WO2018074290A1 - 誘電体磁器組成物及びセラミック電子部品 - Google Patents
誘電体磁器組成物及びセラミック電子部品 Download PDFInfo
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- WO2018074290A1 WO2018074290A1 PCT/JP2017/036728 JP2017036728W WO2018074290A1 WO 2018074290 A1 WO2018074290 A1 WO 2018074290A1 JP 2017036728 W JP2017036728 W JP 2017036728W WO 2018074290 A1 WO2018074290 A1 WO 2018074290A1
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Definitions
- the present invention relates to a dielectric ceramic composition and a ceramic electronic component using the dielectric ceramic composition as a dielectric layer.
- a ceramic electronic component such as a capacitor satisfying such requirements
- a ceramic composition (paraelectric material) exhibiting a paraelectric property such as calcium zirconate
- an electronic component having a dielectric layer made of a paraelectric material has a low dielectric constant of the porcelain composition, and a high-capacity capacitor cannot be obtained.
- ceramic electronic parts often use a base metal such as nickel or copper as the material of the internal electrode.
- a base metal such as nickel or copper
- the dielectric layer and the internal electrode are fired at the same time, so that the base metal is not oxidized during firing, and is fired in a reducing atmosphere including the porcelain composition constituting the dielectric layer.
- Non-Patent Document 1 describes a dielectric porcelain composition having a tungsten bronze structure represented by a general formula M 2 + 6 M 4 + 2 Nb 8 O 30 .
- this non-patent document 1 in order to obtain an experimental sample (sample), after mixing the porcelain composition raw material, this is fired at around 1000 ° C. for 15 hours, and the resulting product is pulverized and dried to form. After that, sintering is further performed at 1250 to 1350 ° C. for 5 to 6 hours.
- Patent Documents 1 to 11 are investigating various dielectric ceramic compositions having a tungsten bronze structure.
- Japanese Patent Laid-Open No. 2002-211975 JP 2007-197277 A Japanese Patent Laid-Open No. 11-043370 JP 2000-169215 A JP 2008-189487 A International publication WO08 / 102608 pamphlet International Publication WO06 / 114914 Pamphlet JP 2013-180906 A JP 2013-180907 A JP 2013-180908 A JP 2012-169635 A
- Non-Patent Document 1 the characteristics of the dielectric ceramic composition itself having a tungsten bronze structure are studied from an academic point of view, while its application (application) is not considered at all. That is, in Non-Patent Document 1, the dielectric ceramic composition is fired in a laboratory under a normal environmental atmosphere, but the inventors have made a dielectric material having a tungsten bronze structure represented by the above general formula. As a result of detailed examination of the porcelain composition, in the case of firing and sintering in a reducing atmosphere required for the dielectric porcelain composition in recent years together with specific additive components, Non-Patent Document 1 It was found that a dielectric ceramic composition having completely different characteristics from that reported in the previous report can be obtained.
- Patent Documents 1 to 11 discuss the dielectric porcelain composition having a tungsten bronze structure, and all of them are “can be fired in a reducing atmosphere” and “a sufficiently high relative dielectric constant can be obtained. None that can simultaneously achieve the effects of "good dielectric characteristics in a wide temperature range” and “small dielectric loss” has not been obtained.
- the object of the present invention is that firing is possible in a reducing atmosphere, the relative dielectric constant is high, and when used as a dielectric layer of a ceramic electronic component such as a multilayer ceramic capacitor, the object of the present invention is, for example, 150 to An object of the present invention is to provide a dielectric porcelain composition having a small change in capacitance under conditions of 200 ° C. and a small dielectric loss at 25 ° C. and 200 ° C., and a ceramic electronic component using the dielectric ceramic composition.
- this invention (1) consists of a 1st component and a 2nd component,
- the content ratio with respect to the total number of moles of the first component is 0 to 35.85 mol% of Ca oxide in terms of CaO and 0 to 47.12 mol in terms of SrO.
- the first component is at least one selected from an oxide of Ca, an oxide of Sr, and an oxide of Ba, at least one selected from an oxide of Ti and an oxide of Zr, an oxide of Nb, and And at least one selected from oxides of Ta as an essential component, and Ca oxide in terms of CaO relative to the total number of moles of the first component when converted to the above oxide, SrO equivalent Sr
- the present invention (2) is characterized in that the content ratio of the Mn oxide in terms of MnO to the total mass of the first component when converted to the oxide is 3.5% by mass or less.
- the dielectric ceramic composition according to (1) is provided.
- this invention (3) consists of a 1st component and a 2nd component,
- the first component the following general formula (1): A a M 1 b M 2 c O d (1)
- A represents the general formula (2): Ba 1-xy Sr x Ca y (2)
- M 1 is at least one selected from Ti, Zr, and Sn
- M 2 is at least one selected from Nb, Ta, and V.
- the present invention (4) is characterized in that the content ratio of the Mn oxide in terms of MnO with respect to the mass of the compound represented by the general formula (1) is 3.5% by mass or less (The dielectric ceramic composition of 3) is provided.
- this invention (5) consists of a 1st component and a 2nd component,
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently a value in the range of 5.70 to 6.30.
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently 0.95 to 1.30. The value is in the range of 05.
- ⁇ 1, ⁇ 2, and ⁇ 3 are each independently values in the range of 0.90 to 1.10, and ⁇ 1, ⁇ 2, and ⁇ 3 are each independently 27.45 to 32.
- M 3 is a value within the range of .50
- M 3 is a general formula (4): Ti 2 - ⁇ - ⁇ Zr ⁇ Sn ⁇ (4) (in the formula (4), 0 ⁇ ⁇ ⁇ 2.0, 0 ⁇ M 4 is represented by the general formula (5): Nb 8- ⁇ - ⁇ Ta ⁇ V ⁇ (5) (in the formula (5), 0 ⁇ ⁇ ⁇ 8.
- the present invention (6) provides the Mn in terms of MnO relative to the mass of the compound within the range surrounded by the line segment connecting points A, B, C, D, and E on the ternary composition diagram.
- a dielectric ceramic composition according to (5) is provided, That.
- an oxide of Mn and an oxide of D (D is Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu, Zn, Ga, Ge) , In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- D is Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu, Zn, Ga, Ge
- the present invention (9) provides the dielectric ceramic composition according to any one of (1) to (8), which contains a tungsten bronze type crystal phase.
- the present invention (10) provides the dielectric ceramic composition according to any one of (1) to (9), wherein the relative dielectric constant at 25 ° C. is 100 or more.
- the present invention (11) provides the dielectric ceramic composition according to (10), wherein the relative dielectric constant at 25 ° C. is 200 or more.
- the present invention (12) provides the dielectric ceramic composition according to (11), wherein the relative dielectric constant at 25 ° C. is 300 or more.
- the invention (13) is characterized in that the rate of change in capacitance is in the range of ⁇ 50% to 50% in the temperature range of ⁇ 55 ° C. to 200 ° C.
- a dielectric ceramic composition is provided.
- the present invention (14) is characterized in that the capacitance change rate is in the range of ⁇ 33% to 22% in the temperature range of ⁇ 55 ° C. to 200 ° C.
- a dielectric ceramic composition is provided.
- the dielectric loss (tan ⁇ ) at 25 ° C. is 10% or less and the dielectric loss (tan ⁇ ) at 200 ° C. is 10% or less.
- the dielectric loss (tan ⁇ ) at 200 ° C. is 10% or less.
- the present invention (16) includes a dielectric layer formed of any one of the dielectric ceramic compositions (1) to (15), and an electrode layer containing a base metal as a conductive component.
- a ceramic electronic component is provided.
- the present invention (17) provides the ceramic electronic component according to (16), wherein the base metal is at least one selected from nickel and copper.
- the present invention provides the ceramic electronic component according to either (16) or (17), wherein a plurality of the dielectric layers and the electrode layers are laminated.
- the dielectric constant is high, and when used as a dielectric layer of a ceramic electronic component such as a multilayer ceramic capacitor, even under a high temperature condition of 150 to 200 ° C.
- the change in capacitance is small, and the rate of change in capacitance is within the range of ⁇ 50% to 50% (hereinafter sometimes referred to as ⁇ 50%) in the temperature range of ⁇ 55 ° C. to 200 ° C.
- ⁇ 50% ⁇ 50% to 50%
- a dielectric ceramic composition having a small dielectric loss at 25 ° C. and 200 ° C., and a ceramic electronic component using the dielectric ceramic composition as a dielectric layer can be provided.
- the ceramic capacitor 1 shown in FIG. 8 includes a rectangular parallelepiped laminated body 10 as a whole.
- the multilayer body 10 includes a plurality of laminated dielectric layers 3 and a plurality of internal electrodes 2 a and 2 b formed along different interfaces of the dielectric layers 3.
- the internal electrodes 2 a and 2 b are alternately arranged in the stacked body 10, and are electrically joined to the external electrode 4 at different ends of the stacked body 10.
- a first plating layer made of nickel, copper, nickel-copper alloy or the like may be formed on the external electrode 4, and a second plating layer made of solder, tin or the like may be formed on the first plating layer. good.
- the plurality of internal electrodes 2a and 2b are formed so as to overlap with each other in the stacking direction of the stacked body 10, thereby accumulating charges between the adjacent internal electrodes 2a and 2b. Further, when the internal electrodes 2a, 2b and the external electrode 4 are electrically connected, the charges are taken out.
