JP2006261351A - Laminated ceramic component and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To integrally provide layers having high and low dielectric constants without any intermediate layers and any symmetrical arrangement. <P>SOLUTION: A component has the laminated section of a low dielectric constant layer of ε<SB>r</SB>≤10 by glass and filler and a high dielectric constant layer of ε<SB>r</SB>≥30. In this case, the glass is in the same composition base. Low dielectric constant layer glass and high dielectric constant layer glass contain Ba25-55 mass%, Zn5-30 mass%, B15-35 mass%, and Si5-30 mass%. The low dielectric constant layer is 35 vol.% or smaller. The high dielectric constant layer is 45 vol.% or smaller. For low dielectric constant layer filler, in [xCaO-yM<SP>1</SP>O-zSiO<SB>2</SB>], M<SP>1</SP>is at least one kind of Mg and Zn, and x, y, and z are a region surrounded by AB, BC, CD, and DA as shown in Fig. For high dielectric constant layer filler, in [aBaO-bTiO<SB>2</SB>-cREO<SB>3/2</SB>-dBiO<SB>3/2</SB>], 0.09≤a≤0.16, 0.54≤b≤0.62, 0.20≤c≤0.34, and 0≤d≤0.10 are met. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a multilayer ceramic component and a method for manufacturing the same. More specifically, the present invention relates to a multilayer ceramic component including a multilayer part in which a high dielectric constant layer and a low dielectric constant layer are adjacently laminated, and a manufacturing method thereof.

  2. Description of the Related Art In recent years, with the demand for downsizing and multi-functionality of electronic devices, the combination of electronic components that make up electronic devices and the reduction in thickness and thickness have been advanced. In miniaturization, a method of increasing the density of resistors and wiring patterns formed on a substrate or a method of integrating chip components at a higher density can be used. However, in these methods, there is a limit to the miniaturization of the substrate and components, and further, noise and line-to-line capacitance are likely to occur due to the densification of the wiring pattern at high frequencies, and there is a concern about quality deterioration.

For this reason, a composite multilayer ceramic component that is integrally provided with a capacitor, a resonator, and the like inside the substrate has attracted attention. However, in order to integrally provide these, it is necessary to integrally fire the high dielectric constant material and the low dielectric constant material without any trouble. However, high dielectric constant materials and low dielectric constant materials are materials that differ greatly in various properties such as sintering shrinkage rate, firing shrinkage behavior, and thermal expansion coefficient, and defects such as cracks, delamination and warping are caused by integral firing. Arise.
On the other hand, the following patent documents 1 to 4 disclose a method of providing an intermediate layer for relaxing the difference in properties between the two materials between the high dielectric constant layer and the low dielectric constant layer. Further, Patent Document 5 below discloses a method of arranging high dielectric constant layers symmetrically in the thickness direction of the multilayer substrate.

JP 63-13318 A JP 7-312511 A JP-A-8-32242 JP-A-9-92978 JP-A-10-308584

  In the methods of Patent Documents 1 to 4, it is necessary to form an intermediate layer that is not originally necessary for the function expression of the electronic component. In addition, the number of processes and the cost for producing the intermediate layer are greatly increased. Furthermore, it becomes an obstacle to miniaturization. Further, in the method of arranging the high dielectric constant layers symmetrically in the thickness direction of the multilayer substrate as in Patent Document 5, the degree of freedom is reduced in circuit design.

  The present invention solves the above problems, and provides a multilayer ceramic component integrally including a high dielectric constant layer and a low dielectric constant layer without providing an intermediate layer and without providing a symmetrical arrangement, and a method for manufacturing the same. The purpose is to do.

  The inventors have found that, when integrally firing a low dielectric constant material and a high dielectric constant material, by using the same composition system for the glass used for each material, it is possible to greatly suppress problems associated with integral firing. The present invention has been completed. Furthermore, the present inventors have found a predetermined inorganic filler capable of realizing a low dielectric constant and a high dielectric constant when a predetermined glass is used, and exhibits high wettability to the same glass while exhibiting a completely different dielectric constant. The present invention was completed by finding various inorganic fillers that exhibit the properties and that can substantially match the firing behavior.

