JP6278380B2 - Surface-treated calcium carbonate, method for producing the same, and ceramic composition comprising the calcium carbonate - Google Patents
Surface-treated calcium carbonate, method for producing the same, and ceramic composition comprising the calcium carbonate Download PDFInfo
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- JP6278380B2 JP6278380B2 JP2013128408A JP2013128408A JP6278380B2 JP 6278380 B2 JP6278380 B2 JP 6278380B2 JP 2013128408 A JP2013128408 A JP 2013128408A JP 2013128408 A JP2013128408 A JP 2013128408A JP 6278380 B2 JP6278380 B2 JP 6278380B2
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- Prior art keywords
- calcium carbonate
- acid
- weight
- surface treatment
- treated
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 253
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 124
- 239000000919 ceramic Substances 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 39
- 239000012756 surface treatment agent Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 27
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000920 calcium hydroxide Substances 0.000 claims description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000004381 surface treatment Methods 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- -1 amine salt Chemical class 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 229910004247 CaCu Inorganic materials 0.000 claims description 2
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims 1
- 235000010216 calcium carbonate Nutrition 0.000 description 111
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 33
- 238000005259 measurement Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 229910002113 barium titanate Inorganic materials 0.000 description 11
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 11
- 235000015165 citric acid Nutrition 0.000 description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920001944 Plastisol Polymers 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000004999 plastisol Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical group COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical group CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical group CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical group COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、有機系表面処理剤で表面処理してなる炭酸カルシウム、その製造方法及び該炭酸カルシウムを配合してなるセラミック組成物に関し、さらに詳しくは、例えば、誘電体セラミックに代表される積層セラミックコンデンサ（ＭＬＣＣ）の主剤として使われるチタン酸バリウムに、電気特性や温度特性の調整剤として本発明の炭酸カルシウムを配合した場合、粒子が均一で優れた分散性を示すことから、チタン酸バリウム粒子と均一に混合することができるため、より熱安定性が高く誘電損失の少ない微細なチタン酸バリウムコンデンサを得ることができる。 The present invention relates to calcium carbonate surface-treated with an organic surface treatment agent, a method for producing the same, and a ceramic composition containing the calcium carbonate. More specifically, for example, a multilayer ceramic represented by a dielectric ceramic When the calcium carbonate of the present invention is blended with the barium titanate used as the main agent of the capacitor (MLCC) as a regulator of electrical characteristics and temperature characteristics, the particles are uniform and exhibit excellent dispersibility. Therefore, a fine barium titanate capacitor with higher thermal stability and less dielectric loss can be obtained.
従来より、電子部品用途にＭＬＣＣで代表されるチタン酸バリウムが、誘電体材料として広く使われているが、安定した電気特性や温度特性を付与する目的で、チタン酸バリウムに不純物が少ない炭酸塩等の添加物を固溶させた部位をシェルとし、固溶していない部位をコアとしたいわゆるコア−シェル構造のセラミックコンデンサーが市販されている（特許文献１参照）。 Conventionally, barium titanate, represented by MLCC, has been widely used as a dielectric material for electronic components, but for the purpose of imparting stable electrical and temperature characteristics, barium titanate has few impurities. A ceramic capacitor having a so-called core-shell structure in which a portion in which an additive such as an additive is dissolved is used as a shell and a portion where the additive is not dissolved is used as a core is commercially available (see Patent Document 1).
近年、携帯電話やモバイルパソコン、液晶テレビに代表される電子機器は、高速化、高性能化が進んでいるが、ＭＬＣＣ等も小型化、大容量化する必要がある。
従って、ＭＬＣＣ等の材料に使われるチタン酸バリウムも、より分散性を保持しながら微細化する必要がある。よって、微細なチタン酸バリウムに加えられる炭酸カルシウムも、チタン酸バリウム個々の粒子に均一に固溶される必要がある。そのためには不純物の含有量が少ないのはもちろんのこと、より分散性を保持した微細な炭酸カルシウムが求められている。
上記課題に対し、本出願人は、水酸化カルシウム水懸濁液に、金属イオンを配位して錯体を形成する物質を添加して、炭酸化反応により微細な炭酸カルシウムを生成させ、熟成させながら一次粒子を極力成長させることなく良好な分散状態が得られる微細な炭酸カルシウムの製造方法を開示している（特許文献２参照）。
しかしながら、前記公報の製造方法は、錯体形成物質を添加してから炭酸反応を行っているため、得られる炭酸カルシウムは連鎖状になる問題がある。高粘性を付与する用途の場合には有効な製法であるが、本発明の目的用途の場合は好ましくない。また、熟成後の炭酸カルシウム水懸濁液系での平均粒子径が示されているものの、乾粉後の平均粒子径ついては何ら示されていない。また目的用途が塩ビゾル等のプラスチゾル用途が主であり、プラスチゾルと相溶性が高い脂肪酸石鹸が表面処理されているため、好ましくない不純物金属が含有され、また水系での固相反応が主であるＭＬＣＣ等の場合には、疎水処理ではなく親水処理が好ましい。
従って、より不純物金属類を低減した水分散性の良好な粉末の表面処理炭酸カルシウムが必要である。
In recent years, electronic devices typified by mobile phones, mobile personal computers, and liquid crystal televisions have been improved in speed and performance, but MLCCs and the like need to be reduced in size and capacity.
Therefore, barium titanate used for materials such as MLCC also needs to be refined while maintaining more dispersibility. Therefore, the calcium carbonate added to the fine barium titanate needs to be uniformly dissolved in the individual particles of barium titanate. For this purpose, there is a demand for fine calcium carbonate having a lower dispersibility as well as more dispersibility.
In response to the above problems, the present applicant adds a substance that forms a complex by coordinating metal ions to a calcium hydroxide aqueous suspension, generates fine calcium carbonate by a carbonation reaction, and matures it. However, the manufacturing method of the fine calcium carbonate from which a favorable dispersion state is obtained, without making a primary particle grow as much as possible is disclosed (refer patent document 2).
However, the production method of the above publication has a problem that the resulting calcium carbonate is chained because the carbonation reaction is performed after the complex-forming substance is added. This is an effective production method for applications that impart high viscosity, but is not preferred for the purposes of the present invention. Moreover, although the average particle diameter in the calcium carbonate aqueous suspension system after aging is shown, there is no indication about the average particle diameter after dry powdering. In addition, plastisol applications such as vinyl chloride sol are mainly used, and since fatty acid soap that is highly compatible with plastisol is surface-treated, it contains undesirable impurity metals and is mainly used for solid-phase reactions in aqueous systems. In the case of MLCC or the like, hydrophilic treatment is preferable instead of hydrophobic treatment.
Accordingly, there is a need for a powdered surface treated calcium carbonate with good water dispersibility with reduced impurity metals.
また、炭酸カルシウム微細粒子を、水洗等により金属含有量を限定して貯蔵安定性を改善した表面処理炭酸カルシウムが開示されている（特許文献３参照）。
しかしながら、前記公報と同様、目的用途が塩ビ等のプラスチゾルへの高粘性付与であるため、前記した理由で、ＭＬＣＣ等の用途には不適である。
In addition, surface-treated calcium carbonate in which calcium carbonate fine particles are improved in storage stability by limiting the metal content by washing or the like is disclosed (see Patent Document 3).
However, as in the above publication, the intended use is to impart high viscosity to plastisol such as vinyl chloride, and therefore, it is unsuitable for uses such as MLCC for the reasons described above.
本発明は、かかる実情に鑑み、上記従来技術の課題を解消し、特に、上記セラミックに好適な水分散能を有する表面処理炭酸カルシウム、その製造方法及び該炭酸カルシウムを配合してなるセラミック組成物を提供することを目的とするものである。 In view of such circumstances, the present invention eliminates the above-mentioned problems of the prior art, and in particular, surface-treated calcium carbonate having water dispersibility suitable for the ceramic, a method for producing the same, and a ceramic composition comprising the calcium carbonate. Is intended to provide.
本発明者らは、上記課題を解決せんと鋭意検討を重ねた結果、炭酸カルシウムに特定の錯体形成物質を含有させることにより粒子成長を抑制し、特定の有機系表面処理剤で表面処理した表面処理炭酸カルシウムは、上記セラミックに好適な水分散能を得ることができることを見い出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have suppressed the particle growth by adding a specific complex-forming substance to calcium carbonate, and surface treated with a specific organic surface treatment agent. It has been found that the treated calcium carbonate can obtain a water dispersibility suitable for the above ceramics, and the present invention has been completed.
即ち、本発明の第一は、有機系表面処理剤で表面処理された炭酸カルシウムが、下記の式（ａ）〜（ｅ）を満足することを特徴とする表面処理炭酸カルシウムを内容とする。
（ａ） １０≦Ｓｗ≦１００ （ｍ2 ／ｇ）
（ｂ） ０．１≦Ａｓ≦５．０ （ｍｇ／ｍ2 ）
（ｃ） ０．０３≦Ｄｘｓ≦３．０ （μｍ）
（ｄ） Ｄｙｓ≦３０ （重量％）
（ｅ） Ｉｓ≦０．１ （μｍｏｌ／ｍ2 ）
但し、
Ｓｗ ：窒素吸着法によるＢＥＴ比表面積（ｍ2 ／ｇ）
Ａｓ ：次式により算出される単位比表面積当たりの熱減量
２００℃〜５００℃の表面処理された炭酸カルシウム１ｇ当たりの熱減量Ｔｇ（ｍｇ／ｇ）／Ｓｗ（ｇ／ｍ2 ）
Ｄｘｓ：レーザー回折式（マルバーン社製：ＭＳ−２０００）により分散媒として水を用いて測定された粒度分布において、大きな粒子側から起算した重量累計５０％平均粒子径（μｍ）。
Ｄｙｓ：上記粒度分布において、３μｍを越える粒子径の重量累計（重量％）
I ｓ ：次式により算出される単位比表面積当たりのアルカリ金属含有量
炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）／Ｓｗ（ｍ2 ／ｇ）
That is, the first of the present invention includes surface-treated calcium carbonate in which the calcium carbonate surface-treated with the organic surface treating agent satisfies the following formulas (a) to (e).
