WO2001030700A1 - Calcium carbonate, and method for producing the same - Google Patents

Calcium carbonate, and method for producing the same Download PDF

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Publication number
WO2001030700A1
WO2001030700A1 PCT/JP2000/007195 JP0007195W WO0130700A1 WO 2001030700 A1 WO2001030700 A1 WO 2001030700A1 JP 0007195 W JP0007195 W JP 0007195W WO 0130700 A1 WO0130700 A1 WO 0130700A1
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Prior art keywords
calcium carbonate
calcium
particles
weight
average
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PCT/JP2000/007195
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French (fr)
Japanese (ja)
Inventor
Yoshihito Sasahara
Yoshimi Goto
Tetsushi Iwashita
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Yabashi Industries Co., Ltd.
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Priority to AU76881/00A priority Critical patent/AU7688100A/en
Priority to KR1020017006248A priority patent/KR20010080481A/en
Publication of WO2001030700A1 publication Critical patent/WO2001030700A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
    • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to calcium carbonate produced by a reaction between calcium hydroxide and carbon dioxide gas and a method for producing the same.
  • the primary particles having a good dispersibility have an average minor axis of 0.1 to 0.5 m
  • the present invention relates to a carbonated calcium carbonate having a primary particle average major axis of 0.15 to 1.5 m and an aspect ratio of 1.5 to 3.0, and a method for producing the same.
  • a typical method of producing synthetic carbonated calcium carbonate is a "liquid-gas" method in which a gaseous carbonate is blown into a hydroxylated calcium sulfate slurry to cause a reaction.
  • concentration of the calcium hydroxide slurry, the reaction temperature, and the reaction method are used. It is known that calcium carbonate having various particle sizes and shapes can be obtained by controlling the reaction conditions such as the presence or absence and the type of additives.
  • the short diameter of primary particles with good dispersibility is 0.1 to 0.5 m, and the average length of primary particles is 0.1 to 0.5 m.
  • the production technology of calcium carbonate with ⁇ of 0.15 to 1.5 yum and aspect ratio of 1.5 to 3.0 has not been established.
  • Such calcium carbonate has various properties such as coating pigments and internal additives for papermaking, which require highly controlled particle size, shape, and particle size distribution, and anti-blocking fillers for magnetic tape. It is suitable for improvement and an inexpensive manufacturing method is desired.
  • the carbonic acid produced does not have a cubic shape and is rhombohedral, so the particles tend to overlap, and when used as a coating pigment for papermaking, the surface smoothness and gloss of the coated paper are also improved. hard.
  • Spindle-shaped calcium carbonate is susceptible to particle corner damage due to its shape. This may reduce the surface strength of the coated paper when used in coating pigments for papermaking, for example, and may cause dropout due to powder generation when used in anti-blocking fillers for magnetic tape. It is possible that
  • an object of the present invention is to provide a primary particle having a good average dispersibility of 0.1 to 0.5 ⁇ m, a primary particle average major axis of 0.1 to 1.5 Atm, and an aspect ratio of 1.5. It is an object of the present invention to provide a carbonated calcium carbonate of about 3.0 and a method for producing calcium carbonate by which such a carbonated calcium can be obtained easily and inexpensively. Disclosure of the invention
  • the present invention provides a method for producing calcium carbonate having excellent dispersibility by reacting calcium hydroxide and carbon dioxide gas, wherein calcium ions and carbonate ions coexist with an organic compound having a hydroxyl group.
  • the method for producing calcium carbonate was constituted by adding organic compounds.
  • the organic compound having a hydroxyl group is added before or after the start of carbonation, and after the start of the carbonation reaction, a predetermined amount of the total amount is added until the carbonation rate becomes about 20%.
  • the organic compound is kneaded with the powdered lime or slaked lime raw material before the start of the carbonation reaction, or added dropwise to digested water. In addition, it is added by spraying powder material in a mixer or by dripping it into calcium hydroxide slurry.
  • the organic compound is added in an amount of 10 to 200 parts by weight based on 100 parts by weight of calcium oxide (CaO) as a raw material calcium source. If the amount is less than 100 parts by weight, the particle shape becomes close to a cubic shape, and the desired shape of rice granules, bales, or rounded columnar carbonic acid calcium particles cannot be obtained. The effect leveled off and was not cost effective. Preferably 50 to 180 parts by weight are added. In this range, the primary particles have an aspect ratio of 2 or more, so that when used as a papermaking pigment or the like, particles having excellent shapes that can easily improve smoothness and the like can be obtained.
  • CaO calcium oxide
  • the raw lime or slaked lime powder raw material is kneaded in a kneading manner or dropped and dissolved in digested water or water used for preparing a slurry. It may be sprayed by a spray in a mixer, or may be dropped onto the calcium hydroxide slurry before the carbonation reaction is started or after the carbonation reaction is started until the carbonation ratio becomes about 20%.
  • the addition method is not particularly limited as long as a state where calcium ions and carbonate ions and an organic compound having a hydroxyl group coexist during the reaction is obtained.
  • the organic compound having a hydroxyl group preferably has a molecular weight of 600 or less, and glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butylene glycol; monoethanolamine And ethanolamines such as diethanolamine and triethanolamine; glycerins such as glycerin and polyglycerin, and mixtures thereof, and are preferably propylene glycol and ethylene glycol.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butylene glycol
  • monoethanolamine And ethanolamines such as diethanolamine and triethanolamine
  • glycerins such as glycerin and polyglycerin, and mixtures thereof, and are preferably propylene glycol and ethylene glycol.
  • the calcium hydroxide slurry is preferably used before the reaction. Adjusted to 10-20 ° C. By blowing carbon dioxide gas or a mixed gas containing carbon dioxide gas into the calcium hydroxide slurry, the reaction is performed until the carbonation ratio becomes substantially 100%. If the concentration of calcium hydroxide is less than 3% by weight, the industrial productivity is poor. If the concentration exceeds 20% by weight, the slurry viscosity increases and the handling properties deteriorate, which is undesirable. Same as the method. On the other hand, if the temperature before the start of the reaction is lower than 10 ° C, on the other hand, aggregates tend to form and form aggregates, whereas if the temperature is higher than 20 ° C, aggregates of spun particles and aggregates of aggregates form. It is also well known that it is difficult to obtain a uniform and well-dispersed product.
  • the primary particles having a good dispersibility have an average minor axis of 0.1 to 0.5 m, The average primary particle diameter is 0.15 to 1.5 m, the aspect ratio is 1.5 to 3.0, and the shape is rice grain, bale, or column with rounded corners.
  • Calcium carbonate can be obtained.
  • the organic compound having a hydroxyl group is preferably added at the latest until the carbonation rate of calcium hydroxide becomes 20%.
  • the generated particles will be agglomerated if the amount of carbon dioxide gas is large, and if the amount is small, the generated particles will be enlarged, resulting in good dispersibility. It is hard to expect to get.
  • the calcium carbonate obtained by the present invention has a very good dispersibility, so it is not necessary to disintegrate it with a media mill or the like. It is desirable to keep the slurry treatment only for a short time.
  • the average primary particle minor axis of uniformity and good dispersibility is 0.1 to 0.5 m, and the average primary particle length is 0.15 to 0.15. 1.5 m and an aspect ratio of 1.5 to 3.0, it is possible to obtain calcium carbonate with high uniformity and rice grain, bale or square column shape.
  • an organic compound having a hydroxyl group is mixed or dissolved in raw material powder, digested water, or a calcium hydroxide slurry having a carbonation ratio of about 20% or less. Only the equipment for addition by existing equipment It can be implemented simply by adding to it, and can be realized simply and inexpensively.
  • the water separated by dewatering is in a state in which the organic compound is dissolved and is circulated as digestion water or water for preparing calcium hydroxide slurry.
  • the uniformity of the particles is good, the glossiness is improved when used as a coating pigment for papermaking, and the anti-blocking property is improved when used as an anti-blocking filler.
  • it has a grain shape, bale shape, or rounded column shape, and coating is difficult because particles do not overlap, improving the smoothness and glossiness of the paper surface, and coating because the corners of the particles are not easily damaged. It is possible to prevent a drop in surface strength of paper and dropout due to generation of powder when used in an anti-blocking filter.
