JP2013063867A - Method for producing barium titanyl oxalate and method for producing barium titanate - Google Patents
Method for producing barium titanyl oxalate and method for producing barium titanate Download PDFInfo
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- JP2013063867A JP2013063867A JP2011202451A JP2011202451A JP2013063867A JP 2013063867 A JP2013063867 A JP 2013063867A JP 2011202451 A JP2011202451 A JP 2011202451A JP 2011202451 A JP2011202451 A JP 2011202451A JP 2013063867 A JP2013063867 A JP 2013063867A
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- barium
- titanyl oxalate
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- oxalic acid
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 76
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 112
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 64
- 238000010304 firing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 30
- 239000000843 powder Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 5
- 229940094800 barium oxalate Drugs 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000007561 laser diffraction method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000790 scattering method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- -1 with a high yield Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
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Abstract
Description
本発明は、特に、圧電体、オプトエレクトロニクス材、誘電体、半導体、センサー等の機能性セラミックの原料として有用なシュウ酸バリウムチタニルの製造方法、及びそれを用いるチタン酸バリウムの製造方法に関するものである。 The present invention particularly relates to a method for producing barium titanyl oxalate useful as a raw material for functional ceramics such as piezoelectric materials, optoelectronic materials, dielectric materials, semiconductors, and sensors, and a method for producing barium titanate using the same. is there.
従来、チタン酸バリウムは、固相法、水熱合成法、アルコキシド法、シュウ酸塩法等により製造されている。 Conventionally, barium titanate is produced by a solid phase method, a hydrothermal synthesis method, an alkoxide method, an oxalate method, or the like.
固相法では、構成原料粉末等を混合し、該混合物を高温で加熱する乾式方法により製造するため、得られた粉末は不規則な形状を呈する凝集体を成し、また、所望の特性を達成するために高温焼成が必要である。また、水熱合成法は、粉体の特性が良好との長所にもかかわらず合成工程が複雑で、オートクレーブを用いるため生産性が劣り、製造粉末の値段が高く工業的に有利でない。また、アルコキシド法も同様、出発物質の取り扱いが難しく、値段が高く工業的に有利でない。 In the solid phase method, constituent raw material powders and the like are mixed, and the mixture is manufactured by a dry method in which the mixture is heated at a high temperature. Therefore, the obtained powder forms an agglomerate having an irregular shape and has desired characteristics. High temperature firing is necessary to achieve. In addition, the hydrothermal synthesis method has a complicated synthesis process in spite of the advantages of good powder characteristics, and is inferior in productivity because of the use of an autoclave, and the production powder is expensive and not industrially advantageous. Similarly, the alkoxide method is difficult to handle starting materials, is expensive, and is not industrially advantageous.
シュウ酸塩法で得られるチタン酸バリウムは、水熱合成法やアルコキシド法に比べ、組成が均一なものを安価に製造することができ、また、固相法で製造したチタン酸バリウムに比べ、組成が均一であるという特徴を有する。従来のシュウ酸塩法としては、ＴｉＣｌ４とＢａＣｌ２との水溶液を、Ｈ２Ｃ２Ｏ４水溶液に攪拌下に滴下して、シュウ酸バリウムチタニルを得、該シュウ酸バリウムチタニルを焼成する方法が一般的である（例えば、非特許文献１及び特許文献１参照）。 Barium titanate obtained by the oxalate method can be manufactured at a low cost compared with hydrothermal synthesis method or alkoxide method, and compared with barium titanate manufactured by solid phase method, It has the feature that the composition is uniform. As a conventional oxalate method, an aqueous solution of TiCl 4 and BaCl 2 is dropped into an H 2 C 2 O 4 aqueous solution while stirring to obtain barium titanyl oxalate, and the barium titanyl oxalate is baked. Is common (see, for example, Non-Patent Document 1 and Patent Document 1).
シュウ酸塩法により得られるチタン酸バリウムは、誘電体セラミックの材料として、優れた性能を発揮するものの、近年の要求性能の高まりから、更なる性能向上が求められている。チタン酸バリウムの誘電体セラミックとしての特性は、一般的には結晶性が高いものが誘電特性もよいことが知られている（例えば、特開２００６−１１７４４６号公報参照）。 Although barium titanate obtained by the oxalate method exhibits excellent performance as a dielectric ceramic material, further improvement in performance is required due to the recent increase in required performance. It is known that the characteristic of barium titanate as a dielectric ceramic is generally high in crystallinity and has good dielectric characteristics (see, for example, JP-A-2006-117446).
本発明者らは、従来の方法で得られるシュウ酸バリウムチタニルについて検討したところ、これらのシュウ酸バリウムチタニルは、バルクのＢａ／Ｔｉモル比は０．９９８〜１．００２の略１であるものの、粒径毎のＢａ／Ｔｉモル比にはバラツキがあり、小さいもの程（言い換えると、「比表面積が大きいもの程」）Ｂａ／Ｔｉモル比が小さく、一方、粒径が大きいもの程（言い換えると、「比表面積が小さいもの程」）Ｂａ／Ｔｉモル比が大きくなっていることを見出した。このため、シュウ酸塩法では、粒径が小さく、Ｂａ／Ｔｉモル比が０．９９８〜１．００２の略１で、結晶性が高いチタン酸バリウムが得られ難いということを見出した。 The present inventors examined barium titanyl oxalate obtained by a conventional method, and these barium titanyl oxalates have a bulk Ba / Ti molar ratio of about 0.998 to 1.002. The Ba / Ti molar ratio for each particle size varies, and the smaller the Ba / Ti molar ratio (in other words, the larger the specific surface area), the smaller the Ba / Ti molar ratio, while the larger the particle size (in other words, And “the smaller the specific surface area”), the Ba / Ti molar ratio was found to be large. For this reason, the oxalate method has found that it is difficult to obtain barium titanate having a small particle size and a Ba / Ti molar ratio of about 0.998 to 1.002 and high crystallinity.
従って、本発明の目的は、シュウ酸塩法で、粒径が小さいにもかかわらず結晶性に優れたチタン酸バリウムを得ることができるシュウ酸バリウムチタニルの製造方法を提供すること。更に、微粒で結晶性に優れたチタン酸バリウムを製造することができる方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing barium titanyl oxalate capable of obtaining barium titanate having excellent crystallinity despite the small particle size by the oxalate method. Furthermore, it is providing the method which can manufacture the barium titanate which was excellent in crystallinity with the fine particle.