- a base metal is used for the internal electrodes 2a and 2b as a conductive component.
- the base metal as the conductive component may be a pure metal such as nickel, copper or aluminum, or an alloy, a mixture or a composite containing the metal component.
- the base metal as the conductive component is particularly preferably one selected from nickel and copper.
- the internal electrodes 2a and 2b may contain conductive components other than base metals, the following common materials, and the like.
- the internal electrodes 2a and 2b may be formed by any method, and examples thereof include a method of forming using a conductive paste obtained by kneading the metal powder containing the base metal together with the binder component.
- a conductive paste obtained by kneading the metal powder containing the base metal together with the binder component.
- the conductive paste may contain a dielectric ceramic composition powder having the same components as those of the dielectric ceramic composition of the present invention described later as a so-called common material for controlling the sintering of the metal powder.
- the internal electrodes 2a and 2b are also formed by a known method such as an inkjet method, a vapor deposition method, or a plating method.
- the dielectric layer 3 is composed of the dielectric ceramic composition of the present invention, which will be described later, so that the capacitance changes in a wide temperature range, particularly in a high temperature range around 200 ° C. while maintaining a high relative dielectric constant.
- the capacitance change rate is within ⁇ 50% in the temperature range of ⁇ 55 ° C. to 200 ° C., and the dielectric loss (tan ⁇ ) at 25 ° C. and 200 ° C. is both 10% or less.
- the dielectric ceramic composition of the present invention is excellent in reduction resistance, and even if it is a case where a base metal is used as the conductive component of the internal electrode and is co-fired in a reducing atmosphere, it is difficult to reduce and does not become a semiconductor. .
- the dielectric ceramic composition of the first aspect of the present invention comprises a first component and a second component,
- the content ratio with respect to the total number of moles of the first component is 0 to 35.85 mol% of Ca oxide in terms of CaO and 0 to 47.12 mol in terms of SrO.
- the first component is at least one selected from an oxide of Ca, an oxide of Sr, and an oxide of Ba, at least one selected from an oxide of Ti and an oxide of Zr, an oxide of Nb, and And at least one selected from oxides of Ta as an essential component, and Ca oxide in terms of CaO relative to the total number of moles of the first component when converted to the above oxide, SrO equivalent Sr
- the dielectric ceramic composition of the first aspect of the present invention comprises a first component and a second component.
- the oxides contained in the dielectric ceramic composition are all contained as the second component except for the oxide contained as the first component.
- the first component according to the dielectric ceramic composition of the first aspect of the present invention includes at least one selected from Ca oxide, Sr oxide and Ba oxide as essential components, and oxidation of Ti. 1 type or more selected from oxides of oxides and oxides, 1 or more types selected from oxides of Nb and Ta, and 1 type selected from the oxides of Sn and V as optional components It consists of the above.
- the dielectric ceramic composition of the first aspect of the present invention it is the content of each oxide occupying the first component, but the content ratio relative to the total number of moles of the first component when converted to the following oxide
- the content of Ca oxide in terms of CaO is 0 to 35.85 mol%
- the content of Sr oxide in terms of SrO is 0 to 47.12 mol%
- the content of Ba oxide in terms of BaO is 0 to 17.36 mol%
- the amount of Zr oxide in terms of ZrO 2 is 0 to 17.36 mol%.
- the content of Sn oxide in terms of SnO 2 is 0 to 2.60 mol%
- the content of Nb oxide in terms of Nb 2 O 5 is 0 to 35.32 mol%
- Ta 2 O 5 content of the oxide of Ta conversion is 0-35 It was 32 mol%
- the content of V oxide in terms of V 2 O 5 is 0 ⁇ 2.65 mol%.
- CaO equivalent Ca oxide, SrO equivalent Sr oxide, and BaO equivalent to the total number of moles of the first component when converted to the above oxide.
- the total content of Ba oxide is 48.72 to 51.22 mol%, preferably 49.37 to 50.62 mol%.
- the oxide of Ti in terms of TiO 2 and the oxidation of Zr in terms of ZrO 2 with respect to the total number of moles of the first component when converted into the above oxide The total content of SnO 2 and Sn oxide in terms of SnO 2 is 15.97 to 17.36 mol%, preferably 16.32 to 17.01 mol%. Further, when the first component contains Sn, SnO 2 conversion Sn relative to the total number of moles of Ti oxide in terms of TiO 2 , Zr oxide in terms of ZrO 2 and Sn oxide in terms of SnO 2 The content rate of an oxide is 15 mol% or less.
- the total content of Ta oxide and V oxide converted to V 2 O 5 is 31.42 to 35.31 mol%, preferably 32.20 to 34.43 mol%.
- the first component contains V
- the content ratio of the oxide of V in terms of V 2 O 5 is 7.5 mol% or less.
- the dielectric ceramic composition of the first aspect of the present invention contains at least an oxide of Mn as the second component. That is, the dielectric ceramic composition of the first aspect of the present invention contains an oxide of Mn as an essential second component.
- the dielectric ceramic composition according to the first aspect of the present invention contains an oxide of Mn as the second component, so that ceramic electronic components such as a multilayer ceramic capacitor are compared with a case where no oxide of Mn is contained.
- the content rate of the oxide of Mn of MnO conversion with respect to the total mass of the 1st component when converted into said oxide exceeds 0 mass% Preferably, it exceeds 0% by mass and is 3.5% by mass or less, particularly preferably 0.005 to 2.0% by mass, and further preferably 0.01 to 1.5% by mass.
- the content of the Mn oxide exceeds the above range, the dielectric loss tends to increase at a high temperature or the change in capacitance tends to increase.
- the dielectric ceramic composition according to the first aspect of the present invention contains an oxide of Mn as an essential component as the second component, but optionally contains an oxide other than the oxide of Mn. Can do.
- the second component is added to the dielectric ceramic composition of the present invention in order to improve reduction resistance and other characteristics.
- the ratio of the total mass of the second component in terms of oxide to the total mass of the first component in terms of the above oxide is preferably 10% by mass or less, particularly preferably 0.1 to 5.5% by mass. is there.
- the optional component of the second component contained in the dielectric ceramic composition of the first aspect of the present invention includes an oxide of D (D is Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu At least one selected from Zn, Ga, Ge, In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu And oxides of Mg, Si, and Y are particularly preferable.
- the dielectric ceramic composition of the first aspect of the present invention contains Mn oxide and D oxide as the second component, it is the total content of Mn oxide and D oxide.
- the ratio of the total mass of the Mn oxide and the D oxide in terms of MnO to the total mass of the first component when converted to the above oxide is preferably 6% by mass or less, particularly preferably 0.1 to 2.5% by mass.
- the mass of oxides of the D is the Li 2 O is for Li, the MgO for Mg, the SiO 2 for Si, the Cr 2 O 3 for Cr, the Al 2 O 3 for Al, Fe for Fe 2 O 3 , Co for CoO, Ni for NiO, Cu for CuO, Zn for ZnO, Ga for Ga 2 O 3 , Ge for GeO 2 , In For In 2 O 3 for W, for WO 3 for Mo, for MoO 3 for Mo, for Y 2 O 3 for Y, for Hf O 2 for Hf, for La 2 O 3 for La and for Ce the CeO 2, to Pr 6 O 11 for Pr, the Nd 2 O 3 for Nd, the Sm 2 O 3 for Sm, the Eu 2 O 3 for Eu, Gd A For Gd 2 O 3, the Tb 4 O 7 for Tb, the Dy 2 O 3 for Dy, the Ho 2 O 3 for Ho, the Er 2 O 3 for Er, for Tm Tm 2 O 3 Further, Yb is a value converted to Yb 2 O 3 and
- the dielectric ceramic composition according to the first aspect of the present invention preferably shows the presence of a tungsten bronze type crystal phase when crystal structure analysis such as X-ray diffraction is performed.
- the average grain size of the dielectric ceramic composition of the first embodiment of the present invention is preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less.
- the dielectric ceramic composition of the second aspect of the present invention comprises a first component and a second component, As the first component, the following general formula (1): A a M 1 b M 2 c O d (1) (In the formula (1), A represents the general formula (2): Ba 1-xy Sr x Ca y (2) (in the formula (2), 0 ⁇ x ⁇ 0.920, 0 ⁇ y ⁇ 0. M 1 is at least one selected from Ti, Zr, and Sn, and M 2 is at least one selected from Nb, Ta, and V.
- the dielectric ceramic composition according to the second aspect of the present invention comprises a first component and a second component.
- the oxides contained in the dielectric ceramic composition are all contained as the second component except for the oxide contained as the first component.
- the first component is represented by the following general formula (1): A a M 1 b M 2 c O d (1) It is a compound represented by these.
- A represents general formula (2): Ba 1-xy Sr x Ca y (2) (in formula (2), 0 ⁇ x ⁇ 0.920, 0 ⁇ y ⁇ 0. 700.) That is, even if A is Ba alone or a combination of any two of Ca, Sr and Ba (Ca and Sr, Ca and Ba, Sr and Ba), It may be a combination.
- M 1 is at least one selected from Ti, Zr, and Sn. However, M 1 must be at least one selected from Ti and Zr. That, M 1 is, Ti alone, Zr alone, the combination of Ti and Sn, Zr and Sn combinations of Ti and Zr in combination, Ti, a combination of Zr and Sn.
