TW539649B - Particulate barium titanate powder, particulate calcium-modified barium titanate powder, and production method thereof - Google Patents

Abstract

The object of the present invention is to provide particulate barium titanate powder with high-reliability, which hardly causes insulation failure when used as a dielectric element, particulate calcium-modified barium titanate powder and a method for manufacturing the particulate barium titanate powder. The method for manufacturing the particulate barium titanate powder is characterized in comprising following steps: a step to prepare a barium hydroxide aqueous solution having 0.20-1.20 mol/l barium hydroxide and a titanium alkoxide alcohol solution having 0.088-1.235 mol/l titanium alkoxide, a step to mix the prepared barium hydroxide solution with the prepared titanium alkoxide alcohol solution so that the Ba/Ti molar ratio is 1.00-1.20 to obtain a mixed solution without incorporating other alkali elements in the mixed solution, and a step to subject the obtained mixed solution to react at 60-100 DEG C.

Description

539649 A7 B7 V. Description of the Invention (Technical Field) The present invention relates to “barium acid particulate powder, calcium modified barium titanate particulate powder and its manufacturing method, which are medium materials for electronic components. Small, large-capacity multilayer chip capacitors with a dielectric element thickness of 1 to several μm, and an average particle diameter of 0.019 to 0.300 μm of barium titanate particulate powder, calcium-modified barium titanate particulate powder, and method for producing the same [Prior art] Conventional methods for producing "barium acid particulate powder" include solid phase method, hydrothermal synthesis method, and hydrolysis method. The hydrolysis method is described in Japanese Patent Laid-Open Publication Nos. 146713 and 1992. It is described in No. 1.2020. According to Japanese Patent Laid-Open Publication No. 146713 of 1986, hydrous titanium oxide, barium hydroxide, and alkali metal hydroxide are present at 60 to 10,000 times the molar equivalent of titanium at 60 to The reaction was carried out at 110 ° C to obtain barium titanate particulate powder having an average particle diameter of 007 to 0.05 μm. In addition, according to Japanese Patent Laid-Open Publication No. 122020, when containing hydrogen Add at least one kind of alkali metal hydroxide or amine in an aqueous solution of barium hydroxide and the barium hydroxide with a molar ratio of 丨: 丨 to 丨: 4 to add an equimolar amount of titanium alkoxide with barium hydroxide at 60 to 90 °. C reaction, and the resulting barium titanate particulate powder is calcined at a temperature that does not allow the microparticles to grow to obtain a barium titanate rhenium granular powder having an average particle diameter of 0.06 to 0.1 μm. With the miniaturization and high integration of electronic devices, in order to miniaturize and increase the capacity of multilayer chip capacitors, the dielectric elements are becoming thinner and thinner. However, with the dielectric layer between the internal electrodes, It becomes thinner and thinner 'if there is a structural defect', the internal electrode will be short-circuited due to this and cannot function as a dielectric element. In order to maintain high reliability, it is necessary to make the internal electrical The uniform structure of the depression. At the same time, due to the requirements, the ceramic powder is micronized to 〇〇〇 ～

The ceramic of the dielectric layer between the electrodes has a large capacity without thinning, which is about 0.25 μm. [Summary of the invention] Barium acetic acid particulate powder is a regular, high quality ceramic powder. But-the general Λ Wanjing system crystal form, is a strong medium, and &, the problem of the average particle size of the right ceramic powder, that is, due to micronization-these questions 4 st ",: close to cubic crystal It is at the same time that the strong electrical conductivity is reduced by two: the size effect. In addition, when the squareness of the finished ceramic powder is small, the problem is the same as that of the laminated ceramics obtained by using the ceramic powder. The capacitance decreases, and the temperature characteristics of the electrostatic capacitance deviate. The finest powders currently sold for particulate materials, such as the acid donation pin of the hydrothermal synthesis method, have the finest powder of 0 · 丨 3 ~ 0.2G μm, and the crystallinity index of ㈣ powder is The squareness (c / a pumping ratio measured by X-ray diffraction) is ⑽. 008. In this way, the micronization of the ceramic powder has a correlation with the squareness. If the ceramic powder is fine, the smaller the squareness is, this becomes One problem with the miniaturization of ceramic powder. In addition, in the conventional hydrolysis method, in order to promote the reaction, a strong alkaline solvent was used, and strong Na (0 solution was added to the reaction material. However, the following problems occurred: ppm of Na remained in the resulting ceramic powder and was processed into laminated tablets After the capacitor, it will cause migration and deteriorate the insulation of the dielectric element. This problem becomes more significant when the dielectric layer is thinned. The problem caused by the main reason is that it is difficult to obtain miniaturization and high density of electronic devices. Necessary Tao Yao powder for small and large-capacity multilayer chip capacitors with a dielectric element thickness of about 丨 pm to several μηι. -5- This paper size applies to China National Standard (CNS) Α4 specification (21〇X (297 mm) 539649

