JP5474310B2 - Granular barium carbonate composition powder - Google Patents
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- JP5474310B2 JP5474310B2 JP2008083944A JP2008083944A JP5474310B2 JP 5474310 B2 JP5474310 B2 JP 5474310B2 JP 2008083944 A JP2008083944 A JP 2008083944A JP 2008083944 A JP2008083944 A JP 2008083944A JP 5474310 B2 JP5474310 B2 JP 5474310B2
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- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 title claims description 220
- 239000000843 powder Substances 0.000 title claims description 89
- 239000000203 mixture Substances 0.000 title claims description 50
- 239000002245 particle Substances 0.000 claims description 70
- 239000000725 suspension Substances 0.000 claims description 50
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 26
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000011164 primary particle Substances 0.000 claims description 18
- 239000012736 aqueous medium Substances 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002609 medium Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000635 electron micrograph Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000790 scattering method Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010191 image analysis Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000011324 bead Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- 229960004106 citric acid Drugs 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003966 growth inhibitor Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、水性媒体への分散性が高い粒状炭酸バリウム組成物粉末及びその製造方法に関するものである。 The present invention relates to a granular barium carbonate composition powder having high dispersibility in an aqueous medium and a method for producing the same.
炭酸バリウム粉末の用途の一つとして、チタン酸バリウム粉末などの誘電体セラミック粉末の製造原料の用途がある。誘電体セラミック粉末は、積層セラミックコンデンサの誘電体セラミック層の構成材料として利用されている。 One use of barium carbonate powder is as a raw material for producing dielectric ceramic powder such as barium titanate powder. Dielectric ceramic powder is used as a constituent material of a dielectric ceramic layer of a multilayer ceramic capacitor.
電子機器の小型化に伴って、積層セラミックコンデンサにおいても小型化が求められている。積層セラミックコンデンサの小型化のためには、積層セラミックコンデンサの誘電体セラミック層の薄層化が必要となる。この誘電体セラミック層の薄層化のためには、微細な誘電体セラミック粉末が不可欠である。 Along with the downsizing of electronic devices, downsizing of multilayer ceramic capacitors is also required. In order to reduce the size of the multilayer ceramic capacitor, it is necessary to reduce the thickness of the dielectric ceramic layer of the multilayer ceramic capacitor. Fine dielectric ceramic powder is indispensable for thinning the dielectric ceramic layer.
微細なチタン酸バリウム粉末を製造するには、微細で、かつ反応性の高い、すなわちＢＥＴ比表面積の大きい二酸化チタン粉末や炭酸バリウム粉末が必要となる。 In order to produce a fine barium titanate powder, a fine and highly reactive titanium dioxide powder or barium carbonate powder having a high BET specific surface area is required.
ＢＥＴ比表面積の大きい炭酸バリウム粉末を製造する方法として、特許文献１には、炭酸バリウムスラリーと粒状媒体との混合物を、好ましくは多価アルコール、アスコルビン酸、ピロリン酸、カルボン酸及びカルボン酸塩から選ばれる粒子成長抑制剤の存在下にて粒状媒体が高速で流動する状態で流動処理する方法が開示されている。この特許文献１には、上記の方法を利用することによって、ＢＥＴ比表面積が５〜５０ｍ2／ｇ、レーザー
回折法により求められる平均粒径が０．０１〜１．０μｍの炭酸バリウム粉末が得られる旨の記載がある。なお、特許文献１には、粒子成長抑制剤として用いることができるカルボン酸及びカルボン酸塩の例として、クエン酸、カルボキシメチルセルロース、シュウ酸、マロン酸、コハク酸、リンゴ酸、マレイン酸、酒石酸、アジピン酸、アクリル酸、ポリカルボン酸、ポリアクリル酸、及びこれらのナトリウム塩、アンモニウム塩の記載がある。
As a method for producing a barium carbonate powder having a large BET specific surface area, Patent Document 1 describes a mixture of a barium carbonate slurry and a granular medium, preferably from a polyhydric alcohol, ascorbic acid, pyrophosphoric acid, carboxylic acid and carboxylate. Disclosed is a method for fluidizing a granular medium in the presence of a selected particle growth inhibitor in a state where it flows at high speed. In Patent Document 1, a barium carbonate powder having a BET specific surface area of 5 to 50 m 2 / g and an average particle diameter of 0.01 to 1.0 μm obtained by a laser diffraction method is obtained by using the above method. There is a statement that it will be. In Patent Document 1, as examples of carboxylic acid and carboxylate that can be used as a particle growth inhibitor, citric acid, carboxymethyl cellulose, oxalic acid, malonic acid, succinic acid, malic acid, maleic acid, tartaric acid, There are descriptions of adipic acid, acrylic acid, polycarboxylic acid, polyacrylic acid, and sodium salts and ammonium salts thereof.
