粒状のカルサイト型炭酸カルシウムであった。When the reaction product was observed with a SEM, it was found to be calcite-type calcium carbonate in the form of fine particles of 0.1 μm or less.
消石灰乳の篩分けを実施しても、相対炭酸ガス吹込速度
を本発明の限度以上で炭酸化を行うと、板状塩基性炭酸
カルシウムは得られなかった。Even if slaked lime milk was sieved, plate-like basic calcium carbonate could not be obtained when carbonation was carried out at a relative carbon dioxide gas blowing rate equal to or higher than the limit of the present invention.
実施例２：本発明（活性度２５０）
活性度２５０の工業用生石灰２６０ｇｒを、４０℃の水
１７６０ｇの中に投入し、攪拌しながら、１５分間消和
を行う。その後分級機で篩分けし、４４μｍ通過の消石
灰乳を取り出し、これに水を加えて消石灰濃度１０重量
％の消石灰乳２ｋｇを得た。これを反応容器（内径１５
０×高さ２２０ｍｍ、内容積４１）に入れ、撹拌しなが
ら（かい型羽根、径６０ｍｍ、７００ｒｐｍ） １０℃
に冷却後、１００％４度の炭酸ガスを０．３４１／１ｌ
Ｉｉｎの速度で導入する。Example 2: Present invention (activity 250) 260g of industrial quicklime with an activity of 250 is put into 1760g of water at 40°C, and slaked for 15 minutes while stirring. Thereafter, it was sieved using a classifier, and the slaked lime milk that had passed through 44 μm was taken out, and water was added to this to obtain 2 kg of slaked lime milk with a slaked lime concentration of 10% by weight. Place this in a reaction container (inner diameter 15
0 x height 220 mm, internal volume 41) and stirred (paddle-shaped impeller, diameter 60 mm, 700 rpm) at 10°C.
After cooling to 0.341/1l of 100% 4 degree carbon dioxide gas
Introduce at a rate of Iin.
この時の相対炭酸ガス吹込速度は１．７ ｍｌ／ｍｉｎ
−ｇ−Ｃａ （ＯＨ）２に当たる。電気伝導度４．５
ｍｓ／ｃｖａで炭酸ガスの吹き込みを停止した。The relative carbon dioxide gas blowing speed at this time was 1.7 ml/min.
-g-Ca (OH)2. Electrical conductivity 4.5
The blowing of carbon dioxide gas was stopped at ms/cva.
反応条件および結果を表３に示す。The reaction conditions and results are shown in Table 3.
反応生成物をＳＥＭで観察したところ、平均径０．８μ
ｍ、厚み０．１５μｍの板状の形状を有していた（第７
図）。凝集部分はほとんど皆無で、良好な分散状態を示
している。When the reaction product was observed with SEM, the average diameter was 0.8μ.
m, and had a plate-like shape with a thickness of 0.15 μm (7th
figure). There were almost no agglomerated parts, indicating a good dispersion state.
一方、５Ａ−ＣＦ２で求めた平均粒径（Ｄ ｓ。）は０
．８８μｍであって（第９図）、これはＳＥＭの値０．
８μｍとよく一致している。分散度は０．８８１０．８
＝１．１である。このことからも、本発明による板状塩
基性炭酸カルシウムは、凝集部分がほとんど皆無で、極
めて良好な分散状態にあることがわかる。結晶粒径も０
．５〜１．５μｍの範囲にあり、その巾も小さいことが
わかる。一方、厚みは０．１５μｍであり、アスペクト
比は０．８８１０．１５’、６である。On the other hand, the average particle diameter (D s.) determined by 5A-CF2 is 0.
．． 88 μm (Figure 9), which has an SEM value of 0.
It is in good agreement with 8 μm. Dispersity is 0.8810.8
=1.1. This also shows that the plate-like basic calcium carbonate according to the present invention has almost no agglomerated parts and is in an extremely good dispersion state. Crystal grain size is also 0
．． It can be seen that the width is in the range of 5 to 1.5 μm, and the width is also small. On the other hand, the thickness is 0.15 μm, and the aspect ratio is 0.8810.15',6.
また、この生成物のＴＧ曲線（第１１図）、ガス分析お
よびｘ１回折図（第１２図）から、カルサイト、消石灰
のピークは見当たらず、２ＣａＣ０３・０．７２Ｃａ
（ＯＨ）２ ・０．９６Ｈ２０の組成式を有する塩基
性炭酸カルシウムであることが確認された。Furthermore, from the TG curve (Fig. 11), gas analysis, and x1 diffraction pattern (Fig. 12) of this product, no peaks of calcite or slaked lime were found, and 2CaC03.0.72Ca
It was confirmed that it was basic calcium carbonate having the composition formula of (OH)2.0.96H20.
