JP2012513365A - Production method of nearly spherical barium sulfate by sulfuric acid method and its use on copper foil substrate - Google Patents

Production method of nearly spherical barium sulfate by sulfuric acid method and its use on copper foil substrate Download PDF

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JP2012513365A
JP2012513365A JP2011542660A JP2011542660A JP2012513365A JP 2012513365 A JP2012513365 A JP 2012513365A JP 2011542660 A JP2011542660 A JP 2011542660A JP 2011542660 A JP2011542660 A JP 2011542660A JP 2012513365 A JP2012513365 A JP 2012513365A
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▲華▼▲東▼
▲劉▼正涛
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重慶科昌科技有限公司
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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
    • C01F11/46—Sulfates
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    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution

Abstract

硫酸バリウム粒子の形態が不定形であり、粒径分布が広いという問題を解決するために、本発明は、硫酸法によるほぼ球形硫酸バリウム製造方法を提供する。具体的に、（ａ）バライトを石炭で焼成して硫化バリウムを生成する工程と、（ｂ）硫化バリウムを水で溶解して濃度が７０〜１３０ｇ／Ｌの硫化バリウム溶液を調製し、硫化バリウム溶液の温度を４５〜８５℃に調節し、硫化バリウムの添加速度が５００Ｌ／ｈ〜７０００Ｌ／ｈとなる状態で該硫化バリウム溶液と過量の硫酸を連続反応器に同時に添加し、反応させて、硫酸バリウムスラリーと硫化水素とを生成する工程と、（ｃ）該硫酸バリウムスラリーに熱空気を流れ込ませて硫化水素を排出させる工程と、（ｄ）硫酸バリウムスラリーを脱水、洗浄、乾燥、粉砕してほぼ球形の硫酸バリウム製品を得る工程とを含む。該製造方法によれば、球形又は球形に近似し、かつ連続的で調整可能な粒径分布の硫酸バリウムが得られる。また、本発明は、ほぼ球形硫酸バリウムをフィラーとした銅箔基板における使用を更に公開している。
【選択図】 図１In order to solve the problem that the shape of the barium sulfate particles is irregular and the particle size distribution is wide, the present invention provides a method for producing a substantially spherical barium sulfate by the sulfuric acid method. Specifically, (a) barite is calcined with coal to produce barium sulfide, (b) barium sulfide is dissolved in water to prepare a barium sulfide solution having a concentration of 70 to 130 g / L, and barium sulfide is produced. The temperature of the solution is adjusted to 45 to 85 ° C., and the barium sulfide solution and an excessive amount of sulfuric acid are simultaneously added to the continuous reactor in a state where the addition rate of barium sulfide is 500 L / h to 7000 L / h, and reacted. A step of generating a barium sulfate slurry and hydrogen sulfide; (c) a step of flowing hot air into the barium sulfate slurry to discharge hydrogen sulfide; and (d) dehydrating, washing, drying and pulverizing the barium sulfate slurry. And obtaining a substantially spherical barium sulfate product. According to this production method, barium sulfate having a spherical shape or a spherical shape and having a continuous and adjustable particle size distribution can be obtained. The present invention further discloses use in a copper foil substrate with substantially spherical barium sulfate as a filler.
[Selection] Figure 1

Description

本発明は、硫酸バリウムに関し、詳しくは、硫酸法による硫酸バリウムの製造方法に関する。   The present invention relates to barium sulfate, and more particularly to a method for producing barium sulfate by a sulfuric acid method.

通常の硫酸バリウムは、ゴム、プラスチック、インク、塗料、製紙など多くの業界に広く用いられている。ナノ硫酸バリウムは、量子効果、サイズ効果、界面効果など重要な構造特性を持ち、その物理特性が通常の材料とは異なり、新規な高級機能性充填材料であり、ゴム、プラスチック、インク、塗料、製紙など多くの工業分野に大いに見込まれるのみならず、医学、セラミック、複合材料などの面においても、更に大いに見込まれている。   Ordinary barium sulfate is widely used in many industries such as rubber, plastic, ink, paint and papermaking. Nano-barium sulfate has important structural characteristics such as quantum effect, size effect, and interface effect, and its physical properties are different from ordinary materials, and it is a new high-class functional filling material, such as rubber, plastic, ink, paint, Not only is it highly expected in many industrial fields such as papermaking, but it is also highly anticipated in the fields of medicine, ceramics, and composite materials.