(A) 10 ≦ Sw ≦ 100 (m 2 / g)
(B) 0.1 ≦ As ≦ 5.0 (mg / m 2 )
(C) 0.03 ≦ Dxs ≦ 3.0 (μm)
(D) Dys ≦ 30 (wt%)
(E) Is ≦ 0.1 (μmol / m 2 )
However,
Sw: BET specific surface area by nitrogen adsorption method (m 2 / g)
As: Heat loss per unit specific surface area calculated by the following formula Heat loss Tg (mg / g) / Sw (g / m 2 ) per 1 g of surface-treated calcium carbonate at 200 ° C. to 500 ° C.
Dxs: laser diffraction (Malvern Co.: MS-2000) in the measured particle size distribution using water as a more dispersant, by weight cumulative 50% average particle diameter was calculated from large particles side ([mu] m).
Dys: Cumulative weight (% by weight) of particle diameters exceeding 3 μm in the above particle size distribution
Is: Alkali metal content per unit specific surface area calculated by the following formula: Metal content per gram of calcium carbonate (μmol / g) / Sw (m 2 / g)
本発明の第二は、水酸化カルシウム水スラリーに炭酸ガスを導通させる炭酸化反応終了後に、０．１〜１０重量％の錯体形成物質を添加した後、さらに有機系表面処理剤で表面処理することを特徴とする上記表面処理炭酸カルシウムの製造方法を内容とする。 In the second aspect of the present invention, after completion of the carbonation reaction for allowing carbon dioxide gas to pass through the calcium hydroxide aqueous slurry, 0.1 to 10% by weight of a complex-forming substance is added, followed by further surface treatment with an organic surface treatment agent. The manufacturing method of the said surface treatment calcium carbonate characterized by the above-mentioned is included.
本発明の第三は、上記表面処理炭酸カルシウムとセラミック材料との混合物が焼成されていることを特徴とするセラミック組成物を内容とする。 The third aspect of the present invention is directed to the content of the ceramic composition characterized Rukoto mixture of the surface-treated calcium carbonate and ceramic material are fired.
本発明の表面処理炭酸カルシウムは、粒子が均一で優れた分散性を有するとともに、上記セラミックに好適な水分散能を有し、Ｘ７Ｒ特性やＸ８Ｒ特性を満足するセラミック組成物を提供することができる。 The surface-treated calcium carbonate of the present invention can provide a ceramic composition having uniform particles and excellent dispersibility, water dispersibility suitable for the ceramic, and satisfying X7R characteristics and X8R characteristics. .
以下、本発明を詳細に説明する。
（ａ）式は、本発明の表面処理炭酸カルシウムの窒素吸着法によるＢＥＴ比表面積（Ｓｗ）であり、１０〜１００ｍ2 ／ｇが必要である。ＢＥＴ比表面積（Ｓｗ）が１０ｍ2 ／ｇ未満の場合は、粉体物性に問題はないが、チタン酸バリウム等のセラミック粒子と均一に分散するには粒子が大き過ぎるため緻密性の面で不向きである。一方、ＢＥＴ比表面積（Ｓｗ）が１００ｍ2 ／ｇを越えると、一次粒子が小さ過ぎるために経時安定性が悪く分散性の面で問題が生じる。従って、好ましくは１５〜７５ｍ2 ／ｇ、より好ましくは２０〜６０ｍ2 ／ｇである。
ＢＥＴ比表面積（Ｓｗ）の測定装置と主な測定条件を下記に示す。
＜測定装置＞
Ｍｏｕｎｔｅｃｈ社製Ｍａｃｓｏｒｂ
＜測定条件＞
前処理温度と時間＝２００℃−１０分
Hereinafter, the present invention will be described in detail.
The formula (a) is the BET specific surface area (Sw) of the surface-treated calcium carbonate of the present invention according to the nitrogen adsorption method, and 10 to 100 m 2 / g is necessary. When the BET specific surface area (Sw) is less than 10 m 2 / g, there is no problem with the powder physical properties, but the particles are too large to be uniformly dispersed with ceramic particles such as barium titanate, which is not suitable in terms of denseness. It is. On the other hand, if the BET specific surface area (Sw) exceeds 100 m 2 / g, the primary particles are too small, so that the temporal stability is poor and a problem arises in terms of dispersibility. Therefore, it is preferably 15 to 75 m 2 / g, more preferably 20 to 60 m 2 / g.
The measurement apparatus and main measurement conditions for the BET specific surface area (Sw) are shown below.
<Measurement device>
Macsorb manufactured by Mounttech
<Measurement conditions>
Pretreatment temperature and time = 200 ° C.-10 minutes
（ｂ）式は、本発明の表面処理炭酸カルシウムの単位比表面積当たりの有機系表面処理剤量（Ａｓ）で、２００℃〜５００℃の表面処理された炭酸カルシウム１ｇ当たりの熱減量Ｔｇ（ｍｇ／ｇ）／Ｓｗ（ｇ／ｍ2 ）により求められる。単位比表面積当たりの有機系表面処理剤量（Ａｓ）は０．１〜５．０ｍｇ／ｍ2 が必要である。従来の炭酸カルシウムの中には、（ａ）式を満足する１次粒子が細かいパウダーはいくつか市販されているが、1 次粒子が細かい炭酸カルシウムは、粒子の自重より粒子間結合の方が強いために、１次粒子が凝集形成して２次粒子を形成させたり、また、さらに２次粒子同士が凝集して３次粒子を形成するため、凝集パウダーを水系で再分散させるには問題がある。従って、有機系表面処理剤で炭酸カルシウムを覆い、水への再分散性を良くする必要がある。単位比表面積当たりの有機系表面処理剤量（Ａｓ）が０．１ｍｇ／ｍ2 未満では、水系での再分散性を十分に得ることができず、例えばセラミック誘電体用のチタン酸バリウム等セラミック粒子の表面を、表面処理炭酸カルシウムで混合処理しようとしても均一に処理することはできない。
一方、単位比表面積当たりの有機系表面処理剤量（Ａｓ）が５．０ｍｇ／ｍ2 を超えると、例えば本発明の目的用途である誘電体セラミックへ配合した場合、結晶の緻密性を損なわせるという問題がある。従って、好ましくは０．３〜４．０ｍｇ／ｍ2 、より好ましくは０．５〜２．０ｍｇ／ｍ2 である。
単位比表面積当りの有機系表面処理剤量（Ａｓ）の測定装置と主な測定条件を下記に示す。
＜測定装置＞
リガク社製ＴＧ−８１１０型
＜測定条件＞
熱天秤（リガク社製ＴＧ−８１１０型）にて、直径１０ｍｍで０．５ｍｌの白金製容器に表面処理した炭酸カルシウム粒子１ｇを入れ、１５℃／分の昇温速度で昇温して２００℃から５００℃までの熱減量を測定し、表面処理した炭酸カルシウム粒子１ｇ当りの熱減量（Ｔｇ）（ｍｇ／ｇ）を求め、ＢＥＴ比表面積（Ｓｗ）（ｇ／ｍ2 ）で除して求める。
The formula (b) is the amount of organic surface treatment agent (As) per unit specific surface area of the surface-treated calcium carbonate of the present invention, and the heat loss Tg (mg) per 1 g of the surface-treated calcium carbonate at 200 ° C. to 500 ° C. / G) / Sw (g / m 2 ). The amount of the organic surface treatment agent per unit specific surface area (As) needs to be 0.1 to 5.0 mg / m 2 . Among conventional calcium carbonates, several powders with fine primary particles satisfying the formula (a) are commercially available, but calcium carbonate with fine primary particles is more bound between particles than the weight of the particles. Due to its strength, primary particles are aggregated to form secondary particles, or secondary particles are aggregated to form tertiary particles, which makes it difficult to redisperse the aggregated powder in an aqueous system. There is. Therefore, it is necessary to cover the calcium carbonate with an organic surface treatment agent to improve redispersibility in water. If the amount of the organic surface treatment agent per unit specific surface area (As) is less than 0.1 mg / m 2 , sufficient redispersibility in an aqueous system cannot be obtained. For example, ceramic such as barium titanate for ceramic dielectrics Even if the surface of the particles is mixed with the surface-treated calcium carbonate, it cannot be uniformly treated.
On the other hand, when the amount of the organic surface treatment agent per unit specific surface area (As) exceeds 5.0 mg / m 2 , for example, when blended with a dielectric ceramic which is the intended use of the present invention, the compactness of the crystal is impaired. There is a problem. Therefore, preferably 0.3~4.0mg / m 2, more preferably 0.5-2.0 mg / m 2.
An apparatus for measuring the amount of organic surface treatment agent (As) per unit specific surface area and main measurement conditions are shown below.
<Measurement device>
TG-8110 type manufactured by Rigaku <Measurement conditions>
With a thermobalance (TG-8110 type manufactured by Rigaku Corporation), 1 g of calcium carbonate particles having a surface treatment of 10 mm in diameter and placed in a 0.5 ml platinum container, the temperature was raised at a rate of 15 ° C./min, and the temperature was increased to 200 ° C. The heat loss from 1 to 500 ° C. is measured, the heat loss per 1 g of the surface treated calcium carbonate particles (Tg) (mg / g) is obtained, and it is obtained by dividing by the BET specific surface area (Sw) (g / m 2 ). .
（ｃ）式、（ｄ）式は、例えば誘電体セラミック中における本発明の表面処理炭酸カルシウムの分散状態を示すもで、（ｃ）式はレーザー回折式（マルバーン社製：ＭＳ−２０００）における粒度分布において、大きな粒子側から起算した重量累計５０％平均粒子径（Ｄｘｓ）（μｍ）、（ｄ）式は上記粒度分布において、３μｍを越える粒子径の重量累計（Ｄｙｓ）（重量％）である。 The formulas (c) and (d) show, for example, the dispersion state of the surface-treated calcium carbonate of the present invention in a dielectric ceramic. The formula (c) is a laser diffraction formula (manufactured by Malvern: MS-2000). In the particle size distribution, the weight cumulative 50% average particle diameter (Dxs) (μm) calculated from the large particle side is expressed as the weight cumulative (Dys) (weight%) of the particle diameter exceeding 3 μm in the above particle size distribution. is there.