比較例２−１：凝集品
実施例２と同じ（消和して、篩分けを行うことなく、消
石灰濃度１３重量％の消石灰乳を２ｋｇ５ｌｉ製した。Comparative Example 2-1: Agglomerated product Same as Example 2 (2 kg 5 li of slaked lime milk with a slaked lime concentration of 13% by weight was produced without slaking and sieving.
この消石灰乳を１５℃まで冷却後、１００％濃度の炭酸
ガスを０．３４１ ／ｍ１ｎ（相対炭酸ガス吹込速度−
１，３ｍｌ／ｍｉｎ−ｇ−Ｃａ （ＯＨ） ２ ）で吹
き込み、炭酸化して、電気伝導度が４．５ ｍｓ／ｃｍ
で吹き込みを停止した。反応条件および結果を表３に示
す。After cooling this slaked lime milk to 15°C, 100% carbon dioxide gas was added at 0.341/m1n (relative carbon dioxide gas blowing rate -
1.3 ml/min-g-Ca (OH) 2 ) and carbonated, the electrical conductivity was 4.5 ms/cm.
The blowing was stopped. The reaction conditions and results are shown in Table 3.
反応生成物をＳＥＭで観察すると、約１．３μｍの一次
粒子が強力に凝集して、約４〜５μｍ大の二次粗大粒子
を構成していた（第８図）。次に５Ａ−ＣＦ２による測
定の結果を示す（第１０図）。When the reaction product was observed by SEM, it was found that primary particles of about 1.3 μm were strongly aggregated to form secondary coarse particles of about 4 to 5 μm in size (FIG. 8). Next, the results of measurement using 5A-CF2 are shown (FIG. 10).
分散度をもとめると、４．４ ／ １．３ ＝ ３．４
と非常に高い値を示していることがわかる。本例におい
ても、比較例１−１と同じく、相対炭酸ガス吹込速度が
本発明に規定する条件内にあっても、消石灰乳の篩分け
を実施していないために凝集品となることを示している
。When calculating the degree of dispersion, 4.4 / 1.3 = 3.4
It can be seen that this shows a very high value. In this example, as in Comparative Example 1-1, even if the relative carbon dioxide gas blowing rate was within the conditions specified in the present invention, the slaked lime milk was not sieved, resulting in agglomerated products. ing.
比較例２−２−粒状炭酸カルシウム
実施例２と同じく消和し、４４μｍで消石灰乳の篩分け
を行って、消石灰濃度１０重量％の消石灰乳を２ｋｇ調
製した。この消石灰乳を１０℃まで冷却後、１００％の
濃度の炭酸ガスを２．５１１／ｗｉｎ（相対炭酸ガス吹
込速度＝ １２．５ｍｌ／ｍｉｎ−ｇ−Ｃａ（ＯＨ）２
）で吹き込み、冷却しながら炭酸化すると、反応開始後
約１０分で電気伝導度が５ ｍｓ／ｃｏ＋まで低下して
、またすぐ上昇した。引き続き炭酸ガスの吹き込みを続
けると、約２０分後に再び低下しはじめ、電気伝導度が
４．５ ｍｓ／ｃｍで停止した。Comparative Example 2-2 - Granular calcium carbonate was slaked in the same manner as in Example 2, and the slaked lime milk was sieved at 44 μm to prepare 2 kg of slaked lime milk with a slaked lime concentration of 10% by weight. After cooling this slaked lime milk to 10°C, 100% concentration of carbon dioxide gas was added at 2.511/win (relative carbon dioxide gas blowing rate = 12.5 ml/min-g-Ca(OH)2
) and carbonation was carried out while cooling, the electrical conductivity decreased to 5 ms/co+ about 10 minutes after the start of the reaction, and then rose again immediately. When the carbon dioxide gas was continued to be blown, the electrical conductivity started to decrease again after about 20 minutes and stopped at 4.5 ms/cm.
反応条件および結果を表３に示す。反応生成物をＳＥＭ
で観察すると、０．１μｍ以下の微細な粒状のカルサイ
ト型炭酸カルシウムであった。比較例１−２と同じく消
石灰乳の篩分けを実施しても、相対炭酸ガスの吹込速度
を本発明の限度以上で炭酸化を行うと、板状塩基性炭酸
カルシウムは得られなかった。The reaction conditions and results are shown in Table 3. SEM of reaction products
When observed, it was found to be calcite-type calcium carbonate in the form of fine particles of 0.1 μm or less. Even if slaked lime milk was sieved as in Comparative Example 1-2, plate-like basic calcium carbonate was not obtained when carbonation was carried out at a relative carbon dioxide gas blowing rate equal to or higher than the limit of the present invention.