一方、微細な二酸化チタン粉末の製造方法としては、特許文献２に硫酸チタニルを水とアルコールとの混合溶液に溶解した後、その溶液を加熱還流する方法が開示されている。この特許文献２によれば、この方法を利用することによって、平均粒子径で５．５〜１２．０ｎｍのナノオーダーの二酸化チタン粉末が得られるとされている。
前記特許文献１に開示されているように、炭酸バリウム粉末を水性媒体中にて粒状媒体を用いて粉砕処理することによって、微細な炭酸バリウム粒子を得ることは可能である。しかしながら、炭酸バリウム粒子は微細になるに伴って凝集性が強くなり、凝集粒子を形成し易くなる傾向がある。このため、水性媒体中にて得られた微細な炭酸バリウム粒子を一旦乾燥して粉末にすると、微細な微粒子として水性溶媒に再分散させることが難しくなることがある。特に、チタン酸バリウム粉末の製造においては、二酸化チタン粉末と炭酸バリウム粉末とを湿式混合法により混合することが一般的に行なわれている。従って、チタン酸バリウム粉末の原料として用いる炭酸バリウム粉末は、水性媒体への分散性が高い方が好ましい。
従って、本発明の目的は、水性媒体への分散性が高い炭酸バリウム粉末及びその製造方法を提供することにある。
As disclosed in Patent Document 1, fine barium carbonate particles can be obtained by pulverizing barium carbonate powder in an aqueous medium using a granular medium. However, as the barium carbonate particles become finer, the cohesiveness becomes stronger and the aggregated particles tend to be easily formed. For this reason, once the fine barium carbonate particles obtained in an aqueous medium are dried to a powder, it may be difficult to redisperse them in an aqueous solvent as fine fine particles. In particular, in the production of barium titanate powder, it is common practice to mix titanium dioxide powder and barium carbonate powder by a wet mixing method. Therefore, it is preferable that the barium carbonate powder used as a raw material for the barium titanate powder has a high dispersibility in an aqueous medium.
Accordingly, an object of the present invention is to provide a barium carbonate powder having high dispersibility in an aqueous medium and a method for producing the same.
本発明は、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーが表面に付着している、ＢＥＴ比表面積が３０ｍ2／ｇ以上で、一次粒子の投影面積円相当径の平均が５〜５０ｎｍであり、該投影面積円相当径の変動係数が４０％以内にある粒状炭酸バリウム組成物粉末にある。投影面積円相当径は、市販の画像解析ソフトウェアを用いて、電子顕微鏡写真に撮された個々の一次粒子の画像を解析することにより求めることができる。 In the present invention, a polymer composed of a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof is attached to the surface, the BET specific surface area is 30 m 2 / g or more, and the projected particle equivalent circle diameter of primary particles In the granular barium carbonate composition powder having a variation coefficient of the projected area equivalent circle diameter within 40%. The projected area equivalent circle diameter can be determined by analyzing an image of each primary particle taken in an electron micrograph using commercially available image analysis software.
本発明の粒状炭酸バリウム組成物粉末の好ましい態様は次の通りである。
（１）ポリマーが側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物である。（２）上記のポリカルボン酸無水物が無水マレイン酸の重合体からなる。
（３）ＢＥＴ比表面積が３０〜５０ｍ2／ｇの範囲にある。
（４）一次粒子のアスペクト比の平均が２以下である。
（５）測定対象の粉末０．５ｇを濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液５０ｍＬに投入し、次いで超音波ホモジナイザーにより出力８０Ｗで５分間分散処理することにより調製した懸濁液に含まれる粒子のレーザー回折散乱法により測定された体積基準の粒度分布から求められる体積基準の平均粒子径が０．５μｍ以下であって、粒子径が１μｍ以上の粒子の含有率が１０体積％以下である。
（６）測定対象の粉末０．５ｇを濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液５０ｍＬに投入し、次いで超音波ホモジナイザーにより出力８０Ｗで５分間分散処理することにより調製した懸濁液とした場合に、その懸濁液の波長６００ｎｍにおける吸光度が１．００以下である。
Preferred embodiments of the granular barium carbonate composition powder of the present invention are as follows.
(1) The polymer is a polycarboxylic acid anhydride having a polyoxyalkylene group in the side chain. (2) The polycarboxylic acid anhydride is a maleic anhydride polymer.
(3) The BET specific surface area is in the range of 30 to 50 m 2 / g.
(4) The average aspect ratio of the primary particles is 2 or less.
(5) 0.5 g of the powder to be measured is put into 50 mL of a sodium hexametaphosphate aqueous solution having a concentration of 0.2% by mass, and then dispersed in a suspension prepared by dispersing with an ultrasonic homogenizer at an output of 80 W for 5 minutes. The volume-based average particle diameter obtained from the volume-based particle size distribution measured by the laser diffraction scattering method of the particles is 0.5 μm or less, and the content of particles having a particle diameter of 1 μm or more is 10% by volume or less. .
(6) When 0.5 g of the powder to be measured is put into 50 mL of a sodium hexametaphosphate aqueous solution having a concentration of 0.2% by mass and then subjected to a dispersion treatment at an output of 80 W for 5 minutes using an ultrasonic homogenizer to obtain a suspension. Further, the absorbance of the suspension at a wavelength of 600 nm is 1.00 or less.
本発明はまた、ＢＥＴ比表面積が３０ｍ2／ｇ以上の炭酸バリウム粉末を水性媒体中にて、平均粒子径が１０〜１０００μｍの範囲にある粒状媒体を用いて、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーの存在下にて１０分以上粉砕し、次いで乾燥することからなる上記本発明の粒状炭酸バリウム組成物粉末の製造方法にもある。 The present invention also provides a polyoxyalkylene group in the side chain of a barium carbonate powder having a BET specific surface area of 30 m 2 / g or more in an aqueous medium, using a granular medium having an average particle diameter in the range of 10 to 1000 μm. There is also a method for producing the granular barium carbonate composition powder of the present invention, which comprises pulverizing for 10 minutes or more in the presence of a polymer comprising polycarboxylic acid or anhydride thereof and then drying.
本発明の粒状炭酸バリウム組成物粉末の製造方法における好ましい態様は次の通りである。
（１）炭酸バリウム粉末が、液温が５〜１５℃の範囲にあり、水酸化バリウム濃度が３〜２０質量％の範囲にある水酸化バリウム水性懸濁液を撹拌しながら、該懸濁液に二酸化炭素ガスを、クエン酸の存在下にて、該懸濁液中の水酸化バリウム１ｇに対して０．５〜２０ｍＬ／分の範囲の流量にて導入することにより、水酸化バリウムを炭酸化させて炭酸バリウム粒子を生成させることにより製造されたものである。
（２）側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーを、炭酸バリウム水性懸濁液の固形分に対して０．１〜２０質量％の範囲にて存在させる。
The preferable aspect in the manufacturing method of the granular barium carbonate composition powder of this invention is as follows.