An object of the present invention is to solve the above-mentioned problems and obtain a barium titanate-based ceramic powder with high reliability, which is less likely to cause poor insulation of dielectric elements by a hydrolysis method. [Solutions to solve the problem] In order to achieve the above-mentioned object, a method for producing barium titanate particulate powder of the present invention is characterized by having the following steps: · preparing an aqueous solution of 0.20 to 1.20 mol / l barium hydroxide and 〇88 ~ 1 235 moles / liter of alcohol solution of stilbene oxyfluorene; The barium hydroxide solution and the alcohol solution of titanium alkoxide are blended at a Ba / Ti molar ratio of 100 to 1.20. The elements are mixed to obtain a mixed solution; the mixed solution is allowed to be between 60 and 100. 〇 Reaction. Another method for producing the barium acid particulate powder according to the present invention is characterized in that, in the above method for producing a barium acetate microparticle powder, after the step of allowing the solution to be mixed, the method further includes heat treatment at 850 to 1000 ° C. step. A method for producing the calcium-modified barium titanate particulate powder of the present invention is characterized by having the following steps: preparing an aqueous solution of 0.20 to 1.20 mol / l barium hydroxide, 0.088 to 1.235 mol / l of titanium alkoxide Alcohol solution and alcohol solution of calcium salt; Blend with a Ba / Ti molar ratio of 0.980 ~ 1.020 and a Ca / Ti molar ratio of less than 0.160 'to obtain a mixed solution without the mixing of other basic elements; let the mixed solution above 60 ~ 10CTC reaction. Another manufacturing method of the calcium-modified barium titanate particulate powder of the present invention is characterized in that the method for manufacturing the calcium-modified barium titanate particulate powder described above is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) Binding 539649 A7 B7 5. In the description of the invention (4), after the step of mixing the solution, 'there is also a step of performing heat treatment at 950 ~ 1 loot. One form of the barium titanate particulate powder of the present invention is obtained by a method for manufacturing the barium titanate particulate powder of the present invention, which is characterized in that the average particle diameter is 0.019 to 0.056 4111 and the specific surface area is 17.99 to 52.64. 1112 / §, the Ba / Ti molar ratio after synthesis is 0.9979 to 1.060. Another form of the barium titanate particulate powder of the present invention is obtained by another method for manufacturing the barium titanate particulate powder of the present invention, which is characterized in that the average particle diameter is 0.105 to 0.300 μm, and X-ray diffraction is used. The measured c / a axis ratio is 1.008 to 1.01. One form of the calcium-modified barium titanate particulate powder of the present invention is a method for manufacturing the # 5 modified barium acidate particulate powder of the present invention. The obtained 'is characterized in that its average particle diameter is 0.019 to 0.025 μm, the specific surface area is 40.36 to 54.05 m 2 / g, and the (Ba + Ca) / Ti molar ratio after synthesis is 0.994 to 1.004. Another aspect of the modified bowel barium acid particulate powder of the present invention is obtained by another manufacturing method of the calcium modified barium titanate particulate powder of the present invention, which is characterized in that its average particle diameter is 0.145 ~ 0.250 μm, and the c / a axis ratio measured by X-ray diffraction is 1.008 ~ 1.01. [Brief Description of the Drawings] Fig. 1 is an explanatory diagram of a synthesis device in a method for producing barium titanate particulate powder according to an embodiment of the present invention. Fig. 2 is a micrograph of a barium titanate particulate powder of sample c in Example 丨 of the present invention. Fig. 3 is a graph showing the barium titanate particulate powder of sample 3 in Example 1 of the present invention, and the scale of the CNS standard grid is 539649 A7.

Micro photo. Fig. 4 is a microphotograph of barium titanate particulate powder of sample 25 in Example 1 of the present invention. Fig. 5 is a photomicrograph of modified barium titanate particulate powder of sample 52 in Example 2 of the present invention. Fig. 6 is a photomicrograph of calcium modified barium titanate particulate powder of sample 58 in Example 2 of the present invention. FIG. 7 is a graph showing the relationship between the average particle size and the axial ratio of barium titanate particulate powders of samples 1 to 58 and samples 63 to 66 using the hydrothermal synthesis method in the ratio k example of the examples of the present invention. . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a method for producing a barium titanate particulate powder according to the present invention will be described below. First of all, prepare an aqueous solution of 0.20 to 1.20 moles / liter of barium hydroxide and an alcohol solution of 88 to 12 moles / liter of titanium alkoxide. If the aqueous solution of barium hydroxide is less than 200 mol / L, the synthesis reaction is difficult to proceed, and the average particle size after synthesis becomes large. While line

When the aqueous solution of barium hydroxide is higher than 120 mol / l, carbon I barium is formed during the synthesis, and the molar ratio of the obtained barium titanate is unstable. In addition, if the alkoxytitanium alcohol solution is less than 0.088 mol / l, a large amount of alcohol is required, which may reduce productivity. If the alcohol solution of titanium alkoxide is higher than .235 mol / l, it will easily react with water 77 in the air to produce titanium oxide. Moreover, the average particle size of 1 barium titanate particulate powder after synthesis It becomes too large, so that the molar ratio after synthesis cannot reach about 1.00. 1 Then, the barium hydroxide solution and the alcohol solution of titanium alkoxide are blended.