That is, the present invention is as follows.
(1) A laminate in which a low dielectric constant layer containing glass and an inorganic filler and having a relative dielectric constant of 10 or less and a high dielectric constant layer containing glass and an inorganic filler and having a relative dielectric constant of 30 or more are laminated. Part
A laminated ceramic component, wherein the glass constituting the low dielectric constant layer and the glass constituting the high dielectric constant layer are of the same composition system.
(2) The multilayer ceramic component according to (1), wherein the glass constituting the low dielectric constant layer is 35% by volume or less with respect to the entire low dielectric constant layer.
(3) The multilayer ceramic component according to (1) or (2), wherein the glass constituting the high dielectric constant layer is 45% by volume or less with respect to the entire high dielectric constant layer.
(4) Each of the glass constituting the low dielectric constant layer and the glass constituting the high dielectric constant layer contains at least each element of Ba, Zn, B and Si, When the total oxide equivalent amount of each element is 100% by mass, Ba is 25 to 55% by mass in terms of BaO, Zn is 5 to 30% by mass in terms of ZnO, and B is in terms of B ₂ O ₃ . The multilayer ceramic component according to any one of (1) to (3), containing 15 to 35% by mass and 5 to 30% by mass of Si in terms of SiO ₂ .
(5) The inorganic filler constituting the low dielectric constant layer is expressed by a composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%). The multilayer ceramic component according to any one of (1) to (4), wherein an alkaline earth metal element-containing filler that satisfies the following condition (1) and condition (2) is a main component.
Condition (1): M ¹ in the composition formula (1) is at least one of Mg and Zn.
Condition (2): x, y and z in the composition formula (1) have values corresponding to the case where the respective correlations are represented using a triangular diagram, such as side AB, side BC in FIG. Side CD and Side DA (Point A is x = 25, y = 0, z = 75, Point B is x = 5, y = 35, z = 60, Point C is x = 30, y = 40, z = 30 And the point D is x = 65, y = 0, z = 35.) However, the side AB, the side BC, the side CD, and the side DA are all included in the region. is there.
(6) The alkaline earth metal element-containing filler has a crystal phase of at least one of diopside, akermanite, merwinite, cristobalite, forsterite, wollastonite, monticerite, enstatite, quartz and tridymite. The multilayer ceramic component according to any one of (1) to (5) above.
(7) The inorganic filler constituting the high dielectric constant layer has a composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (wherein RE is a rare earth metal element, (a), (b), (c) and (d) represent a molar ratio, and (a + b + c + d = 1).) (1) to (6) having a rare earth metal element-containing filler that satisfies the following condition (3) as a main component. A multilayer ceramic component according to any one of the above.
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10.