(1) While stirring the barium hydroxide aqueous suspension in which the barium carbonate powder has a liquid temperature in the range of 5 to 15 ° C. and the barium hydroxide concentration in the range of 3 to 20% by mass, the suspension Carbon dioxide gas is introduced into the suspension at a flow rate in the range of 0.5 to 20 mL / min with respect to 1 g of barium hydroxide in the suspension in the presence of citric acid. To produce barium carbonate particles.
(2) The polymer which consists of polycarboxylic acid which has a polyoxyalkylene group in a side chain, or its anhydride is made to exist in the range of 0.1-20 mass% with respect to solid content of barium carbonate aqueous suspension.
本発明の粒状炭酸バリウム組成物粉末は、従来の炭酸バリウム粉末と比べて微細で、かつ工業的に実用性の高い分散方法を用いて、一次粒子もしくはそれに近い微粒子として水性媒体に分散させることができる。従って、本発明の粒状炭酸バリウム組成物粉末を、湿式混合法を用いて、他の無機物微粉末と混合することにより、容易に均一な粉末混合物を得ることができる。
また、本発明の粒状炭酸バリウム組成物粉末の製造方法を利用することにより、微細でかつ水性媒体への分散性の高い粒状炭酸バリウム組成物粉末を工業的に容易に製造することが可能となる。
The granular barium carbonate composition powder of the present invention is finer than the conventional barium carbonate powder, and can be dispersed in an aqueous medium as primary particles or fine particles close thereto using a dispersion method that is industrially highly practical. it can. Therefore, a uniform powder mixture can be easily obtained by mixing the granular barium carbonate composition powder of the present invention with other inorganic fine powder using a wet mixing method.
Further, by using the method for producing a granular barium carbonate composition powder of the present invention, it is possible to easily produce a fine granular barium carbonate composition powder that is fine and highly dispersible in an aqueous medium. .
本発明の粒状炭酸バリウム組成物粉末は、一次粒子のサイズが投影面積円相当径の平均として５〜５０ｎｍの範囲にあり、その投影面積円相当径の平均に対する変動係数が４０％以内にある。
本発明において、投影面積円相当径（ヘイウッド径ともいう）は、粒子の投影面積と同じ面積を持つ円の直径を意味する。一次粒子の投影面積円相当径は、電子顕微鏡写真の画像解析、すなわち電子顕微鏡写真に写された個々の一次粒子毎に投影面積を求めて、その投影面積と同じ面積を持つ円の直径を算出することにより求めることができる。変動係数は、投影面積円相当径の標準偏差を投影面積円相当径の平均値で割った値の百分率を意味する。一次粒子の投影面積円相当径の平均は、５〜３０ｎｍの範囲にあることが好ましく、５〜２５ｎｍの範囲にあることが特に好ましい。一次粒子の投影面積円相当径の平均に対する変動係数は、３５％以内にあることが好ましい。
In the granular barium carbonate composition powder of the present invention, the size of the primary particles is in the range of 5 to 50 nm as an average of the projected area circle equivalent diameter, and the variation coefficient with respect to the average projected area circle equivalent diameter is within 40%.
In the present invention, the projected area equivalent circle diameter (also referred to as Haywood diameter) means the diameter of a circle having the same area as the projected area of the particles. The projected particle equivalent circle diameter of the primary particle is calculated by calculating the diameter of a circle having the same area as the projected area by analyzing the image of the electron micrograph, that is, obtaining the projected area for each primary particle imaged in the electron micrograph. Can be obtained. The coefficient of variation means a percentage of a value obtained by dividing the standard deviation of the projected area circle equivalent diameter by the average value of the projected area circle equivalent diameter. The average of the projected area equivalent circle diameters of the primary particles is preferably in the range of 5 to 30 nm, and particularly preferably in the range of 5 to 25 nm. The coefficient of variation with respect to the average projected area equivalent circle diameter of the primary particles is preferably within 35%.
本発明の粒状炭酸バリウム組成物粉末は、その表面に、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーが付着している。このポリマーは、側鎖のポリオキシアルキレン基が親水性であるため、粒状炭酸バリウム組成物粉末の水性媒体への分散性を向上させる効果がある。粒状炭酸バリウム組成物粉末の表面に付着しているポリマーは、側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物であることが好ましい。ポリカルボン酸無水物は、無水マレイン酸の重合体からなることが好ましい。側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物の例としては、日本油脂株式会社製のマリアリムＡＫＭ−０５３１、マリアリムＡＫＭ−１５１１−６０、マリアリムＨＫＭ−５０Ａ、マリアリムＨＫＭ−１５０Ａを挙げることができる。粒状炭酸バリウム組成物粉末の表面に上記のポリマーが付着していることは、フーリエ変換赤外分光測定装置（ＦＴ−ＩＲ）を用いて、組成物粉末表面の赤外吸収スペクトルにより確認することができる。 In the granular barium carbonate composition powder of the present invention, a polymer composed of a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof is attached to the surface. This polymer has an effect of improving the dispersibility of the granular barium carbonate composition powder in an aqueous medium because the polyoxyalkylene group in the side chain is hydrophilic. The polymer adhering to the surface of the granular barium carbonate composition powder is preferably a polycarboxylic acid anhydride having a polyoxyalkylene group in the side chain. The polycarboxylic acid anhydride is preferably composed of a maleic anhydride polymer. Examples of polycarboxylic acid anhydrides having a polyoxyalkylene group in the side chain include Marialim AKM-053, Marialim AKM-1511-60, Marialim HKM-50A, and Marialim HKM-150A manufactured by NOF Corporation. it can. The adhesion of the above polymer to the surface of the granular barium carbonate composition powder can be confirmed by the infrared absorption spectrum of the composition powder surface using a Fourier transform infrared spectrometer (FT-IR). it can.