実施例３： （高活性度−篩分粒径−相対炭酸ガス吹込
速度）関係
実施例１に用いたと同じ活性度３５０の工業用生石灰２
４０ｇを４０℃の水１７４０ｇの中に投入し、攪拌しな
がら１５分間消和を行う。消石灰乳の篩分は粒径および
炭酸ガスの吹込速度の条件を各種変更して炭酸化反応を
行った。反応を電気伝導度４．５ ｍｓ／ｃｍで停止し
た。反応条件および結果を表３に示す。Example 3: (High activity - sieved particle size - relative carbon dioxide gas blowing rate) Industrial quicklime 2 with the same activity of 350 as used in Example 1
40g was put into 1740g of water at 40°C and slaked for 15 minutes with stirring. The sifted milk of slaked lime was subjected to a carbonation reaction by varying the particle size and carbon dioxide gas blowing rate. The reaction was stopped at an electrical conductivity of 4.5 ms/cm. The reaction conditions and results are shown in Table 3.
高活性度の生石灰の場合、消石灰乳の篩分は粒度別に対
応して、相対炭酸ガス吹込速度の最大値があり、それ以
下で炭酸化を行う必要があることがわかる。In the case of highly active quicklime, it can be seen that there is a maximum value of the relative carbon dioxide gas blowing rate depending on the particle size of the sifted lime milk, and carbonation needs to be carried out below this value.
実施例４： （低活性度−篩分粒径−相対炭酸ガス吹込
速度）関係
実施例２に用いたと同じ活性度２５０の工業用生石灰２
６０ｇを４０℃の水１７４０ｇの中に投入し、攪拌しな
がら１５分間消和を行う。消石灰乳の篩分は粒度および
炭酸ガスの吹込速度の条件を各種変更して炭酸化反応を
行った。反応は導電度４．５ ｍｓ／ｃｍで停止した。Example 4: (Low activity - sieve particle size - relative carbon dioxide gas blowing rate) Industrial quicklime 2 with the same activity of 250 as used in Example 2
60g was put into 1740g of water at 40°C and slaked for 15 minutes with stirring. The sifted milk of slaked lime was subjected to a carbonation reaction by varying the particle size and carbon dioxide gas blowing rate. The reaction was stopped at a conductivity of 4.5 ms/cm.
反応条件および結果を表３に示す。The reaction conditions and results are shown in Table 3.
低活性度の生石灰の場合、消石灰乳の篩分は粒度別に対
応して、相対炭酸ガス吹込速度の最大値があり、それ以
下で炭酸化を行う必要があることがわかる。In the case of low-activity quicklime, it can be seen that there is a maximum value of the relative carbon dioxide gas blowing rate depending on the particle size of the sieved lime milk, and it is necessary to carry out carbonation below this value.
実施例５： （炭酸ガス濃度の影響）
実施例４で調製した消石灰乳を４４μｍで篩分けして得
た消石灰乳２ｋｇを１０℃に冷却し、炭酸ガス（１００
％濃度）の吹込量を’ｌｌ／ｍｉｎとし、これに窒素ガ
スを混合して、炭酸ガス濃度を変えて、炭酸化反応を行
った。導電度４．５ ａ＋ｓ／ｃ＋ｗで停止した０反応
条件および結果を表３に示す。Example 5: (Influence of carbon dioxide concentration) 2 kg of slaked lime milk prepared by sifting the slaked lime milk prepared in Example 4 through a 44 μm sieve was cooled to 10°C, and carbon dioxide gas (100
% concentration) was set to 1/min, nitrogen gas was mixed therein, and the carbonation reaction was carried out by changing the carbon dioxide concentration. Table 3 shows the reaction conditions and results, which were stopped at a conductivity of 4.5 a+s/c+w.
生成した板状塩基性炭酸カルシウムの粒径は炭酸ガスの
濃度の低下とともに大きくなる傾向にあることがわかる
。It can be seen that the particle size of the produced plate-like basic calcium carbonate tends to increase as the concentration of carbon dioxide gas decreases.
実施例６： （反応開始時の温度の影響）実施例５で調
製した消石灰乳を冷却し、反応開始時の消石灰乳の温度
を変化させて、炭酸化反応を行った０反応条件および結
果を表３に示す。Example 6: (Effect of temperature at the start of the reaction) The slaked lime milk prepared in Example 5 was cooled, and the temperature of the slaked lime milk at the start of the reaction was changed to perform the carbonation reaction. Shown in Table 3.