  • the primary particles having an average dispersibility of 0.1 to 0.5 m, the primary particles having an average length of 0.1 to 1.5 and 1.5% It is possible to obtain calcium carbonate having an energy ratio of 1.5 to 3.0 and preferably in the shape of rice grains, bale, or column with rounded corners.
  • FIG. 1 is an electron micrograph ( ⁇ 10,000) of the calcium carbonate obtained in Example 2.
  • FIG. 2 is an electron micrograph ( ⁇ 10,000) of the calcium carbonate obtained in Example 5.
  • In-house manufactured lime mass (JIS industrial lime quick lime special number) was pulverized to a particle size of 1 mm or less and used as a calcium oxide raw material.
  • this calcium oxide powder 30 parts by weight of ethylene glycol is added and mixed, and about 1.5 times (48 parts by weight) the theoretical amount of water required for calcium oxide to be digested into calcium hydroxide.
  • Water at 20 ° C was stirred and mixed, digested and aged to obtain calcium hydroxide powder.
  • the slurry concentration was adjusted to 7%, and the temperature was adjusted to 15 ° C.
  • the carbonation gas was adjusted to 4 L / min. The reaction was completed by introducing the solution until the concentration reached 00%, and calcium carbonate was obtained.
  • the obtained calcium carbonate was observed with an electron microscope.
  • the average primary particle diameter 0 was 0.4; am, the average primary particle diameter was 0.6 ⁇ , and the median diameter determined by laser diffraction method was 1
  • O ⁇ m was uniform and well-dispersed, and was rice-shaped, bale-shaped, or rounded cylindrical particles. That is, as shown in the electron micrograph of FIG. 1, the particles are roughly cylindrical at the center and hemispherical at both ends. Of course, cylinders and hemispheres contain some distortion.
  • the diameter in the axial direction of the columnar shape is the major axis, and the diameter in the radial direction is the minor axis.
  • the average primary particle diameter is the shortest chord of the particle (i.e., the particle circle) of two diagonal particles in a random electron micrograph taken at 30,000 magnifications with an electronic caliper. The diameter of the column in the semi-monstrous direction) was measured and used as the minor axis of the particle. Similarly, in an electron micrograph, the longest chord of two diagonal particles (that is, the length of the particle in the axial direction of the column) is measured, and this is taken as the major axis of the particle. The average primary particle length S was used.
  • the median diameter obtained by the laser diffraction method is a value measured by a laser diffraction particle size distribution analyzer LA-500 manufactured by Horiba Seisakusho Co., Ltd. I have. The median diameter is this value compared to the primary particle diameter. Is a value indicating that the smaller the value, the better the dispersibility.
  • Calcium carbonate was obtained in the same manner as in Example 1 except that ethylene glycol was added and mixed with 100 parts by weight of calcium oxide powder and 80 parts by weight. Observed by electron microscopy, the resulting calcium carbonate was uniform and dispersed with an average primary particle diameter of 0.4 m, an average primary particle diameter of 0.8 ytm, and a median ⁇ ⁇ ⁇ of 1.2 m by laser diffraction method. It was confirmed that the particles were rice grains having good properties. An electron micrograph (10,000 magnification) is shown in FIG.
  • Calcium carbonate was obtained in the same manner as in Example 1, except that ethylene glycol was added and mixed with 150 parts by weight based on 100 parts by weight of the calcium oxide powder. According to electron microscopic observation, the obtained carbonic acid lumps have a uniform primary particle average of 0.4 m, average primary particle length of 1.0 m, and a median suspicion of 1. with laser-diffraction method and good dispersibility. It was confirmed that the rice grains were fine.
  • FIG. 2 shows a diagram similar to FIG. 1 for the fifth embodiment.
  • Example 4 Average particle diameter of primary particles: 0.2 m. Average particle diameter of primary particles: 0.3 Atm, and uniform and good dispersibility rice granular particles having a median diameter of 0.6 m by a laser diffraction method. : Average particle diameter of primary particles: 0.2 m, average particle diameter of primary particles: 0.4 yam, uniform and good dispersibility rice granular particles having a median ⁇ ⁇ ⁇ by laser diffraction method of 0.6 Aim
  • Example 6 1 Uniform and well-dispersed rice granule particles with average secondary minor particle diameter of 0.2 yam, primary primary particle average major diameter of 0.5 m, and laser-diffraction median diameter of 0.8 m (Example 7)
  • the obtained calcium carbonate has a primary particle average minor axis of 0.4 m, a primary particle average length of 0.8 Atm, and a median diameter by laser diffraction method of 1.3. It was confirmed that the particles were rice granules having uniform m and good dispersibility.
  • a carbonation reaction was carried out in the same process as in Examples 7 to 8 except that the flow rate of the carbon dioxide gas was changed to 10 L / min ⁇ kg-Ca (OH), thereby obtaining carbon dioxide.
  • the results observed with an electron microscope are listed below.
  • Example 9 Uniform and well-dispersed rice granular particles having a primary particle average minor axis of 0.2 m, an average primary particle major axis of 0.3 m, and a median diameter of 0.6 ⁇ m as measured by laser diffraction.
  • Example 10 Uniform and well-dispersed rice granular particles having an average primary particle diameter of 0.2 m, an average primary particle diameter of 0.4 ⁇ , and a median diameter of 0.6 m by laser diffraction method. (Comparative Examples 1-4)
  • Carbonation reaction was performed in the same process as in Examples 1, 4, 7, and 9 except that the added amount of ethylene glycol or propylene glycol was 5% by weight, and the obtained calcium carbonate was observed with an electron microscope.
  • the added amount of ethylene glycol or propylene glycol was 5% by weight, and the obtained calcium carbonate was observed with an electron microscope.
  • Comparative Example 1 Uniform and well-dispersed cubic particles having an average primary particle diameter of 0.5 m and a median diameter of 1.1 m as measured by a laser diffraction method.
  • the average primary particle ⁇ refers to the change of the particle with an electronic caliper for two diagonal particles in an electron micrograph taken at a magnification of 30,000 and photographed at random. This was measured and defined as the particle diameter, and the average value was determined as the primary particle average particle diameter. Comparative Example 2: First-order average particle size 0.2 / am, median ⁇ ⁇ by laser-diffraction method was 0.
  • Comparative Example 3 Primary mean particle diameter 0.4 mm, median diameter determined by laser diffraction method was 0.4 mm.
  • Comparative Example 4 Uniform and well-dispersed cubic particles having a primary average particle diameter of 0.2 xm and a median ⁇ ⁇ ⁇ by laser-diffraction method of 0.6 m
  • a carbonation reaction was carried out in the same manner as in Examples 1, 4, 7, and 9 except that ethylene glycol or propylene glycol was not added, and the results obtained by observing the obtained carbonated calcium carbonate with an electron microscope are listed below. I do.
  • Comparative Example 5 Polyhedral particles having a primary average particle size of more than 1 Atm and a median size of 3 by laser-diffraction
  • Comparative Example 6 Aggregate of aggregated particles having a primary particle average particle size of less than 0.1 Atm and a median diameter of 4.3 Atm by laser diffraction method
  • Comparative Example 7 Polyhedral particle with primary particle average particle exceeding 1 Atm and median ⁇ ⁇ ⁇ 3.1 m by laser-diffraction method
  • Comparative Example 8 Aggregate of aggregated particles having an average primary particle size of less than 0.1 Aim and a median of 4.0 m by laser diffraction method
  • Table 1 summarizes the synthesis conditions and results of the above Examples and Comparative Examples.
  • the calcium carbonate obtained in Examples 1 and 4 and Comparative Examples 1 and 5 was dehydrated by a filter press to obtain a cake having a solid content of 65.5% by weight. Next, 0.6% by weight of a dispersant in terms of solid content was added to the dewatered cake to carry out a dispersion treatment to obtain a high-concentration calcium carbonate slurry having a solid content concentration of 65.0% by weight. This slurry was used as a coating pigment, and 100 parts by weight of calcium carbonate was added to 6 parts by weight of starch (Japanese food processing # 4600), 12 parts by weight of latex (Nippon Synthetic Rubber No.
  • a printability improver Toho Chemical Co., Ltd.-Ito Master GT360
  • water-resistant agent Suditomo Chemical Sumireze Resin 61 3
  • water and a pigment with a solid concentration of 50.0% by weight The composition was prepared and coated on a 65 g / m ; base paper with a hand-painted rod so that the coating amount per side was 15 g / m ; and the super calendering was performed twice. After that, the physical properties of the coated paper were evaluated.