従来技術では、硫酸バリウムの製造方法は、主として天然鉱石加工製粉、芒硝法化学合成及び硫酸法合成などの方法がある。天然鉱石製粉による粒子は、粒径が大きく、かつ粒径の分布が広い。芒硝法による硫酸バリウムには硫化ナトリウムが含まれており、かつ粒径の分布が比較的に広く、その粒子の形態が不定形であることから、一部の業界では、その応用が制限されている。   In the prior art, there are mainly methods for producing barium sulfate such as natural ore processing and milling, mirabilite chemical synthesis and sulfuric acid method synthesis. Particles from natural ore milling have a large particle size and a wide particle size distribution. Barium sulfate by the mirabilite method contains sodium sulfide, has a relatively wide particle size distribution, and the shape of the particles is irregular, which limits the application in some industries. Yes.

特許文献１では、「バライト硫酸法による精製硫酸バリウムの生産工程」が開示されており、特許文献１では、硫酸法を利用して精製硫酸バリウム製品を製造しているが、硫化バリウム溶液に直接的に硫酸を添加して沈殿硫酸バリウムスラリーを生成しているため、硫酸バリウム粒子の形態が不定形であり、且つ、粒径の分布が広いという問題も存在する。   Patent Document 1 discloses “a production process of purified barium sulfate by the barite sulfate method”, and Patent Document 1 manufactures a purified barium sulfate product using the sulfuric acid method. In addition, since sulfuric acid is added to produce a precipitated barium sulfate slurry, there are problems that the form of the barium sulfate particles is indeterminate and the particle size distribution is wide.

中国特許出願公開第１０１１３４５９６号明細書Chinese Patent Application No. 10113596

本発明は、硫酸バリウム粒子の形態が不定形であり、かつ粒径分布が広いという問題を解決するために、ほぼ球形の硫酸バリウムを生産する硫酸法による硫酸バリウムの製造方法を提供することを一つの目的とする。   The present invention provides a method for producing barium sulfate by a sulfuric acid method for producing substantially spherical barium sulfate in order to solve the problem that the shape of barium sulfate particles is irregular and has a wide particle size distribution. One purpose.

上記目的を実現するための本発明の技術案は、硫酸法によるほぼ球形硫酸バリウムの製造方法であって、（ａ）バライトを石炭で焼成して硫化バリウムを生成する工程を含み、それより肝心なのは、
（ｂ）硫化バリウムを水で溶解して濃度が７０〜１３０ｇ／Ｌの硫化バリウム溶液を調製し、該硫化バリウム溶液の温度を４５〜８５℃に調節し、硫化バリウム溶液の添加速度が５００Ｌ／ｈ〜７０００Ｌ／ｈとなる状態で、該硫化バリウム溶液と過量の硫酸を連続反応器に同時に添加し、反応させて、硫酸バリウムスラリーと硫化水素とを生成する工程と、
（ｃ）該硫酸バリウムスラリーに熱空気を流れ込ませて硫化水素を排出させる工程と、
（ｄ）工程（ｃ）の排気による脱気処理を経た硫酸バリウムスラリーを脱水、洗浄、乾燥、粉砕してほぼ球形硫酸バリウム製品を得る工程とを更に含むことを特徴とする。 The technical solution of the present invention for realizing the above object is a method for producing substantially spherical barium sulfate by the sulfuric acid method, and includes (a) a step of producing barium sulfide by calcining barite with coal. What is
(B) Barium sulfide is dissolved in water to prepare a barium sulfide solution having a concentration of 70 to 130 g / L, the temperature of the barium sulfide solution is adjusted to 45 to 85 ° C., and the addition rate of the barium sulfide solution is 500 L / a step of simultaneously adding and reacting the barium sulfide solution and an excessive amount of sulfuric acid to a continuous reactor in a state of h to 7000 L / h to produce a barium sulfate slurry and hydrogen sulfide;
(C) flowing hot air into the barium sulfate slurry to discharge hydrogen sulfide;
And (d) further comprising a step of dehydrating, washing, drying, and pulverizing the barium sulfate slurry that has been degassed by exhaust in step (c) to obtain a substantially spherical barium sulfate product.

本発明の好ましい実施形態として、前記工程（ｃ）において、流れ込ませる熱空気の風量が３０００〜７０００Ｍ３／ｈであり、温度が４５〜８０℃であり、脱気時間が１．５〜３ｈである。 As a preferred embodiment of the present invention, in the step (c), the flow rate of hot air to be introduced is 3000 to 7000 M 3 / h, the temperature is 45 to 80 ° C., and the degassing time is 1.5 to 3 h. is there.