生成した板状塩基性炭酸カルシウムの粒径は反応開始時
の消石灰乳の温度の上昇とともに大きくなる傾向にある
ことがわかる。It can be seen that the particle size of the produced plate-like basic calcium carbonate tends to increase as the temperature of the slaked lime milk increases at the start of the reaction.
実施例７：−次降下点での温度限界
実施例６で調製した消石灰乳を冷却し、１６℃に調整後
、炭酸化反応を開始し、電気伝導度の一次降下点での消
石灰乳の温度を変化させて炭酸化反応を行った。Example 7: - Temperature limit at the first drop point After cooling the slaked lime milk prepared in Example 6 and adjusting it to 16°C, the carbonation reaction was started, and the temperature of the slaked lime milk at the first drop point of electrical conductivity was The carbonation reaction was carried out by changing the
反応条件および結果を表３に示す。The reaction conditions and results are shown in Table 3.
−次降下点の温度で１８℃を超えると、もはや分散性の
良好な板状塩基性炭酸カルシウムは得られないことがわ
かる。It can be seen that when the temperature at the second drop point exceeds 18° C., plate-like basic calcium carbonate with good dispersibility can no longer be obtained.
実施例８：塗工試験
反応容器４０１の規模で、生石灰の活性度、炭酸ガスの
濃度を変えて、任意の粒径の板状塩基性炭酸カルシウム
を調製した。反応条件および結果を表３に示す。平均粒
径０．３μｍと０．７μｍの２種類の分散性の良好な板
状塩基性炭酸カルシウムの水性スラリーを得た。得られ
たスラリーを脱水してウェットケーキとした後、これを
水に再分散せしめて６０重量％の濃度のスラリーとした
。Example 8: Coating test Platy basic calcium carbonate having an arbitrary particle size was prepared by changing the activity of quicklime and the concentration of carbon dioxide gas on the scale of the reaction vessel 401. The reaction conditions and results are shown in Table 3. Two types of aqueous slurries of plate-shaped basic calcium carbonate with average particle diameters of 0.3 μm and 0.7 μm and good dispersibility were obtained. The resulting slurry was dehydrated to form a wet cake, which was then redispersed in water to form a slurry having a concentration of 60% by weight.
次いで、このものを使って塗工試験を行った。Next, a coating test was conducted using this product.
以下においては、これらを０３品および０７品と呼称す
る。Below, these will be referred to as 03 items and 07 items.
対照試料として下記のものを使用した。The following was used as a control sample.
（１）比較例１−１．２−１の凝集物のある板状塩基性
炭酸カルシウムの機械的破砕品
（２）サテンホワイト：市販品
（３）軽質炭酸カルシウム：市販品
（４）本発明品（実施例１）の加熱品（上記６０％スラ
リーを５０℃で３日間加熱熟成したもの）（５） カ
オリンクレー：市販品
（６） 本発明品（実施例１）の噴霧乾燥品（炭酸化
により得られたスラリーを噴霧乾燥し、この乾燥品を水
に再分散せしめ、て６０％スラリーとしたもの）
塗工試験は下記条件で行った。(1) Mechanically crushed plate-like basic calcium carbonate product with aggregates of Comparative Example 1-1.2-1 (2) Satin White: Commercial product (3) Light calcium carbonate: Commercial product (4) Present invention (5) Kaolin clay: Commercially available product (6) Spray-dried product of the present invention (Example 1) (carbonated The resulting slurry was spray-dried, and the dried product was redispersed in water to obtain a 60% slurry.) The coating test was conducted under the following conditions.