本発明の粒状炭酸バリウム組成物粉末は、一次粒子が立方体状もしくは球状又はこれらに近い形状であることが好ましい。一次粒子のアスペクト比（長径／短径）の平均は、２以下であることが好ましい。アスペクト比は、粒子の外郭に接するように、かつその面積が最も小さくなるように描いた長方形の長辺と短辺との比を意味する。 In the granular barium carbonate composition powder of the present invention, the primary particles are preferably cubic, spherical, or a shape close to these. The average of the aspect ratio (major axis / minor axis) of the primary particles is preferably 2 or less. The aspect ratio means the ratio between the long side and the short side of a rectangle drawn so as to be in contact with the outline of the particle and having the smallest area.
本発明の粒状炭酸バリウム組成物粉末は、ＢＥＴ比表面積が３０ｍ2／ｇ以上の炭酸バリウム粉末を水性媒体中にて、平均粒子径が１０〜１０００μｍの範囲にある粒状媒体を用いて、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーの存在下にて１０分以上粉砕し、次いで乾燥することからなる方法により製造することができる。 The granular barium carbonate composition powder of the present invention uses a granular medium having a BET specific surface area of 30 m 2 / g or more in an aqueous medium and an average particle diameter in the range of 10 to 1000 μm. In the presence of a polymer comprising a polycarboxylic acid having a polyoxyalkylene group or an anhydride thereof for 10 minutes or more, and then drying.
ＢＥＴ比表面積が３０ｍ2／ｇ以上の炭酸バリウム粉末は、液温が５〜１５℃の範囲にあり、水酸化バリウム濃度が３〜２０質量％の範囲にある水酸化バリウム水性懸濁液を撹拌しながら、該懸濁液に二酸化炭素ガスを、クエン酸の存在下にて、該懸濁液中の水酸化バリウム１ｇに対して０．５〜２０ｍＬ／分の範囲の流量にて導入することにより、水酸化バリウムを炭酸化させて炭酸バリウム粒子を生成させることにより製造することができる。 Barium carbonate powder having a BET specific surface area of 30 m 2 / g or more is agitated barium hydroxide aqueous suspension having a liquid temperature in the range of 5 to 15 ° C. and a barium hydroxide concentration in the range of 3 to 20% by mass. While introducing carbon dioxide gas into the suspension in the presence of citric acid at a flow rate in the range of 0.5 to 20 mL / min with respect to 1 g of barium hydroxide in the suspension. Thus, barium hydroxide can be carbonated to produce barium carbonate particles.
水酸化バリウム懸濁液の水酸化バリウム濃度は、３〜１０質量％の範囲にあることが好ましい。水酸化バリウム懸濁液に添加するクエン酸の量は、生成する炭酸バリウム粒子に対して３〜１０質量％の範囲であることが好ましく、３〜７質量％の範囲にあることがより好ましい。 The barium hydroxide concentration of the barium hydroxide suspension is preferably in the range of 3 to 10% by mass. The amount of citric acid added to the barium hydroxide suspension is preferably in the range of 3 to 10% by mass and more preferably in the range of 3 to 7% by mass with respect to the generated barium carbonate particles.
水酸化バリウム懸濁液に導入する二酸化炭素ガスの流量は、懸濁液中の水酸化バリウム１ｇに対して０．５〜２０ｍＬ／分の範囲、好ましくは０．５〜１０ｍＬ／分の範囲となる流量である。二酸化炭素ガスは、単独で水酸化バリウム懸濁液に導入してもよいし、窒素、アルゴン、酸素及び空気などの水酸化バリウムに対して不活性なガスとの混合ガスとして水酸化バリウム懸濁液に導入してもよい。水酸化バリウムの炭酸化の終点は、懸濁液のｐＨが７以下となった時点とすることができる。 The flow rate of carbon dioxide gas introduced into the barium hydroxide suspension is in the range of 0.5 to 20 mL / min, preferably in the range of 0.5 to 10 mL / min, with respect to 1 g of barium hydroxide in the suspension. Is the flow rate. Carbon dioxide gas may be introduced alone into the barium hydroxide suspension or suspended as a mixed gas with a gas inert to barium hydroxide such as nitrogen, argon, oxygen and air. It may be introduced into the liquid. The end point of carbonation of barium hydroxide can be the time when the pH of the suspension is 7 or less.
水酸化バリウムの炭酸化により生成した炭酸バリウム粒子は、ろ過、デカンテーションあるいは遠心分離などの通常の方法により懸濁液から分離して、水などで洗浄した後、乾燥することができる。また、懸濁液を直接噴霧乾燥してもよい。 Barium carbonate particles produced by carbonation of barium hydroxide can be separated from the suspension by a usual method such as filtration, decantation or centrifugation, washed with water, and then dried. Alternatively, the suspension may be directly spray dried.
本発明では、上記のようにして得た炭酸バリウム粒子を水性媒体中にてセラミック製ビーズを用いて、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーの存在下で粉砕し、次いで乾燥することによって、微細な炭酸バリウム粉末を製造する。 In the present invention, the barium carbonate particles obtained as described above are used in an aqueous medium using ceramic beads in the presence of a polymer composed of a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof. Fine barium carbonate powder is produced by grinding and then drying.