前記（ｃ）式の５０％平均粒子径（Ｄｘｓ）は０．０３〜３．０μｍである必要がある。５０％平均粒子径（Ｄｘｓ）が０．０３未満の場合、１次もしくは２次粒子の経時安定性が悪くなる。一方、３．０μｍを越えると、前記した如く３次粒子凝集体の再分散性不良が多くなり、チタン酸バリウム等セラミック粒子への均一混合の面で問題となる。従って、好ましくは０．０５〜２．０μm 、より好ましくは０．１〜１．０μｍである。
前記（ｄ）式の粒度分布において、３μｍを越える粒子径の重量累計（Ｄｙｓ）は３０重量％以下である必要がある。該重量累計（Ｄｙｓ）が３０重量％を越えると、誘電体セラミック中での十分な分散性、均一性が得られず、所望の誘電特性が得られにくい。従って、好ましくは２０重量％以下、より好ましくは１０重量％以下である。
The 50% average particle diameter (Dxs) of the formula (c) needs to be 0.03 to 3.0 μm. When the 50% average particle diameter (Dxs) is less than 0.03, the temporal stability of the primary or secondary particles is deteriorated. On the other hand, if it exceeds 3.0 μm, the redispersibility defect of the tertiary particle aggregate increases as described above, which causes a problem in terms of uniform mixing with ceramic particles such as barium titanate. Accordingly, the thickness is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.0 μm.
In the particle size distribution of the formula (d), the cumulative weight (Dys) of the particle diameter exceeding 3 μm needs to be 30% by weight or less. If the cumulative weight (Dys) exceeds 30% by weight, sufficient dispersibility and uniformity in the dielectric ceramic cannot be obtained, and it is difficult to obtain desired dielectric properties. Therefore, it is preferably 20% by weight or less, more preferably 10% by weight or less.
粒度分布測定条件：下記の配合材（Ｉ）と（II）を１４０ｍｌマヨネーズ瓶に秤量し、超音波分散機にて予備分散させたものを試料としてレーザー回折式粒度分布計（マルバーン社製：ＭＳ−２０００）により測定を行う。
（Ｉ）本発明の表面処理炭酸カルシウム １ｇ
（II）水 ６０ｇ
特に、前処理として前記した配合で調整後、予備分散として用いる超音波分散は、一定条件で行う方が好ましく、本発明の合成例で用いる超音波分散機は、チップ式超音波ＵＳ−３００Ｔ（日本精機製作所社製）を用い、電流値３００μＡの下、１８０秒間の一定条件で予備分散させる。
なお、超音波の予備分散時間は、水分散性での指標であり、通常１８０秒であるが、好ましくは１２０秒、より好ましくは６０秒で所望の分散性が得られる。
Particle size distribution measurement conditions: Laser diffraction particle size distribution meter (manufactured by Malvern Co., Ltd .: MS) was prepared by weighing the following compounding materials (I) and (II) into a 140 ml mayonnaise bottle and preliminarily dispersing them with an ultrasonic disperser. -2000).
(I) 1 g of surface treated calcium carbonate of the present invention
(II) Water 60g
In particular, it is preferable that the ultrasonic dispersion used as the pre-dispersion after adjusting with the above-described formulation as the pretreatment is performed under a certain condition, and the ultrasonic disperser used in the synthesis example of the present invention is a chip type ultrasonic US-300T ( Nippon Seiki Seisakusho Co., Ltd.) and pre-dispersed under a constant condition of 180 seconds under a current value of 300 μA.
The ultrasonic pre-dispersion time is an indicator of water dispersibility, and is usually 180 seconds, but the desired dispersibility can be obtained in 120 seconds, more preferably 60 seconds.
（ｅ）式は、本発明の表面処理炭酸カルシウム中に含有される、単位比表面積当たりのアルカリ金属含有量（Ｉｓ）で、０．５μｍｏｌ／ｍ2 以下であることが必要である。アルカリ金属は、焼成しても残留物として存在するため、ＭＬＣＣの電気特性に悪影響を及ぼす。また下限値は特に限定されないが、例えば０．００１μｍｏｌ／ｍ2 未満にするには、炭酸カルシウムの生成量を極めて少なくするか、生成した炭酸カルシウムを過度に水洗する必要性がある。この結果、生産量が極端に少なくなったり、多量の水を必要とするため、生産性が低くコスト高となる。従って、好ましくは０．００５〜０．３μｍｏｌ／ｍ2 、より好ましくは０．０１〜０．１μｍｏｌ／ｍ2 である。
単位比表面積当たりのアルカリ金属含有量（Ｉｓ）の測定装置と主な測定条件を下記に示す。
＜測定装置＞
島津製作所社製原子吸光分光光度計AA-677F 型
＜測定条件＞
検量線法によりアルカリ金属含有量を求める。
The formula (e) is an alkali metal content (Is) per unit specific surface area contained in the surface-treated calcium carbonate of the present invention, and is required to be 0.5 μmol / m 2 or less. Alkali metal exists as a residue even after firing, and thus adversely affects the electrical characteristics of MLCC. The lower limit is not particularly limited, but for example, to make it less than 0.001 μmol / m 2 , it is necessary to extremely reduce the amount of calcium carbonate produced or excessively wash the produced calcium carbonate. As a result, the production volume is extremely reduced or a large amount of water is required, resulting in low productivity and high cost. Therefore, it is preferably 0.005 to 0.3 μmol / m 2 , more preferably 0.01 to 0.1 μmol / m 2 .
An apparatus for measuring alkali metal content (Is) per unit specific surface area and main measurement conditions are shown below.
<Measurement device>
Atomic absorption spectrophotometer AA-677F manufactured by Shimadzu Corporation <Measurement conditions>
The alkali metal content is determined by a calibration curve method.
本発明有表面処理炭酸カルシウムは、更に下記の式（ｇ）、（ｆ）を満足することが好ましい。
（ｆ） Ｉｍ≦０．２ （μｍｏｌ／ｍ2 ）
（ｇ） Ｉｒ≦０．２ （μｍｏｌ／ｍ2 ）
但し、
I ｍ ：次式により算出される単位比表面積当たりのマグネシウム金属含有量
炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）／Ｓｗ（ｍ2 ／ｇ）
I ｒ ：次式により算出される単位比表面積当たりのストロンチウム金属含有量
炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）／Ｓｗ（ｍ2 ／ｇ）
前記（ｆ）式、（ｇ）式は、それぞれ本発明の表面処理炭酸カルシウム中に含有される、単位比表面積当たりのマグネシウム金属の含有量（Ｉｍ）、ストロンチウム金属の含有量（Ｉｒ）を示している。
The surface-treated calcium carbonate of the present invention preferably further satisfies the following formulas (g) and (f).
(F) Im ≦ 0.2 (μmol / m 2 )
(G) Ir ≦ 0.2 (μmol / m 2 )
However,
I m: Magnesium metal content per unit specific surface area calculated by the following formula: Metal content per gram of calcium carbonate (μmol / g) / Sw (m 2 / g)
I r: Strontium metal content per unit specific surface area calculated by the following formula: Metal content per gram of calcium carbonate (μmol / g) / Sw (m 2 / g)
The formulas (f) and (g) indicate the magnesium metal content (Im) and the strontium metal content (Ir) per unit specific surface area contained in the surface-treated calcium carbonate of the present invention, respectively. ing.
マグネシウムやストロンチウムは、カルシウムと同族なアルカリ土類金属であるため、他の金属と比べ含有量が比較的多くなり易く、本発明の目的用途である誘電体セラミックへ配合した場合、格子欠陥による誘電率の低下や品質係数（Ｑ値）の低下を招く場合があるため、０．２μｍｏｌ／ｍ2 以下であることが好ましい。また（Ｉｍ）や（Ｉｒ）の下限値は特に限定されないが、例えば０．０００１μｍｏｌ／ｍ2 未満にするには、前記したように、生産性やコストの面で問題が生じ易い。従って、（Ｉｍ）のより好ましい範囲は０．０００１〜０．１μｍｏｌ／ｍ2 、さらに好ましくは０．０００１〜０．０５μｍｏｌ／ｍ2 である。（Ｉｒ）のより好ましい範囲は、０．０００１〜０．０１μｍｏｌ／ｍ2 、さらに好ましくは０．０００１〜０．００１μｍｏｌ／ｍ2 である。
単位比表面積当たりのマグネシウム金属含有量（I ｍ）及び単位比表面積当たりのストロンチウム金属含有量（I ｒ）の測定装置と主な測定条件を下記に示す。
＜測定装置＞
島津製作所社製原子吸光分光光度計AA-6700F型
＜測定条件＞
検量線法により、Mg金属、Sr金属の含有量を求める。
Magnesium and strontium are alkaline earth metals of the same family as calcium, so their content is likely to be relatively large compared to other metals, and when blended into the dielectric ceramic, which is the intended application of the present invention, The rate is preferably 0.2 μmol / m 2 or less because it may cause a decrease in the rate and a decrease in the quality factor (Q value). Further, the lower limit value of (Im) and (Ir) is not particularly limited. However, for example, if it is less than 0.0001 μmol / m 2 , as described above, problems are likely to occur in terms of productivity and cost. Therefore, a more preferable range of (Im) is 0.0001 to 0.1 μmol / m 2 , and further preferably 0.0001 to 0.05 μmol / m 2 . A more preferable range of (Ir) is 0.0001 to 0.01 μmol / m 2 , and further preferably 0.0001 to 0.001 μmol / m 2 .
An apparatus for measuring magnesium metal content (I m) per unit specific surface area and strontium metal content (I r) per unit specific surface area and main measurement conditions are shown below.