(8) Containing at least each element of Ba, Zn, B and Si, and when the total oxide equivalent amount of each element is 100% by mass, the Ba is 25 to 55% by mass in terms of BaO, the Zn 5 to 30% by mass in terms of ZnO, 15 to 35% by mass in terms of B ₂ O ₃ , and 5 to 30% by mass of Si in terms of SiO ₂ , respectively,
Alkaline earth metal element content satisfying the following condition (1) and condition (2) when represented by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%) An unfired low dielectric constant sheet manufacturing process for forming an unfired low dielectric constant sheet by molding a mixture obtained by mixing an inorganic filler mainly composed of a filler,
The glass and the composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, a, b, c and d represent a molar ratio, a + b + c + d = 1)) A non-fired high dielectric constant sheet formed by molding a mixture obtained by mixing an inorganic filler mainly composed of a rare earth metal element-containing filler satisfying the following condition (3) Unfired high dielectric constant sheet manufacturing process to form,
An unsintered conductor layer forming step of forming an unsintered conductor layer containing Ag on the surface of the unsintered low dielectric constant sheet and / or the unsintered high dielectric constant sheet;
A laminating step for producing an unfired laminate by laminating the unfired low dielectric constant sheet and the unfired high dielectric constant sheet after the unfired conductor layer forming step; and
A method for producing a multilayer ceramic component comprising: a firing step of firing the unfired laminate at 800 to 1050 ° C.
Condition (1): M ¹ in the above composition formula is at least one of Mg and Zn.
Condition (2): x, y, and z in the above composition formula are values corresponding to the cases where the respective correlations are represented using a triangular diagram, such as side AB, side BC, side CD in FIG. Side DA (point A is x = 25, y = 0, z = 75, point B is x = 5, y = 35, z = 60, point C is x = 30, y = 40, z = 30 and point D Is in the region surrounded by x = 65, y = 0, z = 35) (however, side AB, side BC, side CD and side DA are all included in the region).
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10.
(9) When Ba contains at least each element of Ba, Zn, B, and Si, and the total oxide equivalent amount of each element is 100% by mass, the Ba is 25 to 55% by mass in terms of BaO, the Zn 5 to 30% by mass in terms of ZnO, 15 to 35% by mass in terms of B ₂ O ₃ , and 5 to 30% by mass of Si in terms of SiO ₂ , respectively,
Alkaline earth metal element content satisfying the following condition (1) and condition (2) when represented by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%) An unfired low dielectric constant sheet manufacturing process for forming an unfired low dielectric constant sheet by molding a mixture obtained by mixing an inorganic filler mainly composed of a filler,
The glass and the composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, a, b, c and d represent a molar ratio, a + b + c + d = 1)) A non-fired high dielectric constant sheet formed by molding a mixture obtained by mixing an inorganic filler mainly composed of a rare earth metal element-containing filler satisfying the following condition (3) Unfired high dielectric constant sheet manufacturing process to form,
The unfired low dielectric constant sheet and the unfired high dielectric constant sheet are laminated so that a predetermined position and a predetermined number of sheets are laminated, and an unfired conductor layer containing Ag is printed between the laminations. A laminating step for forming and producing a green laminate, and
A method for producing a multilayer ceramic component comprising: a firing step of firing the unfired laminate at 800 to 1050 ° C.
Condition (1): M ¹ in the above composition formula is at least one of Mg and Zn.
Condition (2): x, y, and z in the above composition formula are values corresponding to the cases where the respective correlations are represented using a triangular diagram, such as side AB, side BC, side CD in FIG. Side DA (point A is x = 25, y = 0, z = 75, point B is x = 5, y = 35, z = 60, point C is x = 30, y = 40, z = 30 and point D Is in the region surrounded by x = 65, y = 0, z = 35) (however, side AB, side BC, side CD and side DA are all included in the region).
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10.
(10) The alkaline earth metal element-containing filler is mixed with oxides, carbonates and / or hydroxides of the respective metal elements and calcined at 1000 to 1300 ° C. to obtain a calcined product, The method for producing a multilayer ceramic component according to the above (8) or (9), obtained by pulverizing a calcined product.
(11) The alkaline earth metal element-containing filler has a crystal phase of at least one of diopside, akermanite, merwinite, cristobalite, forsterite, wollastonite, monticerite, enstatite, quartz, and tridymite. The method for producing a multilayer ceramic component according to any one of (8) to (10) above.