炭酸バリウム粒子の粉砕に用いる炭酸バリウム水性懸濁液は、炭酸バリウム粒子が水性媒体に、全体量に対する固形分量として５〜４０質量％の範囲となる量にて分散されていることが好ましい。 It is preferable that the barium carbonate aqueous suspension used for pulverization of barium carbonate particles is dispersed in an aqueous medium in an amount in the range of 5 to 40% by mass as a solid content with respect to the total amount.
側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーの添加量は、炭酸バリウム水性懸濁液の固形分に対して０．５〜２０質量％、特に１〜１０質量％となる範囲であることが好ましい。 The amount of the polymer comprising a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof is 0.5 to 20% by mass, particularly 1 to 10% by mass, based on the solid content of the barium carbonate aqueous suspension. It is preferable that it is the range which becomes.
炭酸バリウム粒子の粉砕に用いる炭酸バリウム水性懸濁液は、水酸化バリウム懸濁液の炭酸化により得られた炭酸バリウム懸濁液をそのまま、あるいは濃縮して用いてもよい。また、水酸化バリウム懸濁液の炭酸化により得られた炭酸バリウム懸濁液を一旦乾燥させ、炭酸バリウム粉末として、この炭酸バリウム粉末を再度、水性媒体に分散させて調製してもよい。 As the barium carbonate aqueous suspension used for pulverizing the barium carbonate particles, the barium carbonate suspension obtained by carbonation of the barium hydroxide suspension may be used as it is or after being concentrated. Alternatively, the barium carbonate suspension obtained by carbonation of the barium hydroxide suspension may be once dried to prepare a barium carbonate powder by dispersing the barium carbonate powder again in an aqueous medium.
セラミック製ビーズとしては、酸化ジルコニウムビーズや酸化アルミニウムビーズなどの通常の粉砕操作に用いられる公知のビーズを用いることができる。ビーズの平均粒子径は、一般に１０〜１０００μｍ、特に３０〜５００μｍの範囲にあることが好ましい。 As the ceramic beads, known beads used in normal pulverization operations such as zirconium oxide beads and aluminum oxide beads can be used. The average particle size of the beads is generally in the range of 10 to 1000 μm, particularly 30 to 500 μm.
粉砕装置には、通常の粒子の粉砕に用いられる公知のメディアミルを用いることができる。メディアミルを用いて炭酸バリウム粒子を粉砕する際のビーズ撹拌羽根の周速は３〜１５ｍ／分の範囲にあることが好ましく、５〜９ｍ／分の範囲にあることが特に好ましい。 A known media mill used for normal particle pulverization can be used for the pulverizer. When the barium carbonate particles are pulverized using a media mill, the peripheral speed of the bead stirring blade is preferably in the range of 3 to 15 m / min, and particularly preferably in the range of 5 to 9 m / min.
粉砕時間は、炭酸バリウム水性懸濁液の炭酸バリウム濃度やセラミック製ビーズの平均粒子径などの要因により異なるが、ミル内の滞留時間で通常は１〜２００分、好ましくは１０〜１００分である。側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーは、粉砕の開始前、あるいは粉砕の途中で炭酸バリウム水性懸濁液に添加することができる。 The pulverization time varies depending on factors such as the barium carbonate concentration of the aqueous barium carbonate suspension and the average particle size of the ceramic beads, but the residence time in the mill is usually 1 to 200 minutes, preferably 10 to 100 minutes. . A polymer comprising a polycarboxylic acid having a polyoxyalkylene group in the side chain or an anhydride thereof can be added to the aqueous barium carbonate suspension before the start of pulverization or during the pulverization.
粉砕後の炭酸バリウム水性懸濁液は、懸濁液の乾燥に通常用いられる装置を用いて乾燥することができるが、スプレードライヤあるいはドラムドライヤを用いて乾燥することが好ましい。 The aqueous barium carbonate suspension after pulverization can be dried using an apparatus usually used for drying the suspension, but is preferably dried using a spray dryer or a drum dryer.
本発明の粒状炭酸バリウム組成物粉末は、従来の炭酸バリウム粉末と比べて、一次粒子が微細で、かつ粒子サイズが揃ったものである。このため、本発明の粒状炭酸バリウム組成物粉末を、超音波分散などの工業的に実用性の高い分散方法を用いて水性媒体に分散させると、炭酸バリウムが一次粒子もしくはそれに近い微粒子として分散した炭酸バリウム懸濁液を得ることができる。例えば、本発明の粒状炭酸バリウム組成物粉末０．５ｇを濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液５０ｍＬに投入し、次いで超音波ホモジナイザーにより出力８０Ｗで５分間分散処理することにより調製した懸濁液は、レーザー回折散乱法によって測定された体積基準の粒度分布から求められる体積基準の平均粒子径が、通常は０．５μｍ以下、好ましくは０．３μｍ以下で、粒子径が１μｍ以上の粒子の含有率が、通常は１０体積％以下、好ましくは５体積％以下であり、凝集粒子が少ない。このため、その炭酸バリウム懸濁液は、波長６００ｎｍにおける吸光度が１．００以下、特に０．１０〜０．９０の範囲と小さい値を示す。なお、上記の方法により求められる体積基準の平均粒子径は、一次粒子の投影面積円相当径の平均の１〜２０倍の範囲にあることが好ましく、１〜１０倍の範囲にあることが特に好ましい。 The granular barium carbonate composition powder of the present invention has fine primary particles and a uniform particle size as compared with the conventional barium carbonate powder. For this reason, when the granular barium carbonate composition powder of the present invention is dispersed in an aqueous medium using an industrially practical dispersion method such as ultrasonic dispersion, the barium carbonate is dispersed as primary particles or fine particles close thereto. A barium carbonate suspension can be obtained. For example, 0.5 g of granular barium carbonate composition powder of the present invention is put in 50 mL of a sodium hexametaphosphate aqueous solution having a concentration of 0.2% by mass, and then dispersed by an ultrasonic homogenizer at an output of 80 W for 5 minutes. The liquid has a volume-based average particle size determined from a volume-based particle size distribution measured by a laser diffraction scattering method, usually 0.5 μm or less, preferably 0.3 μm or less, and particles having a particle size of 1 μm or more. The content is usually 10% by volume or less, preferably 5% by volume or less, and there are few aggregated particles. For this reason, the barium carbonate suspension exhibits an absorbance at a wavelength of 600 nm of 1.00 or less, particularly a small value in the range of 0.10 to 0.90. The volume-based average particle diameter determined by the above method is preferably in the range of 1 to 20 times the average of the projected particle equivalent circle diameter of the primary particles, and particularly in the range of 1 to 10 times. preferable.