- M 2 is at least one selected from Nb, Ta and V. However, M 2 must be at least one selected from Nb and Ta. That is, M 2 is Nb alone, Ta alone, a combination of Nb and V, a combination of Ta and V, a combination of Nb and Ta, and a combination of Nb, Ta and V.
- a is in the range of 5.70 ⁇ a ⁇ 6.30
- b is in the range of 1.90 ⁇ b ⁇ 2.10
- c is 7.20 ⁇ c ⁇
- the range is 8.80
- d is 27.45 ⁇ d ⁇ 32.50.
- the dielectric ceramic composition according to the second aspect of the present invention contains Sn, the total of Ti oxide in terms of TiO 2 , Zr oxide in terms of ZrO 2 , and Sn oxide in terms of SnO 2
- the content ratio of Sn oxide in terms of SnO 2 with respect to the mol number is 15 mol% or less.
- the second dielectric ceramic composition of the present invention when they contain V is, Nb 2 O 5 oxide Nb Conversion, Ta 2 O 5 oxide Conversion Ta and V 2 O 5
- the content ratio of the oxide of V converted to V 2 O 5 is 7.5 mol% or less with respect to the total number of moles of the converted oxide of V.
- the dielectric ceramic composition according to the second aspect of the present invention contains at least an oxide of Mn as the second component. That is, the dielectric ceramic composition of the second aspect of the present invention contains an oxide of Mn as an essential second component.
- the dielectric ceramic composition according to the second aspect of the present invention contains a Mn oxide as the second component, so that the ceramic electronic component such as a multilayer ceramic capacitor is compared with a case where no Mn oxide is contained.
- the content of the product is more than 0% by mass, preferably more than 0% by mass and not more than 3.5% by mass, particularly preferably 0.005 to 2.0% by mass, more preferably 0.01 to 1%. 0.5% by mass.
- the content of the Mn oxide exceeds the above range, the dielectric loss tends to increase at a high temperature or the change in capacitance tends to increase.
- the dielectric ceramic composition of the second aspect of the present invention contains an oxide of Mn as an essential component as a second component, but optionally contains an oxide other than an oxide of Mn. Can do.
- the second component is added to the dielectric ceramic composition of the present invention in order to improve reduction resistance and other characteristics.
- the ratio of the total mass in terms of oxide of the second component to the mass of the compound represented by the general formula (1) is preferably 10% by mass or less, particularly Preferably, the content is 0.1 to 5.5% by mass.
- the optional component of the second component contained in the dielectric ceramic composition of the second aspect of the present invention includes an oxide of D (D is Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu At least one selected from Zn, Ga, Ge, In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu And oxides of Mg, Si, and Y are particularly preferable.
- the dielectric ceramic composition of the second aspect of the present invention contains Mn oxide and D oxide as the second component, it is the total content of Mn oxide and D oxide.
- the ratio of the total mass of the oxide of Mn and the oxide of D in terms of MnO to the mass of the compound represented by the general formula (1) is preferably It is 10% by mass or less, particularly preferably 0.1 to 5.5% by mass.
- the mass of oxides of the D is the Li 2 O is for Li, the MgO for Mg, the SiO 2 for Si, the Cr 2 O 3 for Cr, the Al 2 O 3 for Al, Fe for Fe 2 O 3 , Co for CoO, Ni for NiO, Cu for CuO, Zn for ZnO, Ga for Ga 2 O 3 , Ge for GeO 2 , In For In 2 O 3 for W, for WO 3 for Mo, for MoO 3 for Mo, for Y 2 O 3 for Y, for Hf O 2 for Hf, for La 2 O 3 for La and for Ce the CeO 2, to Pr 6 O 11 for Pr, the Nd 2 O 3 for Nd, the Sm 2 O 3 for Sm, the Eu 2 O 3 for Eu, Gd A For Gd 2 O 3, the Tb 4 O 7 for Tb, the Dy 2 O 3 for Dy, the Ho 2 O 3 for Ho, the Er 2 O 3 for Er, for Tm Tm 2 O 3 Further, Yb is a value converted to Yb 2 O 3 and
- the dielectric ceramic composition of the second aspect of the present invention shows the presence of a tungsten bronze crystal phase when crystal structure analysis such as X-ray diffraction is performed, and the average grain size is preferably 5 ⁇ m or less, Particularly preferably, it is 3 ⁇ m or less.
- the dielectric ceramic composition of the third aspect of the present invention comprises a first component and a second component,
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently a value in the range of 5.70 to 6.30.
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently 0.95 to 1.30.
- the value is in the range of 05.
- ⁇ 1, ⁇ 2, and ⁇ 3 are each independently values in the range of 0.90 to 1.10, and ⁇ 1, ⁇ 2, and ⁇ 3 are each independently 27.45 to 32.
- M 3 is a value within the range of .50
- M 3 is a general formula (4): Ti 2 - ⁇ - ⁇ Zr ⁇ Sn ⁇ (4) (in the formula (4), 0 ⁇ ⁇ ⁇ 2.0, 0 ⁇ M 4 is represented by the general formula (5): Nb 8- ⁇ - ⁇ Ta ⁇ V ⁇ (5) (in the formula (5), 0 ⁇ ⁇ ⁇ 8.
- the dielectric ceramic composition of the third aspect of the present invention comprises a first component and a second component.
- the oxides contained in the dielectric ceramic composition are all contained as the second component except for the oxide contained as the first component.
- the dielectric ceramic composition of the third embodiment of the present invention the first component, Ca shown in FIG. 1 ⁇ 1 M 3 ⁇ 1 M 4 ⁇ 1 O ⁇ 1 -Sr ⁇ 2 M 3 ⁇ 2 M 4 ⁇ 2 O ⁇ 2 -Ba ⁇ 3 M 3
- the point A ( 0.05, 0.95, 0.00)
- point B (0.70, 0.30, 0.00)
- point C (0.70, 0.00, 0.30)
- point D (0.00, 0.00, 1.00)
- the third dielectric ceramic composition of the present invention preferably the first component, Ca shown in FIG. 2 ⁇ 1 M 3 ⁇ 1 M 4 ⁇ 1 O ⁇ 1 -Sr ⁇ 2 M 3 ⁇ 2 M 4 ⁇ 2 O ⁇ 2 -
- point A ′ (0.05, 0.95, 0.00)
- point B ′ (0.60, 0.40, 0) .00)
- point C ′ (0.70, 0.20, 0.10)
- point D ′ (0.70, 0.10, 0.20)
- point E ′ (0.55, 0 .00, 0.45)
- point F ′ (0.40, 0.00, 0.60)
- point G ′ (0.10, 0.10, 0.80)
- point H ′ (0 .00, 0.00, 1.00)
- point I ′ (0.00, 0.40, 0.60)
- point J ′ (0.20, 0.40, 0.40)
- point K ' (0.00, 0.70
- ⁇ 2 and ⁇ 3 are each independently a value in the range of 5.70 to 6.30.
- ⁇ 1, ⁇ 2, and ⁇ 3 are each independently a value in the range of 0.95 to 1.05.
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently a value in the range of 0.90 to 1.10.
- ⁇ 1, ⁇ 2 and ⁇ 3 are each independently a value within the range of 27.45 to 32.50.
- M 3 is represented by the general formula (4): Ti 2 - ⁇ - ⁇ Zr ⁇ Sn ⁇ (4) (in the formula (4), 0 ⁇ ⁇ ⁇ 2.0 and 0 ⁇ ⁇ ⁇ 0.3).
- M 4 is the general formula (5): Nb 8- ⁇ - ⁇ Ta ⁇ V ⁇ (5) (in the formula (5), 0 ⁇ ⁇ ⁇ 8.0 and 0 ⁇ ⁇ ⁇ 0.6). expressed.
- the dielectric ceramic composition according to the third aspect of the present invention contains at least an oxide of Mn as the second component. That is, the dielectric ceramic composition of the third aspect of the present invention contains an oxide of Mn as an essential second component.
- the dielectric ceramic composition according to the third aspect of the present invention contains a Mn oxide as the second component, so that the ceramic electronic component such as a multilayer ceramic capacitor is compared with a case where no Mn oxide is contained.
- the content of the Mn oxide as the second component is within the range surrounded by the line segment connecting point A, point B, point C, point D, and point E on the ternary composition diagram shown in FIG.
- Content ratio of Mn oxide in terms of MnO with respect to the mass of a certain compound (the first component is point A ′, point B ′, point C ′, point D ′, point E ′ on the ternary composition diagram shown in FIG. , Point F ′, point G ′, point H ′, point I ′, point J ′, point K ′, and the compound within the range surrounded by the line segment connecting to the point L ′, the ternary shown in FIG.
- the content ratio of MnO-converted Mn oxide to the mass of the compound within the range surrounded by the line segment connecting ' is more than 0% by mass, preferably more than 0% by mass and 3.5% by mass Below, particularly preferably 0.00 To 2.0 mass%, more preferably 0.01 to 1.5 mass%.
- the content of the Mn oxide exceeds the above range, the dielectric loss tends to increase at a high temperature or the change in capacitance tends to increase.
- the dielectric ceramic composition according to the third aspect of the present invention contains an oxide of Mn as an essential component as the second component, but optionally contains an oxide other than the oxide of Mn. Can do.
- the second component is added to the dielectric ceramic composition of the present invention in order to improve reduction resistance and other characteristics.
- an oxide of D is Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu At least one selected from Zn, Ga, Ge, In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu
- oxides of Mg, Si, and Y are particularly preferable.