539649 A7 _______B7 V. Description of the invention (6 ~~) " A mixed solution with Ba / Ti molar ratio of ^ ~ ^ is obtained. If the Ba / Ti molar ratio is less than 1.00, Ti becomes excessive, and it is not suitable as a dielectric ceramic powder for a multilayer chip capacitor. On the other hand, if the Ba / Ti molar ratio is higher than U, the excess Ba and the c / a axis ratio will decrease, which makes it unsuitable as a dielectric ceramic powder for use in multilayer capacitors. In the above mixed solution, it is necessary to prevent other basic elements (such as criminals) from being mixed in. Because rabbits are mixed with other test elements, the test elements will remain in the resulting barium titanate particulate powder, even if the remaining amount is only Hundreds of ppm, after processing into a multilayer chip capacitor, migration will occur and the insulation of the dielectric element will deteriorate. However, the presence of other basic elements as unavoidable impurities is not a problem. Next, the above mixed liquid is allowed to react at 60 to 100 ° C to generate barium acid particulate powder before heat treatment. If the reaction temperature is lower than 60 ° C, the synthesis reaction is difficult to proceed. On the other hand, the reaction temperature of a mixed solution of water and isopropanol does not exceed 100 ° C. The thus obtained barium titanate particulate powder before heat treatment has an average particle diameter of 0.019 to 0.056 μm, a specific surface area of 17.99 to 52.64 m2 / g, and a Ba / Ti molar ratio after synthesis of 0.9979 to 1.060. Then, the barium titanate particulate powder before the heat treatment is 850 to 10,000. (3) A heat treatment is performed to obtain a barium titanate particulate powder after the heat treatment. The barium titanate particulate powder before the heat treatment of the present invention has a feature that abnormal grain growth is unlikely to occur even if the heat treatment is performed in the above temperature range. After the heat treatment thus obtained, The barium titanate particulate powder has an average particle diameter of 0.105 to 0.300 μηι, and the c / a axis ratio measured by X-ray diffraction is 1.008 to 1.010. The calcium modified barium titanate particulate powder of the present invention is described below. Another embodiment of the manufacturing method will be described. First, prepare an aqueous solution of barium hydroxide of 0. 20 to 1.20 mol / l as the alkoxy-9. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Centimeter) gutter 5. Description of the invention (0.088 ~ 1 235 seater / 4 zenfield solution of titanium-based alcohol solution and isopropanol corresponding to the number of propoxy groups dissolved in the isopropanol solution. If ^ Servants / ㈣ 'first dissolve nitrate on it. · The barium hydroxide aqueous solution is less than 0.20 mol / l, then the average particle size of the unity:,: is larger after synthesis. And if barium hydroxide : / Valley / from 咼 1.2 mol / In the production process, there will be barium carbonate formation in the a-forming process, so that a large amount of alcohol is required per mole / liter, which will reduce the productivity. And if = oxygenated material is high and 35 materials / liter, It is easy to undergo hydrolysis reaction with water in the air to generate ytterbium oxide, and since the average particle size of the granulated powder of the acidic pin M after synthesis becomes larger, the molar ratio after synthesis cannot be made to about 1.00. Then, the barium oxide was dissolved in water; the isopropoxyl and the isopropanolol solution of nitric acid were blended to obtain a Ba / butyl molar ratio of 0 to 1020 and a molar ratio of 0.160 is not a mixed solution. If the Ba / Ti molar ratio is lower than 0098, it will be excessive, and the dielectric ceramic powder used in the multilayer chip capacitor will be unsuitable. If the Ba / Ti molar ratio is higher than 丨· 020, due to the excess on the a side (such as +) and the reduction of the mountain axis ratio, it is not suitable as a dielectric ceramic powder for multilayer capacitors. In the above mixed solution, other alkaline elements (such as shirts, etc.) must be prevented ) Mix in 'This is because if you mix in other basic elements, the basic element It will remain in the produced barium acid particulate powder, even if the residual amount is only a few hundred ppm, it will cause migration after processing into a laminated sheet electric valley, and deteriorate the insulation of the dielectric element. But other alkaline The presence of the element as an unavoidable impurity is not a problem. Next, the above mixed solution is allowed to react at 60 to 100 ° C to generate -10- before heat treatment. This paper size applies Chinese National Standard (CNS) A4 specification (21〇X 297). (Centi) 539649 A7 ------------ B7__ 5. Description of the invention (8) Barium octylate particulate powder. If the reaction temperature is lower than 6 (rc), the synthesis reaction is difficult to proceed. In addition, the reaction temperature of the mixed solution of 'water and isopropanol does not exceed 100 ° C. The thus obtained calcium-modified barium titanate particulate powder before heat treatment has an average particle diameter of 0.019 to 0.025 μm, a specific surface area of 40.36 to 54.05 m2 / g, and a Ba / Ti molar ratio after synthesis of 0.994 to 1.004. Then, 'the barium titanate particulate powder before the heat treatment is 95 to 100. 