本発明の別の好ましい実施形態として、前記工程（ｂ）において、硫酸バリウムスラリーに残される硫酸の濃度が０．５〜２５ｇ／Ｌとなるように制御する。   As another preferred embodiment of the present invention, in the step (b), the concentration of sulfuric acid remaining in the barium sulfate slurry is controlled to be 0.5 to 25 g / L.

本発明の別の好ましい実施形態として、前記工程（ｄ）において、洗浄を経た硫酸バリウムスラリーに珪酸ナトリウム又はアルミン酸ナトリウム又はカップリング剤を加えて１．５〜３ｈ反応した後、脱水、洗浄、乾燥、粉砕を経て硫酸バリウム製品を得る。   As another preferred embodiment of the present invention, in the step (d), sodium silicate, sodium aluminate or a coupling agent is added to the washed barium sulfate slurry and reacted for 1.5 to 3 hours, followed by dehydration, washing, Barium sulfate product is obtained through drying and grinding.

本発明の別の好ましい実施形態として、前記乾燥は、フラッシュ蒸発乾燥が用いられており、乾燥後のほぼ球形硫酸バリウム製品の含水量が０．２％未満である。   In another preferred embodiment of the present invention, the drying uses flash evaporation drying, and the water content of the substantially spherical barium sulfate product after drying is less than 0.2%.

本発明は、ほぼ球形の硫酸バリウムの銅箔基板における使用を提供することをもう一つの目的とする。   Another object of the present invention is to provide use of a substantially spherical barium sulfate in a copper foil substrate.

従来技術に比べて、本発明によれば、下記の有益な効果を奏する。   Compared to the prior art, the present invention has the following beneficial effects.

（１）本発明では、並流連続合成工程を経て球形又は球形に近似する硫酸バリウムを得たので、硫酸バリウムの応用範囲を更に広げた。
（２）本発明では、反応速度を制御することにより、硫酸バリウムの核形成と成長速度を制御し、サブミクロンレベルで、かつ連続的に調整可能な粒径分布の硫酸バリウムを得た。
（３）本発明では、合成反応後に酸性条件において熱気を流れ込ませて脱気することにより、硫酸バリウム製品の白色度を向上させた。
（４）本発明では、カップリング剤による硫酸バリウム粉体の表面修飾及びアルミナなど異なる材料による被覆により、下流産業の応用における分散、沈殿という問題を解決した。
（５）本発明は銅箔基板に使用され、高分散性球近似型サブミクロン粒子の樹脂における連続分散充填に加え、熱伝導係数が比較的に高いため、基板のＴｇ値と難燃性能を高めることができる。しかも、導電イオンの含有量が厳しく制御されているため、高ＣＴＩ基板の生産をサポートできる。さらに、硬度が比較的に低いことは、基板の加工及び成型性能を保証している。 (1) In the present invention, since the barium sulfate approximated to a spherical shape or a spherical shape was obtained through a cocurrent continuous synthesis process, the application range of barium sulfate was further expanded.
(2) In the present invention, the barium sulfate nucleation and growth rate were controlled by controlling the reaction rate to obtain a barium sulfate having a particle size distribution that can be continuously adjusted at the submicron level.
(3) In the present invention, the whiteness of the barium sulfate product is improved by flowing degassed by flowing hot air under acidic conditions after the synthesis reaction.
(4) In the present invention, the problem of dispersion and precipitation in downstream industrial applications was solved by surface modification of barium sulfate powder with a coupling agent and coating with different materials such as alumina.
(5) The present invention is used for a copper foil substrate, and in addition to continuous dispersion filling in a resin of highly dispersible spherical approximate submicron particles, the thermal conductivity coefficient is relatively high, so that the Tg value and flame retardancy of the substrate are reduced. Can be increased. Moreover, since the content of conductive ions is strictly controlled, production of high CTI substrates can be supported. Furthermore, the relatively low hardness guarantees the processing and molding performance of the substrate.

本発明の実施例１による硫酸バリウムの電子顕微鏡走査写真である。It is an electron microscope scanning photograph of the barium sulfate by Example 1 of this invention.

以下、図面と実施例を参照して更に本発明を説明する。   The present invention will be further described below with reference to the drawings and examples.