- the dielectric ceramic composition of the third aspect of the present invention contains Mn oxide and D oxide as the second component, it is the total content of Mn oxide and D oxide.
- the Mn oxide in terms of MnO with respect to the mass of the compound within the range surrounded by the line segment connecting point A, point B, point C, point D, and point E on the ternary composition diagram shown in FIG.
- Ratio of total mass of oxide first component is point A ′, point B ′, point C ′, point D ′, point E ′, point F ′, point G ′ on the ternary composition diagram shown in FIG.
- Total mass of Mn oxide and D oxide in terms of MnO with respect to the mass of the compound in the range Ratio is preferably 10 wt% or less, particularly preferably 0.1 to 5.5 wt%.
- the mass of oxides of the D is the Li 2 O is for Li, the MgO for Mg, the SiO 2 for Si, the Cr 2 O 3 for Cr, the Al 2 O 3 for Al, Fe for Fe 2 O 3 , Co for CoO, Ni for NiO, Cu for CuO, Zn for ZnO, Ga for Ga 2 O 3 , Ge for GeO 2 , In For In 2 O 3 , W for WO 3 , Mo for MoO 3 , Y for Y 2 O 3 , Hf for HfO 2 , La for La 2 O 3 , and Ce for the CeO 2, to Pr 6 O 11 for Pr, the Nd 2 O 3 for Nd, the Sm 2 O 3 for Sm, the Eu 2 O 3 for Eu, the Gd
- the Itewa Gd 2 O 3, the Tb 4 O 7 for Tb, the Dy 2 O 3 for Dy, the Ho 2 O 3 for Ho, the Er 2 O 3 for Er, for Tm Tm 2 O 3 , Yb is converted to Yb 2
- the dielectric ceramic composition of the third aspect of the present invention shows the presence of a tungsten bronze type crystal phase when crystal structure analysis such as X-ray diffraction is performed, and the average grain size is preferably 5 ⁇ m or less, Particularly preferably, it is 3 ⁇ m or less.
- the dielectric ceramic composition of the first aspect of the present invention, the dielectric ceramic composition of the second aspect of the present invention, and the dielectric ceramic composition of the third aspect of the present invention have a relative dielectric constant at 25 ° C. The higher it is, the more preferable it is, and it is 100 or more, preferably 200 or more.
- the capacitance change rates of the dielectric ceramic composition of the first aspect of the present invention, the dielectric ceramic composition of the second aspect of the present invention, and the dielectric ceramic composition of the third aspect of the present invention are: Within the temperature range of 55 ° C. to 200 ° C., it is within ⁇ 50%, preferably within the range of ⁇ 33% to 22%.
- the capacitance change rate is a value obtained by a method described later.
- the dielectric loss (tan ⁇ ) at 25 ° C. ) Is 10% or less and the dielectric loss (tan ⁇ ) at 200 ° C. is 10% or less, and the high-frequency characteristics are good.
- the dielectric ceramic composition of the first aspect of the present invention, the dielectric ceramic composition of the second aspect of the present invention, and the dielectric ceramic composition of the third aspect of the present invention can be fired in a reducing atmosphere. It is.
- the external electrode 4 is usually formed by applying a conductive paste for external electrode to the end portion after simultaneous firing of the laminate 10 and baking it, but the present invention is not limited to this,
- the external electrode 4 may be formed by heat treatment using a paste containing a curable resin or a thermoplastic resin.
- the conductive component used in the conductive paste for external electrodes is not particularly limited.
- pure metals such as nickel, copper, silver, palladium, platinum, and gold
- an alloy, a mixture, or a composite containing the metal component is used. There may be.
- glass frit may be added to the conductive paste as necessary.
- the external electrode 4 may be fired simultaneously with the laminate 10.
- the ceramic capacitor 1 uses the dielectric ceramic composition according to the first aspect of the present invention, the dielectric ceramic composition according to the second aspect of the present invention, or the dielectric ceramic composition according to the third aspect of the present invention. It is produced by a known method. An example will be described below.
- a starting material for forming the dielectric layer 3 is prepared.
- oxide powder such as CaO, SrO, BaO, TiO 2 , ZrO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , V 2 O 5, and the oxide powder by firing are used. Examples include carbonates and nitrates that are produced.
- the starting materials are weighed and mixed so as to have the desired composition, and the obtained mixture is calcined in air at a temperature of about 700 to 900 ° C. for about 3 to 6 hours.
- the obtained product is finely pulverized, and the obtained dielectric material is used as the first component material.
- powder of Mn compound such as MnO or MnCO 3 as a Mn source and other Li, Mg, Si, Cr, Al, Fe, Co, Ni, Cu, Zn, Ga, Ge, and other additives added as necessary.
- a compound containing In, W, Mo, Y, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu is prepared as a raw material for the second component. .
- the raw material for the first component and the raw material for the second component are kneaded and dispersed in an appropriate binder component to prepare a dielectric paste or a dielectric slurry.
- the dielectric paste or the dielectric slurry may contain additives such as a plasticizer as necessary.
- the obtained dielectric paste or dielectric slurry is formed into a sheet shape, and then a conductive pattern is formed on the surface of the obtained green sheet using the above-described conductive paste for internal electrodes. This is repeated a predetermined number of times, laminated, and pressure-bonded to obtain an unfired laminated body (hereinafter referred to as a green chip).
- the binder removal treatment conditions are not particularly limited, and examples include heat treatment at a holding temperature of 180 to 400 ° C. for 1 to 3 hours.
- the green chip is fired at about 1150 to 1350 ° C. in a reducing atmosphere to obtain a fired laminated body 10 (hereinafter referred to as a sintered body 10).
- annealing re-oxidation treatment
- the annealing conditions may be known conditions widely used in the industry.
- the oxygen partial pressure during annealing is higher than the oxygen partial pressure during firing, and the holding temperature is 1100 ° C. or lower. Is preferred.
- the external electrode conductive paste is applied and baked to form the external electrode 4, and the surface of the external electrode 4 as necessary.
- the above-mentioned plating layer is formed in (1).
- the ceramic capacitor 1 thus obtained is mounted on a printed circuit board by soldering or the like and used for various electronic devices.
- the ceramic capacitor has been described above, the same can be applied to other ceramic electronic components such as an inductor and an actuator.
- composition of the dielectric ceramic composition described below is estimated by the raw material composition (prepared composition) or crystal structure analysis, and the same applies to the present specification.
- Example 1 and Comparative Example 1 (1) Production of Dielectric Porcelain Composition Samples 1 to 90 As starting materials for the first component, CaCO 3 , SrCO 3 , BaCO 3 , TiO 2 , ZrO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , Each powder of V 2 O 5 was weighed so as to have the ratios shown in Tables 1, 3 and 5 in terms of oxides, and wet-mixed for 20 hours using pure water in a ball mill. Next, each obtained mixture was dried at 100 ° C., calcined at 750 to 900 ° C. in air for 3 hours, and finely pulverized again in the same manner to obtain a dielectric material for the first component.
- the second component 18.2 mg of MnCO 3 , 32 mg of MgO, 58.6 mg of SiO 2 and 89.5 mg of Y 2 O 3 were weighed and mixed to prepare a second component. Used as raw material. However, in sample 43, only the three components of MnCO 3 , MgO and Y 2 O 3 excluding SiO 2 were used among the above-mentioned second component raw materials. In Sample 44, only the three components of MnCO 3 , SiO 2 and Y 2 O 3 excluding MgO were used as the second component raw material. In Sample 45, only three components of MnCO 3 , MgO and SiO 2 excluding Y 2 O 3 were used.
- samples 78 and 79 only three components of MgO, SiO 2 and Y 2 O 3 excluding MnCO 3 were used.
- the amount of MnCO 3 was changed to 0.404 mg in the second component raw material
- the amount of MnCO 3 was changed to 0.198 g
- the amount of MnCO 3 was changed. Changed to 2.055 g.
- ion-exchange water and polyvinyl alcohol were thrown into the container so that polyvinyl alcohol concentration might be 6 mass%, and it mixed at 90 degreeC for 1 hour, and prepared polyvinyl alcohol aqueous solution.
- each of the first component dielectric raw materials and the above-mentioned amount of the second component raw materials are mixed, and the polyvinyl alcohol is added to the raw material mixture so that the concentration of the polyvinyl alcohol aqueous solution is 10% by mass with respect to these mixtures.
- Aqueous solution was added and mixed and granulated in a mortar to produce granulated powder.
- the obtained granulated powder was put into a mold having a diameter of 14.0 mm and press-molded at a pressure of 1 ton / cm 2 to obtain a disk-shaped green molded body.
- the obtained green molded body was fired in a reducing atmosphere to produce a sintered body.
- the heating rate was 300 ° C./hr
- the holding temperature was 1150 to 1300 ° C.
- the holding time was 2 hours.
- the atmosphere gas was a humidified hydrogen / nitrogen mixed gas (hydrogen concentration 0.5%), and a wetter (wetter temperature 35 ° C.) was used for humidification.
- the result of the X-ray diffraction measurement of the sample 15 is shown in FIG.
- the lower part of the figure is a reference tungsten bronze type crystal phase, and it was confirmed that Sample 15 contained a tungsten bronze type crystal phase.
- Tables 2, 4, and 6 show the results of X-ray diffraction measurement including other samples. The symbol “T” in the table indicates that the presence of the tungsten bronze type crystal phase was confirmed.