本発明者らは、上記実情に鑑み鋭意研究を重ねた結果、少なくともシュウ酸及び塩化バリウムを含有する溶液（Ａ液）に、四塩化チタンを含む水溶液（Ｂ液）を添加し反応を行うことにより、平均粒径が４μｍ以下の微粒であってもＢａ／Ｔｉモル比が０．９９８〜１．００２の略１のシュウ酸バリウムチタニルが得られること、また、該シュウ酸バリウムチタニルを用いることにより、粒径が小さいにもかかわらず結晶性が高いチタン酸バリウムが得られるので、優れた性能を有する誘電体セラミック材料を提供できること等を見出し、本発明を完成させるに到った。 As a result of intensive studies in view of the above circumstances, the present inventors have added an aqueous solution (liquid B) containing titanium tetrachloride to a reaction containing at least oxalic acid and barium chloride (liquid A). To obtain barium titanyl oxalate having a Ba / Ti molar ratio of 0.998 to 1.002 even when the average particle diameter is 4 μm or less, and to use the barium titanyl oxalate. Thus, since barium titanate having high crystallinity can be obtained even though the particle size is small, it has been found that a dielectric ceramic material having excellent performance can be provided, and the present invention has been completed.
即ち、本発明が提供しようとする第１の発明は、少なくともシュウ酸及び塩化バリウムを含有する溶液（Ａ液）に、四塩化チタンを含む水溶液（Ｂ液）を添加し反応を行うことを特徴とするシュウ酸バリウムチタニルの製造方法である。 That is, the first invention to be provided by the present invention is characterized in that an aqueous solution (liquid B) containing titanium tetrachloride is added to a solution (liquid A) containing at least oxalic acid and barium chloride to carry out the reaction. And a method for producing barium titanyl oxalate.
また、本発明が提供しようとする第２の発明は、前記第１の発明により得られたシュウ酸バリウムチタニルを焼成することを特徴とするチタン酸バリウムの製造方法である。 A second invention to be provided by the present invention is a method for producing barium titanate, characterized by firing the barium titanyl oxalate obtained by the first invention.
本発明によれば、平均粒径が４μｍ以下と小さくとも、Ｂａ／Ｔｉモル比が０．９９８〜１．００２の略１のシュウ酸バリウムチタニルを提供することができる。そして、このようなシュウ酸バリウムチタニルを用いることにより、シュウ酸塩法で、粒径が小さいにもかかわらず結晶性が高く、優れた性能を有する誘電体セラミック材料を提供できる。 According to the present invention, it is possible to provide approximately 1 barium titanyl oxalate having a Ba / Ti molar ratio of 0.998 to 1.002 even when the average particle size is as small as 4 μm or less. By using such barium titanyl oxalate, a dielectric ceramic material having high crystallinity and excellent performance can be provided by the oxalate method even though the particle size is small.
以下、本発明をその好ましい実施形態に基づき説明する。
本発明の製造方法は、少なくともシュウ酸及び塩化バリウムを含有する溶液（Ａ液）に、四塩化チタンを含む水溶液（Ｂ液）を添加し反応を行うことを特徴とするものである。本発明の製造方法に従い製造されるシュウ酸バリウムチタニルは、好適にはＴｉに対するＢａのモル比（以下、「Ｂａ／Ｔｉモル比」という）が０．９９８〜１．００２、好ましくは略１であり、レーザー回折・散乱法により求められる平均粒径が４μｍ以下、好ましくは０．１〜４μｍで微細なシュウ酸バリウムチタニルである。
Hereinafter, the present invention will be described based on preferred embodiments thereof.
The production method of the present invention is characterized in that an aqueous solution (liquid B) containing titanium tetrachloride is added to a solution (liquid A) containing at least oxalic acid and barium chloride to carry out the reaction. The barium titanyl oxalate produced according to the production method of the present invention preferably has a Ba to Ti molar ratio (hereinafter referred to as “Ba / Ti molar ratio”) of 0.998 to 1.002, preferably about 1. There is a fine barium titanyl oxalate having an average particle size of 4 μm or less, preferably 0.1 to 4 μm, determined by a laser diffraction / scattering method.
本発明で用いるＡ液は、少なくともシュウ酸及び塩化バリウムを含む溶液である。本発明に係るＡ液は水、シュウ酸及び塩化バリウム以外の成分としてシュウ酸バリウム、更には塩酸等の塩素イオン源を含有させることができる。Ａ液のシュウ酸及び塩化バリウム、又はシュウ酸、塩化バリウム及びシュウ酸バリウム、更には塩素イオン源のＡ液への配合割合は、Ａ液中のシュウ酸とバリウムの濃度及びシュウ酸とバリウムのモル比、更には塩素イオン濃度が後述する範囲内であれば、各原料の配合割合は特に制限されない。 The solution A used in the present invention is a solution containing at least oxalic acid and barium chloride. The liquid A according to the present invention can contain barium oxalate as a component other than water, oxalic acid and barium chloride, and further a chlorine ion source such as hydrochloric acid. The mixing ratio of oxalic acid and barium chloride of liquid A, or oxalic acid, barium chloride and barium oxalate, and the chlorine ion source to liquid A is determined by the concentration of oxalic acid and barium in liquid A and the concentration of oxalic acid and barium. If the molar ratio and further the chlorine ion concentration is within the range described later, the blending ratio of each raw material is not particularly limited.
Ａ液中の組成はシュウ酸（Ｈ２Ｃ２Ｏ４）換算で０．７〜２．５モル／Ｌ、好ましくは１．０〜２．２モル／Ｌで、Ｂａ換算で０．４〜１．３モル／Ｌ、好ましくは０．９〜１．１モル／Ｌであり、且つＢａに対するシュウ酸のモル比（シュウ酸／Ｂａ）が１．５〜２．５、好ましくは１．８〜２．２であることが、高い収率でＢａ／Ｔｉモル比が略１のシュウ酸バリウムチタニルが得られるという観点から好ましい。また、Ａ液中の塩素イオン濃度は、Ｃｌ換算で０．７〜２．５モル／Ｌ、好ましくは１．０〜２．２モル／Ｌであると高い収率でＢａ／Ｔｉモル比が略１で微粒のシュウ酸バリウムチタニルを得られるという観点から好ましい。 The composition in the liquid A is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of oxalic acid (H 2 C 2 O 4 ), and 0.4 to 0.4 in terms of Ba. 1.3 mol / L, preferably 0.9 to 1.1 mol / L, and the molar ratio of oxalic acid to Ba (oxalic acid / Ba) is 1.5 to 2.5, preferably 1.8 It is preferable from the viewpoint that barium titanyl oxalate having a Ba / Ti molar ratio of about 1 is obtained in a high yield. The chlorine ion concentration in the liquid A is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of Cl, and the Ba / Ti molar ratio is high with a high yield. From the viewpoint that approximately 1 and fine barium titanyl oxalate can be obtained.