  • Table 2 summarizes the physical properties of coated paper in application examples. Table 2

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Abstract

Calcium carbonate particles having an average shorter diameter of primary particles of 0.1 to 0.5 νm, an average longer diameter of primary particles of 0.15 to 1.5 νm and an aspect ratio of 1.5 to 3.0 and preferably in the shape of a grain of rice, a straw ricebag or a cylinder having rounded corners; and a method for producing calcium carbonate through the reaction of calcium hydroxide with carbon dioxide, characterized in that an organic compound having a hydroxyl group is added to the carbonization reaction system in an amount of 20 to 200 parts by weight relative to 100 parts by weight of calcium oxide which is a raw material used as the source of calcium. Said calcium carbonate particles exhibit good dispersibility and are produced by the above method.

Description

明 細 書 炭酸カルシウム、 及びその製造方法 技術分野  Description Calcium carbonate and its manufacturing method
本発明は、 水酸化カルシウムと炭酸ガスとの反応により生成される炭酸カルシ ゥム及びその製造方法に関し、 特に分散性の良好な 1次粒子平均短径が 0 . 1〜 0 . 5 m、 1次粒子平均長径が 0 . 1 5〜1 . 5 m及びアスペク ト比が 1 . 5 - 3 . 0である炭酸力ルシゥム及びその製造方法に関する。 背景技術  The present invention relates to calcium carbonate produced by a reaction between calcium hydroxide and carbon dioxide gas and a method for producing the same. Particularly, the primary particles having a good dispersibility have an average minor axis of 0.1 to 0.5 m, The present invention relates to a carbonated calcium carbonate having a primary particle average major axis of 0.15 to 1.5 m and an aspect ratio of 1.5 to 3.0, and a method for producing the same. Background art
合成炭酸力ルシゥムの製造方法としては、 水酸化力ルシゥ厶スラリーに炭酸ガ スを吹き込んで反応させる" 液—ガス"法が代表的であり、 水酸化カルシウムス ラリーの濃度、 反応温度、 反応方法、 添加剤の有無とその種類など反応条件を制 御することにより、 種々の粒子径、 形状の炭酸カルシウムを得られることが知ら れている。  A typical method of producing synthetic carbonated calcium carbonate is a "liquid-gas" method in which a gaseous carbonate is blown into a hydroxylated calcium sulfate slurry to cause a reaction. The concentration of the calcium hydroxide slurry, the reaction temperature, and the reaction method are used. It is known that calcium carbonate having various particle sizes and shapes can be obtained by controlling the reaction conditions such as the presence or absence and the type of additives.
しかしながら、 現在工業的に広く採用されている"液一ガス" 法によると、 分 散性の良好な短径 1次粒子平均短径が 0 . 1〜0 . 5 m、 1次粒子平均長 ί圣が 0 . 1 5〜1 . 5 yu m及びアスペク ト比が 1 . 5〜3 . 0である炭酸カルシウム の製造技術は確立されていない。 このような炭酸カルシウムは粒子の大きさ、 形 状、 粒度分布が高度に制御されている必要のある製紙用の塗工顔料及び内添材、 磁気テープ用のアンチブロッキングフイラ一等として各種性能向上のために好適 であり、 その安価な製造方法が望まれている。 この課題を解決するために、 核と なる種晶なるものを成長媒体となる水酸化カルシウムスラリーまたは一部炭酸化 された水酸化カルシウムスラリーに添加する方法が、 特公平 7— 5 3 0 3号及び 特公平 3— 1 9 1 6 5号の各公報に記載されているが、 種晶の調製が別工程で且 つガス流量の制御を伴うものであるため、 工程全体として煩雑なものになるとい う問題がある。 また、 p H値が0 . 2以上降下しない条件で一部炭酸化を行なって板状塩基性 炭酸力ルシゥムを生成させ、 ついで反応が完結するまで炭酸化を行なう方法が特 公平 3— 3 6 0 5号公報に記載されている。 しかし、 炭酸ガスの流量を低〈抑え つつ p H値によりガス流量を切り換える必要があり、 製造時に時間がかかる上に 工程が煩雑となる。 However, according to the “liquid-gas” method that is currently widely used in industry, the short diameter of primary particles with good dispersibility is 0.1 to 0.5 m, and the average length of primary particles is 0.1 to 0.5 m. The production technology of calcium carbonate with 圣 of 0.15 to 1.5 yum and aspect ratio of 1.5 to 3.0 has not been established. Such calcium carbonate has various properties such as coating pigments and internal additives for papermaking, which require highly controlled particle size, shape, and particle size distribution, and anti-blocking fillers for magnetic tape. It is suitable for improvement and an inexpensive manufacturing method is desired. To solve this problem, a method of adding a seed crystal serving as a nucleus to a calcium hydroxide slurry serving as a growth medium or a partially carbonated calcium hydroxide slurry has been disclosed in Japanese Patent Publication No. 7-53003. And Japanese Patent Publication No. 3-191658, but since the preparation of the seed crystal is a separate process and involves controlling the gas flow rate, the whole process becomes complicated. There is a problem. In addition, a method is known in which carbonation is partially performed under conditions that the pH value does not drop by more than 0.2 to form plate-like basic carbonated calcium carbonate, and then carbonation is performed until the reaction is completed. No. 05. However, it is necessary to switch the gas flow rate depending on the pH value while keeping the flow rate of the carbon dioxide gas low, which takes time during production and complicates the process.
さらに、 一部炭酸化された水酸化カルシウムスラリーを湿式摩碎後、 二次水酸 化カルシウムスラリーを添加し炭酸化を完結させる方法が特開平 5— 2 2 1 6 3 4号公報に記載されているが、 一部炭酸化を行なった後にサンドグラインダーで 湿式摩砕しているために、 やはり工程全体が煩雑になってしまう。  Further, a method of wet milling a partially carbonated calcium hydroxide slurry and then adding a secondary calcium hydroxide slurry to complete the carbonation is described in Japanese Patent Application Laid-Open No. H5-2221634. However, after partial carbonation, wet grinding with a sand grinder also complicates the entire process.
以上の化合法は生成する炭酸力ルシゥムが立方体なし、し菱面体であるため粒子 が重なりやすく、 製紙用塗工顔料等に用いた場合には塗工紙表面の平滑性、 光沢 等も向上し難い。  In the above compounding method, the carbonic acid produced does not have a cubic shape and is rhombohedral, so the particles tend to overlap, and when used as a coating pigment for papermaking, the surface smoothness and gloss of the coated paper are also improved. hard.
—方、 紡鍾状炭酸カルシウムを得る方法が、 特公昭 5 4— 2 8 3 9 9号、 特開 平 6— 5 6 4 2 2号及び特公平 8— 1 8 8 2 7号の各公報に記載されているが、 これも種晶なるものを調製し添加したり、 原料となる水酸化カルシウムスラリー を湿式摩碎するなど工程が煩雑なものとなっている。  —Methods of obtaining spun calcium carbonate are disclosed in Japanese Patent Publication No. 54-2839, Japanese Patent Application Laid-Open No. Hei 6-56492 and Japanese Patent Publication No. Hei 8-18827. However, the steps are also complicated, such as preparation and addition of seed crystals, and wet milling of a calcium hydroxide slurry as a raw material.
紡鍾状炭酸カルシウムは、 その形状故に粒子の角の破損が起きやすい。 これは 例えば製紙用塗工顔料等に用いた場合、 塗工紙の表面強度を低下させる可能性が あり、 磁気テープ用アンチブロッキングフィラーに用いた場合には粉発生によつ てドロップアウトの原因となる可能性がある。  Spindle-shaped calcium carbonate is susceptible to particle corner damage due to its shape. This may reduce the surface strength of the coated paper when used in coating pigments for papermaking, for example, and may cause dropout due to powder generation when used in anti-blocking fillers for magnetic tape. It is possible that
よって本発明の目的は、 分散性の良い 1次粒子平均短 ί圣 0 . 1〜0 . 5 u m、 1次粒子平均長径が 0 . 1 5〜1 . 5 At m及びアスペクト比が 1 . 5〜3 . 0の 炭酸力ルシゥ厶及びそのような炭酸力ルシゥ厶を簡便且つ安価に得ることのでき る炭酸カルシウムの製造方法を提供することにある。 発明の開示  Therefore, an object of the present invention is to provide a primary particle having a good average dispersibility of 0.1 to 0.5 μm, a primary particle average major axis of 0.1 to 1.5 Atm, and an aspect ratio of 1.5. It is an object of the present invention to provide a carbonated calcium carbonate of about 3.0 and a method for producing calcium carbonate by which such a carbonated calcium can be obtained easily and inexpensively. Disclosure of the invention
上記目的を達成するために本発明は、 水酸化カルシウムと炭酸ガスとの反応に よって分散性の優れた炭酸カルシウムを生成せしめるために、 カルシウムイオン 及び炭酸イオンとヒドロキシル基を有する有機化合物とが共存するように前記有 機化合物を添加して炭酸カルシゥムの製造方法を構成した。 In order to achieve the above object, the present invention provides a method for producing calcium carbonate having excellent dispersibility by reacting calcium hydroxide and carbon dioxide gas, wherein calcium ions and carbonate ions coexist with an organic compound having a hydroxyl group. To have The method for producing calcium carbonate was constituted by adding organic compounds.