- the capacitance C was measured at a reference temperature of 25 ° C. using an LCR meter (4284A manufactured by Agilent Technologies) with a frequency of 1 kHz and a measurement voltage of 1 V rms . Thereafter, the relative dielectric constant was calculated based on the thickness of the sintered body, the effective electrode area, and the capacitance C obtained as a result of the measurement. The relative dielectric constant was calculated in the same manner at a reference temperature of 200 ° C. In addition, the one where a relative dielectric constant is higher is preferable, and it was considered that it was 100 or more at 25 ° C.
- the transition of the capacitance change rate from ⁇ 55 ° C. to 200 ° C. for Samples 8, 15 and 66 is shown in FIG.
- the symbol “x” is the sample 8
- “ ⁇ ” is the sample 15
- “ ⁇ ” is the capacitance change rate of the sample 66.
- the transition of the capacitance change rate from ⁇ 55 ° C. to 200 ° C. for Samples 15 and 78 is shown in FIG.
- the symbol “ ⁇ ” in the figure indicates the capacitance change rate of the sample 15, and “X” indicates the capacitance change rate of the sample 78.
- tan-delta ⁇ Dielectric loss (tan ⁇ )> About each capacitor
- the oxide equivalent composition of the first component is mol% in terms of oxide described in the table of each oxide with respect to the total mol number in terms of oxide described in the table of each oxide component of the first component.
- Mn oxide content is the mass% of Mn oxide in terms of MnO with respect to the total mass in terms of oxide described in the table of each oxide component of the first component, and the oxide of the second component The total content of is the total mass% of the oxide of the second component with respect to the total mass in terms of oxide described in the table of each oxide component of the first component.
- the oxide equivalent composition of the first component is mol% in terms of oxide described in the table of each oxide with respect to the total mol number in terms of oxide described in the table of each oxide component of the first component.
- Mn oxide content is the mass% of Mn oxide in terms of MnO with respect to the total mass in terms of oxide described in the table of each oxide component of the first component, and the oxide of the second component The total content of is the total mass% of the oxide of the second component with respect to the total mass in terms of oxide described in the table of each oxide component of the first component.
- the oxide equivalent composition of the first component is mol% in terms of oxide described in the table of each oxide with respect to the total mol number in terms of oxide described in the table of each oxide component of the first component.
- Mn oxide content is the mass% of Mn oxide in terms of MnO with respect to the total mass in terms of oxide described in the table of each oxide component of the first component, and the oxide of the second component The total content of is the total mass% of the oxide of the second component with respect to the total mass in terms of oxide described in the table of each oxide component of the first component.
- the sample in the range surrounded by the line ABCDE in FIG. 1 had a relative dielectric constant of 100 or more at 25 ° C. That is, it was confirmed that the dielectric ceramic composition of the present invention has ferroelectricity. Further, the sample within the range surrounded by the line ABCDE in FIG. 1 has a change rate of the capacitance within ⁇ 50% in the temperature range of ⁇ 55 ° C. to 200 ° C. The dielectric loss (tan ⁇ ) at 25 ° C. and 200 ° C. is 10% or less. Further, the line segment point A'-point B'-point C'-point D'-point E'-point F'-point G'-point H'-point I'-point J'-point K 'in FIG.
- sample numbers 5 8, 12, 15, 17, 18, 23 to 25, 27, 29 to 36, 38, 41, and 43 to 45 have a relative dielectric constant of 500 or more, and are particularly preferable.
- Sample numbers 1 to 4, 7 to 13, 16 to 18, 23 to 28, 38 to 40, 46, 47, 49 to 62, and 87 to 90 have capacitances in a temperature range of ⁇ 55 ° C. to 200 ° C.
- the change rate ⁇ C t / C 25 is ⁇ 33% to + 22%, and the temperature characteristics are particularly excellent.
- sample numbers 65 to 86 outside the scope of the present invention good characteristics were not obtained with respect to the performance of one or more of the relative dielectric constant, the capacitance change rate, and tan ⁇ .
- the rate of change in capacitance is from ⁇ 30% to ⁇ 55 ° C. to 200 ° C. It can be seen that the rate of change in capacitance of Sample 66, which is within the range of 30% but is outside the range of the present invention, rapidly increases from around 150 ° C.
- Sample 15 and sample 78 differ only in the presence or absence of an oxide of Mn as the second component, but it is understood that the characteristics of both are greatly different as shown in FIG.
- Example 2 The first component raw material described above was weighed to have the composition shown in Table 7 in terms of oxide, and MnCO 3 and SiO 2 were further weighed as the second component raw material to have the composition shown in Table 7 in terms of oxide.
- the oxide equivalent composition of the first component is mol% in terms of oxide described in the table of each oxide with respect to the total mol number in terms of oxide described in the table of each oxide component of the first component.