（１） コート原紙：約８０ｇｒ１０ｆ上質紙（２）
塗工方法：ワイヤバー手塗り
使用ワイヤバー：１ｌｋＬ１２
塗被量ζ２０ｇｒ／ｒｒｒ
（３） カラー配合
１）カラーピグメントの種類および配合比（固形分とし
て）
下記の配合品（配合割合：表４〜８）
１００部
カオリンクレー
サチンホワイト
重質炭酸カルシウム
軽質炭酸カルシウム
本発明品および破砕品
２）バインダー
ラテックス（ＳＢＲ系） １０部澱粉（酸化澱粉
系） ５部３）潤滑剤 （ステアリン酸
系）１．０部４）分散剤 （ポリカルボン酸系）０．６
部５）塗被液 固形物濃度＃６０％
（４）スーパーカレンダー処理条件
線圧 １００ｋｇ／ｃｍ
温度 ５５・Ｃ
通過回数 ３回
カレンダー速度 ８ｍ／ｌｌ１ｉｎ
（５）測定方法
白色度 ハンター白色度計“ＭＲ−２”白紙光
沢 グロスメーター“ＧＭ−２６０”印刷光沢
グロスメーター“Ｇ？ｌ−２６０”Ｋ＆Ｎ白度低
度低下ンター白色度計“ＭＲ−２” ２分値。(1) Coated base paper: Approximately 80gr10f high-quality paper (2)
Coating method: Wire bar Hand-painted Wire bar used: 1lkL12 Coating amount ζ20gr/rrr (3) Color formulation 1) Type and blending ratio of color pigments (as solid content) The following blended products (blending ratio: Tables 4 to 8) 100 Part Kaolin Cresatin White Heavy Calcium Light Calcium Carbonate Product of the invention and crushed product 2) Binder latex (SBR type) 10 parts Starch (oxidized starch type) 5 parts 3) Lubricant (stearic acid type) 1.0 parts 4 ) Dispersant (polycarboxylic acid type) 0.6
Part 5) Coating liquid Solids concentration #60% (4) Super calender processing conditions Linear pressure 100 kg/cm Temperature 55・C Number of passes 3 times Calender speed 8 m/ll1in (5) Measurement method Brightness Hunter whiteness meter "MR" -2” White paper gloss Gloss meter “GM-260” Print gloss
Gloss meter "G?l-260"K&N whiteness low degree drop whiteness meter "MR-2" 2 minute value.
使用インク：フタロシアニ
ンブルー
印刷 ＲＩ印刷試験器
使用インク：ＴＶＩ２、Ｒｅｄ
回転数：３Ｏｒｐｍ
ＲＩ Ｄｒｙ Ｐｉｃｋ ＴＶＩ ８ Ｒｅｄ６
０ｒｐｍ＋、５段階評価。Ink used: Phthalocyanine blue printing RI printing tester Ink used: TVI2, Red Number of revolutions: 3 Orpm RI Dry Pick TVI 8 Red6
0rpm+, 5-level rating.
Ｂ粘度 ＢＬ型、６０ｒｐｍ 塗工試験の結果は下記の通りである。B viscosity BL type, 60 rpm The results of the coating test are as follows.
ＣＩ）市販品との比較（表４） ：
配合割合：供試品１５部／カオリンクレー８５部（１）
本発明の０３品と０７品の比較において、白色度、
印刷光沢ともに０３品が優る。一方、ＲＩＤｒｙ Ｐｉ
ｃｋ強度は０７品が優っている。CI) Comparison with commercial products (Table 4): Blending ratio: 15 parts of sample/85 parts of kaolin clay (1)
In comparing products 03 and 07 of the present invention, whiteness,
Product 03 is superior in both print gloss. On the other hand, RIDry Pi
The 07 product is superior in ck strength.
（２）板状塩基性炭酸カルシウムで凝集物のあるものを
機械的破砕しても、良好な分散性は得られず、白紙光沢
、印刷光沢ともに本発明品より劣る。(2) Even when plate-shaped basic calcium carbonate containing aggregates is mechanically crushed, good dispersibility cannot be obtained, and both white paper gloss and printing gloss are inferior to the products of the present invention.
（３） サチンホワイトと本発明品とを比較すれば、
大同小異であり、優るとも劣らぬ結果である。作業性で
ははるかに本発明品が優れている。(3) Comparing Sachin White and the product of the present invention,
The results are much the same, and the results are no better. The product of the present invention is far superior in workability.
（４）市販軽質炭酸カルシウムと本発明品とを比較すれ
ば、明らかに本発明品が白紙光沢、印刷光沢ともに優っ
ている。(4) When comparing commercially available light calcium carbonate with the product of the present invention, the product of the present invention is clearly superior in both white paper gloss and print gloss.
（ｎ）市販品との比較（表５）
配合割合：供試品３０部／重炭酸カルシウム３０部／カ
オリンクレー４０部
（１）市販軽質炭酸カルシウムと本発明品とを比較すれ
ば、白紙光沢、印刷光沢ともに本発明品の方が優れた結
果を示している。(n) Comparison with commercially available products (Table 5) Blending ratio: 30 parts of sample / 30 parts of calcium bicarbonate / 40 parts of kaolin clay (1) Comparing commercially available light calcium carbonate and the product of the present invention, white paper gloss The product of the present invention shows superior results in both print gloss and printing gloss.