〇 Heat treatment was performed to obtain barium titanate particulate powder after heat treatment. The # 5 modified barium titanate particulate powder before the heat treatment of the present invention has a characteristic that abnormal grain growth is unlikely to occur even if the heat treatment is performed in the above temperature range. In this way, each heat-treated calcium-modified barium titanate particulate powder was obtained, the average particle diameter of which was 0.145 to 0.250 μm, and the c / a axis ratio measured by X-ray diffraction was ≦ on 〇10. The ethoxy group and the alcohol solution are not limited to the above embodiment, and may be appropriately selected, for example, ethoxylate, butoxide, ethanol, butanol, and the like. In addition, the above-mentioned salt is not limited to the above-mentioned embodiment, and for example, bromine # 5, chlorination and nitric acid can be appropriately selected. In another method for producing the barium titanate particulate powder of the present invention, as the mixed solution, an aqueous solution of barium hydroxide, an alcohol solution of a titanium alkoxide, and an alcohol solution of a calcium salt may be mixed at the same time, or while stirring Each solution was sequentially injected and mixed. Next, a synthesis device in a method for producing barium titanate particulate powder according to the present invention will be described in detail with reference to FIG. The synthesis device 1 consists of N2 tank 2, bubbler holes and 2d, Ba solution tank 3, Ti solution tank 4, pumps 5a, 5b'5c, static mixer such as equivalent, aging tank 8, pipeline 2a, and , 4a, 7 constitute. -11-The size of this paper is compliant with China's standard ^ ---- binding line 539649 A7 B7 V. Description of the invention (9) The tank 2 is a gas storage tank for supplying N2 gas to the Ba solution tank 3 and the aging tank 8. The bubblers% and 2d are devices for releasing N2 gas supplied from the N2 tank 2 into the Ba solution tank 3 and the Ti solution tank 4 in a bubble form. The Ba solution tank 3 is a container filled with a barium hydroxide aqueous solution. The Ti solution tank 4 is a container into which an alcohol solution of titanium alkoxide is injected. The pumps 5a, 5b, and 5c are devices for feeding an aqueous solution of barium hydroxide, an alcohol solution of titanium alkoxide, and a solution of barium acid, respectively, into a static mixer. The static mixers 6a and 61) are mixers for mixing solutions. The aging tank 8 is a container for aging the synthesized barium titanate particulate powder. The pipes 2a, 2c, 3a, 4a, and 7 are pipes for conveying N2 gas and solution. First, 1 ^ 2 gas is sent to the bubbler 2b provided in the Ba solution tank 3 through a pipe 2a connected to the% tank 2. Similarly, N2 gas is sent to the bubbler 2d provided in the aging tank 8 through the pipe 2c. Then, the aqueous solution of barium hydroxide is poured into the Ba solution tank 3, and the alcohol solution of the titanium alkoxide is injected into the Ti solution tank 4, and the solution is sent to the fruits 5a and 5b through the pipes 3a and 4a. Then, the chestnuts 5a and 5b are pumped. The two solutions sent out are mixed in the static mixer 6a, and the mixed solution is usually pipe 7 sent to the aging tank 8. In order to stabilize the crystal lattice, the aging tank 8 is maintained at 60 to 90 ° C, and aging is performed for 1 to several hours. During the aging in the aging tank 8, the barium titanate solution in the aging tank 8 is sent to the pump 5c through the pipeline 8a, mixed and aged by the static mixer 6b, and then returned to the aging tank 8 through the pipeline 8b. Aging. Next, after the aging is completed, solid-liquid separation is performed using a centrifugal separator or the like to obtain barium titanate particulate powder. This was washed with boiling pure water, and then solid-liquid separation was performed. -12- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 539649 V. Description of the invention (Soluble to displace water such as acetic acid I, material 14 6 alcohol, etc.) After the water in the granular powder is replaced and removed, solid-liquid separation is performed, = powder is dried, and finally the "acid-locked micro" before heat treatment with a specified molar ratio is obtained. [Example] (Constant Example 1) " ^ 先 #chloride oxidation Barium 8 hydrate was added to pure water heated to 90 ° C. and stirred to make it completely dissolve to obtain a barium hydroxide aqueous solution, and titanium isopropoxide solution in isopropanol was used to obtain a calcined oxyfluorene. The aqueous solution of alcohol is injected into the solution tank 3, and the alkoxide titanium solution of titanium alkoxide is poured into the Ti solution tank 4 'as shown in Table 丨 the molar amount of Ba, the molar amount of Ti and the molar ratio of Ba / Ti The ratio was adjusted by using the method described in the above embodiment, and the barium titanate particulate powders of the samples A to κ before the heat treatment were used. In addition, the reaction conditions were that the aging tank 8 was maintained at 80t and the aging time was 丨 hours. Then, X-ray diffraction was applied to the barium titanate of the obtained samples A to κ before the heat treatment. The granular powder was analyzed to determine that it was a cubic phase barium titanate single phase. In addition, the synthetic rhenium Ba / Ti molar ratio was 0.99979 to L 0.60, the average particle diameter (the corresponding diameter calculated based on the specific surface ^ ) Is 0.019 ~ 0.056 μm, with a narrow and uniform particle size distribution. The micrograph of the barium titanate particulate powder of the heat-treated sample c is shown in Figure 2. [Table 1] This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) -13- 539649