本発明によると、 ヒドロキシル基を有する有機化合物は、 炭酸化の開始前ある いは開始後に添加され、 炭酸化反応開始後炭酸化率が約 2 0 %になるまでに所定 量の全量を添加するのが好ましい。 有機化合物は、 炭酸化反応の開始前に生石灰 または消石灰の粉体原料に混練し、 あるいは消化水に滴下する。 その他ミキサー 内での粉体原料への吹きつけや、 水酸化カルシウムスラリ一に滴下することによ り添加される。  According to the present invention, the organic compound having a hydroxyl group is added before or after the start of carbonation, and after the start of the carbonation reaction, a predetermined amount of the total amount is added until the carbonation rate becomes about 20%. Is preferred. The organic compound is kneaded with the powdered lime or slaked lime raw material before the start of the carbonation reaction, or added dropwise to digested water. In addition, it is added by spraying powder material in a mixer or by dripping it into calcium hydroxide slurry.
有機化合物は、 原料となるカルシウム源の酸化カルシウム （C a O ) 換算 1 0 0重量部に対して、 1 0〜2 0 0重量部を添加する。 1 0重量部以下では、 粒子 形状が立方状に近くなり、 所望の形状の米粒状、 俵状または角が取れた円柱状炭 酸力ルシゥム粒子が得られず、 2 0 0重量部以上になると効果が頭打ちとなり、 コスト的に有効でない。 好ましくは 5 0 ~ 1 8 0重量部を添加する。 この範囲に おいては 1次粒子のァスぺク 卜比が 2以上となるため製紙用顔料等とした場合に 平滑性等が向上しやすい優良な形状の粒子が得られる。  The organic compound is added in an amount of 10 to 200 parts by weight based on 100 parts by weight of calcium oxide (CaO) as a raw material calcium source. If the amount is less than 100 parts by weight, the particle shape becomes close to a cubic shape, and the desired shape of rice granules, bales, or rounded columnar carbonic acid calcium particles cannot be obtained. The effect leveled off and was not cost effective. Preferably 50 to 180 parts by weight are added. In this range, the primary particles have an aspect ratio of 2 or more, so that when used as a papermaking pigment or the like, particles having excellent shapes that can easily improve smoothness and the like can be obtained.
添加方法としては、 生石灰または消石灰粉体原料に二一ダ一により混練し、 ま たは消化水やスラリーを調製するために使用する水に滴下して溶解させる。 また ミキサー内におけるスプレーによる吹きつけでもよく、 炭酸化反応を開始する前 または炭酸化反応開始後炭酸化率が約 2 0 %になるまでに、 水酸化カルシウムス ラリーへ滴下してもよい。 しかし、 反応に際しカルシウムイオン及び炭酸イオン とヒドロキシル基を有する有機化合物が共存する状態が得られる限り、 添加方法 は特に限定されるものではない。  As an addition method, the raw lime or slaked lime powder raw material is kneaded in a kneading manner or dropped and dissolved in digested water or water used for preparing a slurry. It may be sprayed by a spray in a mixer, or may be dropped onto the calcium hydroxide slurry before the carbonation reaction is started or after the carbonation reaction is started until the carbonation ratio becomes about 20%. However, the addition method is not particularly limited as long as a state where calcium ions and carbonate ions and an organic compound having a hydroxyl group coexist during the reaction is obtained.
ここでヒドロキシル基を有する有機化合物は、 好ましくは分子量 6 0 0以下で あり、 エチレングリコール、 ジエチレングリコール、 トリエチレングリコール、 ポリエチレングリコール、 プロピレングリコール、 ポリプロピレングリコール及 びブチレングリコールのようなグリコール類；モノエタノ一ルァミン、 ジエタ ノールァミン及び卜リエタノ一ルァミンのようなェタノ一ルァミン類； グリセリ ン及びポリグリセリンのようなグリセリン類及びこれらの混合物が例示され、 好 ましくはプロピレングリコール及びエチレングリコールである。  Here, the organic compound having a hydroxyl group preferably has a molecular weight of 600 or less, and glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and butylene glycol; monoethanolamine And ethanolamines such as diethanolamine and triethanolamine; glycerins such as glycerin and polyglycerin, and mixtures thereof, and are preferably propylene glycol and ethylene glycol.
反応前、 水酸化カルシウムスラリーは、 好まし〈は濃度 3 ~ 2 0重量％、 温度 1 0〜2 0 °Cに調整される。 この水酸化カルシウムスラリーに炭酸ガスまたは炭 酸ガスを含む混合ガスを吹き込むことによって炭酸化率が実質的に 1 0 0 %にな るまで反応させる。 水酸化カルシウムの濃度が 3重量％未満では工業的生産性に 劣り、 2 0重量％を超えるとスラリー粘度が高くなつてハンドリング性が悪くな るため望ましくないことは、 従来の水酸化カルシウムの製造方法と同様である。 また、 反応開始前の温度が 1 0 °C未満では、 膠質カルサイ 卜が生成して凝集体と なりやすい一方、 2 0 °Cを超えると紡鍾状粒子や膠質カルサイ 卜の凝集体となつ てしまい、 均一かつ分散性の良いものが得られにく くなることもよく知られてい る。 Before the reaction, the calcium hydroxide slurry is preferably used. Adjusted to 10-20 ° C. By blowing carbon dioxide gas or a mixed gas containing carbon dioxide gas into the calcium hydroxide slurry, the reaction is performed until the carbonation ratio becomes substantially 100%. If the concentration of calcium hydroxide is less than 3% by weight, the industrial productivity is poor. If the concentration exceeds 20% by weight, the slurry viscosity increases and the handling properties deteriorate, which is undesirable. Same as the method. On the other hand, if the temperature before the start of the reaction is lower than 10 ° C, on the other hand, aggregates tend to form and form aggregates, whereas if the temperature is higher than 20 ° C, aggregates of spun particles and aggregates of aggregates form. It is also well known that it is difficult to obtain a uniform and well-dispersed product.
以上のような条件において、 カルシウムイオン及び炭酸イオンとヒドロキシル 基を有する有機化合物とを共存させて炭酸化反応を行なうと、 分散性の良い 1次 粒子平均短径 0 . 1〜 0 . 5 m、 1次粒子平均長径が 0 . 1 5〜 1 . 5 m及 びァスぺク 卜比が 1 . 5 ~ 3 . 0であり、 かつ形状が米粒状、 俵状または角が取 れた円柱状の炭酸カルシウムを得ることができる。 ただし、 ヒドロキシル基を有 する有機化合物は、 遅くとも水酸化カルシウムの炭酸化率が 2 0 %になるまでに 添加するのが好ましい。 炭酸化率が 2 0 %を超えてから有機化合物を添加すると、 炭酸ガス量の多い場合は生成粒子が膠質化してしまい、 少ない場合には生成粒子 が巨大化してしまい、 分散性の良し、ものを得ることが期待しがたい。  Under the above conditions, when the carbonation reaction is carried out in the presence of calcium ions and carbonate ions and an organic compound having a hydroxyl group, the primary particles having a good dispersibility have an average minor axis of 0.1 to 0.5 m, The average primary particle diameter is 0.15 to 1.5 m, the aspect ratio is 1.5 to 3.0, and the shape is rice grain, bale, or column with rounded corners. Calcium carbonate can be obtained. However, the organic compound having a hydroxyl group is preferably added at the latest until the carbonation rate of calcium hydroxide becomes 20%. If an organic compound is added after the carbonation rate exceeds 20%, the generated particles will be agglomerated if the amount of carbon dioxide gas is large, and if the amount is small, the generated particles will be enlarged, resulting in good dispersibility. It is hard to expect to get.