According to the multilayer ceramic component of the present invention, a low dielectric constant layer and a high layer can be formed without providing an intermediate layer or the like and without symmetrical arrangement (need to be symmetric in either the multilayer arrangement or the planar arrangement). It can be set as the laminated ceramic component integrally provided with a dielectric constant layer. For this reason, a small electronic component can be obtained efficiently with fewer steps. In addition, while maintaining excellent dielectric properties and sinterability, the glass content can be reduced as compared with the conventional case, and an electronic component can be obtained at a low cost.
When the glass constituting the low dielectric constant layer is 35% by volume or less, the sinterability of the multilayer ceramic component is maintained while the amount of the glass used is small. Dielectric loss can be reduced.
When the glass constituting the high dielectric constant layer is 45 volume% or less, the sinterability of the multilayer ceramic component is maintained while the amount of glass used is small, and particularly the high dielectric constant layer The Q value can be increased.
When the glass constituting the low dielectric constant layer and the high dielectric constant layer is a predetermined glass, it is possible to reduce the amount of glass used, and to obtain a multilayer ceramic part free from delamination and cracking. Can do.
When the inorganic filler constituting the low dielectric constant layer is a predetermined inorganic filler, the compatibility with the predetermined glass is particularly good and excellent sinterability is exhibited.
When the alkaline earth metal element-containing filler has a predetermined crystal phase, the dielectric loss of the low dielectric constant layer can be particularly reduced.
When the inorganic filler constituting the high dielectric constant layer is a predetermined inorganic filler, the compatibility with the predetermined glass is particularly good and excellent sinterability is exhibited.

According to the manufacturing method of the present invention, a low dielectric constant layer and a high dielectric constant can be provided without providing an intermediate layer or the like, and without a symmetrical arrangement (need to be symmetrical in either a laminated arrangement or a planar arrangement). A monolithic ceramic part integrally including the rate layer can be obtained. For this reason, a small electronic component can be obtained efficiently with fewer steps. In addition, while maintaining excellent dielectric properties and sinterability, the glass content can be reduced as compared with the conventional case, and an electronic component can be obtained at a low cost (because glass is expensive).
According to another manufacturing method of the present invention, without providing an intermediate layer or the like, and without a symmetrical arrangement (it is not necessary to be symmetrical in either the laminated arrangement or the planar arrangement), the low dielectric constant layer and A multilayer ceramic component integrally provided with a high dielectric constant layer can be obtained. For this reason, a small electronic component can be obtained efficiently with fewer steps. In addition, while maintaining excellent dielectric properties and sinterability, the glass content can be reduced as compared with the conventional case, and an electronic component can be obtained at a low cost (because glass is expensive).
When the alkaline earth metal element-containing filler is obtained by pulverizing a calcined product obtained by calcining at 1000 to 1300 ° C., particularly excellent sinterability can be obtained.
When the alkaline earth metal element-containing filler has a predetermined crystal phase, the dielectric loss of the low dielectric constant layer can be particularly reduced.

The present invention will be described in detail below.
[1] Multilayer ceramic component The multilayer ceramic component of the present invention includes a low dielectric constant layer containing glass and an inorganic filler and having a relative dielectric constant of 10 or less, a glass and inorganic filler, and a relative dielectric constant of 30 or more. And a glass comprising the low dielectric constant layer and the glass constituting the high dielectric constant layer are of the same composition system. .

The “low dielectric constant layer” contains glass (hereinafter also simply referred to as “low dielectric constant layer-constituting glass”) and an inorganic filler (hereinafter also simply referred to as “low dielectric constant inorganic filler”), and has a relative dielectric constant of 10 The following layers.
The “glass” (low dielectric constant layer-constituting glass) is a glass having the same composition system as a glass constituting a high dielectric constant layer (hereinafter also simply referred to as “high dielectric constant layer constituting glass”). The composition of the low dielectric constant layer-constituting glass is not particularly limited as long as it has the same composition system as the high dielectric constant layer constituting glass. This “same composition system” means that the elements contained in the low dielectric constant layer-constituting glass are accumulated in order of increasing content (in oxide equivalent), the element species accumulated up to 70% by mass, and the high dielectric It means that the element species accumulated in the same manner for the rate layer constituting glass are the same. However, the element species accumulated up to more than 40% by mass are the same, there are two or more other element types that are commonly contained, and the content of each of these two or more common element species When the difference is within 2N mass% between both glasses (where N is the number of common element species), the same composition system is assumed. In addition, when the oxide conversion content of the element contained in one glass is the same in two or more types, both elements are included in the element type for judging the same composition system. The above oxide conversion is based on the most stable oxide in each element.