以上のように本発明の粒状炭酸バリウム組成物粉末は、微細で、かつ水性媒体への分散性が高いため、湿式混合法などの通常の方法を用いて、二酸化チタンなどの他の無機物粉末と均一に混合することができる。従って、本発明の粒状炭酸バリウム組成物粉末は、微細で、かつ組成が均一なことが要求されるチタン酸バリウムなどの誘電体セラミック粉末の原料粉末として有利に使用することができる。 As described above, since the granular barium carbonate composition powder of the present invention is fine and highly dispersible in an aqueous medium, it can be mixed with other inorganic powders such as titanium dioxide using a normal method such as a wet mixing method. Uniform mixing is possible. Therefore, the granular barium carbonate composition powder of the present invention can be advantageously used as a raw material powder for dielectric ceramic powder such as barium titanate, which is required to be fine and have a uniform composition.
［実施例１］
冷却装置付き反応容器に、純水３０００ｇを投入し、水温を１０℃に調節した後、純水にクエン酸・１水和物１３．９ｇと、水酸化バリウム・８水和物４０４．８ｇとを加えて混合して、水酸化バリウム濃度６．４質量％、クエン酸濃度０．３７質量％（生成する炭酸バリウムに対して５質量％）の水酸化バリウム懸濁液を調製した。
この水酸化バリウム懸濁液の液温を１０℃にした後、ポリテトラフルオロエチレン製撹拌翼にて４００ｒｐｍの回転速度で撹拌しながら、懸濁液に二酸化炭素ガスを０．５Ｌ／分（水酸化バリウム１ｇに対して２．３ｍＬ／分）の流量にて、懸濁液のｐＨが７．０になるまで導入して、水酸化バリウムを炭酸化させて、炭酸バリウム粒子の懸濁液を製造した。なお、二酸化炭素ガス導入中は、懸濁液の液温は１０℃に調節した。得られた炭酸バリウム粒子の懸濁液の一部を取り出して、ろ過し、水洗した後、乾燥した。得られた炭酸バリウム粉末のＢＥＴ比表面積は、５３．３ｍ2／ｇであった。また、得られた炭酸バリウム粉末を電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ、（株）日立ハイテクノロジーズ製Ｓ−４８００）を用いて観察したところ、炭酸バリウム粉末の粒子形状は針状であることが確認された。
[Example 1]
After putting 3000 g of pure water into a reaction vessel with a cooling device and adjusting the water temperature to 10 ° C., 13.9 g of citric acid monohydrate, 404.8 g of barium hydroxide octahydrate and Were added and mixed to prepare a barium hydroxide suspension having a barium hydroxide concentration of 6.4% by mass and a citric acid concentration of 0.37% by mass (5% by mass with respect to the generated barium carbonate).
After the liquid temperature of this barium hydroxide suspension was 10 ° C., carbon dioxide gas was added to the suspension at 0.5 L / min (water) while stirring at a rotation speed of 400 rpm with a stirring blade made of polytetrafluoroethylene. Introducing the suspension of barium carbonate particles at a flow rate of 2.3 mL / min) with respect to 1 g of barium oxide until the pH of the suspension becomes 7.0 to carbonate the barium hydroxide. Manufactured. During the introduction of carbon dioxide gas, the liquid temperature of the suspension was adjusted to 10 ° C. A part of the obtained barium carbonate particle suspension was taken out, filtered, washed with water, and dried. The obtained barium carbonate powder had a BET specific surface area of 53.3 m 2 / g. Moreover, when the obtained barium carbonate powder was observed using a field emission scanning electron microscope (FE-SEM, S-4800 manufactured by Hitachi High-Technologies Corporation), the particle shape of the barium carbonate powder was needle-like. Was confirmed.
得られた炭酸バリウム水性懸濁液を、メディアミルに投入し、直径３００μｍの酸化ジルコニウム製ビーズを用いて、ビーズ充填量８０体積％、ローター周速７．０ｍ／秒の条件にて、炭酸バリウム粒子を粉砕した。滞留時間が３０分を経過した時点で、側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物からなるポリマー分散剤（日本油脂（株）製、マリアリムＡＫＭ−１５１１−６０）を懸濁液中の固形分に対して８質量％となる量にて添加して、さらに同じ条件で滞留時間が６０分間となるまで粉砕処理した。次いで、粉砕処理終了後の炭酸バリウム水性懸濁液を、スプレードライヤにて乾燥した。 The obtained barium carbonate aqueous suspension was put into a media mill, and using barium carbonate beads having a diameter of 300 μm, under conditions of a bead filling amount of 80 vol% and a rotor peripheral speed of 7.0 m / sec. The particles were crushed. When the residence time has passed 30 minutes, a polymer dispersant comprising a polycarboxylic acid anhydride having a polyoxyalkylene group in the side chain (Marialim AKM-1511-60, manufactured by NOF Corporation) is suspended in the suspension. Was added in an amount of 8% by mass with respect to the solid content, and further pulverized under the same conditions until the residence time was 60 minutes. Next, the barium carbonate aqueous suspension after completion of the pulverization treatment was dried with a spray dryer.