本発明によって得られた炭酸カルシウムは分散性が非常に良いため、 メディア ミル等による解砕を行なう必要はなく、 むしろ粒子の破損を防ぐために、 高濃度 スラリーとする場合には、 分散剤添加による短時間スラリ一化処理のみにとどめ ておくことが望ましい。  The calcium carbonate obtained by the present invention has a very good dispersibility, so it is not necessary to disintegrate it with a media mill or the like. It is desirable to keep the slurry treatment only for a short time.
本発明に係る米粒状炭酸カルシウムの製造方法によれば、 均一かつ分散性の良 い 1次粒子平均短径 0 . 1〜 0 . 5 m、 1次粒子平均長 ί圣が 0 . 1 5〜 1 . 5 m及びァスぺク卜比が 1 . 5〜3 . 0であり、 均一性が高く、 かつ形状が米粒 状、 俵状または角の取れた円柱状の炭酸カルシウムを得ることができる。 本発明 に係る米粒状炭酸カルシウムの製造方法は、 原料粉体、 消化水あるいは炭酸化率 が約 2 0 %以内の水酸化カルシウムスラリーに、 ヒドロキシル基を有する有機化 合物を混合または溶解させることにより添加するための装置のみを、 既存の設備 に付加するだけで実施可能であり、 簡便かつ安価に実現することができる。 また、 添加した有機化合物は炭酸カルシウムの結晶に取り込まれることはないため、 脱 水による分離水は有機化合物が溶解した状態であり、 消化水あるいは水酸化カル シゥムスラリ一を調製するための水として循環使用することで、 より安価に米粒 状、 俵状または角の取れた円柱状の炭酸カルシウムを製造することが可能となる c 本発明に係る炭酸力ルシゥムの製造方法により製造した炭酸力ルシゥムは分散 性に優れており、 高濃度スラリー化することが容易であるため、 特に製紙用に塗 ェ顔料や内添材等として利用した場合、 白色度、 光沢度、 平滑性、 不透明度等の 各種性能を向上させることができ、 磁気テープ用に使用した場合も高度に制御さ れたアンチブロッキングフイラ一としてエチレングリコール分散体等の形態にて 利用可能であり、 高い性能をもたらすことが期待できる。 また粒子の均一性が良 いため、 製紙用塗工顔料として使用した場合に光沢度が向上し、 またアンチブ ロッキングフイラ一とした場合にはァンチブロッキング性が向上する。 さらに米 粒状、 俵状または角の取れた円柱状の形状を有し、 粒子が重なりにくいので塗工 紙表面の平滑性、 光沢等が向上し、 また粒子の角が破損しにくいので、 塗工紙の 表面強度の低下やアンチプロッキングフイラ—に用いた場合の粉発生によるド ロップアゥ卜を防止することができる。 According to the method for producing rice granular calcium carbonate according to the present invention, the average primary particle minor axis of uniformity and good dispersibility is 0.1 to 0.5 m, and the average primary particle length is 0.15 to 0.15. 1.5 m and an aspect ratio of 1.5 to 3.0, it is possible to obtain calcium carbonate with high uniformity and rice grain, bale or square column shape. . In the method for producing rice granular calcium carbonate according to the present invention, an organic compound having a hydroxyl group is mixed or dissolved in raw material powder, digested water, or a calcium hydroxide slurry having a carbonation ratio of about 20% or less. Only the equipment for addition by existing equipment It can be implemented simply by adding to it, and can be realized simply and inexpensively. Also, since the added organic compound is not incorporated into the calcium carbonate crystals, the water separated by dewatering is in a state in which the organic compound is dissolved and is circulated as digestion water or water for preparing calcium hydroxide slurry. by using more cheaply rice grain-like, bale-like or corners rounded cylindrical carbonate force Rushiumu produced by the method for producing carbonic force Rushiumu according to c present invention made it possible to produce a calcium carbonate dispersion It is easy to make a high-concentration slurry, and when used as a paint or internal additive for papermaking, various properties such as whiteness, glossiness, smoothness, opacity, etc. When used for magnetic tape, highly controlled anti-blocking filter in the form of ethylene glycol dispersion etc. Is capable of use, it can be expected to lead to high performance. In addition, since the uniformity of the particles is good, the glossiness is improved when used as a coating pigment for papermaking, and the anti-blocking property is improved when used as an anti-blocking filler. Furthermore, it has a grain shape, bale shape, or rounded column shape, and coating is difficult because particles do not overlap, improving the smoothness and glossiness of the paper surface, and coating because the corners of the particles are not easily damaged. It is possible to prevent a drop in surface strength of paper and dropout due to generation of powder when used in an anti-blocking filter.
本発明に係る炭酸カルシウムの製造方法によれば、 分散性の良い 1次粒子平均 短佳 0 . 1 ~ 0 . 5 m , 1次粒子平均長怪が 0 . 1 5〜1 . 5 及びァスぺ ク卜比が 1 . 5〜3 . 0であり、 好まし〈は形状が米粒状、 俵状または角の取れ た円柱状である炭酸カルシウムを得ることができる。 図面の簡単な説明  According to the method for producing calcium carbonate according to the present invention, the primary particles having an average dispersibility of 0.1 to 0.5 m, the primary particles having an average length of 0.1 to 1.5 and 1.5% It is possible to obtain calcium carbonate having an energy ratio of 1.5 to 3.0 and preferably in the shape of rice grains, bale, or column with rounded corners. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 実施例 2により得られた炭酸カルシウムの電子顕微鏡写真 （ 1 0， 0 0 0倍） である。  FIG. 1 is an electron micrograph (× 10,000) of the calcium carbonate obtained in Example 2.
図 2は、 実施例 5により得られた炭酸カルシウムの電子顕微鏡写真 （ 1 0 , 0 0 0倍） である。 実施例 FIG. 2 is an electron micrograph (× 10,000) of the calcium carbonate obtained in Example 5. Example
以下本発明の実施例について説明する。 本発明は下記の実施例に限定されるも のではなく、 本発明の要旨の範囲内において適宜変形実施可能であることはいう までもない。  Hereinafter, embodiments of the present invention will be described. It is needless to say that the present invention is not limited to the following examples, and can be appropriately modified and implemented within the scope of the present invention.
(実施例 1 )  (Example 1)
自社製生石灰塊 （ J I S工業石灰 生石灰特号） を粒度 1 mm以下に粉砕して 酸化カルシウム原料とした。 この酸化カルシウム粉末 1 00重量部に対してェチ レングリコールを 30重量部添加混合し、 酸化カルシウムが水酸化カルシウムに 消化するのに必要な理論水量の 1. 5倍 （48重量部） の約 20°Cの水を攪拌混 合して消化、 熟成し、 水酸化カルシウム粉末を得た。 この水酸化カルシウム粉末 を用いスラリー濃度 7 %、 温度 1 5°Cとなるように調整し、 炭酸ガスを 4 L/m i n ■ k g-C a (OH) ' の流速で炭酸化率が実質的に 1 00%になるまで導 入することで反応を完結させ炭酸カルシウムを得た。  In-house manufactured lime mass (JIS industrial lime quick lime special number) was pulverized to a particle size of 1 mm or less and used as a calcium oxide raw material. To 100 parts by weight of this calcium oxide powder, 30 parts by weight of ethylene glycol is added and mixed, and about 1.5 times (48 parts by weight) the theoretical amount of water required for calcium oxide to be digested into calcium hydroxide. Water at 20 ° C was stirred and mixed, digested and aged to obtain calcium hydroxide powder. Using this calcium hydroxide powder, the slurry concentration was adjusted to 7%, and the temperature was adjusted to 15 ° C. The carbonation gas was adjusted to 4 L / min. The reaction was completed by introducing the solution until the concentration reached 00%, and calcium carbonate was obtained.