本発明に係るＡ液はシュウ酸と塩化バリウムとを水溶媒中で接触させて得られるものをそのまま用いることができる。通常、シュウ酸と塩化バリウムとを水溶媒中で接触させると、一部シュウ酸と塩化バリウムが反応して微細なシュウ酸バリウムが析出したものになる。この際のＡ液の組成は、水、シュウ酸、塩化バリウム、更にはそれ以外の成分としてシュウ酸バリウム及び塩酸が含有されたものになるが、本製造方法において、このように調製されたＡ液は四塩化チタンとの反応性が高く、高い収率で目的とするシュウ酸バリウムチタニルを得ることができるという観点から特に好ましく用いられる。なお、シュウ酸と塩化バリウムの配合割合はＡ液中のシュウ酸とバリウムの濃度及びシュウ酸とバリウムのモル比、更には塩素イオン濃度が上記範囲内となるような範囲であればよい。 As the solution A according to the present invention, a solution obtained by contacting oxalic acid and barium chloride in an aqueous solvent can be used as it is. Usually, when oxalic acid and barium chloride are brought into contact with each other in an aqueous solvent, oxalic acid and barium chloride partially react to precipitate fine barium oxalate. The composition of the liquid A at this time is water, oxalic acid, barium chloride, and further contains barium oxalate and hydrochloric acid as other components. In this production method, A prepared in this way The liquid is particularly preferably used from the viewpoint that the reactivity with titanium tetrachloride is high and the target barium titanyl oxalate can be obtained in a high yield. The mixing ratio of oxalic acid and barium chloride may be in a range such that the concentration of oxalic acid and barium in the liquid A, the molar ratio of oxalic acid and barium, and the chlorine ion concentration are within the above ranges.
Ａ液の調製に係る前記シュウ酸と塩化バリウムの接触は、攪拌下に行うことにより、析出した微細なシュウ酸バリウムが均一に分散した懸濁液を得ることができる。前記接触温度は、特に制限はなく、多くの場合、１００℃以下、好ましくは室温付近（１５〜３０℃）で十分である。また、Ａ液の調製におけるシュウ酸と塩化バリウムの接触時間は、特に制限はないが多くの場合、０．２５時間以上、好ましくは０．５〜２時間で満足のいく物性のＡ液が得られる。 The contact of the oxalic acid and barium chloride relating to the preparation of the liquid A can be performed with stirring, whereby a suspension in which the precipitated fine barium oxalate is uniformly dispersed can be obtained. The contact temperature is not particularly limited, and in many cases, it is 100 ° C. or less, preferably about room temperature (15 to 30 ° C.). The contact time between oxalic acid and barium chloride in the preparation of the liquid A is not particularly limited, but in many cases, a liquid A having satisfactory physical properties can be obtained in 0.25 hours or more, preferably 0.5 to 2 hours. It is done.
シュウ酸と塩化バリウムの接触方法としては、例えば、１）シュウ酸水溶液に、塩化バリウムを水溶液或いは粉体として添加する方法、２）塩化バリウム水溶液に、シュウ酸を水溶液或いは粉体として添加する方法、３）水を仕込んだ容器にシュウ酸及び塩化バリウムを添加する方法、４）シュウ酸及び塩化バリウムを仕込んだ容器に水を添加する方法等が挙げられるが、装置、操作性等を考慮して適宜有利な方法を選択して行うことができる。 Examples of contact methods of oxalic acid and barium chloride include 1) a method of adding barium chloride as an aqueous solution or powder to an oxalic acid aqueous solution, and 2) a method of adding oxalic acid as an aqueous solution or powder to an aqueous barium chloride solution. 3) A method of adding oxalic acid and barium chloride to a container charged with water, 4) A method of adding water to a container charged with oxalic acid and barium chloride, etc. Thus, an advantageous method can be selected as appropriate.
本発明で用いるＢ液は、四塩化チタンを含む水溶液である。Ｂ液中の四塩化チタンの濃度はＴｉとして０．１〜１．２モル／Ｌ、特に０．３〜１．０モル／Ｌであると、高い収率でＢａ／Ｔｉモル比が略１のシュウ酸バリウムチタニルを得られるという観点から好ましい。また、Ｂ液中の塩素イオン濃度は、Ｃｌ換算で０．７〜２．５モル／Ｌ、好ましくは１．０〜２．２モル／Ｌであると高い収率で、微粒で、且つＢａ／Ｔｉモル比が略１のシュウ酸バリウムチタニルを得るという観点から好ましい。 The B liquid used in the present invention is an aqueous solution containing titanium tetrachloride. When the concentration of titanium tetrachloride in the liquid B is 0.1 to 1.2 mol / L as Ti, particularly 0.3 to 1.0 mol / L, the Ba / Ti molar ratio is about 1 with high yield. From the viewpoint that barium titanyl oxalate can be obtained. Further, the chlorine ion concentration in the liquid B is 0.7 to 2.5 mol / L, preferably 1.0 to 2.2 mol / L in terms of Cl, with a high yield, fine particles, and Ba From the viewpoint of obtaining barium titanyl oxalate having a / Ti molar ratio of about 1.
本製造方法において、Ａ液とＢ液の組成が前記範囲であることに加えて、Ａ液中の塩素イオン濃度に対するＢ液中の塩素イオン濃度の比（Ｂ／Ａ）が重量比で０．５〜５．０、好ましくは０．７５〜３．０となるようにＡ液及びＢ液を調整して反応を行うことにより、いっそう微細で、且つＢａ／Ｔｉモル比が０．９９８〜１．００２、好ましくは略１のシュウ酸バリウムチタニルを得やすくなる。
なお、Ａ液及びＢ液には、塩素イオン濃度の調整のため、塩素イオン源を添加することができる。塩素イオン源としては、例えば塩酸、塩化ナトリウム、塩化カリウム、塩化リチウム、塩素イオンを含む有機化合物等が挙げられる。
In this production method, in addition to the composition of the liquid A and the liquid B being in the above ranges, the ratio of the chlorine ion concentration in the liquid B to the chlorine ion concentration in the liquid A (B / A) is 0. By adjusting the liquid A and the liquid B so as to be 5 to 5.0, preferably 0.75 to 3.0, the reaction is further fined, and the Ba / Ti molar ratio is 0.998 to 1 It is easy to obtain 0.002 and preferably about 1 barium titanyl oxalate.