粉砕処理終了後の炭酸バリウム懸濁液を、ドラムドライヤにて乾燥して、炭酸バリウム粉末を得た。得られた炭酸バリウム粉末の表面をフーリエ変換赤外分光測定装置（ＦＴ−ＩＲ）を用いて１回反射ＡＴＲ法（ダイヤモンド４５°、分解能４ｃｍ-1）にて分析した。その結果、側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物からなるポリマー分散剤に起因する赤外吸収ピークが検出され、炭酸バリウム粉末は表面に、側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物からなるポリマー分散剤が付着している組成物粉末であることが確認された。 The barium carbonate suspension after completion of the pulverization treatment was dried with a drum dryer to obtain barium carbonate powder. The surface of the obtained barium carbonate powder was analyzed by a single reflection ATR method (diamond 45 °, resolution 4 cm −1 ) using a Fourier transform infrared spectrometer (FT-IR). As a result, an infrared absorption peak due to the polymer dispersant comprising a polycarboxylic acid anhydride having a polyoxyalkylene group in the side chain was detected, and the barium carbonate powder had a polyoxyalkylene group in the side chain on the surface. It was confirmed that the composition powder had a polymer dispersant made of carboxylic acid anhydride attached thereto.
得られた炭酸バリウム粉末をＦＥ−ＳＥＭを用いて観察した。その結果、炭酸バリウム粉末の粒子形状は粒状であることが確認された。ＦＥ−ＳＥＭ写真から画像解析ソフトウェア（（株）マウンテック製、ＭａｃＶｉｅｗ ｖｅｒ３．５）を用いて、一次粒子の投影面積円相当径とアスペクト比を測定した結果、投影面積円相当径の平均は３０ｎｍであり、その投影面積円相当径の平均に対する変動係数は２０．５％であり、そしてアスペクト比の平均は１．３１であった。また、得られた炭酸バリウム粉末のＢＥＴ比表面積は３９．３ｍ2／ｇであった。 The obtained barium carbonate powder was observed using FE-SEM. As a result, it was confirmed that the particle shape of the barium carbonate powder was granular. As a result of measuring the projected area circle equivalent diameter and the aspect ratio of the primary particles from the FE-SEM photograph using image analysis software (manufactured by Mountec Co., Ltd., MacView ver 3.5), the average projected area circle equivalent diameter was 30 nm. The coefficient of variation relative to the average projected area equivalent circle diameter was 20.5%, and the average aspect ratio was 1.31. Further, the BET specific surface area of the obtained barium carbonate powder was 39.3 m 2 / g.
上記の粒状炭酸バリウム組成物粉末０．５ｇと濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液５０ｍＬとを、容量１００ｍＬのガラス製ビーカに投入し、超音波ホモジナイザー（ＵＳ−３００Ｔ、定格出力：３００Ｗ、直径２６ｍｍチップ使用、（株）日本精機製作所製）に出力８０Ｗ（電流値：３００μＡ）で５分間分散処理を行なって粒状炭酸バリウム組成物懸濁液を調製した。そして、該懸濁液に含まれる炭酸バリウム粒子の体積基準の粒度分布と吸光度とを測定した。その結果、体積基準の粒度分布から求めた平均粒子径は０．１４μｍ、粒子径が１μｍ以上の粒子の含有率は３．７体積％であり、吸光度は０．８０であった。この結果から、該懸濁液には、微細な炭酸バリウム組成物粒子が均一に分散していることが確認された。 0.5 g of the above granular barium carbonate composition powder and 50 mL of sodium hexametaphosphate aqueous solution having a concentration of 0.2% by mass were put into a glass beaker having a capacity of 100 mL, and an ultrasonic homogenizer (US-300T, rated output: 300 W, A particle barium carbonate composition suspension was prepared by carrying out a dispersion treatment for 5 minutes at an output of 80 W (current value: 300 μA) using a 26 mm diameter chip, manufactured by Nippon Seiki Seisakusho Co., Ltd. Then, the volume-based particle size distribution and absorbance of the barium carbonate particles contained in the suspension were measured. As a result, the average particle size obtained from the volume-based particle size distribution was 0.14 μm, the content of particles having a particle size of 1 μm or more was 3.7% by volume, and the absorbance was 0.80. From this result, it was confirmed that fine barium carbonate composition particles were uniformly dispersed in the suspension.
［粒度分布の測定方法］
粒状炭酸バリウム組成物懸濁液を、レーザー回折散乱式粒度分布測定装置［日機装（株）製、マイクロトラック粒度分布測定装置９３２０ＨＲＡ（Ｘ−１００）］に投入し、体積基準の粒度分布を測定する。
[Measuring method of particle size distribution]
The granular barium carbonate composition suspension is put into a laser diffraction / scattering particle size distribution measuring device [manufactured by Nikkiso Co., Ltd., Microtrac particle size distribution measuring device 9320HRA (X-100)], and the volume-based particle size distribution is measured. .