得られた炭酸カルシウムに対して電子顕微鏡観察を行なった結果、 1次粒子平 均短 ί圣が 0. 4;am、 1次粒子平均長径が 0. 6μπι、 レーザー回折法によるメ ジアン径が 1. O^mの均一かつ分散性良好な、 米粒状、 俵状または角の取れた 円柱状の粒子であることを確認した。 すなわち図 1の電子顕微鏡写真に示すよう に、 概形的には中央部が円柱状で両端部が半球状の粒子である。 もちろん、 円柱 及び半球はある程度の歪みを含んでいる。 円柱状の軸線方向の径が長径、 半径方 向の径が短径となる。  The obtained calcium carbonate was observed with an electron microscope. As a result, the average primary particle diameter 0 was 0.4; am, the average primary particle diameter was 0.6 μπι, and the median diameter determined by laser diffraction method was 1 It was confirmed that O ^ m was uniform and well-dispersed, and was rice-shaped, bale-shaped, or rounded cylindrical particles. That is, as shown in the electron micrograph of FIG. 1, the particles are roughly cylindrical at the center and hemispherical at both ends. Of course, cylinders and hemispheres contain some distortion. The diameter in the axial direction of the columnar shape is the major axis, and the diameter in the radial direction is the minor axis.
なお 1次粒子平均短径とは、 無作為に撮影した倍率 30, 000倍の電子顕微 鏡写真において 2本の対角線上の粒子に対して電子ノギスにて粒子の最も短い弦 (すなわち粒子の円柱状の半怪方向の径の長さ） を測定してこれを粒子の短径と し、 その平均値を求め 1次粒子平均短径とした。 同様に、 電子顕微鏡写真におい て 2本の対角線上の粒子の最も長い弦 （すなわち粒子の円柱状の軸線方向の径の 長さ） を測定してこれを粒子の長径とし、 その平均値を求め 1次粒子平均長 Sと した。 また、 レーザ一回折法によるメジアン径とは、 株式会社堀場製作所製レー ザ一回折式粒度分布測定装置 LA— 500により測定を行なつた値であり、 2次 凝集状態の粒子径を測定している。 メジアン径は、 1次粒子径に比較してこの値 が小さいほど分散性が良好であることを示す値である。 The average primary particle diameter is the shortest chord of the particle (i.e., the particle circle) of two diagonal particles in a random electron micrograph taken at 30,000 magnifications with an electronic caliper. The diameter of the column in the semi-monstrous direction) was measured and used as the minor axis of the particle. Similarly, in an electron micrograph, the longest chord of two diagonal particles (that is, the length of the particle in the axial direction of the column) is measured, and this is taken as the major axis of the particle. The average primary particle length S was used. The median diameter obtained by the laser diffraction method is a value measured by a laser diffraction particle size distribution analyzer LA-500 manufactured by Horiba Seisakusho Co., Ltd. I have. The median diameter is this value compared to the primary particle diameter. Is a value indicating that the smaller the value, the better the dispersibility.
(実施例 2)  (Example 2)
エチレングリコールを酸化カルシウム粉末 1 00重量部に対して 80重量部添 加混合した以外は実施例 1 と同様の過程によって炭酸カルシウムを得た。 電子顕 微鏡観察により、 得られた炭酸カルシウムが 1次粒子平均短径 0. 4 m、 1次 粒子平均長径 0. 8ytm、 レーザ一回折法によるメジアン ί圣が 1 . 2 mの均一 かつ分散性良好な米粒状粒子であることを確認した。 電子顕微鏡写真 （ 1 0, 0 00倍） を図 1として示す。  Calcium carbonate was obtained in the same manner as in Example 1 except that ethylene glycol was added and mixed with 100 parts by weight of calcium oxide powder and 80 parts by weight. Observed by electron microscopy, the resulting calcium carbonate was uniform and dispersed with an average primary particle diameter of 0.4 m, an average primary particle diameter of 0.8 ytm, and a median に よ る of 1.2 m by laser diffraction method. It was confirmed that the particles were rice grains having good properties. An electron micrograph (10,000 magnification) is shown in FIG.
(実施例 3)  (Example 3)
エチレングリコールを酸化カルシウム粉末 1 00重量部に対して 1 50重量部 添加混合した以外は実施例 1 と同様の過程によって炭酸カルシウムを得た。 電子 顕微鏡観察により、 得られた炭酸力ルシゥムが 1次粒子平均短佳 0. 4 m、 1 次粒子平均長径 1 . 0 m、 レーザ—回折法によるメジアン怪が 1 . の均 一かつ分散性良好な米粒状粒子であることを確認した。  Calcium carbonate was obtained in the same manner as in Example 1, except that ethylene glycol was added and mixed with 150 parts by weight based on 100 parts by weight of the calcium oxide powder. According to electron microscopic observation, the obtained carbonic acid lumps have a uniform primary particle average of 0.4 m, average primary particle length of 1.0 m, and a median suspicion of 1. with laser-diffraction method and good dispersibility. It was confirmed that the rice grains were fine.
(実施例 4)  (Example 4)
実施例 1 ~3における炭酸ガスの流速を 1 O L/m i n · k g-Ca (OH) ;と した以外は同様の過程で炭酸化反応を行なった結果、 炭酸カルシウムを得た。 電 子顕微鏡で観察した結果を以下に列記する。 なお図 2に実施例 5についての図 1 と同様の図を示す。 A carbonation reaction was carried out in the same manner as in Examples 1 to 3, except that the flow rate of the carbon dioxide gas was 1 OL / min · kg-Ca (OH) ; As a result, calcium carbonate was obtained. The results observed with an electron microscope are listed below. FIG. 2 shows a diagram similar to FIG. 1 for the fifth embodiment.
実施例 4 ： 1次粒子平均短径 0. 2 m. 1次粒子平均長径 0. 3Atm、 レー ザ—回折法によるメジアン径が 0. 6 mの均一且つ分散性良好な米粒状粒子 実施例 5 ： 1次粒子平均短径 0. 2 m, 1次粒子平均長径 0. 4yam、 レー ザ—回折法によるメジアン ί圣が 0 · 6 Aimの均一且つ分散性良好な米粒状粒子 実施例 6 ： 1次粒子平均短径 0. 2yam、 1次粒子平均長径 0. 5 m、 レー ザ—回折法によるメジアン径が 0. 8 mの均一且つ分散性良好な米粒状粒子 (実施例 7) Example 4: Average particle diameter of primary particles: 0.2 m. Average particle diameter of primary particles: 0.3 Atm, and uniform and good dispersibility rice granular particles having a median diameter of 0.6 m by a laser diffraction method. : Average particle diameter of primary particles: 0.2 m, average particle diameter of primary particles: 0.4 yam, uniform and good dispersibility rice granular particles having a median に よ る by laser diffraction method of 0.6 Aim Example 6: 1 Uniform and well-dispersed rice granule particles with average secondary minor particle diameter of 0.2 yam, primary primary particle average major diameter of 0.5 m, and laser-diffraction median diameter of 0.8 m (Example 7)
自社製消石灰粉 （ J I S工業用消石灰 消石灰特号） の酸化カルシウム換算 1 00重量部 （消石灰粉 1 32重量部） に対してプロピレングリコールを 30重量 部添加混合し、 これに濃度 7重量％となるように水を加え、 温度を 1 5°Cに調整 して水酸化カルシウムスラリーを得た。 ついで実施例 1 と同様にして炭酸化反応 を行なった結果、 炭酸カルシウムを得た。 電子顕微鏡観察により、 得られた炭酸 酸力ルシゥムが 1次粒子平均短径 0 . 4 μ m、 1次粒子平均長 ί圣が 0 . 6 At m、 レーザー回折法によるメジアン径が 1 . 0 mの均一かつ分散性良好な米粒状粒 子であることを確認した。 30 parts by weight of propylene glycol is added to 100 parts by weight of calcium oxide equivalent (132 parts by weight of slaked lime powder) of in-house manufactured slaked lime powder (JIS industrial slaked lime slaked lime special number), and the concentration becomes 7% by weight. And adjust the temperature to 15 ° C Thus, a calcium hydroxide slurry was obtained. Then, a carbonation reaction was carried out in the same manner as in Example 1 to obtain calcium carbonate. According to electron microscopic observation, the obtained acid carbonate had a primary particle average minor diameter of 0.4 μm, a primary particle average length of 0.6 Atm, and a median diameter determined by laser diffraction method of 1.0 m. It was confirmed that the rice grains were uniform and had good dispersibility.