<Measurement device>
Atomic absorption spectrophotometer AA-6700F manufactured by Shimadzu Corporation <Measurement conditions>
Obtain the contents of Mg metal and Sr metal by the calibration curve method.
本発明の表面処理炭酸カルシウムの表面処理を行う前の炭酸カルシウムの調整方法は水酸化カルシウム水スラリーに炭酸ガスを導通する炭酸ガス法が好ましく、炭酸化反応で粒子径を調整した後、錯体形成物質を所定量添加し、微細な炭酸カルシウム粒子を保持調整する方法が例示できる。但し、原料となる石灰石は、一般的な緻密質石灰石を利用しても構わないが、前記した（ｅ）式を満たすために、カルシウムと同族元素であるマグネシウムやストロンチウム等の不純物金属元素が除去された水酸化カルシルシウム懸濁液が好ましく、例えば特開平１０−１３００２０に記載の如く、不純物金属元素が比較的少ない溶液反応を利用した炭酸カルシウムを原料として用いるのが好ましい。 The method for adjusting calcium carbonate before the surface treatment of the surface-treated calcium carbonate of the present invention is preferably a carbon dioxide method in which carbon dioxide gas is conducted to a calcium hydroxide aqueous slurry, and after adjusting the particle size by carbonation reaction, complex formation A method of adding a predetermined amount of a substance and holding and adjusting fine calcium carbonate particles can be exemplified. However, as the raw material limestone, general dense limestone may be used, but in order to satisfy the above-mentioned formula (e), impurity metal elements such as magnesium and strontium, which are elements similar to calcium, are removed. The calcium hydroxide suspension is preferably used. For example, as described in JP-A-10-130020, calcium carbonate using a solution reaction with a relatively small amount of impurity metal elements is preferably used as a raw material.
また、錯体形成物質を添加する場合、焼成後の灰分が残存しないものが好ましい。具体的には、クエン酸、シュウ酸、リンゴ酸等のヒドロキシカルボン酸とそのアンモニウム塩及びアミン塩；グルコン酸、酒石酸等のポリヒドロキシカルボン酸とそのアンモニウム塩及びアミン塩；イミノジ酢酸、エチレンジアミン４酢酸、ニトリロトリ酢酸等のアミノポリカルボンとアンモニウム塩及びアミン塩；アセルアセトン、アセト酢酸メチル、アセト酢酸アリル等のケトン類等が挙げられ、これらは単独であるいは２種類以上組み合わせて使用される。中でもヒドロキカルボン酸類は、カルシウムとの結合性が高く、特にクエン酸で代表されるヒドロキシカルボン酸系が、カルシウムの錯体形成効果が高く好適に使用することができる。 Moreover, when adding a complex formation substance, the thing in which the ash after baking does not remain | survive is preferable. Specifically, hydroxycarboxylic acids such as citric acid, oxalic acid and malic acid and ammonium salts and amine salts thereof; polyhydroxycarboxylic acids such as gluconic acid and tartaric acid and ammonium salts and amine salts thereof; iminodiacetic acid and ethylenediaminetetraacetic acid And aminopolycarboxylic acids such as nitrilotriacetic acid and ammonium salts and amine salts; ketones such as acetacetone, methyl acetoacetate and allyl acetoacetate, and the like. These may be used alone or in combination of two or more. Of these, hydroxycarboxylic acids have a high binding property with calcium, and hydroxycarboxylic acids represented by citric acid are particularly preferable because of their high calcium complexing effect.
錯体形成物質の添加量は、（ａ）式に示した表面処理炭酸カルシウムのＢＥＴ比表面積（Ｓｗ）や、（ｂ）式に示した単位比表面積当たりの有機系表面処理剤量（Ａｓ）により左右されるため、一概には測定できないが、通常０．１〜１０重量％である。錯体形成物質の添加量が、０．１重量％未満の場合は、カルシウムとのキレート効果が低く、１０重量％を超えると錯体形成物質の劣化で炭酸カルシウムの分散安定性を低下させる場合がある。従って、好ましくは０．３〜５重量％、より好ましくは０．５〜３重量％である。
錯体形成物質は、炭酸化反応を終了した直後の炭酸カルシウム水スラリーに添加され、５〜６０分程度攪拌する。
The addition amount of the complex-forming substance depends on the BET specific surface area (Sw) of the surface-treated calcium carbonate represented by the formula (a) and the organic surface treatment agent amount (As) per unit specific surface area represented by the formula (b). However, it is generally 0.1 to 10% by weight although it cannot be measured in general. When the addition amount of the complex-forming substance is less than 0.1% by weight, the chelate effect with calcium is low, and when it exceeds 10% by weight, the dispersion stability of the calcium carbonate may be lowered due to the deterioration of the complex-forming substance. . Therefore, it is preferably 0.3 to 5% by weight, more preferably 0.5 to 3% by weight.
The complex-forming substance is added to the calcium carbonate water slurry immediately after the carbonation reaction is completed, and is stirred for about 5 to 60 minutes.
上記の如き方法で炭酸カルシウム水スラリーを調整した後、炭酸カルシウムは有機系表面処理剤で表面処理（表面被覆）される。
本発明で用いられる有機系表面処理剤は、セラミック誘電体の混合系が主に水系である場合が多いため、数平均分子量（ゲル浸透圧クロマトグラフ測定）が５００〜５００００程度の親水性界面活性剤であることが好ましい。数平均分子量が５００未満の場合は炭酸カルシウムへの表面処理率が低下する傾向があり、また５００００を越える場合、疎水化により炭酸カルシウムの均一な処理が悪化する場合がある。従って、より好ましくは２０００〜３００００の範囲である。
After adjusting the calcium carbonate water slurry by the method as described above, the calcium carbonate is subjected to surface treatment (surface coating) with an organic surface treatment agent.
Since the organic surface treatment agent used in the present invention is mainly an aqueous ceramic dielectric mixture, the hydrophilic surface activity has a number average molecular weight (gel osmotic pressure chromatographic measurement) of about 500 to 50,000. It is preferable that it is an agent. When the number average molecular weight is less than 500, the surface treatment rate to calcium carbonate tends to decrease, and when it exceeds 50,000, the uniform treatment of calcium carbonate may deteriorate due to hydrophobization. Therefore, the range of 2000 to 30000 is more preferable.
具体的には、α、βモノエチレン性不飽和カルボン酸系が例示できる。不飽和カルボン酸としては、アクリル酸、メタクリル酸、クロトン酸等から選ばれるα、β不飽和モノカルボン酸、マレイン酸、イタコン酸、フマール酸等から選ばれるα、β不飽和ジカルボン酸を例示することができる。
また本発明の有機表面処理剤の重合体は、（Ｉ）α、βモノエチレン性不飽和カルボン酸又はその塩の１種又は２種以上の単独重合体、及び（II）α、βモノエチレン性不飽和カルボン酸又は共重合体、及びα、βモノエチレン性不飽和カルボン酸又は共重合体、及び（III)α、βモノエチレン性不飽和カルボン酸又はその塩と共重合性を有する単量体を１種以上共重合した有機系表面処理剤が例示できる。
Specific examples include α and β monoethylenically unsaturated carboxylic acid systems. Examples of unsaturated carboxylic acids include α, β unsaturated monocarboxylic acids selected from acrylic acid, methacrylic acid, crotonic acid, etc., α, β unsaturated dicarboxylic acids selected from maleic acid, itaconic acid, fumaric acid, etc. be able to.
The polymer of the organic surface treating agent of the present invention comprises (I) one or more homopolymers of α, β monoethylenically unsaturated carboxylic acid or a salt thereof, and (II) α, β monoethylene. Unsaturated carboxylic acid or copolymer, and α, β monoethylenically unsaturated carboxylic acid or copolymer, and (III) α, β monoethylenically unsaturated carboxylic acid or a salt thereof. Examples thereof include organic surface treating agents obtained by copolymerizing one or more monomers.
また、（III)の共重合性を有する具体的な単量体としては、下記の（Ａ）〜（Ｅ）のものが例示できる。
（Ａ）アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソブチル、メタクリル酸２−エチルヘキシル等のアクリル酸アルキルエステル及びメタクリル酸アルキルエステル系。
（Ｂ）メトキシエチルアクリレート、メトシキエチルメタクリレート、エトキシエチルアクリレート、エトキシエチルメタクリレート等のアルコキシ基を有するアクリレート及びメタクリレート系。
（Ｃ）シクロヘキシルアクリレート、シクロヘキシルメタクリレート等のシクロヘキシル基を有するアクリレート及びメタクリレート系。
（Ｄ）２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート等のα、βモノエチレン性不飽和ヒドロキシエステル系。
（Ｅ）ポリエチレングリコールモノアクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノアクリレート、ポリプロピレングリコールモノメタクリレート、ポリエチレングリコールポリプロピレングリコールモノメタクリレート、メトキシポリエチレングリコールポリテトラメチレングリコールモノメタクリレート、メトキシポリエチレングリコールモノメタクリレート等のポリアルキレングリコールモノアクリレート及びモノメタクリレート系。
中でも（Ｅ）群の重合性単量体は、炭酸カルシウムの分散性において、好適に用いることができる。
Specific examples of the monomer (III) having copolymerizability include the following (A) to (E).
(A) Acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate Alkyl esters and methacrylic acid alkyl esters.
(B) Acrylates and methacrylates having alkoxy groups such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate and the like.
(C) Acrylates and methacrylates having a cyclohexyl group, such as cyclohexyl acrylate and cyclohexyl methacrylate.
(D) α, β monoethylenically unsaturated hydroxyesters such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
(E) Polyalkylene glycols such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate, methoxypolyethylene glycol polytetramethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate Monoacrylate and monomethacrylate.
Among them, the polymerizable monomer of group (E) can be preferably used in terms of the dispersibility of calcium carbonate.