- Mn oxide content is the mass% of Mn oxide in terms of MnO with respect to the total mass in terms of oxide described in the table of each oxide component of the first component, and the oxide of the second component The total content of is the total mass% of the oxide of the second component with respect to the total mass in terms of oxide described in the table of each oxide component of the first component.
Abstract
Description
すなわち、本発明(1)は、第一成分と第二成分とからなり、
第一成分が、下記の酸化物に換算したときの第一成分の合計mol数に対する含有割合が、CaO換算で0~35.85mol%のCaの酸化物と、SrO換算で0~47.12mol%のSrの酸化物と、BaO換算で0~51.22mol%のBaの酸化物と、TiO2換算で0~17.36mol%のTiの酸化物と、ZrO2換算で0~17.36mol%のZrの酸化物と、SnO2換算で0~2.60mol%のSnの酸化物と、Nb2O5換算で0~35.32mol%のNbの酸化物と、Ta2O5換算で0~35.32mol%のTaの酸化物と、V2O5換算で0~2.65mol%のVの酸化物と、からなり、
該第一成分は、Caの酸化物、Srの酸化物及びBaの酸化物から選ばれる少なくとも1種と、Tiの酸化物及びZrの酸化物から選ばれる少なくとも1種と、Nbの酸化物及びTaの酸化物から選ばれる少なくとも1種と、を必須成分として含有し、且つ、上記の酸化物に換算したときの第一成分の合計mol数に対するCaO換算のCaの酸化物、SrO換算のSrの酸化物及びBaO換算のBaの酸化物の合計の含有割合が48.72~51.22mol%であり、TiO2換算のTiの酸化物、ZrO2換算のZr酸化物及びSnO2換算のSnの酸化物の合計の含有割合が15.97~17.36mol%であり、Nb2O5換算のNbの酸化物、Ta2O5換算のTa酸化物及びV2O5換算のVの酸化物の合計の含有割合が31.42~35.31mol%であり、
第二成分として、少なくともMnの酸化物を含有すること、
を特徴とする誘電体磁器組成物を提供するものである。
第一成分として、下記一般式(1):
AaM1 bM2 cOd (1)
(式(1)中、Aは、一般式(2):Ba1-x-ySrxCay(2)(式(2)中、0≦x≦0.920、0≦y≦0.700である。)で表される。M1は、Ti、Zr及びSnから選ばれる少なくとも1種である。M2は、Nb、Ta及びVから選ばれる少なくとも1種である。5.70≦a≦6.30、1.90≦b≦2.10、7.20≦c≦8.80、27.45≦d≦32.50である。)
で表される化合物(但し、Snを含有する場合は、TiO2換算のTiの酸化物、ZrO2換算のZrの酸化物及びSnO2換算のSnの酸化物の合計mol数に対するSnO2換算のSnの酸化物の含有割合が15mol%以下であり、Vを含有する場合は、Nb2O5換算のNbの酸化物、Ta2O5換算のTaの酸化物及びV2O5換算のVの酸化物の合計mol数に対するV2O5換算のVの酸化物の含有割合が7.5mol%以下である。)を含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物を提供するものである。
下記一般式(3):
α・Caη1M3 θ1M4 φ1Oω1-β・Srη2M3 θ2M4 φ2Oω2-γ・Baη3M3 θ3M4 φ3Oω3 (3)
(式(3)中、η1、η2及びη3は、それぞれ独立して5.70~6.30の範囲内の値である。θ1、θ2及びθ3は、それぞれ独立して0.95~1.05の範囲内の値である。φ1、φ2及びφ3は、それぞれ独立して0.90~1.10の範囲内の値である。ω1、ω2及びω3はそれぞれ独立して27.45~32.50の範囲内の値である。M3は、一般式(4):Ti2-ρ-σZrρSnσ(4)(式(4)中、0≦ρ≦2.0、0≦σ≦0.3である。)で表される。M4は、一般式(5):Nb8-π-ψTaπVψ(5)(式(5)中、0≦π≦8.0、0≦ψ≦0.6である。)で表される。α、β及びγは、α+β+γ=1.00を満たす。)
で表され、3元組成図上の任意の点を(α,β,γ)と表すときに、点A=(0.05,0.95,0.00)、点B=(0.70,0.30,0.00)、点C=(0.70,0.00,0.30)、点D=(0.00,0.00,1.00)、点E=(0.00,0.90,0.10)を結ぶ線分で囲まれる範囲内にある化合物を第一成分として含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物を提供するものである。
図8に示すセラミックコンデンサ1は、全体として直方体形状の積層体10を備えている。積層体10は、積層された複数の誘電体層3と、誘電体層3の異なる界面に沿って形成される複数の内部電極2a、2bにより構成される。内部電極2a、2bは、積層体10内において交互に配置され、それぞれ積層体10の異なる端部で外部電極4と電気的に接合している。外部電極4の上には、必要に応じてニッケル、銅、ニッケル-銅合金などからなる第1のめっき層や、その上に更に半田、錫などからなる第2のめっき層が形成されても良い。
本発明において内部電極2a、2bには、導電成分として卑金属が用いられる。導電成分としての卑金属としては、ニッケル、銅、アルミニウムなどの純金属の他、当該金属成分を含む合金や混合物あるいは複合物であっても良い。そして、導電成分としての卑金属として、特に好ましくは、ニッケル及び銅から選ばれる1種である。また、本発明の作用効果を阻害しないのであれば、内部電極2a、2bには、卑金属以外の導電成分や後出の共材などが含まれていてもよい。
誘電体層3は、後述する本発明の誘電体磁器組成物で構成されることによって、高い比誘電率を維持しつつ、幅広い温度領域、特に200℃前後の高温領域においても静電容量の変化が小さく、静電容量変化率が-55℃~200℃の温度範囲で±50%以内となり、25℃及び200℃における誘電損失(tanδ)が共に10%以下となる。しかも、本発明の誘電体磁器組成物は、耐還元性に優れており、内部電極の導電成分として卑金属を用い、還元雰囲気下で同時焼成する場合であっても、還元され難く、半導体化しない。
本発明の第一の形態の誘電体磁器組成物は、第一成分と第二成分とからなり、
第一成分が、下記の酸化物に換算したときの第一成分の合計mol数に対する含有割合が、CaO換算で0~35.85mol%のCaの酸化物と、SrO換算で0~47.12mol%のSrの酸化物と、BaO換算で0~51.22mol%のBaの酸化物と、TiO2換算で0~17.36mol%のTiの酸化物と、ZrO2換算で0~17.36mol%のZrの酸化物と、SnO2換算で0~2.60mol%のSnの酸化物と、Nb2O5換算で0~35.32mol%のNbの酸化物と、Ta2O5換算で0~35.32mol%のTaの酸化物と、V2O5換算で0~2.65mol%のVの酸化物と、からなり、
該第一成分は、Caの酸化物、Srの酸化物及びBaの酸化物から選ばれる少なくとも1種と、Tiの酸化物及びZrの酸化物から選ばれる少なくとも1種と、Nbの酸化物及びTaの酸化物から選ばれる少なくとも1種と、を必須成分として含有し、且つ、上記の酸化物に換算したときの第一成分の合計mol数に対するCaO換算のCaの酸化物、SrO換算のSrの酸化物及びBaO換算のBaの酸化物の合計の含有割合が48.72~51.22mol%であり、TiO2換算のTiの酸化物、ZrO2換算のZr酸化物及びSnO2換算のSnの酸化物の合計の含有割合が15.97~17.36mol%であり、Nb2O5換算のNbの酸化物、Ta2O5換算のTa酸化物及びV2O5換算のVの酸化物の合計の含有割合が31.42~35.31mol%であり、
第二成分として、少なくともMnの酸化物を含有すること、
を特徴とする誘電体磁器組成物である。
第一成分として、下記一般式(1):
AaM1 bM2 cOd (1)
(式(1)中、Aは、一般式(2):Ba1-x-ySrxCay(2)(式(2)中、0≦x≦0.920、0≦y≦0.700である。)で表される。M1は、Ti、Zr及びSnから選ばれる少なくとも1種である。M2は、Nb、Ta及びVから選ばれる少なくとも1種である。5.70≦a≦6.30、1.90≦b≦2.10、7.20≦c≦8.80、27.45≦d≦32.50である。)
で表される化合物(但し、Snを含有する場合は、TiO2換算のTiの酸化物、ZrO2換算のZrの酸化物及びSnO2換算のSnの酸化物の合計mol数に対するSnO2換算のSnの酸化物の含有割合が15mol%以下であり、Vを含有する場合は、Nb2O5換算のNbの酸化物、Ta2O5換算のTaの酸化物及びV2O5換算のVの酸化物の合計mol数に対するV2O5換算のVの酸化物の含有割合が7.5mol%以下である。)を含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物である。
AaM1 bM2 cOd (1)
で表される化合物である。
下記一般式(3):
α・Caη1M3 θ1M4 φ1Oω1-β・Srη2M3 θ2M4 φ2Oω2-γ・Baη3M3 θ3M4 φ3Oω3 (3)
(式(3)中、η1、η2及びη3は、それぞれ独立して5.70~6.30の範囲内の値である。θ1、θ2及びθ3は、それぞれ独立して0.95~1.05の範囲内の値である。φ1、φ2及びφ3は、それぞれ独立して0.90~1.10の範囲内の値である。ω1、ω2及びω3はそれぞれ独立して27.45~32.50の範囲内の値である。M3は、一般式(4):Ti2-ρ-σZrρSnσ(4)(式(4)中、0≦ρ≦2.0、0≦σ≦0.3である。)で表される。M4は、一般式(5):Nb8-π-ψTaπVψ(5)(式(5)中、0≦π≦8.0、0≦ψ≦0.6である。)で表される。α、β及びγは、α+β+γ=1.00を満たす。)
で表され、3元組成図上の任意の点を(α,β,γ)と表すときに、点A=(0.05,0.95,0.00)、点B=(0.70,0.30,0.00)、点C=(0.70,0.00,0.30)、点D=(0.00,0.00,1.00)、点E=(0.00,0.90,0.10)を結ぶ線分で囲まれる範囲内にある化合物を第一成分として含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物である。
外部電極4は、通常、積層体10を同時焼成した後の端部に外部電極用導電ペーストを付与し、これを焼き付けることによって形成されるが、本発明はこれに限られるものではなく、熱硬化型樹脂や熱可塑性樹脂を含むペーストを用いて加熱処理して外部電極4が形成されても良い。外部電極用導電ペーストに使用される導電成分は、特に限定されず、例えば、ニッケル、銅、銀、パラジウム、白金、金などの純金属の他、当該金属成分を含む合金や混合物又は複合物であっても良い。また、その他、必要に応じて導電ペーストにはガラスフリットが添加されることもある。また、外部電極4は積層体10と共に同時に焼成される場合もある。
セラミックコンデンサ1は、本発明の第一の形態の誘電体磁器組成物、本発明の第二の形態の誘電体磁器組成物又は本発明の第三の形態の誘電体磁器組成物を用いる他は、公知の方法により製造される。以下、その一例を説明する。
(1)誘電体磁器組成物試料1~90の作製
第一成分の出発原料として、CaCO3、SrCO3、BaCO3、TiO2、ZrO2、SnO2、Nb2O5、Ta2O5、V2O5の各粉末を、酸化物換算で表1、表3及び表5に示す比率になるよう秤量し、ボールミルで純水を用いて20時間湿式混合した。
次に、得られた各混合物を100℃で乾燥した後、大気中、750~900℃で3時間仮焼し、再び同様にボールミルで細かく粉砕し、第一成分用誘電体原料とした。