(実施例 8 )  (Example 8)
実施例 7で用いた消石灰粉の酸化カルシウム換算 1 0 0重量部に対して 8 0重 量部のプロピレングリコールを予め使用水中に溶解させておき、 これに濃度が 7 重量％となるように消石灰粉を添加し、 さらに温度が 1 5 °Cとなるように調整し て水酸化カルシウムスラリーを得た。 電子顕微鏡観察により、 得られた炭酸カル シゥムが 1次粒子平均短径が 0 . 4 m、 1次粒子平均長 ί圣が 0 . 8 At m、 レー ザ—回折法によるメジアン径が 1 . 3 mの均一かつ分散性良好な米粒状粒子で あることを確認した。  80 parts by weight of propylene glycol was previously dissolved in use water with respect to 100 parts by weight of calcium oxide of the slaked lime powder used in Example 7, and the concentration of slaked lime was adjusted to 7% by weight. Powder was added, and the temperature was adjusted to 15 ° C. to obtain a calcium hydroxide slurry. According to electron microscopic observation, the obtained calcium carbonate has a primary particle average minor axis of 0.4 m, a primary particle average length of 0.8 Atm, and a median diameter by laser diffraction method of 1.3. It was confirmed that the particles were rice granules having uniform m and good dispersibility.
(実施例 9〜1 0 )  (Examples 9 to 10)
実施例 7〜8において炭酸ガスの流速を 1 0 L /m i n · k g -C a ( O H ) とした以外は同様の過程で炭酸化反応を行なつた結果、 炭酸力ルシゥムを得た。 電子顕微鏡で観察した結果を以下に列記する。  A carbonation reaction was carried out in the same process as in Examples 7 to 8 except that the flow rate of the carbon dioxide gas was changed to 10 L / min · kg-Ca (OH), thereby obtaining carbon dioxide. The results observed with an electron microscope are listed below.
実施例 9 ： 1次粒子平均短径 0 . 2 m、 1次粒子平均長径 0 . 3 m、 レー ザ—回折法によるメジァン径が 0 . 6 μ mの均一且つ分散性良好な米粒状粒子 実施例 1 0 ： 1次粒子平均短径 0 . 2 m、 1次粒子平均長径 0 . 4 μ πι、 レ— ザ一回折法によるメジァン径が 0 . 6 mの均一且つ分散性良好な米粒状粒子 (比較例 1〜4 ) Example 9: Uniform and well-dispersed rice granular particles having a primary particle average minor axis of 0.2 m, an average primary particle major axis of 0.3 m, and a median diameter of 0.6 μm as measured by laser diffraction. Example 10: Uniform and well-dispersed rice granular particles having an average primary particle diameter of 0.2 m, an average primary particle diameter of 0.4 μπι, and a median diameter of 0.6 m by laser diffraction method. (Comparative Examples 1-4)
実施例 1、 4、 7、 9においてエチレングリコールまたはプロピレングリコ一 ルの添加量を 5重量％とした以外は同様の過程で炭酸化反応を行ない、 得られた 炭酸カルシウムについて電子顕微鏡で観察した結果を以下に列記する。  Carbonation reaction was performed in the same process as in Examples 1, 4, 7, and 9 except that the added amount of ethylene glycol or propylene glycol was 5% by weight, and the obtained calcium carbonate was observed with an electron microscope. Are listed below.
比較例 1 ： 1次粒子平均粒子径 0 . 5 m、 レーザ—回折法によるメジアン佳が 1 . 1 mの均一且つ分散性良好な立方状粒子 Comparative Example 1: Uniform and well-dispersed cubic particles having an average primary particle diameter of 0.5 m and a median diameter of 1.1 m as measured by a laser diffraction method.
なお、 1次粒子平均粒子 ί圣とは、 無作為に撮影した倍率 3 0 , 0 0 0倍の電子 顕微鏡写真において 2本の対角線上の粒子に対して電子ノギスにて粒子の一変を 測定してこれを粒子径とし、 その平均値を求め 1次粒子平均粒子径とした。 比較例 2 ： 1次平均粒子怪 0. 2/am、 レーザ—回折法によるメジアン ί圣が 0.In addition, the average primary particle 、 refers to the change of the particle with an electronic caliper for two diagonal particles in an electron micrograph taken at a magnification of 30,000 and photographed at random. This was measured and defined as the particle diameter, and the average value was determined as the primary particle average particle diameter. Comparative Example 2: First-order average particle size 0.2 / am, median ί 圣 by laser-diffraction method was 0.
7 mの均一且つ分散性良好な立方状粒子 7 m uniform and well-dispersed cubic particles
比較例 3 ： 1次平均粒子径 0. 4 ΠΊ、 レーザ一回折法によるメジアン径が 0.Comparative Example 3: Primary mean particle diameter 0.4 mm, median diameter determined by laser diffraction method was 0.4 mm.
8 mの均一且つ分散性良好な立方状粒子 8 m uniform and well-dispersed cubic particles
比較例 4 ： 1次平均粒子径 0. 2 xm、 レーザ—回折法によるメジアン ί圣が 0. 6 mの均一且つ分散性良好な立方状粒子 Comparative Example 4: Uniform and well-dispersed cubic particles having a primary average particle diameter of 0.2 xm and a median に よ る by laser-diffraction method of 0.6 m
(比較例 5〜8)  (Comparative Examples 5 to 8)
実施例 1、 4、 7、 9においてエチレングリコールまたはプロピレングリコ一 ルを添加しない以外は同様の過程で炭酸化反応を行ない、 得られた炭酸力ルシゥ ムについて電子顕微鏡で観察した結果を以下に列記する。  A carbonation reaction was carried out in the same manner as in Examples 1, 4, 7, and 9 except that ethylene glycol or propylene glycol was not added, and the results obtained by observing the obtained carbonated calcium carbonate with an electron microscope are listed below. I do.
比較例 5 ： 1次平均粒子径が 1 Atmを超え、 レーザ—回折法によるメジアン径が 3. の多面体粒子 Comparative Example 5: Polyhedral particles having a primary average particle size of more than 1 Atm and a median size of 3 by laser-diffraction
比較例 6 ： 1次粒子平均粒子怪が 0. l Atm未満で、 レーザ一回折法によるメジ アン径が 4. 3 At mの膠質化した粒子の凝集体 Comparative Example 6: Aggregate of aggregated particles having a primary particle average particle size of less than 0.1 Atm and a median diameter of 4.3 Atm by laser diffraction method
比較例 7 ： 1次粒子平均粒子 が 1 Atmを超え、 レーザ—回折法によるメジアン ί圣が 3. 1 mの多面体粒子 Comparative Example 7: Polyhedral particle with primary particle average particle exceeding 1 Atm and median に よ る 3.1 m by laser-diffraction method
比較例 8 ： 1次粒子平均粒子径が 0. 1 Aim未満で、 レーザー回折法によるメジ ァン ί圣が 4. 0 mの膠質化した粒子の凝集体 Comparative Example 8: Aggregate of aggregated particles having an average primary particle size of less than 0.1 Aim and a median of 4.0 m by laser diffraction method
表 1は上記実施例及び比較例の合成条件と結果をまとめたものである。 Table 1 summarizes the synthesis conditions and results of the above Examples and Comparative Examples.
s加割 S加方法 s加量 炭義ガス St量 ΐ ί¾«子 β »状 s Addition S addition method s addition Charcoal gas St amount 状 ί¾ «child β»
(tHini)  (tHini)
工 ンク'リコ- 生石灰に通 30 4 il. .4«mk 1. 0 米 ttttNK 'Rico-quick lime through 30 4 il. .4 «m k 1.0 rice tttt
ΆΛΛΐίιη ΆΛΛΐίιη
ifレンク'リコ- 生石灰に ΪΒ会 6 4 1. 1 Λ方状 比 MM 5 一 ― ― 4 Ι¾>ΐ Βΐη 3. 4 多面体 エチレンク'リコ- 1 生石灰に》会 80 4 1. Z 米 tt状 レンク'リコ- 1 生石灰に通合 160 4 Ilfi.4«m. 1. 3 米 tt状
Figure imgf000012_0001
if renku 'rico-quick lime 6 4 1. 1 Orthogonal ratio MM 5 1 ― ― 4 Ι¾> ΐ Βΐη 3.4 polyhedral ethylenek' riko-1 quick lime tied 80 4 1.Z rice tt-shaped lentk 'Rico-1 Quick lime pass 160 4 Ilfi.4 «m. 1.3 rice tt-shaped
Figure imgf000012_0001
«1ΙΜ エチレンク'リコ- 1 生石灰に；厘合 30 10 Ιΐ£.2«πν Q. β«1ΙΜ Ethyleneclicone-1 to quicklime; Rin 30 30 Ιΐ £ .2« πν Q. β
Figure imgf000012_0002
Figure imgf000012_0002
比 «M 2 I レンク'リコ- 1 生石灰に 6 10 種 ¾0·2*ιη 0. 7 立 TTtt 比 Mff fl ― 一 - 10 li*<0.1 «m 4. 3 nm レンク *リコ- * 生石灰に通 80 10 ll«.2«m 0. Θ 米 伏 Ratio «M 2 I Lenk 'Rico-1 6 10 species for quick lime ¾0.2 * ιη 0.7 Standing TTtt ratio Mff fl ― 1-10 li * <0.1« m 4.3 nm Lenk * Rico-* Quick lime 80 10 ll «.2« m 0.