（Ｉ［［）カラー配合の混合相乗効果（表６）カオリン
、本発明品（０３品）、市販軽質炭酸カルシウムを、そ
れぞれ、単味（１００部）および配合（配合割合：供試
品２０部／カオリン８０部）で用いた。(I[[) Mixing synergistic effect of color combination (Table 6) Kaolin, the product of the present invention (product 03), and commercially available light calcium carbonate were used alone (100 parts) and in combination (blending ratio: 20 parts of sample), respectively. /80 parts of kaolin).
（１１本発明品とカオリンの組み合わせの場合は、それ
ぞれの単味の白紙光沢、印刷光沢より、いずれも優れた
値をとり、相乗効果が期待される好結果を得た。(11) In the case of the combination of the product of the present invention and kaolin, both the white paper gloss and the printing gloss were superior to each other, and good results were obtained in which a synergistic effect was expected.
（２）一方、市販軽質炭酸カルシウムとカオリンの組み
合わせの場合には、上記に引き換え、それぞれの単味の
値の中間的な値となった。(2) On the other hand, in the case of a combination of commercially available light calcium carbonate and kaolin, in contrast to the above, the value was intermediate between the values of each single component.
（ＩＶ）加熱効果（５０℃×３日間、表７）（１）
加熱により白紙光沢、印刷光沢ともに明らかに向上した
。(IV) Heating effect (50°C x 3 days, Table 7) (1)
Both white paper gloss and print gloss were clearly improved by heating.
（Ｖ）乾燥品試験（噴霧乾燥品、表８）（１）スラリー
とこれを噴霧乾燥した粉末との比較塗工試験では、両者
間にはほとんど差はないといえる。(V) Dry product test (spray-dried product, Table 8) (1) In the comparative coating test of the slurry and the powder obtained by spray-drying it, it can be said that there is almost no difference between the two.
（２）乾燥粉末状態で、市販軽質炭酸カルシウムとの比
較試験においても、白紙光沢、印刷光沢ともに数段本発
明品が優れていることがわかる。(2) In a comparative test with commercially available light calcium carbonate in dry powder form, it was found that the product of the present invention was several orders of magnitude superior in terms of both white paper gloss and print gloss.
以下余白 表 ５ 表 ６ 表 ７ 表 ８Margin below Table 5 Table 6 Table 7 Table 8
第１図、第２図はそれぞれ実施例１および比較例１−１
で得られた塩基性炭酸カルシウムの結晶粒子構造を示す
走査型電子顕微鏡写真である。
第３図、第４図はそれぞれ実施例１および比較例１−１
で得られた塩基性炭酸カルシウムの結晶粒径の光透過式
粒度測定器による測定結果を示すグラフである。
第５図は実施例１の熱重量分析における温度とｆＩｉ量
変化との関係を示すグラフである。
第６図は実施例１で得られた生成物のＸ線回折図である
。
第７図、第８図はそれぞれ実施例２および比較例２−１
で得られた塩基性炭酸カルシウムの結晶粒子構造を示す
走査型電子顕微鏡写真である。
第９図、第１０図はそれぞれ実施例２および比較例２−
１で得られた塩基性炭酸カルシウムの結晶粒径の光透過
式粒度測定器による測定結果を示すグラフである。
第１１図および第１２図はそれぞれ実施例２についての
熱重量分析およびＸ線回折の結果を示す図である。
第１３図および第１４図は凝集物の破砕品の走査型電子
顕微鏡写真および光透過式粒度測定結果である。Figures 1 and 2 are Example 1 and Comparative Example 1-1, respectively.
This is a scanning electron micrograph showing the crystal particle structure of basic calcium carbonate obtained in . Figures 3 and 4 are Example 1 and Comparative Example 1-1, respectively.
2 is a graph showing the measurement results of the crystal grain size of basic calcium carbonate obtained using a light transmission type particle size measuring device. FIG. 5 is a graph showing the relationship between temperature and change in fIi amount in thermogravimetric analysis of Example 1. FIG. 6 is an X-ray diffraction diagram of the product obtained in Example 1. Figures 7 and 8 are Example 2 and Comparative Example 2-1, respectively.
This is a scanning electron micrograph showing the crystal particle structure of basic calcium carbonate obtained in . Figures 9 and 10 are Example 2 and Comparative Example 2-
1 is a graph showing the measurement results of the crystal grain size of basic calcium carbonate obtained in Example 1 using a light transmission type particle size analyzer. FIG. 11 and FIG. 12 are diagrams showing the results of thermogravimetric analysis and X-ray diffraction for Example 2, respectively. FIGS. 13 and 14 are scanning electron micrographs of crushed aggregates and the results of light transmission particle size measurement.