α、βモノエチレン系不飽和モノカルボン酸から選ばれる少なくとも１種に、該α、βモノエチレン系不飽和ジカルボン酸との共重合性を有するその他の単量体との共重合体において、該α、βモノエチレン系不飽和ジカルボン酸の占める割合は、α、βモノエチレン不飽和モノカルボン酸１００重量部当たり、０〜２００重量部であることが好ましい。 α、βモノエチレン系不飽和モノカルボン酸から選ばれる少なくとも１種に、前記（Ａ）〜（Ｅ）の共重合性を有する単量体の占める割合は、α、βモノエチレン不飽和モノカルボン酸１００重量部当たり、１０〜２００重量部であることが好ましい。当該単量体の効果を十分に発揮させるためには、５〜１５０重量が好ましく、１０〜１００重量部がより好ましい。 In at least one selected from α, β monoethylenically unsaturated monocarboxylic acid, a copolymer with the other monomer having copolymerizability with the α, β monoethylenically unsaturated dicarboxylic acid, The proportion of the α, β monoethylenically unsaturated dicarboxylic acid is preferably 0 to 200 parts by weight per 100 parts by weight of the α, β monoethylenically unsaturated monocarboxylic acid. The proportion of the monomers (A) to (E) having copolymerizability in at least one selected from α and β monoethylenically unsaturated monocarboxylic acids is α, β monoethylenically unsaturated monocarboxylic acid. The amount is preferably 10 to 200 parts by weight per 100 parts by weight of the acid. In order to fully exhibit the effect of the monomer, 5 to 150 parts by weight is preferable, and 10 to 100 parts by weight is more preferable.
表面処理剤の表面処理量は、炭酸カルシウムのＢＥＴ比表面積によって左右されるため、（ｂ）式に示した単位比表面積当たりの有機系表面処理剤量（Ａｓ）の範囲内の吸着量であれば特に限定されないが、通常０．１〜１０重量％である。表面処理剤量が０．１重量％未満の場合、本発明の微細で高分散性である炭酸カルシウムの表面を十分に覆うことができず、乾燥・粉末化の際、未処理面同士で２次凝集を形成し易いため、該表面処理炭酸カルシウムとしての効果が十分発揮できにくくなる。また、１０重量％を越えると、焼成の際に表面処理剤過多によるセラミック誘電体に空孔ができ、製品の安定性や信頼性に影響を与える原因となる場合がある。従って、より好ましくは０．５〜７重量％、さらに好ましくは１〜５重量％である。 Since the surface treatment amount of the surface treatment agent depends on the BET specific surface area of calcium carbonate, it may be an adsorption amount within the range of the organic surface treatment agent amount (As) per unit specific surface area shown in the formula (b). Although it will not specifically limit if it is 0.1 to 10 weight% normally. When the amount of the surface treatment agent is less than 0.1% by weight, the fine and highly dispersible calcium carbonate surface of the present invention cannot be sufficiently covered. Since secondary agglomeration is easily formed, the effect as the surface-treated calcium carbonate cannot be sufficiently exhibited. On the other hand, when the content exceeds 10% by weight, pores are formed in the ceramic dielectric due to excessive surface treatment agent during firing, which may cause an influence on the stability and reliability of the product. Therefore, it is more preferably 0.5 to 7% by weight, still more preferably 1 to 5% by weight.
表面処理後、さらに分散効果を高めるために、湿式であればサンドグラインダーミルや湿式ジェット粉砕機、ホモジナイザー等を、乾式であれば振動ボールミルや乾式ジェット粉砕機を通過させ、所望の粒度になるよう調整する方法は好ましい態様である。 After the surface treatment, in order to further enhance the dispersion effect, if it is wet, it is passed through a sand grinder mill, wet jet pulverizer, homogenizer, etc. The method of adjusting is a preferred embodiment.
次に、本発明のセラミック組成物について説明する。
先ず本発明の表面処理炭酸カルシウムが使われるセラミック組成物は、誘電体もしくは圧電体構造であれば特に限定されるものでなく、BaTiO3系、SrTiO3系、CaTiO3系、PbTiO3系、PbZrO3系、CaZrO3系、CaCu3Ti4O12 系などのセラミック組成物が例示できる。中でも特に、ニッケル（Ni）を内部電極に用いたチタン酸バリウム（BaTiO3）系積層セラミックコンデンサで知られる強誘電体用途に効果が極めて高く、本発明の目的用途から、Ｘ７Ｒ特性やＸ８Ｒ特性を満足したセラミック組成物として例示することができる。
また、各種センサーやフィルター用途に使われる焦電体も強誘電体セラミックとして問題なく、本発明の表面処理炭酸カルシウムを使用することができる。
Next, the ceramic composition of the present invention will be described.
First, the ceramic composition in which the surface-treated calcium carbonate of the present invention is used is not particularly limited as long as it is a dielectric or piezoelectric structure. BaTiO 3 , SrTiO 3 , CaTiO 3 , PbTiO 3 , PbZrO Examples of the ceramic composition include 3 series, CaZrO 3 series, and CaCu 3 Ti 4 O 12 series. In particular, it is extremely effective for ferroelectric applications known as barium titanate (BaTiO 3 ) multilayer ceramic capacitors using nickel (Ni) as an internal electrode. From the intended use of the present invention, X7R characteristics and X8R characteristics are improved. It can be exemplified as a satisfactory ceramic composition.
In addition, the pyroelectric material used for various sensors and filters can be used as the ferroelectric ceramic without any problem, and the surface-treated calcium carbonate of the present invention can be used.
BaTiO3系セラミックの構造は、BaTiO3系に炭酸カルシウム（CaCO3 ）を含む各種添加剤を固溶させるのが一般的である。俗にいう、コア層にBaTiO3系、シェル層にCaCO3 を含む添加剤を配合したコア−シェル構造を有する構造体であってもよい。
具体的に各種添加剤としては、CaCO3 以外に、BaCO3 、SrCO3 、SiO2等のガラス系焼結材の他、Y2O3、Dy2O3 、Ho2O3 等の希土類酸化物で代表される絶縁抵抗材、MgO で代表される拡散制御材、MnCO3 やCr2O3 で代表される電気抵抗材等が例示できる。
BaTiO3系セラミック組成物は、固相法、水熱合成法、蓚酸法、ゾルゲル法等で調整することができる。さらにキュリー点等を制御する目的等でBaサイトにCaやSr、Pb、Bi、Zn等の酸化物を添加し固溶させても問題ない。
本発明の表面処理炭酸カルシウムを含む、各種主剤や添加剤を混合分散した水懸濁液を乾燥後、任意の大きさに調整し、任意の焼成条件で還元焼成等を行い、本発明のセラミック組成物を得ることができる。
The structure of BaTiO 3 ceramic is generally obtained by dissolving various additives including calcium carbonate (CaCO 3 ) in the BaTiO 3 system. The core may be a structure having a core-shell structure in which an additive containing BaTiO 3 in the core layer and CaCO 3 in the shell layer is blended.
Specifically, in addition to CaCO 3 , various additives include glass-based sintered materials such as BaCO 3 , SrCO 3 , and SiO 2 , and rare earth oxidation such as Y 2 O 3 , Dy 2 O 3 , and Ho 2 O 3. Insulation resistance materials typified by materials, diffusion control materials typified by MgO 2, electrical resistance materials typified by MnCO 3 and Cr 2 O 3 , etc. can be exemplified.
The BaTiO 3 ceramic composition can be prepared by a solid phase method, a hydrothermal synthesis method, an oxalic acid method, a sol-gel method, or the like. Furthermore, there is no problem even if an oxide such as Ca, Sr, Pb, Bi, or Zn is added to the Ba site and dissolved in order to control the Curie point or the like.
The aqueous suspension containing the surface treated calcium carbonate of the present invention, in which various main ingredients and additives are mixed and dispersed, is dried, adjusted to any size, subjected to reduction firing under any firing conditions, and the ceramic of the present invention A composition can be obtained.
実施例１
特開平１０−１３００２０号公報に記載の実施例３に従い、濃度１．６mol/L の炭酸アンモニウム水溶液と、濃度０．８mol/L の液体塩化カルシウム水溶液を各１００Ｌ用意し共に液温１０℃に温調した。次に、炭酸アンモニウム水溶液側に塩化カルシウム水溶液１００Ｌを動力０．５ｋｗの攪拌条件で、滴下混合を開始し、６００秒後に炭酸化反応を終了した。
該炭酸カルシウム水スラリーを遠心脱水機を用いて濃縮し、濃縮液に水を加えて再度希釈し攪拌した希釈液を遠心脱水機を用いて濃縮し、遠心脱水機の濾液の電気伝導度が２００μＳ／cm以下に降下するまで水洗濃縮し、平均系２．６μｍの炭酸カルシウム（カルサイト結晶）を得た。
該炭酸カルシウムをロータリーキルンで焼成し生石灰を得、純水で消化して水酸化カルシム水スラリーを調整した。
次に、濃度７重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、温度１５℃に冷却後、水酸化カルシウム１ｋｇ当たり６００Ｌ／ｈｒの二酸化炭素ガスを導入し、ｐＨ７．０まで炭酸化反応を行った。炭酸化反応を終了した直後の炭酸カルシウム水スラリーに、錯体形成物質としてクエン酸を炭酸カルシウムに対し０．５重量％添加し１０分間攪拌した。その後、フィルタープレスを用いて含水率約６０％に脱水し、攪拌下で表１に示す表面処理剤を炭酸カルシウムに対して２重量％添加し表面処理した後、常法に従い、粉砕、乾燥を行うことにより本発明の表面処理炭酸カルシウムを得た。
Example 1
According to Example 3 described in Japanese Patent Laid-Open No. 10-130020, 100 L each of a 1.6 mol / L ammonium carbonate aqueous solution and a 0.8 mol / L liquid calcium chloride aqueous solution were prepared and heated to a liquid temperature of 10 ° C. Adjusted. Next, dropwise mixing of 100 L of calcium chloride aqueous solution on the ammonium carbonate aqueous solution side under stirring conditions with a power of 0.5 kw was started, and the carbonation reaction was terminated after 600 seconds.