In addition, a chlorine ion source can be added to A liquid and B liquid for adjustment of chlorine ion concentration. Examples of the chlorine ion source include hydrochloric acid, sodium chloride, potassium chloride, lithium chloride, organic compounds containing chlorine ions, and the like.
反応操作は、Ｂ液をＡ液へ添加し反応を行う。Ｂ液のＡ液への添加は、添加後の反応液におけるチタン原子に対するバリウム原子のモル比が１．０〜１．５、特に１．１〜１．３となるように行うと、Ｂａ／Ｔｉモル比が略１のシュウ酸バリウムチタニルが高収率で得られるので好ましい。 In the reaction operation, the liquid B is added to the liquid A to carry out the reaction. When the addition of the B liquid to the A liquid is performed so that the molar ratio of barium atoms to titanium atoms in the reaction liquid after the addition is 1.0 to 1.5, particularly 1.1 to 1.3, Ba / Since barium titanyl oxalate having a Ti molar ratio of about 1 is obtained in a high yield, it is preferable.
Ｂ液の添加速度は、速ければ速いほど、単位時間当たりの核発生が多くなり，より微細なものが得られる傾向がある。添加速度は、反応容器の大きさ、反応液の量等により、適宜選択されるが、例えば０．５Ｌスケールの実験室レベルでは、Ｂ液の添加速度は５Ｌ／時間以上、好ましくは８〜１１Ｌ／時間とすることが好ましい。 As the addition speed of the liquid B increases, the number of nuclei generated per unit time increases, and a finer product tends to be obtained. The addition rate is appropriately selected depending on the size of the reaction vessel, the amount of the reaction solution, etc. For example, at the laboratory level of 0.5 L scale, the addition rate of solution B is 5 L / hour or more, preferably 8 to 11 L. / Hour is preferable.
Ｂ液のＡ液への添加温度は、４０℃以下、好ましくは２５〜４０℃である。シュウ酸塩法において、多くの場合、この添加温度は５０℃以上の温度で行われるが、本製造方法では添加温度を４０℃まで下げることで、生成されるシュウ酸バリウムチタニルからＢａの溶出を抑制し、微細なシュウ酸バリウムチタニルのモル比の変化を抑制することができるので、Ｂａ／Ｔｉモル比がより１に近いものが得られやすくなる。なお、Ｂ液の温度は特に限定されないが、Ａ液の温度と同様の範囲内にあると、反応操作が容易となるので好ましい。 The addition temperature of B liquid to A liquid is 40 degrees C or less, Preferably it is 25-40 degreeC. In the oxalate method, this addition temperature is often performed at a temperature of 50 ° C. or higher, but in this production method, the elution of Ba from the barium titanyl oxalate produced by lowering the addition temperature to 40 ° C. Since it can suppress and the change of the molar ratio of fine barium titanyl oxalate can be suppressed, it becomes easy to obtain a Ba / Ti molar ratio closer to 1. The temperature of the B liquid is not particularly limited, but it is preferable that the temperature is within the same range as the temperature of the A liquid because the reaction operation becomes easy.
Ｂ液のＡ液への添加は攪拌下に行うことが好ましい。本製造方法において、攪拌を強くすることにより急激な反応を行わせ，これにより核成長を抑えて、より微粉なものが得られる傾向がある。攪拌速度は、反応容器の大きさ、攪拌羽の径、反応液の量等により、適宜選択されるが、例えば０．５Ｌスケールの実験室レベルを基準にすると、攪拌羽の周速０．５〜２．０ｍ／秒以上が好ましく、攪拌羽の周速１．６〜１．８ｍ／秒が特に好ましい。 It is preferable to add the B liquid to the A liquid with stirring. In this production method, the agitation is strengthened to cause a rapid reaction, thereby suppressing the nucleus growth and obtaining a finer powder. The stirring speed is appropriately selected depending on the size of the reaction vessel, the diameter of the stirring blade, the amount of the reaction solution, and the like. For example, on the basis of a laboratory level of 0.5 L scale, the peripheral speed of the stirring blade is 0.5. -2.0 m / sec or more is preferable, and the peripheral speed of the stirring blade is particularly preferably 1.6-1.8 m / sec.
Ｂ液の添加終了後、高い収率でシュウ酸バリウムチタニルを得る為に熟成を行なうことが好ましい。熟成温度は特に制限されないが、反応温度と同じであると操作がし易く好ましい。また熟成時間に特に制限はないが多くの場合、０．５時間以上、好ましくは０．５〜２時間である。熟成終了後は、常法により固液分離し、次いで水で洗浄する。洗浄方法は特に制限されるものではない。リパルプ等で洗浄を行うと洗浄効率がよいので好ましい。次いで、乾燥、必要により粉砕或いは解砕してシュウ酸バリウムチタニルを得る。 After completion of the addition of solution B, aging is preferably performed to obtain barium titanyl oxalate with a high yield. The aging temperature is not particularly limited, but is preferably the same as the reaction temperature for easy operation. The aging time is not particularly limited, but in many cases, it is 0.5 hours or more, preferably 0.5 to 2 hours. After completion of aging, the solid and liquid are separated by a conventional method and then washed with water. The cleaning method is not particularly limited. Washing with repulp or the like is preferable because the washing efficiency is good. Next, it is dried and, if necessary, ground or crushed to obtain barium titanyl oxalate.
かくして得られるシュウ酸バリウムチタニルの好ましい物性としては、レーザー回折・散乱法により求められる平均粒径が４μｍ以下、好ましくは０．１〜４μｍである。また、該シュウ酸バリウムチタニルの組成は、Ｂａ／Ｔｉモル比が０．９９８〜１．００２、好ましくは略１である。 As a preferable physical property of the barium titanyl oxalate thus obtained, an average particle size determined by a laser diffraction / scattering method is 4 μm or less, preferably 0.1 to 4 μm. The composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 0.998 to 1.002, preferably about 1.