Claims (1)
が０．２〜２．０μｍ、平均厚みが０．０５〜０．２５
μｍ、平均径／平均厚みの比が４〜２０であることを特
徴とする、分散性良好な板状塩基性炭酸カルシウム。 ２、組成式ＸＣａＣＯ＿３・ＹＣａ（ＯＨ）＿２・ＺＨ
＿２Ｏで示される、特許請求の範囲第１項記載の板状塩
基性炭酸カルシウム。但し、Ｘ＝２とした場合、Ｙ＝０
．５〜１．０であり、Ｚ＝０．７〜１．５であるものと
する。 ３、板状部分の平均径（Ｄａｖ）に対して０．５Ｄａｖ
〜２．０Ｄａｖの径を有する粒子が全体の８０％以上を
占める、特許請求の範囲第１項記載の板状塩基性炭酸カ
ルシウム。 ４、分散度が１．５以下であり、かつ板状部分の平均径
が０．２〜２．０μｍ、平均厚みが０．０５〜０．２５
μｍ、平均径／平均厚みの比が４〜２０である、分散性
良好な板状塩基性炭酸カルシウムを製造するに当たり、
生石灰の活性度が２００〜４００であり、その消和物で
ある消石灰乳の篩分最大粒度が４４μｍ〜２５０μｍで
ある時、これらの活性度および篩分最大粒度のそれぞれ
の組み合わせに対応して一次降下点までの相対炭酸ガス
吹込速度の最大値を２３ｍｌ／ｍｉｎ・ｇ−Ｃａ（ＯＨ
）２〜３ｍｌ／ｍｉｎ・ｇ−Ｃａ（ＯＨ）＿２の範囲で
、消石灰乳を炭酸化することを特徴とする、板状塩基性
炭酸カルシウムの製造方法。 ５、生石灰の活性度が２５０〜３８０であり、その消和
物である消石灰の篩分最大粒度が４４μｍ〜２５０μｍ
である時、それぞれの組み合わせに対応して一次降下点
までの相対炭酸ガス吹込速度の最大値が２１ｍｌ／ｍｉ
ｎ・ｇ−ａ（ＯＨ）＿２〜５ｍｌ／ｍｉｎ・ｇ−Ｃａ（
ＯＨ）＿２の範囲にある、特許請求の範囲第４項記載の
方法。[Claims] 1. The degree of dispersion is 1.5 or less, and the average diameter of the plate-shaped portion is 0.2 to 2.0 μm, and the average thickness is 0.05 to 0.25.
Plate-shaped basic calcium carbonate with good dispersibility, characterized in that the ratio of average diameter/average thickness is 4 to 20. 2. Composition formula XCaCO_3・YCa(OH)_2・ZH
The plate-like basic calcium carbonate according to claim 1, which is represented by _2O. However, if X=2, Y=0
．． 5 to 1.0, and Z=0.7 to 1.5. 3. 0.5Dav for the average diameter (Dav) of the plate-shaped part
The plate-shaped basic calcium carbonate according to claim 1, wherein particles having a diameter of ~2.0Dav account for 80% or more of the total. 4. The degree of dispersion is 1.5 or less, and the average diameter of the plate-shaped portion is 0.2 to 2.0 μm, and the average thickness is 0.05 to 0.25.
In producing plate-like basic calcium carbonate with good dispersibility, having an average diameter/average thickness ratio of 4 to 20 μm,
When the activity of quicklime is 200 to 400 and the maximum sieve particle size of slaked lime milk, which is its slaked product, is 44 μm to 250 μm, the primary The maximum relative carbon dioxide gas blowing rate up to the drop point was set at 23 ml/min・g-Ca (OH
) A method for producing plate-like basic calcium carbonate, comprising carbonating slaked lime milk in a range of 2 to 3 ml/min.g-Ca(OH)_2. 5. The activity of quicklime is 250 to 380, and the maximum particle size of the slaked lime, which is its slaked product, is 44 μm to 250 μm.
, the maximum relative carbon dioxide gas blowing speed up to the primary drop point is 21 ml/mi for each combination.