Example C 0.40 0.34ΓΊ 1.100 1.0060 0.027 36.76 D 0.40 _〇651 1.100 1.0005 0.039 25.34 E 0.40 _U35 1.110 0.9989 0.056 17.99 F 0.60 _〇509 1.030 1.0015 0.024 41.24 G 0.60 _〇Ό88 1.100 0.9979 0.033 30.10 Η 0.80 0.647 1.054 0.9990 0.030 33.56 I 1.20 1.100 0.9998 0.023 43.64 J 0.20 _0〇40 1.200 1.0016 0.051 19.64 K 0.50 0.647 1.000 0.9980 0.033 30.63, and the heating furnace is used at 850, 900, 950, and 1000t respectively: For the four samples before heat treatment, A ~ K & The barium titanate particulate powder was heat-treated for 2 hours to obtain barium titanate particulate powders of samples 1 to 44 having a large tetragonality of ferroelectric shells. Next, the specific surface area, average particle diameter, and c / a axis ratio of the barium titanate particulate powders of Samples 1 to 44 were determined and summarized in Table 2. Micrographs of barium titanate M fe powders of samples 3 and 25 are shown in Figs. 3 and 4, respectively. [Table 2] Standard test heat treatment temperature ___0C)

A Specific surface area (m2 / g) Average particle size (μm) c

D 850 Examples

G

H

K

A 900 c

D 8.69 9.29 9.57 7.52 6.53 8 98 6.95 9.24 6.95 8.74 —9: 06 8.07Ύπ6Ύΐ \ 6.18 0.115 0.108 0.105 0.133 0.138 0.111 0.144 0.108 0.144 0.114 0.110 0.124 0.129 0.122 0.162 c / a Shaft ratio 1.008 1.009 1.009 1.008 1.008 1.008 1.008 1.008 1.008 1.008 1.008 1.008 1.008 1.008 T〇Q9 1.009 1.009 Order-14 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 539649 A7 B7 16 Ε --------- 0.186 1.009 17 F — 7.86 0.127 1.008 Real 18 G — 0.208 1.009 Application 19 Η — 0.121 1.008 Example 20 I — 5.27 0.190 1.009 21 J — 7J9__ 0.132 1.008 22 Κ: __—— 0.130 1.008 23 A 丨 0.136 1.009 24 B ^ 83__ 0.146 1.010 25 C 0.136 1.010 26 D 5.28 0.189 1.009 27 E — 4.66 0.240 1.009 28 F 950 6.28__ 0.159 1.008 29 G — 0.252 1.009 30 Η — TrT 0.148 1.008 31 I 4.16 0.240 1.009 32 J 6.31 0.158 '1.009 33 Κ — ^ 〇9__ 0.164 1.008 34 A 5.66 0.177 1.009 35 B 5 ^ 2__ 0.178 1.010 36 C __---- · 0.194 1.009 37 D 0.235 1.009 38 E _ 0.300 1.009 39 F 1000 0.209 1.008 40 G 334__ 0.300 1.009 41 H __—— 4.39_ 0.228 1.009 42 I ____ 一 — 3.36 0.297 1.009 43 J 5.23 — 0.191 1.009 44 K 0.242 1.009 As can be seen from Table 2, barium titanate of sample 丨 ~ 44 The average particle size of the particulate powder is five. Explanation of the invention (12 0.105 ~ 0.300 μιη, c / a axis ratio is 1.008 ~ 1.010, despite being fine particles, the squareness is greater than 0 (Example 2) First, barium hydroxide 8 Hydrate is added into pure water heated to 90 ° C. -15- This paper size applies Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) 539649 A7 B7 V. Description of the invention (13) Stir to completely dissolve, obtain a barium hydroxide aqueous solution, and dissolve titanium isopropoxide in isopropanol, obtain an alcohol aqueous solution of titanium alkoxy, and dissolve calcium chloride in isopropanol To obtain an alcohol solution of calcium salt. Next, an aqueous solution of barium hydroxide was poured into the solution tank 3, and an alcohol aqueous solution of titanium alkoxide and an alcohol solution of calcium salt were mixed in advance, and the mixed solution was poured into the Ti solution tank 4, and these were added in the molar amounts of Ba shown in Table 3. , Ti molar amount, Ca molar amount, Ba / Ti molar ratio, and Ca / Ti molar ratio were blended, and the calcium-modified barium titanate particulates of samples L to Q before the heat treatment were obtained by the method described in the above embodiment. powder. The reaction conditions were that the aging tank 8 was maintained at 80 ° C and the aging time was 1 hour. Then, the obtained calcium-modified barium titanate particulate powders of the samples L to Q before the heat treatment were analyzed by X-ray diffraction to determine that it was a cubic barium titanate single phase. In addition, the (Ba + Ca) / Ti mole after synthesis is 0.994 to 1.004, the average particle size (corresponding diameter calculated from the specific surface area) is 0.019 to 0.025 μm, and the particle size distribution is narrow and uniform. [Table 3] Conversion after sample preparation (before heat treatment) Conversion dt (molar mole, specific molar ratio average particle size (μιη) Specific surface area (m2 / g) Ba Ti Ca Ba / Ti Ca / Ti (Ba + Ca ) / Ti Ba / Ti Ca / Ti Example L 0.50 0.650 0.029 1.020 0.045 1.002 0.961 0.041 0.025 40.36 M 0.50 0.650 0.036 1.010 0.055 0.996 0.945 0.051 0.023 43,54 N 0.50 0.650 0.042 1.010 0.065 1.004 0.946 0.058 0.024 42.07 〇0.50 0.650 0.049 1.000 0.075 0.994 0.927 0.067 0.023 43.42 P 0.50 0.650 0.065 0.980 0.100 1.004 0.906 0.098 0.019 52.65 Q 0.50 0.650 0.128 0.986 0.160 0.998 0.846 0.152 0.019 54.05 Then, use a heating furnace at 950, 1000, 1050 and 1100 ° C before heat treatment-16 -This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 539649 A7 4 kinds of L ~ Q calcium modified barium titanate particulate powder described in the invention heat treatment for 2 hours, obtained as & 篆'丨 The sample with a large tetragonality of 45 ~% of the modified sample of acid-locked particulate powder.' The specific surface area of the calcium-modified barium titanate particulate