本発明の製造方法で得られるシュウ酸バリウムチタニルは、誘電体セラミック材料のチタン酸バリウム系セラミックの製造原料として好適に用いることが出来る。本発明のチタン酸バリウムの製造方法は以下の通りである。 Barium titanyl oxalate obtained by the production method of the present invention can be suitably used as a production raw material for a barium titanate-based ceramic as a dielectric ceramic material. The manufacturing method of the barium titanate of this invention is as follows.
本発明のチタン酸バリウムの製造方法は、前述の方法で得られたシュウ酸バリウムチタニルを焼成することを特徴とするものである。 The method for producing barium titanate of the present invention is characterized in that barium titanyl oxalate obtained by the above-described method is fired.
最終製品に含まれるシュウ酸由来の有機物は、材料の誘電体特性を損なうとともに、セラミック化のための熱工程における挙動の不安定要因となるので好ましくない。従って、本発明では焼成によりシュウ酸バリウムチタニルを熱分解して目的とするチタン酸バリウムを得ると共に、シュウ酸由来の有機物を十分除去する必要がある。焼成条件は、焼成温度が好ましくは６００〜１２００℃、更に好ましくは７００〜１１００℃である。焼成温度が６００℃未満では、単一相のチタン酸バリウムが得られにくい。一方、焼成温度が１２００℃を超えると、粒径のバラツキが大きくなる。焼成時間は好ましくは２〜３０時間、更に好ましくは５〜２０時間である。また、焼成雰囲気は、特に制限されず、不活性ガス雰囲気下、真空雰囲気下、酸化性ガス雰囲気下、大気中のいずれであってもよく、或いは水蒸気を導入しながら前記雰囲気中で焼成を行ってもよい。 The organic material derived from oxalic acid contained in the final product is not preferable because it impairs the dielectric properties of the material and causes unstable behavior in the thermal process for ceramization. Therefore, in the present invention, it is necessary to thermally decompose barium titanyl oxalate by firing to obtain the target barium titanate and to sufficiently remove organic substances derived from oxalic acid. The firing conditions are such that the firing temperature is preferably 600 to 1200 ° C, more preferably 700 to 1100 ° C. When the firing temperature is less than 600 ° C., it is difficult to obtain single-phase barium titanate. On the other hand, when the firing temperature exceeds 1200 ° C., the variation in particle diameter increases. The firing time is preferably 2 to 30 hours, more preferably 5 to 20 hours. The firing atmosphere is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the air, or firing is performed in the atmosphere while introducing water vapor. May be.
焼成は所望により何度行ってもよい。或いは、粉体特性を均一にする目的で、一度焼成したものを粉砕し、次いで再焼成を行ってもよい。 Firing may be performed as many times as desired. Alternatively, for the purpose of making the powder characteristics uniform, the fired material may be pulverized and then refired.
焼成後、適宜冷却し、必要に応じ粉砕してチタン酸バリウムの粉末を得る。必要に応じて行われる粉砕は、焼成して得られるチタン酸バリウムがもろくブロック状のものである場合等に適宜行うが、チタン酸バリウムの粒子自体は下記特定の平均粒径、ＢＥＴ比表面積を有するものである。即ち、前記で得られるチタン酸バリウムの粉末は、走査型電子顕微鏡写真（ＳＥＭ）から求められる平均粒径が好ましくは０．５μｍ以下、更に好ましくは０．０５〜０．５μｍである。ＢＥＴ比表面積は、好ましくは２〜２０ｍ２／ｇ、更に好ましくは２．０〜１０ｍ２／ｇである。更に、本発明の製造方法で得られるチタン酸バリウムの組成は、ＢａとＴｉのモル比（Ｂａ／Ｔｉ）が０．９９８〜１．００２、特に略１であることが好ましい。また、結晶性の指標となるｃ軸／ａ軸比が１．００７以上、好ましくは１．００８５以上の結晶性が高いものであることがより好ましい。 After firing, the mixture is appropriately cooled and pulverized as necessary to obtain a barium titanate powder. The pulverization performed as necessary is appropriately performed when the barium titanate obtained by firing is fragile and in a block shape, but the barium titanate particles themselves have the following specific average particle diameter and BET specific surface area. It is what you have. That is, the barium titanate powder obtained above has an average particle size determined from a scanning electron micrograph (SEM) of preferably 0.5 μm or less, more preferably 0.05 to 0.5 μm. The BET specific surface area is preferably 2 to 20 m 2 / g, more preferably 2.0 to 10 m 2 / g. Furthermore, the composition of barium titanate obtained by the production method of the present invention is preferably such that the molar ratio of Ba to Ti (Ba / Ti) is 0.998 to 1.002, particularly about 1. Further, it is more preferable that the c-axis / a-axis ratio serving as an index of crystallinity is 1.007 or higher, preferably 1.0085 or higher.
また、本発明のチタン酸バリウムの製造方法を行い得られるチタン酸バリウムには、必要により誘電特性や温度特性を調整する目的で、副成分元素含有化合物を本発明のチタン酸バリウムの製造方法を行い得られるチタン酸バリウムに添加して、副成分元素を含有させることができる。用いることができる副成分元素含有化合物としては、例えば、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕの希土類元素、Ｂａ、Ｌｉ、Ｂｉ、Ｚｎ、Ｍｎ、Ａｌ、Ｓｉ、Ｃａ、Ｓｒ、Ｃｏ、Ｎｉ、Ｃｒ、Ｆｅ、Ｍｇ、Ｔｉ、Ｖ、Ｎｂ、Ｍｏ、Ｗ及びＳｎからなる群より選ばれる少なくとも１種の元素を含有する化合物が挙げられる。 In addition, the barium titanate obtained by carrying out the method for producing barium titanate of the present invention is prepared by adding the subcomponent element-containing compound to the method for producing barium titanate of the present invention for the purpose of adjusting dielectric properties and temperature characteristics as necessary. In addition to the barium titanate obtained, subcomponent elements can be contained. Examples of the subcomponent element-containing compound that can be used include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu rare earth elements. At least one selected from the group consisting of Ba, Li, Bi, Zn, Mn, Al, Si, Ca, Sr, Co, Ni, Cr, Fe, Mg, Ti, V, Nb, Mo, W and Sn Examples include compounds containing elements.