［実施例１］
（ａ）バライトと無煙炭とを粉砕して混合し、焼成炉に投入して焼成した。温度は１２００℃に制御し、焼成時間は２時間とした。硫化バリウムを６０％ほど含む粗硫化バリウムが生成した。 [Example 1]
(A) Barite and anthracite were pulverized and mixed, put into a firing furnace, and fired. The temperature was controlled at 1200 ° C. and the firing time was 2 hours. Crude barium sulfide containing about 60% of barium sulfide was produced.

（ｂ）上記粗硫化バリウムを浸出槽に入れ８０℃の湯に浸し、硫化バリウムを１１４ｇ／Ｌ含有する溶液を調製し、該硫化バリウム溶液の温度を６７℃に調節し、該硫化バリウム溶液と過量の硫酸（工業硫酸、９８％）を同時に連続反応器に添加して、反応させて硫酸バリウムスラリーと硫化水素とを生成した。硫化バリウム溶液の添加速度は４０００Ｌ／ｈであり、硫酸の添加量は、反応完成後に硫酸バリウムスラリーに残される硫酸の濃度が２．７ｇ／Ｌとなるように計算した。   (B) The crude barium sulfide is placed in a leaching tank and immersed in hot water at 80 ° C. to prepare a solution containing 114 g / L of barium sulfide, the temperature of the barium sulfide solution is adjusted to 67 ° C., and the barium sulfide solution and An excessive amount of sulfuric acid (industrial sulfuric acid, 98%) was simultaneously added to the continuous reactor and reacted to produce a barium sulfate slurry and hydrogen sulfide. The addition rate of the barium sulfide solution was 4000 L / h, and the addition amount of sulfuric acid was calculated so that the concentration of sulfuric acid remaining in the barium sulfate slurry after the completion of the reaction was 2.7 g / L.

（ｃ）該硫酸バリウムスラリーに熱空気を流れ込ませて硫化水素を脱気させた。流れ込ませる熱空気の風量は３５００Ｍ３／ｈであり、温度は５４℃であり、脱気時間は２ｈとした。 (C) Hydrogen sulfide was degassed by flowing hot air into the barium sulfate slurry. The flow rate of hot air to be introduced was 3500 M 3 / h, the temperature was 54 ° C., and the degassing time was 2 h.

（ｄ）工程（ｃ）の脱気処理を経た硫酸バリウムスラリーを脱水、洗浄（材料／水＝１:７、温度：９０℃、時間：２．０ｈ）して、それからフラッシュ蒸発乾燥し、ハンマリング・粉砕してほぼ球形の硫酸バリウム製品を得た。製品を電子顕微鏡で検査すると、図１に示すように、硫酸バリウムが球形か球形に近似した形態であった。   (D) The barium sulfate slurry that has been subjected to the deaeration process in step (c) is dehydrated and washed (material / water = 1: 7, temperature: 90 ° C., time: 2.0 h), and then flash-evaporated and dried. Ring and pulverization gave a nearly spherical barium sulfate product. When the product was inspected with an electron microscope, as shown in FIG. 1, the barium sulfate had a spherical shape or a shape similar to a spherical shape.

実施例１で得た硫酸バリウムをエキポシガラス繊維銅箔基板組成物に入れた。硫酸バリウムの添加量は組成物の全重量の２〜３５％とした。   The barium sulfate obtained in Example 1 was put in an epoxy glass fiber copper foil substrate composition. The amount of barium sulfate added was 2 to 35% of the total weight of the composition.

［実施例２］
（ａ）バライトと無煙炭とを粉砕して混合し、焼成炉に投入して焼成した。温度は１２００℃に制御し、焼成時間は２時間とした。硫化バリウムを６０％ほど含む粗硫化バリウムが生成した。 [Example 2]
(A) Barite and anthracite were pulverized and mixed, put into a firing furnace, and fired. The temperature was controlled at 1200 ° C. and the firing time was 2 hours. Crude barium sulfide containing about 60% of barium sulfide was produced.