［吸光度の測定方法］
粒状炭酸バリウム組成物懸濁液と濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液とを、それぞれ開口径１×１ｃｍの石英製吸光度測定用角柱セルに投入して、分光光度計（（株）日立ハイテクノロジーズ製、分光光度計Ｕ−２８００）を用いて波長６００ｎｍの吸光度を測定し、粒状炭酸バリウム組成物懸濁液の吸光度から濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液の吸光度を引いた値を求める。
[Measurement method of absorbance]
A granular barium carbonate composition suspension and an aqueous sodium hexametaphosphate solution having a concentration of 0.2% by mass were introduced into a quartz prism cell having an aperture diameter of 1 × 1 cm, respectively, and a spectrophotometer (Hitachi Co., Ltd.). A value obtained by measuring the absorbance at a wavelength of 600 nm using a spectrophotometer U-2800 manufactured by High Technologies, and subtracting the absorbance of a sodium hexametaphosphate aqueous solution having a concentration of 0.2% by mass from the absorbance of the granular barium carbonate composition suspension. Ask for.
［比較例１］
側鎖にポリオキシアルキレン基を有するポリカルボン酸無水物からなるポリマー分散剤の代わりに、ポリカルボン酸アンモニウム分散剤（サンノプコ（株）製、ＳＮディスパーサント５４６８）を懸濁液の固形分に対して８質量％となるように添加する以外は、実施例１と同様にして炭酸バリウム粉末を製造した。
[Comparative Example 1]
Instead of a polymer dispersant comprising a polycarboxylic acid anhydride having a polyoxyalkylene group in the side chain, an ammonium polycarboxylate dispersant (manufactured by San Nopco Co., Ltd., SN Dispersant 5468) is added to the solid content of the suspension. A barium carbonate powder was produced in the same manner as in Example 1 except that the amount was 8 mass%.
得られた炭酸バリウム粉末の表面を実施例１と同様にＦＴ−ＩＲを用いて１回反射ＡＴＲ法にて分析した。その結果、ポリカルボン酸アンモニウム分散剤に起因する赤外吸収ピークが検出され、炭酸バリウム粉末の表面に、ポリカルボン酸アンモニウム分散剤が付着していることが確認された。 The surface of the obtained barium carbonate powder was analyzed by the single reflection ATR method using FT-IR in the same manner as in Example 1. As a result, an infrared absorption peak due to the ammonium polycarboxylate dispersant was detected, and it was confirmed that the ammonium polycarboxylate dispersant was adhered to the surface of the barium carbonate powder.
得られた炭酸バリウム粉末をＦＥ−ＳＥＭを用いて観察した。その結果、炭酸バリウム粉末の粒子形状は粒状であることが確認された。ＦＥ−ＳＥＭ写真から画像解析ソフトウェアを用いて、一次粒子の投影面積円相当径とアスペクト比を測定した結果、投影面積円相当径の平均は３０ｎｍであり、その投影面積円相当径の平均に対する変動係数は２２．０％であり、そしてアスペクト比の平均は１．３１であった。また、得られた炭酸バリウム粉末のＢＥＴ比表面積は８０．０ｍ2／ｇであった。 The obtained barium carbonate powder was observed using FE-SEM. As a result, it was confirmed that the particle shape of the barium carbonate powder was granular. As a result of measuring the projected area circle equivalent diameter and aspect ratio of the primary particles from the FE-SEM photograph using image analysis software, the average projected area circle equivalent diameter was 30 nm, and the variation relative to the average projected area circle equivalent diameter was The coefficient was 22.0% and the average aspect ratio was 1.31. Further, the BET specific surface area of the obtained barium carbonate powder was 80.0 m 2 / g.
上記の粒状炭酸バリウム組成物粉末０．５ｇと濃度０．２質量％のヘキサメタリン酸ナトリウム水溶液５０ｍＬとを、容量１００ｍＬのガラス製ビーカに投入し、実施例１と同様に分散処理を行なって粒状炭酸バリウム組成物懸濁液を調製した。そして、該懸濁液に含まれる炭酸バリウム粒子の体積基準の粒度分布と吸光度とを実施例１と同様に測定した。その結果、体積基準の粒度分布から求めた平均粒子径は９．８７μｍ、粒子径が１μｍ以上の粒子の含有率は１００体積％であり、吸光度は１．７０であった。この結果から、該懸濁液には、炭酸バリウム組成物粒子が大きな凝集体を形成して分散していることが確認された。 0.5 g of the above granular barium carbonate composition powder and 50 mL of a 0.2 mass% sodium hexametaphosphate aqueous solution are put into a glass beaker having a capacity of 100 mL and subjected to a dispersion treatment in the same manner as in Example 1 to form granular carbonic acid. A barium composition suspension was prepared. Then, the volume-based particle size distribution and absorbance of the barium carbonate particles contained in the suspension were measured in the same manner as in Example 1. As a result, the average particle size obtained from the volume-based particle size distribution was 9.87 μm, the content of particles having a particle size of 1 μm or more was 100% by volume, and the absorbance was 1.70. From this result, it was confirmed that the barium carbonate composition particles formed a large aggregate and dispersed in the suspension.
Claims (10)
組成物粉末。 The granular barium carbonate composition powder according to claim 1, wherein the BET specific surface area is in the range of 30 to 50 m 2 / g.
が１０〜１０００μｍの範囲にある粒状媒体を用いて、側鎖にポリオキシアルキレン基を有するポリカルボン酸もしくはその無水物からなるポリマーの存在下にて１０分以上粉砕し、次いで乾燥することからなる請求項１に記載の粒状炭酸バリウム組成物粉末の製造方法。 A polycarboxylic acid having a polyoxyalkylene group in the side chain using a granular medium having a BET specific surface area of 30 m 2 / g or more in an aqueous medium and an average particle diameter in the range of 10 to 1000 μm or The method for producing a granular barium carbonate composition powder according to claim 1, comprising grinding for 10 minutes or more in the presence of the polymer comprising the anhydride and then drying.
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