また、第二成分として、MnCO3を18.2mg、MgOを32mg、SiO2を58.6mg、Y2O3を89.5mgずつ秤量し、これらを混合したものを準備し、第二成分用原料とした。但し、試料43では上記第二成分用原料の内、SiO2を除いたMnCO3、MgO及びY2O3の3成分のみとした。試料44では第二成分用原料としてMgOを除いたMnCO3、SiO2及びY2O3の3成分のみとした。試料45ではY2O3を除いたMnCO3、MgO及びSiO2の3成分のみとした。試料78及び79ではMnCO3を除いたMgO、SiO2及びY2O3の3成分のみとした。また、試料41では、上記第二成分用原料の内、MnCO3の量を0.404mgに変更し、試料42ではMnCO3の量を0.198gに変更し、試料80ではMnCO3の量を2.055gに変更した。
また、ポリビニルアルコール濃度が6質量%となるように、イオン交換水とポリビニルアルコールを容器に投入し、90℃で1時間混合して、ポリビニルアルコール水溶液を準備した。
そして、各第一成分用誘電体原料25gと上記量の第二成分用原料とを混合し、これらの混合物に対し、ポリビニルアルコール水溶液の濃度が10質量%となるように、原料混合物にポリビニルアルコール水溶液を添加し、乳鉢中で混合及び造粒して造粒粉を作製した。
更に得られた造粒粉を直径14.0mmの金型に投入して、1ton/cm2の圧力でプレス成形することによって、円板状のグリーン成形体を得た。
次いで、得られたグリーン成形体を還元性雰囲気中で焼成することによって、焼結体を作製した。この際の焼成では、昇温速度を300℃/hr、保持温度を1150~1300℃、保持時間を2時間とした。雰囲気ガスは加湿した水素/窒素混合ガス(水素濃度0.5%)とし、加湿にはウェッター(ウェッター温度35℃)を用いた。
上述のようにして得られた試料1~90に対応する円板状のセラミックコンデンサに対して、以下に示す方法により、グレインサイズ、結晶相、比誘電率、静電容量変化率及び誘電損失(tanδ)をそれぞれ分析した。その結果を表2、表4及び表6に示す。
各コンデンサの表面を、走査型電子顕微鏡(SEM)を用いて観察し、無作為に抽出した20個の結晶粒子の粒界から求めた円相当径の平均値をグレインサイズとした。なお、図3~図5は、それぞれ、試料8、15及び66のSEM像である。
X線回折測定により、結晶相の特定を行った。代表例として試料15のX線回折測定の結果を図9に示す。図中の下段はリファレンスのタングステンブロンズ型結晶相であり、試料15がタングステンブロンズ型結晶相を含有することを確認できた。その他の試料を含めたX線回折測定結果を表2、表4及び表6に示す。なお、表中の符号“T”はタングステンブロンズ型結晶相の存在を確認できたことを示す。
各コンデンサに対し、基準温度25℃において、LCRメータ(アジレント・テクノロジー社製4284A)を用いて、周波数1kHz、測定電圧1Vrmsとして静電容量Cを測定した。その後、焼結体の厚みと、有効電極面積と、測定の結果得られた静電容量Cとに基づいて比誘電率を算出した。また基準温度200℃においても同様にして比誘電率を算出した。
なお、比誘電率は高い方が好ましく、25℃において100以上であれば良好とした。
比誘電率の測定と同様な条件(アジレント・テクノロジー社製4284A、周波数1kHz、測定電圧1Vrms)で、-55℃から200℃の温度領域における各温度tの静電容量Ctを測定した。そして、基準となる25℃の静電容量C25から、静電容量変化率=((Ct-C25)/C25)×100(%)(以下、静電容量変化率をΔCt/C25と記すことがある。)を算出した。
なお、静電容量変化率は0に近い方が好ましく、±50%以内であれば良好とした。
また、試料8、15及び66について、-55℃から200℃までの静電容量変化率の推移を、図6に記した。なお、図中の符号“×”は試料8、“○”は試料15、“△”は試料66の静電容量変化率である。更に、試料15及び78について、-55℃から200℃までの静電容量変化率の推移を、図7に記した。図中の符号“○”は試料15、“×”は試料78の静電容量変化率である。
各コンデンサ試料について、LCRメータ(アジレント・テクノロジー社製4284A)を用いて、周波数1kHz、測定電圧1Vrmsとしてtanδを測定した。tanδは25℃及び200℃において、共に10%以下であれば良好とした。
*Mn酸化物の含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対するMnO換算のMn酸化物の質量%であり、また、第二成分の酸化物の合計含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対する第二成分の酸化物の合計の質量%である。
*Mn酸化物の含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対するMnO換算のMn酸化物の質量%であり、また、第二成分の酸化物の合計含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対する第二成分の酸化物の合計の質量%である。
*Mn酸化物の含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対するMnO換算のMn酸化物の質量%であり、また、第二成分の酸化物の合計含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対する第二成分の酸化物の合計の質量%である。
以上の分析結果から、図1の線分A-B-C-D-Eにより囲まれる範囲内にある試料は、25℃における比誘電率が100以上であった。すなわち、本発明の誘電体磁器組成物は、強誘電性を有していることが確認できた。また、図1の線分A-B-C-D-Eにより囲まれる範囲内にある試料は、静電容量の変化率が-55℃~200℃の温度範囲で±50%以内であり、25℃及び200℃における誘電損失(tanδ)が10%以下である。
更に、図2の線分点A’-点B’-点C’-点D’-点E’-点F’-点G’-点H’-点I’-点J’-点K’-点L’により囲まれる範囲内にある試料は、25℃における比誘電率が200以上であった。
中でも試料番号5、8、12、15、17、18、23~25、27、29~36、38、41、43~45は、比誘電率が500以上を示しており、特に好ましい。
また、試料番号1~4、7~13、16~18、23~28、38~40、46、47、49~62、87~90は、-55℃から200℃の温度領域における静電容量変化率ΔCt/C25が-33%~+22%を示し、特に温度特性が優れている。
また、図6に示される通り、本発明の誘電体磁器組成物(試料8、15)を用いた場合には、静電容量変化率は-55℃から200℃の温度範囲において-30%~30%の範囲内にあるが、本発明の範囲外である試料66は150℃を越えたあたりから静電容量変化率が急激に増加していることが分かる。
また、試料15と試料78は、第二成分としてのMnの酸化物の有無のみが異なる試料であるが、図7に示される通り、両者の特性が大きく異なっていることが分かる。
上述した第一成分原料を酸化物換算で表7に示す組成になるよう秤量し、更に、第二成分原料としてMnCO3及びSiO2を酸化物換算で表7に示す組成になるよう秤量した以外は実施例1と同様にして試料91~107を作製し、それぞれの試料に対応する円板状のセラミックコンデンサを得た。
その後、実施例1と同様に、グレインサイズ、結晶相、比誘電率、静電容量変化率及び誘電損失(tanδ)を測定し、その結果を表8に示した。
これらの結果から、酸化物換算の第一成分の合計質量に対し、第二成分としてのMnO換算のMn含有量が3.5質量%以下の試料では、比誘電率、静電容量変化率及びtanδについて良好な結果が得られていることが分かる。
*Mn酸化物の含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対するMnO換算のMn酸化物の質量%であり、また、第二成分の酸化物の合計含有量は、第一成分の各酸化物成分の表中に記載する酸化物換算の合計質量に対する第二成分の酸化物の合計の質量%である。
2 誘電体層
3 内部電極層
4 外部電極
10 積層体
Claims (18)
- 第一成分と第二成分とからなり、
第一成分が、下記の酸化物に換算したときの第一成分の合計mol数に対する含有割合が、CaO換算で0~35.85mol%のCaの酸化物と、SrO換算で0~47.12mol%のSrの酸化物と、BaO換算で0~51.22mol%のBaの酸化物と、TiO2換算で0~17.36mol%のTiの酸化物と、ZrO2換算で0~17.36mol%のZrの酸化物と、SnO2換算で0~2.60mol%のSnの酸化物と、Nb2O5換算で0~35.32mol%のNbの酸化物と、Ta2O5換算で0~35.32mol%のTaの酸化物と、V2O5換算で0~2.65mol%のVの酸化物と、からなり、
該第一成分は、Caの酸化物、Srの酸化物及びBaの酸化物から選ばれる少なくとも1種と、Tiの酸化物及びZrの酸化物から選ばれる少なくとも1種と、Nbの酸化物及びTaの酸化物から選ばれる少なくとも1種と、を必須成分として含有し、且つ、上記の酸化物に換算したときの第一成分の合計mol数に対するCaO換算のCaの酸化物、SrO換算のSrの酸化物及びBaO換算のBaの酸化物の合計の含有割合が48.72~51.22mol%であり、TiO2換算のTiの酸化物、ZrO2換算のZr酸化物及びSnO2換算のSnの酸化物の合計の含有割合が15.97~17.36mol%であり、Nb2O5換算のNbの酸化物、Ta2O5換算のTa酸化物及びV2O5換算のVの酸化物の合計の含有割合が31.42~35.31mol%であり、
第二成分として、少なくともMnの酸化物を含有すること、
を特徴とする誘電体磁器組成物。 - 前記の酸化物に換算したときの第一成分の合計質量に対するMnO換算の前記Mnの酸化物の含有割合が、3.5質量%以下であることを特徴とする請求項1記載の誘電体磁器組成物。
- 第一成分と第二成分とからなり、
第一成分として、下記一般式(1):
AaM1 bM2 cOd (1)
(式(1)中、Aは、一般式(2):Ba1-x-ySrxCay(2)(式(2)中、0≦x≦0.920、0≦y≦0.700である。)で表される。M1は、Ti、Zr及びSnから選ばれる少なくとも1種である。M2は、Nb、Ta及びVから選ばれる少なくとも1種である。5.70≦a≦6.30、1.90≦b≦2.10、7.20≦c≦8.80、27.45≦d≦32.50である。)
で表される化合物(但し、Snを含有する場合は、TiO2換算のTiの酸化物、ZrO2換算のZrの酸化物及びSnO2換算のSnの酸化物の合計mol数に対するSnO2換算のSnの酸化物の含有割合が15mol%以下であり、Vを含有する場合は、Nb2O5換算のNbの酸化物、Ta2O5換算のTaの酸化物及びV2O5換算のVの酸化物の合計mol数に対するV2O5換算のVの酸化物の含有割合が7.5mol%以下である。)を含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物。 - 前記一般式(1)で表される化合物の質量に対するMnO換算の前記Mnの酸化物の含有割合が、3.5質量%以下であることを特徴とする請求項3記載の誘電体磁器組成物。
- 第一成分と第二成分とからなり、
下記一般式(3):
α・Caη1M3 θ1M4 φ1Oω1-β・Srη2M3 θ2M4 φ2Oω2-γ・Baη3M3 θ3M4 φ3Oω3 (3)
(式(3)中、η1、η2及びη3は、それぞれ独立して5.70~6.30の範囲内の値である。θ1、θ2及びθ3は、それぞれ独立して0.95~1.05の範囲内の値である。φ1、φ2及びφ3は、それぞれ独立して0.90~1.10の範囲内の値である。ω1、ω2及びω3はそれぞれ独立して27.45~32.50の範囲内の値である。M3は、一般式(4):Ti2-ρ-σZrρSnσ(4)(式(4)中、0≦ρ≦2.0、0≦σ≦0.3である。)で表される。M4は、一般式(5):Nb8-π-ψTaπVψ(5)(式(5)中、0≦π≦8.0、0≦ψ≦0.6である。)で表される。α、β及びγは、α+β+γ=1.00を満たす。)
で表され、3元組成図上の任意の点を(α,β,γ)と表すときに、点A=(0.05,0.95,0.00)、点B=(0.70,0.30,0.00)、点C=(0.70,0.00,0.30)、点D=(0.00,0.00,1.00)、点E=(0.00,0.90,0.10)を結ぶ線分で囲まれる範囲内にある化合物を第一成分として含有し、
第二成分として、Mnの酸化物を含有すること、