（ｂ）上記粗硫化バリウムを浸出槽に入れ８０℃の湯に浸し、硫化バリウムを１１０ｇ／Ｌ含有する溶液を調製し、該硫化バリウム溶液の温度を６５℃に調節し、該硫化バリウム溶液と過量の硫酸（工業硫酸、９８％）を同時に連続反応器に添加して、反応させて硫酸バリウムスラリーと硫化水素とを生成した。硫化バリウム溶液の添加速度は３０００Ｌ／ｈであり、硫酸の添加量は、反応完成後に硫酸バリウムスラリーに残される硫酸の濃度が１２．５ｇ／Ｌとなるように計算した。   (B) Put the crude barium sulfide in a leaching tank and immerse it in hot water at 80 ° C. to prepare a solution containing 110 g / L of barium sulfide, adjust the temperature of the barium sulfide solution to 65 ° C., and An excessive amount of sulfuric acid (industrial sulfuric acid, 98%) was simultaneously added to the continuous reactor and reacted to produce a barium sulfate slurry and hydrogen sulfide. The addition rate of the barium sulfide solution was 3000 L / h, and the amount of sulfuric acid added was calculated so that the concentration of sulfuric acid remaining in the barium sulfate slurry after completion of the reaction was 12.5 g / L.

（ｃ）該硫酸バリウムスラリーに熱空気を流れ込ませて硫化水素を脱気させた。流れ込ませる熱空気の風量は３５００Ｍ３／ｈであり、温度は６０℃であり、脱気時間は２.５ｈとした。 (C) Hydrogen sulfide was degassed by flowing hot air into the barium sulfate slurry. The volume of hot air to be introduced was 3500 M 3 / h, the temperature was 60 ° C., and the degassing time was 2.5 h.

（ｄ）工程（ｃ）の脱気処理を経た硫酸バリウムスラリーをろ過して脱水し、水で洗浄し、それからろ過ケーキを水に溶解して硫酸バリウムスラリーを生成し、該硫酸バリウムスラリーに珪酸ナトリウム又はアルミン酸ナトリウムを添加し、２時間反応した後、ろ過して脱水し、再び水で３回洗浄し（材料／水＝１:７、温度：９０℃、時間：２．０ｈ）して、それからフラッシュ蒸発乾燥し、粉砕して、酸化アルミニウムに被覆されたほぼ球形の硫酸バリウム製品を得た。   (D) The barium sulfate slurry that has been subjected to the deaeration treatment in step (c) is filtered and dehydrated, washed with water, and then the filter cake is dissolved in water to form a barium sulfate slurry. Silica is added to the barium sulfate slurry. Add sodium or sodium aluminate, react for 2 hours, filter and dehydrate, wash again with water 3 times (material / water = 1: 7, temperature: 90 ° C., time: 2.0 h) And then flash evaporated to dryness and pulverized to obtain a nearly spherical barium sulfate product coated with aluminum oxide.

実施例２で得た硫酸バリウムをフェノール樹脂銅箔基板組成物に入れた。硫酸バリウムの添加量は組成物の全重量の２〜３５％とした。   The barium sulfate obtained in Example 2 was put into a phenolic resin copper foil substrate composition. The amount of barium sulfate added was 2 to 35% of the total weight of the composition.

［実施例３］
工程（ｄ）において、脱水、洗浄後にろ過ケーキを水に溶解して硫酸バリウムスラリーを生成して、該硫酸バリウムスラリーにカップリング剤ＫＨ−５６０を添加することを除いて、他の工程は実施例２と同様に行なった。
[Example 3]
In step (d), after the dehydration and washing, the filter cake is dissolved in water to form a barium sulfate slurry, and the other steps are performed except that the coupling agent KH-560 is added to the barium sulfate slurry. Performed as in Example 2.

（ｄ）工程（ｃ）の脱気処理を経た硫酸バリウムスラリーをろ過して脱水し、水で洗浄し、それからろ過ケーキを水に溶解して硫酸バリウムスラリーを生成し、該硫酸バリウムスラリーにアルミン酸ナトリウムを添加し、２時間反応した後、ろ過して脱水し、再び水で３回洗浄し（材料／水＝１:７、温度：９０℃、時間：２．０ｈ）して、それからフラッシュ蒸発乾燥し、粉砕して、酸化アルミニウムに被覆されたほぼ球形の硫酸バリウム製品を得た。

Step (d) by filtration barium sulfate slurry after the deaeration process (c) dehydrated, washed with water, then with the filter cake was dissolved in water to produce a barium sulfate slurry, aluminate to barium sulfate slurry Add sodium acid , react for 2 hours, filter, dehydrate, wash again with water 3 times (material / water = 1: 7, temperature: 90 ° C., time: 2.0 h), then flush Evaporated to dryness and ground to obtain a nearly spherical barium sulfate product coated with aluminum oxide.