powder of samples 45 ~ 58, The average particle diameter and c / a axis ratio are summarized in Table 4. The photomicrographs of the paternal lock micronized powders of samples 5 2 and 5 8 are shown in FIG. 5 and FIG. 6, respectively. [Table 4 ] Heat treatment temperature Specific surface area (m2 / g) Average particle size c / a Axial ratio--. (Table 3) (° C) (μ m) 45 Μ 950 5.18 0.179 1.010 46 Q 7.40 0.145 1.008 47 Μ 4.43 0.209 1.009 48 Ν 1000 5.23 0.167 1.010 49 Q 4.85 0.221 1.009 Actual 50 L 4.88 0.166 1.008 Application 51 M 3.11 0.250 1.010 Example 52 N 1050 5.14 0.174 1.009 53 0 4.65 0.174 1.009 `` 4 P 5.59 0.157 1.009 55 L 3.71 0.194 1.008 56 N 1 1 AA 4.15 0.193 1.010 57 〇1100 3.89 0.219 1.009 58 P 4.63 0.250 1.010 As can be seen from Table 4, the average particle size of the calcium-modified barium titanate particulate powder of samples 45 to 58 is 0.145 to 0.250 μηι, and the c / a axis ratio It is 1.008 to 1.010, and although it is a fine particle, its squareness is large. (Example 3) First, prepare an aqueous solution of 0.20 ~ 1-20 mol / l barium hydroxide and 0.088 ~ 1.235 -17- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 539649 A7 B7 V. Invention Note (15) mol / l of an alcohol solution of titanium alkoxide, the barium hydroxide solution and the alcohol solution of titanium alkoxide are blended according to a molar ratio of Ba / Ti to the ratio of 划 to 划, without making other tests Elements are mixed in. The mixed solution was reacted at 60 ~ 10 ° C to prepare barium titanate particulate powder before heat treatment. The heat treatment was performed in a heating furnace at 85 ° C to obtain a specific surface area, average particle size, and c shown in Table 5. / a axis ratio of sample 59 and rhenium barium titanate particulate powder. Next, a barium hydroxide aqueous solution outside the above molar concentration range and a titanium alkoxide solution outside the above molar concentration range were prepared and mixed. The solution was reacted at 60 to 100 t to prepare barium titanate particulate powder before heat treatment, and heat treated at 85 ° C. in a heating furnace to obtain a specific surface area, average particle diameter, and c / a axis ratio shown in Table 5 as a comparative example. The barium titanate particulate powder of samples 6 and 62. The c / a axis ratio of the barium titanate particulate powder of sample 61 is smaller than ⑶, which is outside the scope of the present invention, and the barium titanate of sample 62 is The average particle size of the particulate powder is greater than 0.300 μηι, which is also out of the scope of the present invention. J Μ: Sample heat treatment temperature_rci_ Specific surface area (m2 / g) Average particle size (μm) c / a Axial ratio 59 5.29 0.189 1.010 cases 60 850 4.43 0.226 1.009 t dagger 61 7.68 0.130 1. 007 Example 62 ----- L — 3.11 _ 1 1 0.322 ^ 1 1.010 Then 'prepared a ceramic raw material layer with a thickness of one consisting of barium osmate fine powder of samples 59 to 62 as the main component. The number of pieces of pottery is an electrode film printed as an internal electrode on the surface of the raw material layer so that one end edge is exposed at -18-539649 A7 B7 V. Description of the invention (16) Any end face side of the ceramic raw material layer will be specified The number of pieces of these ceramic raw material layers were laminated, pressed, and fired to obtain a ceramic laminate of samples 59 to 62 with an electrode film area of 1.23 mm2. Next, on both end faces of the ceramic laminate of samples 59 to 62, The conductive paste for forming a terminal electrode is dip-coated, and dried and fired to form a pair of terminal electrodes that are electrically connected and mechanically bonded to the internal electrodes. Then, a Ni plating film is formed on the pair of terminal electrodes by electroplating, and then The Sn plating film was formed on the Ni plating film by electroplating to obtain multilayer ceramic capacitors of samples 59 to 62. The dielectric constant, dielectric loss, electrostatic capacity, and capacitance change of the multilayer ceramic capacitors of samples 59 to 62 were measured. Rate and average failure Occurrence time, find the average of n = 75, and summarize them in Table 6. In addition, the dielectric constant, dielectric loss, capacitance change rate and capacitance are all under the conditions of 1 kHz and 0.5 Vmis / Vm Measured. The capacitance change rate is based on the capacitance at 20 ° C, and the capacitance change rates at -55 ° C, -25 ° C, 85 ° C, and 125 ° C are calculated. In addition, the average failure time (MTTF) was measured by an accelerated life test (HALT) at 150 ° C, 10 V / μηι. Sample permittivity and dielectric loss (%) Capacitance (nF). Capacitance change rate (△ c / c20 /%) Mean time to failure (hours) -55 ° C -25 ° C 85 ° C 125 ° C Example 59 2617 9.90 1906 -7.0 -3.0 -2.1 • 21.6 56 60 3224 10.70 2349 -4.0 0.0 -4.7 -20.5 59 Better than the father's example 61 4325 11.20 3150 12.1 22.1 19.9 -52.3 Untested 62 4310 10.40 3140 -3.0 1.0- 7.6 -20.4 19 -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 539649 A7