The calcium carbonate aqueous slurry is concentrated using a centrifugal dehydrator, and the diluted liquid is diluted again by adding water to the concentrated liquid, and the stirred diluted liquid is concentrated using a centrifugal dehydrator. The electric conductivity of the filtrate of the centrifugal dehydrator is 200 μS. The solution was concentrated by washing with water until it dropped below / cm, and an average system of 2.6 μm calcium carbonate (calcite crystal) was obtained.
The calcium carbonate was calcined in a rotary kiln to obtain quicklime, and digested with pure water to prepare a calcium hydroxide water slurry.
Next, 20 L of a calcium hydroxide water slurry adjusted to a concentration of 7% by weight is prepared, cooled to a temperature of 15 ° C., carbon dioxide gas of 600 L / hr per 1 kg of calcium hydroxide is introduced, and the carbonation reaction is carried out to pH 7.0. Went. To the calcium carbonate water slurry immediately after the carbonation reaction was completed, 0.5% by weight of citric acid as a complex-forming substance was added to the calcium carbonate and stirred for 10 minutes. Then, after dehydrating to a moisture content of about 60% using a filter press and adding 2% by weight of the surface treatment agent shown in Table 1 to the calcium carbonate with stirring, the surface treatment was performed, followed by pulverization and drying according to conventional methods. By performing, the surface-treated calcium carbonate of the present invention was obtained.
実施例２
濃度５重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、温度１０℃に冷却後、水酸化カルシウム１ｋｇ当たり６００Ｌ／ｈｒの二酸化炭素ガスを導入し、ｐＨ７．０まで炭酸化反応を行った。炭酸化反応を終了した直後の炭酸カルシウム水スラリーに、錯体形成物質としてクエン酸を炭酸カルシウムに対し１．０重量％添加に変更した以外は、実施例１と同様の方法で炭酸カルシウムを調整した。
その後、表１に示す表面処理剤を炭酸カルシウムに対して４重量％添加した以外は実施例１と同様の方法により本発明の表面処理炭酸カルシウムを得た。
Example 2
20 L of calcium hydroxide water slurry adjusted to a concentration of 5% by weight was prepared, cooled to a temperature of 10 ° C., carbon dioxide gas of 600 L / hr per 1 kg of calcium hydroxide was introduced, and the carbonation reaction was carried out to pH 7.0. . The calcium carbonate was adjusted in the same manner as in Example 1 except that citric acid was added to the calcium carbonate water slurry immediately after the carbonation reaction as a complex-forming substance in an amount of 1.0% by weight based on calcium carbonate. .
Then, the surface treatment calcium carbonate of this invention was obtained by the method similar to Example 1 except having added 4 weight% of surface treatment agents shown in Table 1 with respect to calcium carbonate.
実施例３
濃度３重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、温度８℃に冷却後、水酸化カルシウム１ｋｇ当たり６００Ｌ／ｈｒの二酸化炭素ガスを導入し、ｐＨ７．０まで炭酸化反応を行った。炭酸化反応を終了した直後の炭酸カルシウム水スラリーに、錯体形成物質としてクエン酸を炭酸カルシウムに対し２．０重量％添加に変更した以外は、実施例１と同様の方法で炭酸カルシウムを調整した。
その後、表１に示す表面処理剤を炭酸カルシウムに対して５．５重量％添加した以外は実施例１と同様の方法により本発明の表面処理炭酸カルシウムを得た。
Example 3
20 L of calcium hydroxide water slurry adjusted to a concentration of 3% by weight was prepared, cooled to a temperature of 8 ° C., and then carbon dioxide gas of 600 L / hr per 1 kg of calcium hydroxide was introduced to conduct a carbonation reaction to pH 7.0. . Calcium carbonate was prepared in the same manner as in Example 1 except that citric acid was added to the calcium carbonate water slurry immediately after the carbonation reaction was added to 2.0% by weight of calcium carbonate as a complex-forming substance. .
Then, the surface treatment calcium carbonate of this invention was obtained by the method similar to Example 1 except having added 5.5 weight% of surface treatment agents shown in Table 1 with respect to calcium carbonate.
実施例４
濃度１０重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、錯体形成物質としてクエン酸を炭酸カルシウムに対し０．１重量％添加に変更した以外は、実施例１と同様の方法で炭酸カルシウムを調整した。
Example 4
Calcium carbonate was prepared in the same manner as in Example 1 except that 20 L of a calcium hydroxide aqueous slurry adjusted to a concentration of 10% by weight was prepared, and citric acid was changed to 0.1% by weight added to calcium carbonate as a complex-forming substance. Adjusted.
実施例５
濃度０．８mol/L の工業用塩化カルシウム水溶液と、濃度１．６mol/L の液体苛性ソーダ水溶液を各１００Ｌ用意した。塩化カルシウム水溶液側の液温を９５℃に温調し、動力０．５ｋｗの攪拌条件で苛性ソーダ水溶液を滴下混合開始し、約２００分に消化反応を終了した。
得られた水酸化カルシウム水スラリーを、遠心脱水機を用いて濃縮し、該濃縮液に純水を加えて希釈し攪拌した後、再度希釈液を遠心脱水機で濃縮し、遠心脱水機の濾液の電気伝導度が１０００μＳ／cm以下に降下するまで水洗濃縮し、水酸化カルシウム水スラリーを得た。それ以降は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
次に濃度５重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、温度１３℃に冷却後、水酸化カルシウム１ｋｇ当たり６００Ｌ／ｈｒの二酸化炭素ガスを導入しｐＨ７．０まで炭酸化を行った。調整した炭酸カルシウム水スラリーに、錯体形成物質としてクエン酸を炭酸カルシウムに対し０．５重量％添加し十分撹拌した。
その後、表１に示す表面処理剤を炭酸カルシウムに対して２重量％添加した以外は、実施例１と同様の方法により本発明の表面処理炭酸カルシウムを得た。
Example 5
100 L each of an industrial calcium chloride aqueous solution having a concentration of 0.8 mol / L and a liquid caustic soda aqueous solution having a concentration of 1.6 mol / L were prepared. The liquid temperature on the calcium chloride aqueous solution side was adjusted to 95 ° C., and the caustic soda aqueous solution was dropped and mixed under a stirring condition with a power of 0.5 kw, and the digestion reaction was completed in about 200 minutes.
The obtained calcium hydroxide aqueous slurry is concentrated using a centrifugal dehydrator, and pure water is added to the concentrate to dilute and stir, and then the diluted solution is concentrated again using a centrifugal dehydrator, and the filtrate of the centrifugal dehydrator is added. The resulting solution was concentrated by washing with water until the electric conductivity of the solution dropped to 1000 μS / cm or less to obtain a calcium hydroxide aqueous slurry. Thereafter, the surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1.
Next, 20 L of calcium hydroxide water slurry adjusted to a concentration of 5 wt% was prepared, cooled to a temperature of 13 ° C., and then carbonized to 600 by introducing 600 L / hr of carbon dioxide gas per kg of calcium hydroxide. . To the adjusted calcium carbonate aqueous slurry, 0.5% by weight of citric acid as a complex-forming substance was added with respect to calcium carbonate and sufficiently stirred.
Then, the surface treatment calcium carbonate of this invention was obtained by the method similar to Example 1 except having added 2 weight% of surface treatment agents shown in Table 1 with respect to calcium carbonate.
実施例６
得られた水酸化カルシウム水懸濁液を、遠心脱水機を用いて濃縮し、濃縮液に純水を加えて希釈し攪拌した後、再度希釈液を遠心脱水機で濃縮し、遠心脱水機の濾液の電気伝導度が６００μＳ／ｃｍ以下に降下するまで水洗濃縮し、水酸化カルシウム水懸濁液を得た以外は、実施例５と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 6
Concentrate the obtained calcium hydroxide aqueous suspension using a centrifugal dehydrator, add pure water to the concentrate, dilute and stir, and then concentrate the diluted solution again with a centrifugal dehydrator. The surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 5 except that the filtrate was washed and concentrated until the electrical conductivity dropped to 600 μS / cm or less to obtain a calcium hydroxide aqueous suspension.
実施例７
錯体形成物質としてクエン酸の添加量を炭酸カルシウムに対して６重量％に変更した以外は、実施例５と同様の方法で表面処理炭酸カルシウムを得た。
Example 7
Surface-treated calcium carbonate was obtained in the same manner as in Example 5 except that the amount of citric acid added as a complex-forming substance was changed to 6% by weight with respect to calcium carbonate.
実施例８
都市ガスを熱源に灰色緻密質石灰石をキルンで焼成し、得られた生石灰を水道水で溶解して水酸化カルシウム水スラリーを得た。それ以降は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 8
Gray dense limestone was calcined in a kiln using city gas as a heat source, and the obtained quicklime was dissolved in tap water to obtain a calcium hydroxide water slurry. Thereafter, the surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1.
実施例９
表面処理剤の重合性単量体として、アクリル酸マレイン酸の共重合体に変更した以外は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 9
The surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1 except that the monomer for the surface treatment agent was changed to a copolymer of maleic acrylate.
実施例１０
表面処理剤の重合性単量体として、ポリエチレングリコールモノメタクリレートをアクリル酸メチルに変更した以外は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 10
The surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1 except that polyethylene glycol monomethacrylate was changed to methyl acrylate as the polymerizable monomer for the surface treatment agent.
実施例１１
表面処理剤の重合性単量体として、ポリエチレングリコールモノメタクリレートをメトキシエチルアクリレートに変更した以外は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 11
The surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1 except that polyethylene glycol monomethacrylate was changed to methoxyethyl acrylate as the polymerizable monomer for the surface treatment agent.
実施例１２
表面処理剤の重合性単量体として、ポリエチレングリコールモノメタクリレートをシクロヘキシルアクリレートに変更し、さらにアンモニウム塩をアミン塩に変更した以外は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 12
As a polymerizable monomer for the surface treatment agent, the surface-treated calcium carbonate of the present invention was prepared in the same manner as in Example 1 except that polyethylene glycol monomethacrylate was changed to cyclohexyl acrylate and the ammonium salt was changed to an amine salt. Obtained.