Claims (6)

（ａ）バライトを石炭で焼成して硫化バリウムを生成する工程を含むことに加えて、
（ｂ）硫化バリウムを水で溶解して濃度が７０〜１３０ｇ／Ｌの硫化バリウム溶液を調製し、前記硫化バリウム溶液の温度を４５〜８５℃に調節し、前記硫化バリウム溶液の添加速度が５００Ｌ／ｈ〜７０００Ｌ／ｈとなる状態で前記硫化バリウム溶液と過量の硫酸を連続反応器に同時に添加し、反応させて、硫酸バリウムスラリーと硫化水素とを生成する工程と、
（ｃ）前記硫酸バリウムスラリーに熱空気を流れ込ませて前記硫化水素を排出させる工程と、
（ｄ）工程（ｃ）の排出による脱気処理を経た前記硫酸バリウムスラリーを脱水、洗浄、乾燥、粉砕してほぼ球形の硫酸バリウム製品を得る工程と、
を更に含むことを特徴とする、硫酸法によるほぼ球形の硫酸バリウムの製造方法。 (A) In addition to including the step of firing barite with coal to produce barium sulfide,
(B) Barium sulfide is dissolved in water to prepare a barium sulfide solution having a concentration of 70 to 130 g / L, the temperature of the barium sulfide solution is adjusted to 45 to 85 ° C., and the addition rate of the barium sulfide solution is 500 L A step of simultaneously adding and reacting the barium sulfide solution and an excessive amount of sulfuric acid to a continuous reactor in a state of / h to 7000 L / h, and generating a barium sulfate slurry and hydrogen sulfide;
(C) letting hot air flow into the barium sulfate slurry to discharge the hydrogen sulfide;
(D) dehydrating, washing, drying, and pulverizing the barium sulfate slurry that has been degassed by discharging in step (c) to obtain a substantially spherical barium sulfate product;
The method for producing substantially spherical barium sulfate by the sulfuric acid method, further comprising: 前記工程（ｃ）において、前記流れ込ませる熱空気の風量が３０００〜７０００Ｍ３／ｈであり、温度が４５〜８０℃であり、脱気時間が１．５〜３ｈであることを特徴とする、請求項１に記載の硫酸法によるほぼ球形硫酸バリウムの製造方法。 In the step (c), the flow rate of hot air to be introduced is 3000 to 7000 M 3 / h, the temperature is 45 to 80 ° C., and the deaeration time is 1.5 to 3 h, A method for producing substantially spherical barium sulfate by the sulfuric acid method according to claim 1. 前記工程（ｂ）において、前記硫酸バリウムスラリーに残される前記硫酸の濃度が０．５〜２５ｇ／Ｌとなるように制御することを特徴とする、請求項１に記載の硫酸法によるほぼ球形硫酸バリウムの製造方法。   2. The substantially spherical sulfuric acid according to claim 1, wherein the concentration of the sulfuric acid remaining in the barium sulfate slurry is controlled to be 0.5 to 25 g / L in the step (b). A method for producing barium. 前記工程（ｄ）において、洗浄を経た前記硫酸バリウムスラリーに珪酸ナトリウム又はアルミン酸ナトリウム又はカップリング剤を加えて１．５〜３ｈ反応させた後、脱水、洗浄、乾燥、粉砕を経て硫酸バリウム製品を得ることを特徴とする、請求項１に記載の硫酸法によるほぼ球形硫酸バリウムの製造方法。   In the step (d), sodium silicate, sodium aluminate or a coupling agent is added to the washed barium sulfate slurry and reacted for 1.5 to 3 hours, followed by dehydration, washing, drying, and pulverization to produce a barium sulfate product. The method for producing substantially spherical barium sulfate by the sulfuric acid method according to claim 1, wherein: 前記乾燥は、フラッシュ蒸発乾燥が用いられており、乾燥後の前記ほぼ球形の硫酸バリウム製品の含水量が０．２％未満であることを特徴とする、請求項１又は４に記載の硫酸法によるほぼ球形の硫酸バリウムの製造方法。   The sulfuric acid method according to claim 1 or 4, wherein the drying uses flash evaporation drying, and the water content of the substantially spherical barium sulfate product after drying is less than 0.2%. Method for producing nearly spherical barium sulfate. ほぼ球形の硫酸バリウムをフィラーとする銅箔基板における使用。
Use on copper foil substrate with nearly spherical barium sulfate as filler.
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