副成分元素含有化合物は、無機物又は有機物のいずれであってもよい。例えば、前記の元素を含む酸化物、水酸化物、塩化物、硝酸塩、蓚酸塩、カルボン酸塩及びアルコキシド等が挙げられる。副成分元素含有化合物がＳｉ元素を含有する化合物である場合は、酸化物等に加えて、シリカゾルや珪酸ナトリウム等も用いることができる。副成分元素含有化合物は１種又は２種以上適宜組み合わせて用いることができる。その添加量や添加化合物の組み合わせは、常法に従って行えばよい。 The subcomponent element-containing compound may be either inorganic or organic. Examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates and alkoxides containing the above elements. In the case where the subcomponent element-containing compound is a compound containing Si element, silica sol, sodium silicate, or the like can be used in addition to the oxide or the like. The subcomponent element-containing compounds can be used alone or in combination of two or more. What is necessary is just to perform the combination of the addition amount and an addition compound according to a conventional method.
チタン酸バリウムに副成分元素を含有させるには、例えば、チタン酸バリウムと副成分元素含有化合物を均一混合後、焼成を行えばよい。或いは、シュウ酸バリウムチタニルと副成分元素含有化合物を均一混合後、焼成を行ってもよい。 In order to contain the subcomponent element in the barium titanate, for example, barium titanate and the subcomponent element-containing compound may be uniformly mixed and then fired. Alternatively, baking may be performed after uniformly mixing barium titanyl oxalate and the subcomponent element-containing compound.
本発明のチタン酸バリウムの製造方法を行い得られたチタン酸バリウムを用いて、例えば積層セラミックコンデンサを製造する場合には、先ず、チタン酸バリウムの粉末を、副成分元素を含め従来公知の添加剤、有機系バインダ、可塑剤、分散剤等の配合剤と共に適当な溶媒中に混合分散させてスラリー化し、シート成形を行う。これにより、積層セラミックコンデンサの製造に用いられるセラミックシートを得る。該セラミックシートから積層セラミックコンデンサを作製するには、先ず、該セラミックシートの一面に内部電極形成用導電ペーストを印刷する。乾燥後、複数枚の前記セラミックシートを積層し、厚み方向に圧着することにより積層体とする。次に、この積層体を加熱処理して脱バインダ処理を行い、焼成して焼成体を得る。さらに、該焼成体にＮｉペースト、Ａｇペースト、ニッケル合金ペースト、銅ペースト、銅合金ペースト等を塗布し焼き付けて、積層セラミックコンデンサが得られる。 For example, when producing a multilayer ceramic capacitor using the barium titanate obtained by the method for producing barium titanate according to the present invention, first, a known addition of barium titanate powder including subcomponent elements is added. A sheet is formed by mixing and dispersing in an appropriate solvent together with a compounding agent such as an agent, an organic binder, a plasticizer, and a dispersing agent. Thereby, the ceramic sheet used for manufacture of a multilayer ceramic capacitor is obtained. In order to produce a multilayer ceramic capacitor from the ceramic sheet, first, an internal electrode forming conductive paste is printed on one surface of the ceramic sheet. After drying, a plurality of the ceramic sheets are laminated and pressed in the thickness direction to obtain a laminated body. Next, this laminate is heat treated to remove the binder, and fired to obtain a fired body. Further, a Ni paste, an Ag paste, a nickel alloy paste, a copper paste, a copper alloy paste or the like is applied to the fired body and baked to obtain a multilayer ceramic capacitor.
また、本発明のチタン酸バリウムの製造方法を行い得られたチタン酸バリウムの粉末を、例えばエポキシ樹脂、ポリエステル樹脂、ポリイミド樹脂等の樹脂に配合して、樹脂シート、樹脂フィルム、接着剤等とすると、プリント配線板や多層プリント配線板等の材料として用いることができる他、内部電極と誘電体層との収縮差を抑制するための共材、電極セラミック回路基板、ガラスセラミックス回路基板、回路周辺材料及び無機ＥＬ用の誘電体材料としても用いることができる。 In addition, the barium titanate powder obtained by the method for producing barium titanate of the present invention is blended with a resin such as an epoxy resin, a polyester resin, or a polyimide resin, and a resin sheet, a resin film, an adhesive, and the like. Then, it can be used as a material for printed wiring boards and multilayer printed wiring boards, as well as co-materials for suppressing shrinkage differences between internal electrodes and dielectric layers, electrode ceramic circuit boards, glass ceramic circuit boards, circuit peripherals It can also be used as a material and a dielectric material for inorganic EL.
また、本発明のチタン酸バリウムの製造方法を行い得られたチタン酸バリウムは、排ガス除去、化学合成等の反応時に使用される触媒や、帯電防止、クリーニング効果を付与する印刷トナーの表面改質材として好適に用いられる。 Further, the barium titanate obtained by the method for producing barium titanate of the present invention is a catalyst used in reactions such as exhaust gas removal and chemical synthesis, and surface modification of printing toner that imparts antistatic and cleaning effects. It is suitably used as a material.
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
〔実施例１〜１４〕
（Ａ液の調製）
純水に、塩化バリウム２水塩と、シュウ酸２水塩を３０℃で表１に示す割合となるように添加し、撹拌速度１．３m/秒で０．５時間撹拌して得られた懸濁液をＡ液とした。
（Ｂ液の調製）
市販の１５重量％の四塩化チタン水溶液を純水で希釈することにより表１に示す組成のものをＢ液とした。
Ｂ液をＡ液へ表２に示す条件にて添加し、１時間熟成を行った。熟成終了後、濾過してシュウ酸バリウムチタニルを回収した。
次いで、回収したシュウ酸バリウムチタニルを純水でリパルプして入念に洗浄した。その後１０５℃で２時間乾燥してシュウ酸バリウムチタニルの粉末を得た。得られたシュウ酸バリウムチタニルの諸物性を表３に示す。ＢａとＴｉのモル比は蛍光Ｘ線で測定した。平均粒径は、レーザー回折・散乱法粒度分布測定装置で測定した。その結果を表３に併記した。
[Examples 1 to 14]
(Preparation of solution A)
It was obtained by adding barium chloride dihydrate and oxalic acid dihydrate to pure water so as to have the ratio shown in Table 1 at 30 ° C. and stirring for 0.5 hour at a stirring speed of 1.3 m / sec. The suspension was designated as liquid A.
(Preparation of liquid B)
A commercially available 15 wt% aqueous solution of titanium tetrachloride was diluted with pure water to obtain a solution B having the composition shown in Table 1.
Liquid B was added to liquid A under the conditions shown in Table 2 and aged for 1 hour. After completion of aging, filtration was performed to recover barium titanyl oxalate.