実施例１３
表面処理剤の重合性単量体として、ポリエチレングリコールモノメタクリレートを２−ヒドロキシエチルアクリレートに変更した以外は、実施例１と同様の方法で本発明の表面処理炭酸カルシウムを得た。
Example 13
The surface-treated calcium carbonate of the present invention was obtained in the same manner as in Example 1 except that polyethylene glycol monomethacrylate was changed to 2-hydroxyethyl acrylate as the polymerizable monomer for the surface treatment agent.
比較例１
錯体形成物質としてクエン酸を添加しない以外は、実施例１と同様の方法で炭酸化反応を行った。次いで、該炭酸カルシウム水スラリーを、温度５０〜５５℃で４８時間撹拌熟成を行った。その後、表１に示す表面処理剤を炭酸カルシウムに対して１．２重量％添加した以外は実施例１と同様の方法により本発明の表面処理炭酸カルシウムを得た。
Comparative Example 1
A carbonation reaction was performed in the same manner as in Example 1 except that citric acid was not added as a complex-forming substance. Next, the calcium carbonate water slurry was aged and stirred at a temperature of 50 to 55 ° C. for 48 hours. Then, the surface treatment calcium carbonate of this invention was obtained by the method similar to Example 1 except having added 1.2 weight% of surface treatment agents shown in Table 1 with respect to calcium carbonate.
比較例２
濃度７重量％に調整した水酸化カルシウム水スラリーを２０Ｌ用意し、温度１５℃に冷却後、錯体形成物質としてクエン酸を水酸化カルシウムに対し３．０重量％添加し、水酸化カルシウム１ｋｇ当たり６００Ｌ／ｈｒの二酸化炭素ガスを導入し、ｐＨ７．０まで炭酸化反応を行った。次いで該炭酸カルシウム水スラリーを、温度５０〜５５℃で５０時間撹拌熟成を行った。その後、表１に示す表面処理剤を炭酸カルシウムに対して６．５重量％添加した以外は実施例１と同様の方法により本発明の表面処理炭酸カルシウムを得た。
Comparative Example 2
20 L of calcium hydroxide water slurry adjusted to a concentration of 7% by weight is prepared, cooled to a temperature of 15 ° C., and 3.0% by weight of citric acid as a complex-forming substance is added to the calcium hydroxide, and 600 L per kg of calcium hydroxide. / Hr carbon dioxide gas was introduced to carry out carbonation reaction to pH 7.0. Next, the calcium carbonate water slurry was aged and stirred at a temperature of 50 to 55 ° C. for 50 hours. Then, the surface treatment calcium carbonate of this invention was obtained by the method similar to Example 1 except having added 6.5 weight% of surface treatment agents shown in Table 1 with respect to calcium carbonate.
比較例３
錯体形成物質としてクエン酸の添加量を炭酸カルシウムに対して１１重量％に変更した以外は、実施例５と同様の方法で表面処理炭酸カルシウムを得た。
Comparative Example 3
Surface-treated calcium carbonate was obtained in the same manner as in Example 5 except that the amount of citric acid added as a complex-forming substance was changed to 11% by weight with respect to calcium carbonate.
比較例４
試薬（和光純薬社製：３Ｎ）の炭酸カルシウムを用いて焼成した以外は実施例１と同様にして調整して得た水酸化カルシウム水スラリーを、濃度７．５％重量％、温度１６℃に調整後、撹拌しながら水酸化カルシウム１ｋｇ当たり３００Ｌ／ｈｒとなるよう二酸化炭素ガスを導入しｐＨ７．０まで炭酸化反応を行った。炭酸化後のＢＥＴ比表面積は２９．６ｍ2 ／g であった。さらに３時間攪拌熟成した後、表２に示す表面処理剤を３．４重量％添加した後、常法に従い、粉砕、乾燥を行うことにより表面処理炭酸カルシウムを得た。
Comparative Example 4
A calcium hydroxide aqueous slurry obtained by adjusting in the same manner as in Example 1 except that baking was performed using calcium carbonate as a reagent (manufactured by Wako Pure Chemical Industries, Ltd .: 3N). Then, carbon dioxide gas was introduced with stirring to 300 L / hr per 1 kg of calcium hydroxide, and the carbonation reaction was carried out to pH 7.0. The BET specific surface area after carbonation was 29.6 m 2 / g. After further agitation and aging for 3 hours, 3.4% by weight of the surface treatment agent shown in Table 2 was added, followed by pulverization and drying according to conventional methods to obtain surface-treated calcium carbonate.
比較例５
特開平１０−１３００２０号公報に記載の比較例６に従い、濃度０．５mol/L の工業用炭酸ナトリウム水溶液と２５重量％アンモニア水を４．５Ｌ加えた混合水溶液と、濃度０．５mol/L の液体塩化カルシウム水溶液を各１００Ｌ用意し共に液温１７℃に温調した。次に、炭酸ナトリウム水溶液側に塩化カルシウム水溶液１００Ｌを動力０．５ｋｗの攪拌条件で滴下混合を開始し、２５０秒後に炭酸化反応を終了した。
該炭酸カルシウム水スラリーを遠心脱水機を用いて濃縮し、濃縮液に水を加えて希釈し攪拌した後、再度希釈液を遠心脱水機を用いて濃縮し、遠心脱水機の濾液の電気伝導度が２００μＳ／cm以下に降下するまで水洗濃縮し、平均径１１．３μｍの炭酸カルシウム（カルサイト結晶）を得た。
該炭酸カルシウムをロータリーキルンで焼成し生石灰を得、純水で消化して水酸化カルシム水スラリーを調整した。その後、実施例１と同様の操作を行い、表面処理炭酸カルシウムを得た。
Comparative Example 5
According to Comparative Example 6 described in JP-A-10-130020, a mixed aqueous solution in which 4.5 L of an industrial sodium carbonate aqueous solution having a concentration of 0.5 mol / L and 25 wt% ammonia water was added, and a concentration of 0.5 mol / L 100 L each of liquid calcium chloride aqueous solution was prepared, and the temperature was adjusted to 17 ° C. Next, 100 L of calcium chloride aqueous solution was added dropwise to the sodium carbonate aqueous solution side under stirring conditions with a power of 0.5 kw, and the carbonation reaction was completed after 250 seconds.
Concentrate the calcium carbonate aqueous slurry using a centrifugal dehydrator, add water to the concentrate, dilute and stir, and then concentrate the diluted solution again using a centrifugal dehydrator. The electrical conductivity of the filtrate of the centrifugal dehydrator The solution was concentrated by washing with water until it decreased to 200 μS / cm or less to obtain calcium carbonate (calcite crystal) having an average diameter of 11.3 μm.
The calcium carbonate was calcined in a rotary kiln to obtain quicklime, and digested with pure water to prepare a calcium hydroxide water slurry. Then, operation similar to Example 1 was performed and the surface treatment calcium carbonate was obtained.
実施例１４〜２６、比較例６〜１０
CaTiO3-NdAlO3 系誘電体の作製
下記に示した配合系で混合し、ポットミルにてジルコニアボールと共に１時間粉砕した。
次に、400 ℃で乾燥させた後、１３２０℃で１０時間仮焼させた。
さらに、仮焼したものを再び純水と混合し、再度ポットミルにてジルコニアアボールと共に５時間粉砕した。次に、純水を１００℃で乾燥後、直径10mm×厚み2mm の錠剤を作製し、１４２０℃で２時間で本焼し、NdAlO3を含有したCaTiO3系マイクロ波誘電体を作製した。
表３に、実施例１４〜２６及び比較例６〜１０で得られたマイクロ波誘電体について、誘電率（ε）と品質係数（Ｑ値）を示した。
誘電率と品質係数の測定装置と主な測定条件を下記に示す。
＜測定装置＞
ウイルトロン社製ネットワクークアナライザー360B。
＜測定条件＞
空洞共振器を使用し、中心周波数（f0）、中心周波数から10db低下した高周波数側の周波数(fH)、低周波数側の周波数(fL)、中心周波数での挿入損失（dB）から誘電率（ε）、誘電損失（tan δ）、Qf値はQxf0で求めた。但し、品質係数(Q) は、1/tan δである。
表３から明らかなように、実施例１４〜２６のマイクロ波誘電体は比較例６〜１０のマイクロ波誘電体に比べ、誘電率（ε）と品質係数（Ｑ）共に高いことが認められた。
＜CaTiO3-NdAlO3 の配合＞
（混合〜仮焼）
実施例１〜１３、比較例１〜５の炭酸カルシウム：４１．２６ｇ
酸化チタン（東邦チタニウム社製：３Ｎ） ：２３．９４ｇ
Nd2O3 （和光純薬社製：３Ｎ） ：１４．８２ｇ
Al2O3 （和光純薬社製：３Ｎ） ： ４．５１ｇ
純水 ：２５０ｍｌ
（混合〜本焼）
CaTiO3/(NdAl)O3 ：８４．５５ｇ
純水 ：２５０ｍｌ
Examples 14 to 26, Comparative Examples 6 to 10
Preparation of CaTiO 3 —NdAlO 3 System Dielectric Material The following compounding system was used, and the mixture was pulverized with a zirconia ball for 1 hour in a pot mill.
Next, after drying at 400 ° C., it was calcined at 1320 ° C. for 10 hours.
Further, the calcined product was mixed with pure water again, and pulverized again with a zirconia aball in a pot mill for 5 hours. Next, pure water was dried at 100 ° C., and then a tablet having a diameter of 10 mm × thickness of 2 mm was prepared and baked at 1420 ° C. for 2 hours to prepare a CaTiO 3 -based microwave dielectric containing NdAlO 3 .
Table 3 shows dielectric constant (ε) and quality factor (Q value) for the microwave dielectrics obtained in Examples 14 to 26 and Comparative Examples 6 to 10.
The measuring device and main measurement conditions for dielectric constant and quality factor are shown below.
<Measurement device>
Wiltron Network Cook Analyzer 360B.