The dielectric constant and σ of the capacitor are known, and the laminated ceramic materials of samples 59 to 62 have excellent dielectric loss and electrostatic capacity. — Another: Bu Guang used the sample 59 of the barium titanate particulate powder within the scope of the present invention and / or the Japanese-style ceramic capacitors, and the capacitance of the said stage changed, ^ ^ 〇 2'1%, absolute The value is small and excellent. In addition, even at 125 ° C, the "狰: H change rate is only -21 · 6 to _20 · 5%. In contrast, the sample type ceramic capacitor of sample 61 is 121 to 221%, which has a large absolute value. In addition, the capacitance change rate at 125 ° C is -52.3%, which is extremely poor. Therefore, the sample 卯 using barium titanate particulate powder within the scope of the present invention and a 60 ° multilayer ceramic capacitor The average failure occurrence time is π, hours, long, and excellent. The multilayer ceramic capacitor of sample 62 as a comparative example has an average failure occurrence time of 19 hours, which is short and poor. In addition, as The multilayer ceramic capacitors of the samples 59 and 60 of the embodiment of the present invention have a dielectric constant pen valley I smaller than that of the samples 61 and 62 as comparative examples, which is mainly due to the average particle size of the barium U-shaped powder. Diameter, c / a axis ratio, and the dielectric constant and capacitance of the sample are not practically problematic. (Example 4) Below, as a comparative example, a barium titanate particulate powder was prepared by a hydrothermal synthesis method. That is, 6 spoons of an aqueous solution of titanium sulfate (Ti (S04) 2) (120 g / L, 1L) stirred at 15 ° C at the same time will be The temperature was maintained at 15 and 17 g of sodium peroxide (Na2O2) was gradually added. After the addition was completed, a 10N sodium hydroxide aqueous solution was added to cause precipitation. After the addition, stirring was continued for 30 minutes. Then, the obtained aqueous solution was stirred. At the same time, the temperature was raised to 50 ° C. and kept for 5 hours to obtain a precipitate. This was filtered and washed with water. The obtained filter, cake and 244 g of barium chloride dihydrate (BaCl2 · 2H20) were dispersed in water to prepare- 20- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) binding line 539649 A7 _________ Β7 ____ V. Description of the invention (18) 2L slurry, then sealed with nitrogen replacement, it reacts for 10 hours at 150 After the reaction is completed, the resulting slurry is filtered, washed with water, and dried to obtain a microcapsule-shaped acetic acid lock before heat treatment with a Ba / Ti molar ratio of 0.996, a particle size of 0.055 μπι, and a specific surface area of 15 3 ^ 仏. Next, the barium titanate particulate powder before the heat treatment was heat-treated at _ ° C, 850 ° C, 900 ° C, and 1000 ° C, respectively, to obtain samples 63 to 66 as comparative examples. Barium particulate powder. The specific surface area, average particle size, and c / a axis ratio of the barium titanate particulate powders of samples 63 to 66 are summarized in Table 7. [Table 7] Sample heat treatment temperature CC) Specific surface area (m2 / g) Average particle size (μm) c / a ratio of axial ratio 63 800 7.69 0.130 1.0055 than 64 850 5.62 0.178 1.0075 Example 65 900 4.48 0.223 1.0086 66 1000 2.57 0.389 1.0102 Table 7 shows that 'Sample 63, 64, and 66 barium titanate The particulate powder has a c / a axis ratio outside the range of 1.008 to 1.010. The average particle size of the barium titanate particulate powder of sample 66 is greater than 0.300 μm. Here, 'the sample S prepared by the hydrolysis method within the scope of the present invention, the titanium S pin pin powder of 58 and the sample pin 63-66 powder obtained by the hydrothermal synthesis method as a comparative example were used. The relationship between the average particle diameter and the c / a axis ratio is shown in FIG. 7. As can be seen from FIG. 7, although the barium titanate particulate powder of Sample 65 indicated by ▲, its specific surface area, average particle diameter, and c / a axis ratio are all within the range of the barium titanate particulate powder of the present invention ( Within the rectangular range shown in Figure 7), but the same as' -21-This paper size applies the Chinese National Standard (CMS) A4 specification (210 X 297 mm) 539649 A7