Subsequently, the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder. Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
〔比較例１〕
（Ａ液の調製）
純水にシュウ酸２水塩を３０℃で表１に示す割合で添加し、撹拌速度１．３m/秒で０．５時間撹拌して得られた懸濁液をＡ液とした。
（Ｂ液の調製）
純水に塩化バリウム２水塩と市販の１５重量％の四塩化チタン水溶液を添加することにより得られた表１に示す組成のものをＢ液とした。
Ｂ液をＡ液へ表２に示す条件にて添加し、１時間熟成を行った。熟成終了後、濾過してシュウ酸バリウムチタニルを回収した。
次いで、回収したシュウ酸バリウムチタニルを純水でリパルプして入念に洗浄した。その後１０５℃で２時間乾燥してシュウ酸バリウムチタニルの粉末を得た。得られたシュウ酸バリウムチタニルの諸物性を表３に示す。ＢａとＴｉのモル比は蛍光Ｘ線で測定した。平均粒径は、レーザー回折・散乱法粒度分布測定装置で測定した。その結果を表３に併記した。
[Comparative Example 1]
(Preparation of solution A)
A suspension obtained by adding oxalic acid dihydrate to pure water at a rate shown in Table 1 at 30 ° C. and stirring for 0.5 hour at a stirring speed of 1.3 m / sec was designated as solution A.
(Preparation of liquid B)
Liquid B was obtained by adding barium chloride dihydrate and 15% by weight aqueous titanium tetrachloride aqueous solution to pure water and having the composition shown in Table 1.
Liquid B was added to liquid A under the conditions shown in Table 2 and aged for 1 hour. After completion of aging, filtration was performed to recover barium titanyl oxalate.
Subsequently, the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder. Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
〔比較例２〕
（Ａ液の調製）
純水にシュウ酸２水塩と市販の１５重量％の四塩化チタン水溶液を３０℃で表１に示す割合で添加し、撹拌速度１．３m/秒で０．５時間撹拌して得られた液をＡ液とした。
（Ｂ液の調製）
純水に塩化バリウム２水塩を溶解させて得られた表１に示す組成のものをＢ液とした。
Ｂ液をＡ液へ表２に示す条件にて添加し、１時間熟成を行った。熟成終了後、濾過してシュウ酸バリウムチタニルを回収した。
次いで、回収したシュウ酸バリウムチタニルを純水でリパルプして入念に洗浄した。その後１０５℃で２時間乾燥してシュウ酸バリウムチタニルの粉末を得た。得られたシュウ酸バリウムチタニルの諸物性を表３に示す。ＢａとＴｉのモル比は蛍光Ｘ線で測定した。平均粒径は、レーザー回折・散乱法粒度分布測定装置で測定した。その結果を表３に併記した。
[Comparative Example 2]
(Preparation of solution A)
It was obtained by adding oxalic acid dihydrate and a commercially available 15 wt% titanium tetrachloride aqueous solution to pure water at a rate shown in Table 1 at 30 ° C. and stirring for 0.5 hours at a stirring speed of 1.3 m / sec. The liquid was designated as liquid A.
(Preparation of liquid B)
Liquid B was prepared by dissolving barium chloride dihydrate in pure water and having the composition shown in Table 1.
Liquid B was added to liquid A under the conditions shown in Table 2 and aged for 1 hour. After completion of aging, filtration was performed to recover barium titanyl oxalate.
Subsequently, the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder. Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
〔比較例３〕
（Ａ液の調製）
純水に塩化バリウム２水塩を３０℃で表１に示す割合で添加し、撹拌速度１．３m/秒で０．５時間撹拌して得られた液をＡ液とした。
（Ｂ液の調製）
純水にシュウ酸２水塩と市販の１５重量％の四塩化チタン水溶液を添加することにより得られた表１に示す組成のものをＢ液とした。
Ｂ液をＡ液へ表２に示す条件にて添加し、１時間熟成を行った。熟成終了後、濾過してシュウ酸バリウムチタニルを回収した。
次いで、回収したシュウ酸バリウムチタニルを純水でリパルプして入念に洗浄した。その後１０５℃で２時間乾燥してシュウ酸バリウムチタニルの粉末を得た。得られたシュウ酸バリウムチタニルの諸物性を表３に示す。ＢａとＴｉのモル比は蛍光Ｘ線で測定した。平均粒径は、レーザー回折・散乱法粒度分布測定装置で測定した。その結果を表３に併記した。
[Comparative Example 3]
(Preparation of solution A)
Barium chloride dihydrate was added to pure water at a rate shown in Table 1 at 30 ° C., and a liquid obtained by stirring for 0.5 hour at a stirring speed of 1.3 m / sec was designated as liquid A.
(Preparation of liquid B)
Liquid B was obtained by adding oxalic acid dihydrate and a commercially available 15% by weight aqueous titanium tetrachloride solution to pure water and having the composition shown in Table 1.
Liquid B was added to liquid A under the conditions shown in Table 2 and aged for 1 hour. After completion of aging, filtration was performed to recover barium titanyl oxalate.
Subsequently, the recovered barium titanyl oxalate was repulped with pure water and carefully washed. Thereafter, it was dried at 105 ° C. for 2 hours to obtain barium titanyl oxalate powder. Table 3 shows properties of the barium titanyl oxalate obtained. The molar ratio of Ba and Ti was measured by fluorescent X-ray. The average particle size was measured with a laser diffraction / scattering particle size distribution analyzer. The results are also shown in Table 3.
表３より実施例にて得られたシュウ酸バリウムチタニルは、レーザー回折・散乱法により求められる平均粒径が４μｍ以下で、また、該シュウ酸バリウムチタニルの組成は、Ｂａ／Ｔｉモル比が１．０００〜１．００２の略１であった。
表３より比較例にて得られたシュウ酸バリウムチタニルは、レーザー回折・散乱法により求められる平均粒径が４μｍより大きく、また、該シュウ酸バリウムチタニルの組成は、Ｂａ／Ｔｉモル比が０．９９７〜１．００１であった。
From Table 3, the barium titanyl oxalate obtained in the examples has an average particle size of 4 μm or less determined by the laser diffraction / scattering method, and the composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 1. It was about 1 of .000 to 1.002.
From Table 3, the barium titanyl oxalate obtained in the comparative example has an average particle size larger than 4 μm determined by the laser diffraction / scattering method, and the composition of the barium titanyl oxalate has a Ba / Ti molar ratio of 0. .997 to 1.001.