を特徴とする誘電体磁器組成物。 - 前記3元組成図上の点A、点B、点C、点D、点Eを結ぶ線分で囲まれる範囲内にある化合物の質量に対するMnO換算の前記Mnの酸化物の含有割合が、3.5質量%以下であることを特徴とする請求項5記載の誘電体磁器組成物。
- 前記第一成分が、前記3元組成図において、点A’=(0.05,0.95,0.00)、点B’=(0.60,0.40,0.00)、点C’=(0.70,0.20,0.10)、点D’=(0.70,0.10,0.20)、点E’=(0.55,0.00,0.45)、点F’=(0.40,0.00,0.60)、点G’=(0.10,0.10,0.80)、点H’=(0.00,0.00,1.00)、点I’=(0.00,0.40,0.60)、点J’=(0.20,0.40,0.40)、点K’=(0.00,0.70,0.30)、点L’=(0.00,0.90,0.10)を結ぶ線分で囲まれる範囲内にある化合物であることを特徴とする請求項5記載の誘電体磁器組成物。
- 第二成分として、Mnの酸化物及びDの酸化物(Dは、Li、Mg、Si、Cr、Al、Fe、Co、Ni、Cu、Zn、Ga、Ge、In、W、Mo、Y、Hf、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及びLuから選ばれる少なくとも1種である。)を含有することを特徴とする請求項1~7いずれか1項記載の誘電体磁器組成物。
- タングステンブロンズ型結晶相を含有することを特徴とする請求項1~8いずれか1項記載の誘電体磁器組成物。
- 25℃における比誘電率が100以上であることを特徴とする請求項1~9いずれか1項記載の誘電体磁器組成物。
- 25℃における比誘電率が200以上であることを特徴とする請求項10記載の誘電体磁器組成物。
- 25℃における比誘電率が300以上であることを特徴とする請求項11記載の誘電体磁器組成物。
- 静電容量変化率が-55℃~200℃の温度範囲において-50%~50%の範囲内であることを特徴とする請求項1~12いずれか1項記載の誘電体磁器組成物。
- 静電容量変化率が-55℃~200℃の温度範囲において-33%~22%の範囲内であることを特徴とする請求項1~13いずれか1項記載の誘電体磁器組成物。
- 25℃における誘電損失(tanδ)が10%以下であり且つ200℃における誘電損失(tanδ)が10%以下であることを特徴とする請求項1~14いずれか1項記載の誘電体磁器組成物。
- 請求項1~15いずれか1項記載の誘電体磁器組成物で形成されている誘電体層と、導電成分として卑金属を含む電極層と、を含むことを特徴とするセラミック電子部品。
- 前記卑金属がニッケル及び銅から選ばれる少なくとも1種であることを特徴とする請求項16記載のセラミック電子部品。
- 前記誘電体層と前記電極層が複数積層されていることを特徴とする請求項16又は17いずれか1項記載のセラミック電子部品。
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Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03274607A (ja) * | 1990-03-26 | 1991-12-05 | Toshiba Corp | 誘電体組成物 |
JPH1143370A (ja) | 1997-07-22 | 1999-02-16 | Taiyo Yuden Co Ltd | 誘電体磁器組成物とこの誘電体磁器組成物を用いたセラミック電子部品 |
JP2000169215A (ja) | 1998-11-30 | 2000-06-20 | Kyocera Corp | 誘電体磁器組成物 |
JP2002211975A (ja) | 2001-01-10 | 2002-07-31 | Murata Mfg Co Ltd | 非還元性誘電体セラミック、セラミック電子部品および積層セラミックコンデンサ |
JP2004062032A (ja) * | 2002-07-31 | 2004-02-26 | Toppan Forms Co Ltd | 導電性トナー及びこれを用いた導電性回路を有するシート |
WO2006114914A1 (ja) | 2005-04-18 | 2006-11-02 | Murata Manufacturing Co., Ltd. | 誘電体セラミック組成物及び積層セラミックコンデンサ |
JP2007197277A (ja) | 2006-01-27 | 2007-08-09 | Kyocera Corp | 誘電体磁器組成物および誘電体磁器、ならびにemiフィルタ |
JP2008189487A (ja) | 2007-02-01 | 2008-08-21 | Murata Mfg Co Ltd | 誘電体セラミック組成物及び積層セラミックコンデンサ |
WO2008102608A1 (ja) | 2007-02-22 | 2008-08-28 | Murata Manufacturing Co., Ltd. | 誘電体セラミック組成物及び積層セラミックコンデンサ |
JP2013063874A (ja) * | 2011-09-16 | 2013-04-11 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180908A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180907A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180906A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2015163576A (ja) * | 2014-01-29 | 2015-09-10 | キヤノン株式会社 | 圧電セラミックス、その製造方法、圧電素子、積層圧電素子、液体吐出ヘッド、液体吐出装置、超音波モータ、光学機器、振動装置、塵埃除去装置、撮像装置および電子機器 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW209210B (en) | 1993-01-11 | 1993-07-11 | Taiwan Cement Corp | High electric constant type layered ceramic composition |
WO2000007194A1 (en) * | 1998-07-27 | 2000-02-10 | Georgetown University | Preparation of tungsten bronzes for nuclear waste storage forms and electronic materials |
EP1862568A1 (en) * | 2006-05-30 | 2007-12-05 | Siemens Aktiengesellschaft | Thermal barrier coating with tungsten-bronze structure |
KR100808472B1 (ko) | 2006-12-01 | 2008-03-03 | (주)써모텍 | 유전체 세라믹 조성물 및 그 제조방법 |
CN101531512B (zh) * | 2009-04-11 | 2011-11-30 | 桂林工学院 | 一种温度稳定型钨青铜结构介电陶瓷及其制备方法 |
JP6249669B2 (ja) | 2012-08-27 | 2017-12-20 | キヤノン株式会社 | 圧電材料、圧電素子、および電子機器 |
WO2017163844A1 (ja) * | 2016-03-24 | 2017-09-28 | Tdk株式会社 | 誘電体組成物、誘電体素子、電子部品及び積層電子部品 |
JP6881433B2 (ja) * | 2016-03-24 | 2021-06-02 | Tdk株式会社 | 誘電体組成物、誘電体素子、電子部品及び積層電子部品 |
EP3434658A4 (en) * | 2016-03-24 | 2019-11-27 | TDK Corporation | DIELECTRIC COMPOSITION, DIELECTRIC ELEMENT, ELECTRONIC COMPONENT AND ELECTRONIC LAMINATE COMPONENT |
-
2017
- 2017-10-11 US US16/342,515 patent/US11066332B2/en active Active
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Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03274607A (ja) * | 1990-03-26 | 1991-12-05 | Toshiba Corp | 誘電体組成物 |
JPH1143370A (ja) | 1997-07-22 | 1999-02-16 | Taiyo Yuden Co Ltd | 誘電体磁器組成物とこの誘電体磁器組成物を用いたセラミック電子部品 |
JP2000169215A (ja) | 1998-11-30 | 2000-06-20 | Kyocera Corp | 誘電体磁器組成物 |
JP2002211975A (ja) | 2001-01-10 | 2002-07-31 | Murata Mfg Co Ltd | 非還元性誘電体セラミック、セラミック電子部品および積層セラミックコンデンサ |
JP2004062032A (ja) * | 2002-07-31 | 2004-02-26 | Toppan Forms Co Ltd | 導電性トナー及びこれを用いた導電性回路を有するシート |
JP2012169635A (ja) | 2005-04-18 | 2012-09-06 | Murata Mfg Co Ltd | 積層セラミックコンデンサ |
WO2006114914A1 (ja) | 2005-04-18 | 2006-11-02 | Murata Manufacturing Co., Ltd. | 誘電体セラミック組成物及び積層セラミックコンデンサ |
JP2007197277A (ja) | 2006-01-27 | 2007-08-09 | Kyocera Corp | 誘電体磁器組成物および誘電体磁器、ならびにemiフィルタ |
JP2008189487A (ja) | 2007-02-01 | 2008-08-21 | Murata Mfg Co Ltd | 誘電体セラミック組成物及び積層セラミックコンデンサ |
WO2008102608A1 (ja) | 2007-02-22 | 2008-08-28 | Murata Manufacturing Co., Ltd. | 誘電体セラミック組成物及び積層セラミックコンデンサ |
JP2013063874A (ja) * | 2011-09-16 | 2013-04-11 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180908A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180907A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2013180906A (ja) | 2012-02-29 | 2013-09-12 | Tdk Corp | 誘電体磁器組成物および電子部品 |
JP2015163576A (ja) * | 2014-01-29 | 2015-09-10 | キヤノン株式会社 | 圧電セラミックス、その製造方法、圧電素子、積層圧電素子、液体吐出ヘッド、液体吐出装置、超音波モータ、光学機器、振動装置、塵埃除去装置、撮像装置および電子機器 |
Non-Patent Citations (1)
Title |
---|
MAT. RES. BULL., vol. 27, 1992, pages 677 - 684 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7338533B2 (ja) | 2020-03-30 | 2023-09-05 | Tdk株式会社 | 誘電体組成物および電子部品 |
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