539649 A7

The measurement conditions of the capacitance change rate, the electrostatic capacity, and the average failure occurrence time are the same as those in Example 3 described above. [Table 8] Sample permittivity, dielectric loss (%), capacitance (nF), capacitance change rate __ (AC / C2〇 /%), average failure occurrence time (small day, -55 ° C -25 ° C 85 ° C 125 ° C Example 25 1510 1.15 1100 1.3 2.6 -7.2 -14.5 / lOo | Comparative Example 64 ^ 2320 4.41 1720— -12.8 -7.2 17.9 -37.9 ------ ^ _ 81 From Table 8 It can be seen that the multilayer ceramic capacitor using the sample 25 of the barium titanate particulate powder within the scope of the present invention has a dielectric loss of 115%, which is very small and very favorable. The temperature is -55 C, -25 ° C and The capacitance change rate at 85t is -7 · 2 ~ 丨 .3%. The absolute value is small and excellent. In addition, the average failure time is 428 hours, which is long and excellent. The capacitance change rate at 125 ° C is also excellent. It is only -14 · 5%, which is small and excellent. The dielectric loss of the multilayer ceramic capacitor of Sample 64 as a comparative example is 4.41%, which is large, and has a static electricity of -55 ^, -25t & 85t. The rate of change in capacity is 17.9 ~ -7.2% 'The absolute value is large, the average failure time is 81 hours, which is very short, and these results are very poor. In addition, the rate of change in electrostatic capacity at l25t: _37 9%, extremely poor. Although the dielectric constant and electrostatic capacity of sample 25 as an example of the present invention are smaller than those of sample 64 as a comparative example, this is mainly due to the average particle size of barium titanate particulate powder And c / a axis ratio, and there is no practical problem in the dielectric constant and capacitance of the sample 25. As described above, the method for producing the barium titanate particulate powder of the present invention has a production ratio of 0.20 to 1.20 mol / liter. A step of the aqueous solution of barium hydroxide and an alcohol solution of 〇88 ~ 1 235 mol / l of the alcohol solution, the barium hydroxide solution and the alcohol solution of the oxyhydrogen group at a Ba / Ti molar ratio of ι ·· 〇〇 ～ ι · 2〇 ratio of blending, not at -23-

539649 A7 ----------- 5. Description of the invention (21) The steps of obtaining a mixed solution with the addition of other experimental elements and the step of allowing the mixed solution to react at 60 to 10 Gt are characterized. As a result, it is possible to obtain a highly reliable barium titanate particulate powder that does not cause poor insulation of the interposer, and it is possible to obtain a multilayer ceramic electronic component that is now compact, integrated, and large-capacity. % The method described above is further characterized in that after the step of reacting the mixed solution, heat treatment is performed at 850 to 1000 ° C to recover the ceramic powder. The effect is that barium titanate particulate powder with moderate grain growth without abnormal grain growth can be obtained. Such barium titanate particulate powder is very suitable for the manufacture of laminated ceramic electronic cells that can achieve small, high integration and large capacity. Device. The method for producing the calcium-modified barium titanate particulate powder of the present invention includes the preparation of an aqueous solution of 0.20 to 1.20 mol / L of barium hydroxide, an alcohol solution of 0.0088 to 1 235 mol / L of titanium alkoxide, and calcium. The step of the alcohol solution of the salt is performed by mixing a Ba / Ti molar ratio of 0.980 to 1.020 and a Ca / Ti molar ratio of 0.160 or less, obtaining a mixed solution without mixing other experimental elements, and allowing the above mixed solution to It is characterized by a reaction step at 60 to 100 ° C. As a result, it is possible to obtain a highly reliable calcium-modified barium titanate particulate powder that does not easily cause poor insulation of an interposer, and obtain a multilayer ceramic electronic element that can achieve small size, high integration, and large capacity. Device. The above method is further characterized in that after the step of reacting the mixed solution ', a heat treatment is performed at 950 to 100 ° C to recover the ceramic powder. The effect is that calcium-modified barium titanate particulate powder with moderate grain growth and no abnormal grain growth can be obtained. Such calcium-modified barium titanate particulate powder is very suitable for producing small and highly integrated Large-capacity multilayer ceramic electronic device-24- This paper size is suitable for financial affairs_CNS) M test (21G x 297 public love) — 539649 A7 B7 Five invention descriptions (22 pieces. In addition, the manufacturing method according to the present invention The obtained barium titanate particulate powder and calcium-modified barium titanate particulate powder can be wet synthesized in a liquid in the reaction system without the need to add basic elements such as Na and K to the reaction liquid, so they have no The effect of impurities, high purity, and large squareness. Binding-25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 public love i 8 8 8 8 AB c D 539649) 6. Scope of patent application. Surface area is 17.99 ~ 52.64 m2 / g, and the Ba / Ti molar ratio after synthesis is 0. 9979 ~ 1.0060. 6. A granular barium titanate powder, which is obtained by the manufacturing method of the second patent application scope, characterized in that its average particle diameter is 〇105 ~ 〇300μm, and The c / a axis ratio measured by X-ray diffraction is 1.008 to 1.010. 7. A kind of granular barium acid powder which is about modified, which is obtained by the manufacturing method of the third item of the patent application, which is characterized by its average The particle size is 〇19 ～ 0.025 μηι ', the specific surface area is 40.36 ~ 54.05 m2 / g, and the (Ba + Ca) / Ti molar ratio after synthesis is 0.994 ~ 1.004. 8 · A granular calcium modified titanium Barium acid powder, which is obtained by the manufacturing method of item 4 of the scope of patent application, is characterized in that its average particle diameter is 0145 ~ 0.25 μm, and the * -axis ratio measured by X-ray diffraction is 0.0008 〇1〇 -27- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)