n・ga(OH)_2-5ml/min・g-Ca(
OH)_2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62274671A JPH01119512A (en) | 1987-10-31 | 1987-10-31 | Platy basic calcium carbonate and its production |
| JP4212311A JPH0640717A (en) | 1987-10-31 | 1992-07-17 | Planer basic calcium carbonate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62274671A JPH01119512A (en) | 1987-10-31 | 1987-10-31 | Platy basic calcium carbonate and its production |
| JP4212311A JPH0640717A (en) | 1987-10-31 | 1992-07-17 | Planer basic calcium carbonate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4212311A Division JPH0640717A (en) | 1987-10-31 | 1992-07-17 | Planer basic calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01119512A true JPH01119512A (en) | 1989-05-11 |
| JPH054929B2 JPH054929B2 (en) | 1993-01-21 |
Family
ID=26519143
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62274671A Granted JPH01119512A (en) | 1987-10-31 | 1987-10-31 | Platy basic calcium carbonate and its production |
| JP4212311A Pending JPH0640717A (en) | 1987-10-31 | 1992-07-17 | Planer basic calcium carbonate |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4212311A Pending JPH0640717A (en) | 1987-10-31 | 1992-07-17 | Planer basic calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPH01119512A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0356551A (en) * | 1989-07-26 | 1991-03-12 | Agency Of Ind Science & Technol | Stabilizer for pvc |
| US5275651A (en) * | 1990-05-28 | 1994-01-04 | Maruo Calcium Company Limited | Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof |
| US6312659B1 (en) | 1991-06-04 | 2001-11-06 | Kenneth J. Wise | Precipitated calcium carbonate particles from basic calcium carbonate |
| US7361324B2 (en) | 2004-06-21 | 2008-04-22 | J. M. Huber Corporation | Precipitated calcium carbonate |
| CN109480098A (en) * | 2018-12-29 | 2019-03-19 | 长沙兴嘉生物工程股份有限公司 | Application of the preparation method and hydroxy carbonate calcium of hydroxy carbonate calcium in field of animal feed |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06315418A (en) * | 1993-05-07 | 1994-11-15 | Sekisui Chem Co Ltd | Sink with auxiliary device |
| EP3124436A1 (en) * | 2015-07-31 | 2017-02-01 | Omya International AG | Precipitated calcium carbonate with improved resistance to structural breakdown |
| JP2017218361A (en) * | 2016-06-10 | 2017-12-14 | 宇部マテリアルズ株式会社 | Oxygen sustained release agent, manufacturing method therefor and oxygen supply method |
| EP3530805A1 (en) * | 2018-02-21 | 2019-08-28 | Imertech Sas | Bimodal precipitated calcium carbonate slurries suitable for paper and board applications, methods for making the same and their uses |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56160322A (en) * | 1980-05-06 | 1981-12-10 | Shiraishi Chuo Kenkyusho:Kk | Manufacture of calcium carbonate with superior dispersibility |
| JPS62113718A (en) * | 1985-11-14 | 1987-05-25 | Okutama Kogyo Kk | Production of hexagonal complex of calcium carbonate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5551852A (en) * | 1978-10-09 | 1980-04-15 | Ichimura Sangyo Kk | Weft yarn detector of water jet loom |
| JPS61219715A (en) * | 1985-03-25 | 1986-09-30 | Agency Of Ind Science & Technol | Plate basic calcium carbonate and its production |
| JPS6232130A (en) * | 1985-08-05 | 1987-02-12 | Shinto Paint Co Ltd | Expanded plastic bead |
-
1987
- 1987-10-31 JP JP62274671A patent/JPH01119512A/en active Granted
-
1992
- 1992-07-17 JP JP4212311A patent/JPH0640717A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56160322A (en) * | 1980-05-06 | 1981-12-10 | Shiraishi Chuo Kenkyusho:Kk | Manufacture of calcium carbonate with superior dispersibility |
| JPS62113718A (en) * | 1985-11-14 | 1987-05-25 | Okutama Kogyo Kk | Production of hexagonal complex of calcium carbonate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0356551A (en) * | 1989-07-26 | 1991-03-12 | Agency Of Ind Science & Technol | Stabilizer for pvc |
| US5275651A (en) * | 1990-05-28 | 1994-01-04 | Maruo Calcium Company Limited | Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof |
| US5494651A (en) * | 1990-05-28 | 1996-02-27 | Maruo Calcium Company Limited | Method for manufacturing monodisperse vaterite type calcium carbonate |
| US6312659B1 (en) | 1991-06-04 | 2001-11-06 | Kenneth J. Wise | Precipitated calcium carbonate particles from basic calcium carbonate |
| US7361324B2 (en) | 2004-06-21 | 2008-04-22 | J. M. Huber Corporation | Precipitated calcium carbonate |
| CN109480098A (en) * | 2018-12-29 | 2019-03-19 | 长沙兴嘉生物工程股份有限公司 | Application of the preparation method and hydroxy carbonate calcium of hydroxy carbonate calcium in field of animal feed |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH054929B2 (en) | 1993-01-21 |
| JPH0640717A (en) | 1994-02-15 |
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| EXPY | Cancellation because of completion of term |