<Measurement conditions>
Using a cavity resonator, the center frequency (f0), the high frequency side (fH) 10db lower than the center frequency, the low frequency side (fL), the insertion loss (dB) at the center frequency to the dielectric constant ( ε), dielectric loss (tan δ), and Qf value were determined by Qxf0. However, the quality factor (Q) is 1 / tan δ.
As is apparent from Table 3, the microwave dielectrics of Examples 14 to 26 were found to have higher dielectric constant (ε) and quality factor (Q) than the microwave dielectrics of Comparative Examples 6 to 10. .
<Composition of CaTiO 3 -NdAlO 3 >
(Mixed to calcined)
Calcium carbonate of Examples 1 to 13 and Comparative Examples 1 to 5: 41.26 g
Titanium oxide (Toho Titanium Co., Ltd .: 3N): 23.94 g
Nd 2 O 3 (Wako Pure Chemical Industries, Ltd .: 3N): 14.82 g
Al 2 O 3 (Wako Pure Chemical Industries, Ltd .: 3N): 4.51 g
Pure water: 250ml
(Mixed to main firing)
CaTiO 3 / (NdAl) O 3 : 84.55 g
Pure water: 250ml
実施例２７〜３９、比較例１１〜１５
BaTiO3系コア−シェル誘電体の作製
下記に示した配合系で、（１）表面処理炭酸カルシウム、（２）MgO 、（３）MnCO3 、（４）Y2O3、（５）BaCO3 、（６）SiO2の順に個々を純水に分散混合し、最後に（７）BaTiO3を投入した。
（混合系）
（１）実施例１〜１３、比較例１〜５の表面処理炭酸カルシウム：１１６．７３７ｇ
（２）MgO （和光純薬社製：純度３Ｎ） ： ０．４０３ｇ
（３）MnCO3 （和光純薬社製：純度３Ｎ） ： ０．０５８ｇ
（４）Y2O3（日本イットリウム社製：純度３Ｎ ： １．６９５ｇ
（５）BaCO3 （和光純薬社製：純度３Ｎ） ： １．７８１ｇ
（６）SiO2（和光純薬社製：純度３Ｎ） ： ０．９０２ｇ
（７）BaTiO3（富士チタン社製：蓚酸法） ： ０．９０２ｇ
ジルコニアボールと共に１時間混合分散後、バインダーを加えて直径10mm×厚み2mm の錠剤を成形した。
焼成1 段目は、水素3%濃度の還元雰囲気で1300℃で2 時間焼成し、その後400 ℃まで降下させ、酸化性雰囲気で2 時間エージングさせた。
焼成2 段目は、酸化性雰囲気囲のまま1100℃で5 時間焼成して焼結体（錠剤）を得た。 表４に、（ａ）５０℃の誘電率（ε’）及び（ｂ）１２５℃の誘電率（ε”）と、（ｂ）／（ａ）により求められる誘電率の損失率を示す。
誘電率と品質係数の測定装置と主な測定条件を下記に示す。
＜測定装置＞
回路設計ブッロク社製LCR メ−タ−ZM2353。
＜測定条件＞
測定周波数10KHz 、測定温度（室温〜150 ℃) まで可変し、１℃間隔にLCR メータで誘電率（ε）、誘電損失（tan δ）を測定した。
表４から明らかなように、実施例２７〜３９のコア−シェル誘電体は比較例１１〜１５のコア−シェル誘電体に比べ、誘電率が高く損失率も低いことが認められた。
Examples 27-39, Comparative Examples 11-15
Preparation of BaTiO 3 Core-Shell Dielectric In the compounding system shown below, (1) surface treated calcium carbonate, (2) MgO, (3) MnCO 3 , (4) Y 2 O 3 , (5) BaCO 3 , (6) SiO 2 were dispersed and mixed in pure water in the order, and (7) BaTiO 3 was finally added.
(Mixed system)
(1) Surface treated calcium carbonate of Examples 1 to 13 and Comparative Examples 1 to 5: 116.737 g
(2) MgO (Wako Pure Chemical Industries, Ltd .: purity 3N): 0.403 g
(3) MnCO 3 (Wako Pure Chemical Industries, Ltd .: purity 3N): 0.058 g
(4) Y 2 O 3 (manufactured by Japan Yttrium Co., Ltd .: Purity 3N: 1.695 g
(5) BaCO 3 (Wako Pure Chemical Industries, Ltd .: purity 3N): 1.781 g
(6) SiO 2 (Wako Pure Chemical Industries, Ltd .: purity 3N): 0.902 g
(7) BaTiO 3 (Fuji Titanium Co., Ltd .: oxalic acid method): 0.902 g
After mixing and dispersing with zirconia balls for 1 hour, a binder was added to form a tablet having a diameter of 10 mm and a thickness of 2 mm.
The first stage was fired at 1300 ° C. for 2 hours in a reducing atmosphere containing 3% hydrogen, then lowered to 400 ° C. and aged in an oxidizing atmosphere for 2 hours.
In the second firing stage, a sintered body (tablet) was obtained by firing at 1100 ° C. for 5 hours in an oxidizing atmosphere. Table 4 shows (a) the dielectric constant (ε ′) at 50 ° C. and (b) the dielectric constant (ε ″) at 125 ° C., and the loss rate of the dielectric constant obtained by (b) / (a).
The measuring device and main measurement conditions for dielectric constant and quality factor are shown below.
<Measurement device>
LCR meter ZM2353 from circuit design block.
<Measurement conditions>
The measurement frequency was changed to 10 KHz and the measurement temperature (room temperature to 150 ° C.), and the dielectric constant (ε) and dielectric loss (tan δ) were measured with an LCR meter at 1 ° C. intervals.
As is apparent from Table 4, the core-shell dielectrics of Examples 27 to 39 were found to have a higher dielectric constant and lower loss factor than the core-shell dielectrics of Comparative Examples 11 to 15.
叙上のとおり、本発明の表面処理炭酸カルシウムは、粒子が均一で優れた分散性を有するとともに、Ｘ７Ｒ特性やＸ８Ｒ特性を満足するセラミックに好適な水分散能を有し、Ｘ７Ｒ特性やＸ８Ｒ特性を満足するセラミック組成物を提供することができる。 As mentioned above, the surface-treated calcium carbonate of the present invention has uniform and excellent dispersibility, and has a water dispersibility suitable for ceramics satisfying X7R characteristics and X8R characteristics, and X7R characteristics and X8R characteristics. Can be provided.
Claims (7)
（ａ） １０≦Ｓｗ≦１００ （ｍ2 ／ｇ）
（ｂ） ０．１≦Ａｓ≦５．０ （ｍｇ／ｍ2 ）
（ｃ） ０．０３≦Ｄｘｓ≦３．０ （μｍ）
（ｄ） Ｄｙｓ≦３０ （重量％）
（ｅ） Ｉｓ≦０．１ （μｍｏｌ／ｍ2 ）
但し、
Ｓｗ ：窒素吸着法によるＢＥＴ比表面積（ｍ2 ／ｇ）
Ａｓ ：次式により算出される単位比表面積当たりの有機系表面処理剤量
２００℃〜５００℃の表面処理された炭酸カルシウム１ｇ当たりの熱減量Ｔｇ（ｍｇ／ｇ）／Ｓｗ（ｇ／ｍ2 ）
Ｄｘｓ：レーザー回折式（マルバーン社製：ＭＳ−２０００）により分散媒として水を用いて測定された粒度分布において、大きな粒子側から起算した重量累計５０％平均粒子径（μｍ）。
Ｄｙｓ：上記粒度分布において、３μｍを越える粒子径の重量累計（重量％）
I ｓ ：次式により算出される単位比表面積当たりのアルカリ金属含有量
｛炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）｝／Ｓｗ（ｍ2 ／ｇ） A surface-treated calcium carbonate, wherein the calcium carbonate surface-treated with an organic surface treatment agent satisfies the following formulas (a) to (e):
(A) 10 ≦ Sw ≦ 100 (m 2 / g)
(B) 0.1 ≦ As ≦ 5.0 (mg / m 2 )
(C) 0.03 ≦ Dxs ≦ 3.0 (μm)
(D) Dys ≦ 30 (wt%)
(E) Is ≦ 0.1 (μmol / m 2 )
However,
Sw: BET specific surface area by nitrogen adsorption method (m 2 / g)
As: Amount of organic surface treatment agent per unit specific surface area calculated by the following formula Heat loss Tg (g / g) / Sw (g / m 2 ) per 1 g of surface-treated calcium carbonate at 200 ° C. to 500 ° C.
Dxs: laser diffraction (Malvern Co.: MS-2000) in the measured particle size distribution using water as a more dispersant, by weight cumulative 50% average particle diameter was calculated from large particles side ([mu] m).
Dys: Cumulative weight (% by weight) of particle diameters exceeding 3 μm in the above particle size distribution
Is: Alkali metal content per unit specific surface area calculated by the following formula {Metal content per gram of calcium carbonate (μmol / g)} / Sw (m 2 / g)
（ｆ） Ｉｍ≦０．２ （μｍｏｌ／ｍ2 ）
（ｇ） Ｉｒ≦０．２ （μｍｏｌ／ｍ2 ）
但し、
I ｍ ：次式により算出される単位比表面積当たりのマグネシウム金属含有量
｛炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）｝／Ｓｗ（ｍ2 ／ｇ）
I ｒ ：次式により算出される単位比表面積当たりのストロンチウム金属含有量
｛炭酸カルシウム１ｇ当たりの金属含有量（μｍｏｌ／ｇ）｝／Ｓｗ（ｍ2 ／ｇ） The surface-treated calcium carbonate according to claim 1, further satisfying the following formulas (f) to (g).
(F) Im ≦ 0.2 (μmol / m 2 )
(G) Ir ≦ 0.2 (μmol / m 2 )
However,
I m: Magnesium metal content per unit specific surface area calculated by the following formula {Metal content per gram of calcium carbonate (μmol / g)} / Sw (m 2 / g)
I r: Strontium metal content per unit specific surface area calculated by the following formula {Metal content per gram of calcium carbonate (μmol / g)} / Sw (m 2 / g)
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