WtM6 エチレンク'リコ- 1» 生石灰に通合 I SO 10 Il.«.2frrv 0. β フ'ロビレンゲリ： >— 4 消 に》合 30 4 Il«.4|nv 1 . 0 ゲロビレンゲリ 3- JU 消石灰に通含 6 4 0. B 立方伏 比《W! 7 4 3. 7 多舊体 me フ '。ビレンク 調鏊水に 80 4 fffl.4«lm. 1 . 2 来 tttt フ' 'レンゲリコー 消石灰に »合 30 10 ilfi.2«nv 0. β 来 tttt フ' Bt'レンゲリ 生石灰に通合 5 10 0. β 立方状 比 10 Wf:く 0.1 dm 4. 0 nm 例 10 フ ビレンク 'リ 3— 調整水に》台 80 10 Ilfi.2nm. α. β 来 (応用例） WtM6 Ethylene liquorite-1 Combined with quick lime I SO 10 Il. «. 2frrv 0. β Frovilengeri:> —4 ext. 30 4 Il« .4 | nv 1.0 Gerovirengeri 3-JU hydrated lime 6 4 0. B Cubic ratio <W! 7 4 3. 7 Bireng water for preparation 80 4 fffl.4 «lm. 1.2 coming tttt f 'Lengericho to slaked lime» 30 30 ilfi.2 «nv 0. β coming tttt f' Bt 'lengeri for quick lime 5 10 0.β cubic ratio 10 Wf: about 0.1 dm 4.0 nm Example 10 (Application example)
実施例 1、 4及び比較例 1、 5で得た炭酸カルシウムをフィルタ—プレスによ り脱水処理を行ない、 固形分濃度 65. 5重量％のケーキを得た。 次いでこの脱 水ケーキに固形分換算で 0. 6重量％の分散剤を添加して分散処理を行ない、 固 形分濃度 65. 0重量％の高濃度炭酸カルシウムスラリーとした。 このスラリー を塗工用顔料として用い、 その炭酸カルシウム 1 00重量部にスターチ （日本食 品加工 #4600) 6重量部、 ラテックス （日本合成ゴム No. 1 02) 1 2 重量部、 印刷適性向上剤 （東邦化学 ゥ Iッ 卜マスタ— GT360) 0. 75重 量部、 耐水化剤 （住友化学 スミレーズレジン 61 3) 0. 35重量部と水を加 え、 固形分濃度 50. 0重量％の顔料組成物を調製し、 65 g/m; の原紙に片 面あたり塗工量が 1 5 g/m; となるように手塗りロッ ドで塗工を行ない、 スー パーカレンダ一処理を 2回行なった後に塗工紙の物性評価を行なった。 The calcium carbonate obtained in Examples 1 and 4 and Comparative Examples 1 and 5 was dehydrated by a filter press to obtain a cake having a solid content of 65.5% by weight. Next, 0.6% by weight of a dispersant in terms of solid content was added to the dewatered cake to carry out a dispersion treatment to obtain a high-concentration calcium carbonate slurry having a solid content concentration of 65.0% by weight. This slurry was used as a coating pigment, and 100 parts by weight of calcium carbonate was added to 6 parts by weight of starch (Japanese food processing # 4600), 12 parts by weight of latex (Nippon Synthetic Rubber No. 102), and 12 parts by weight of a printability improver ( Toho Chemical Co., Ltd.-Ito Master GT360) 0.75 parts by weight, water-resistant agent (Sumitomo Chemical Sumireze Resin 61 3) 0.35 parts by weight, water and a pigment with a solid concentration of 50.0% by weight The composition was prepared and coated on a 65 g / m ; base paper with a hand-painted rod so that the coating amount per side was 15 g / m ; and the super calendering was performed twice. After that, the physical properties of the coated paper were evaluated.
表 2は、 応用例における塗工紙物性をまとめたものである。 表 2  Table 2 summarizes the physical properties of coated paper in application examples. Table 2
Figure imgf000013_0001
測定方法
Figure imgf000013_0001
Measuring method
光沢度： J I S P 81 42にて測定、 数値が大きいぼど高光沢 Glossiness: Measured according to JISP 81 42, large numerical value, high gloss
平滑度： Perker print-surf roughness&porosity tester MODEL PPS78 DIGITAL Smoothness: Perker print-surf roughness & porosity tester MODEL PPS78 DIGITAL
H20kg/cm2 にて測定、 1 0点平均、 数値が小さいほど良 Measured at H20kg / cm 2, 1 0-point average, smaller value good
不透明度： J I S P 81 38にて測定、 数値が大きいほど良 Opacity: Measured by JISP 81 38, the larger the value, the better
ハンター白色度： J I S P 81 23にて測定 よって実施例 1、 4で得られた炭酸カルシウムスラリーを用いた塗工紙におけ る物性は、 比較例 1、 5で得られたそれと比較して全体的に優れているというこ とができる。 Hunter whiteness: Measured by JISP 81 23 Therefore, it can be said that the physical properties of the coated paper using the calcium carbonate slurries obtained in Examples 1 and 4 are generally superior to those obtained in Comparative Examples 1 and 5.

Claims

請 求 の 範 囲 The scope of the claims
1 . 1次粒子平均短径が 0. 1〜0. 5Aim、 1次粒子平均長径が 0. 1 5~1.Primary particle average minor axis is 0.1 ~ 0.5Aim, primary particle average major axis is 0.15 ~
1 . 5Atm及びアスペク ト比が 1 . 5〜3. 0である炭酸カルシウム。 Calcium carbonate with 1.5 Atm and aspect ratio of 1.5 to 3.0.
2. 形状が米粒状、 俵状または角の取れた円柱状である請求項 1に記載の炭酸 カルシウム。  2. The calcium carbonate according to claim 1, wherein the shape is a rice grain, a bale, or a rounded column.
3. 水酸化カルシウムと炭酸ガスの反応によって炭酸カルシウムを製造する方 法において、  3. In the method of producing calcium carbonate by the reaction of calcium hydroxide and carbon dioxide gas,
原料となるカルシウム源の酸化カルシウム換算 1 00重量部に対して、 ヒドロ キシル基を有する有機化合物を 20〜200重量部の割合で添加し、 炭酸化反応 を行なうことを特徴とする炭酸カルシウムの製造方法。  Producing calcium carbonate, wherein an organic compound having a hydroxyl group is added at a ratio of 20 to 200 parts by weight to 100 parts by weight of calcium oxide as a raw material calcium source, and a carbonation reaction is carried out. Method.
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JP2013079192A (en) * 2005-04-11 2013-05-02 Omya Development Ag Precipitated calcium carbonate pigment, especially applicable as coating for paper designed for ink-jet printing
JP2012224535A (en) * 2011-04-08 2012-11-15 Oji Holdings Corp Light calcium carbonate-containing slurry for coating, and coated paper using the same
WO2021029351A1 (en) * 2019-08-15 2021-02-18 日本製紙株式会社 Paper filled with light calcium carbonate
JPWO2021029351A1 (en) * 2019-08-15 2021-11-04 日本製紙株式会社 Paper with light calcium carbonate inside
JP7029028B2 (en) 2019-08-15 2022-03-02 日本製紙株式会社 Paper with light calcium carbonate inside
CN111874933A (en) * 2020-08-14 2020-11-03 王权广 Quick preparation process of rice-grain light calcium carbonate

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