〔実施例１５、１６及び比較例４〜６〕
＜チタン酸バリウムの製造＞
実施例１及び比較例１〜３で得られたシュウ酸バリウムチタニル試料の８ｇを、大気中、８７５或いは９００℃で２４時間で焼成した。冷却後、解砕してそれぞれチタン酸バリウムの粉末を得た。得られたチタン酸バリウムの諸物性を表４に示した。ＢａとＴｉのモル比は前記と同様な方法で求めた。平均粒径はＳＥＭ写真から、比表面積はＢＥＴ法で求めた。また、得られたチタン酸バリウムについて、結晶性の指標であるｃ軸とａ軸の長さの比(ｃ軸／ａ軸比)をＸＲＤによって測定した。
[Examples 15 and 16 and Comparative Examples 4 to 6]
<Manufacture of barium titanate>
8 g of the barium titanyl oxalate sample obtained in Example 1 and Comparative Examples 1 to 3 was baked in the air at 875 or 900 ° C. for 24 hours. After cooling, it was crushed to obtain barium titanate powder. Various physical properties of the obtained barium titanate are shown in Table 4. The molar ratio of Ba and Ti was determined by the same method as described above. The average particle size was determined from the SEM photograph, and the specific surface area was determined by the BET method. Further, for the obtained barium titanate, the ratio of the c-axis to a-axis length (c-axis / a-axis ratio), which is an index of crystallinity, was measured by XRD.
表４より、焼成温度を同じ温度（９００℃）にした場合、本発明で得られるシュウ酸バリウムチタニル（実施例１５）を用いたものは、比較例のものと比べ、ｃ軸／ａ軸比が高いチタン酸バリウムが得られることが分かる。また、焼成温度を８７５℃まで低くした場合（実施例１６）でも得られるチタン酸バリウムはｃ軸／ａ軸比が１．００８５以上と高いことが分かる。 From Table 4, when the firing temperature is the same temperature (900 ° C.), the one using barium titanyl oxalate (Example 15) obtained in the present invention has a c-axis / a-axis ratio as compared with the comparative example. It can be seen that high barium titanate is obtained. It can also be seen that the barium titanate obtained even when the firing temperature is lowered to 875 ° C. (Example 16) has a high c-axis / a-axis ratio of 1.0085 or more.
本発明によれば、平均粒径が４μｍ以下と小さくとも、Ｂａ／Ｔｉモル比が０．９９８〜１．００２の略１のシュウ酸バリウムチタニルを提供することができる。そして、このようなシュウ酸バリウムチタニルを用いることにより、シュウ酸塩法で、粒径が小さいにもかかわらず結晶性が高く、優れた性能を有する誘電体セラミック材料を提供できる。 According to the present invention, it is possible to provide approximately 1 barium titanyl oxalate having a Ba / Ti molar ratio of 0.998 to 1.002 even when the average particle size is as small as 4 μm or less. By using such barium titanyl oxalate, a dielectric ceramic material having high crystallinity and excellent performance can be provided by the oxalate method even though the particle size is small.
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| KR1020147006674A KR101904579B1 (en) | 2011-09-15 | 2012-09-12 | Method for producing barium titanyl oxalate and method for producing barium titanate |
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| WO2021251451A1 (en) * | 2020-06-12 | 2021-12-16 | 日本化学工業株式会社 | Barium titanyl oxalate, method for producing same, and method for producing barium titanate |
| WO2022107695A1 (en) * | 2020-11-19 | 2022-05-27 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP2022081059A (en) * | 2020-11-19 | 2022-05-31 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP2022081058A (en) * | 2020-11-19 | 2022-05-31 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
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| JP6217599B2 (en) | 2014-11-17 | 2017-10-25 | 株式会社村田製作所 | Method for producing barium titanate powder |
| CN107311224B (en) * | 2017-07-14 | 2019-04-19 | 安徽拓吉泰新型陶瓷科技有限公司 | A kind of preparation method of barium carbonate powder |
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| KR100434883B1 (en) | 2001-08-14 | 2004-06-07 | 삼성전기주식회사 | A method for the manufacturing of Barium-Titanate based Powder |
| CN1712356A (en) * | 2004-06-21 | 2005-12-28 | 肇庆羚华有限责任公司 | Reactor, reacting method and product for preparing barium titanate powder |
| JP2012077068A (en) * | 2010-09-07 | 2012-04-19 | Nippon Chem Ind Co Ltd | Barium titanyl oxalate particle, method for producing the same and method for producing barium titanate |
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| JPH0388720A (en) * | 1989-08-30 | 1991-04-15 | Tdk Corp | Production of titanyl barium oxalate particles |
| JPH03103322A (en) * | 1989-09-14 | 1991-04-30 | Tdk Corp | Production of titanyl barium oxalate particle |
| JPH03103323A (en) * | 1989-09-14 | 1991-04-30 | Tdk Corp | Production of titanyl barium oxalate particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021251451A1 (en) * | 2020-06-12 | 2021-12-16 | 日本化学工業株式会社 | Barium titanyl oxalate, method for producing same, and method for producing barium titanate |
| JP2021195329A (en) * | 2020-06-12 | 2021-12-27 | 日本化学工業株式会社 | Barium titanyl oxalate, production method thereof and production method of barium titanate |
| JP7102462B2 (en) | 2020-06-12 | 2022-07-19 | 日本化学工業株式会社 | Barium titanyl oxalate, its production method and barium titanate production method |
| KR20230024274A (en) | 2020-06-12 | 2023-02-20 | 니폰 가가쿠 고교 가부시키가이샤 | Barium titanyl oxalate, method for producing the same, and method for producing barium titanate |
| WO2022107695A1 (en) * | 2020-11-19 | 2022-05-27 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP2022081059A (en) * | 2020-11-19 | 2022-05-31 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP2022081058A (en) * | 2020-11-19 | 2022-05-31 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP7110305B2 (en) | 2020-11-19 | 2022-08-01 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| JP7110306B2 (en) | 2020-11-19 | 2022-08-01 | 日本化学工業株式会社 | Method for producing barium titanyl oxalate and method for producing barium titanate |
| KR20230109634A (en) | 2020-11-19 | 2023-07-20 | 니폰 가가쿠 고교 가부시키가이샤 | Method for producing barium titanyl oxalate and method for producing barium titanate |
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