This low dielectric constant layer-constituting glass preferably contains at least each element of Ba, Zn, B, and Si. Furthermore, when the oxide conversion total amount of these elements is 100% by mass, Ba is 25 to 55% by mass in terms of BaO, Zn is 5 to 30% by mass in terms of ZnO, and B is in terms of B ₂ O _3. It is preferable to contain 15 to 35% by mass and Si in an amount of 5 to 30% by mass in terms of SiO ₂ . That is, the low dielectric constant layer-constituting glass has a composition formula (4) [kBaO · lZnO · mB ₂ O ₃ · nSiO ₂ ] {where k, l, m, and n represent the content ratio, and k + l + m + n = 100 (mass%) ). }, 25 ≦ k ≦ 55, 5 ≦ l ≦ 30, 15 ≦ m ≦ 35, and 5 ≦ n ≦ 30.

Said Ba is 25-55 mass% in conversion of BaO, Preferably it is 20-50 mass%, More preferably, it is 30-45 mass%. In this range, the sinterability is particularly excellent and the dielectric loss is small.
The Zn is 5 to 30% by mass in terms of ZnO, preferably 7 to 25% by mass, and more preferably 10 to 20% by mass. In this range, the sinterability is particularly excellent.
Part B _is 15 to 35 wt% in terms _of B 2 _{O 3,} preferably 17-33 wt%, more preferably 20 to 30 wt%. In this range, the sinterability is particularly excellent and the dielectric loss is small.
The Si is 5 to 30 mass% in terms of SiO _2, preferably from 7 to 25 wt%, more preferably 10 to 20 wt%. In this range, the sinterability is particularly excellent and the dielectric loss is small.

In the low dielectric constant layer-constituting glass, when the total low dielectric constant layer constituting glass is 100% by mass, the total content of Ba, Zn, B, and Si in terms of oxides is 50% by mass or more (more preferably 60% It is preferably at least 80% by mass, more preferably at least 80% by mass, particularly preferably at least 90% by mass and 100% by mass). In this range, a particularly dense sintered body can be obtained by low-temperature firing.
Furthermore, the low dielectric constant layer-constituting glass may contain other elements in addition to the above elements. Other elements include alkali metal elements (such as Li, Na, and K), alkaline earth metal elements other than Ba (such as Mg, Ca, and Sr), and other metal elements (such as Ti, Zr, Al, and Si). Can be mentioned. However, this low dielectric constant layer-constituting glass can contain Pb that improves the low-temperature sintering performance, but is preferably not included from the viewpoint of environmental protection.

  Moreover, it is preferable that the glass transition point of this low dielectric constant layer structure glass is 550 degrees C or less, More preferably, it is 500 degrees C or less (usually 350 degrees C or more). Within this range, the low temperature firing property is more excellent. The glass transition point can be measured by differential thermal analysis (DTA).

Further, the content of the low dielectric constant layer constituting glass in the low dielectric constant layer (volume ratio of the low dielectric constant layer constituting glass when the entire low dielectric constant layer is 100% by volume) is not particularly limited. 35 volume% is preferable, 5-25 volume% is more preferable, and 10-25 volume% is still more preferable. If it is this range, it can sinter at low temperature of 850-1050 degreeC, and also can make a dielectric loss small. That is, for example, the dielectric loss at 10 GHz is set to 5 × 10 ⁻⁴ to 50 × 10 ⁻⁴ (further 5 × 10 ^{−4 to} 33 × 10 ⁻⁴ , particularly 15 × 10 ^{−4 to} 33 × 10 ⁻⁴ ). be able to.

The “inorganic filler” (low dielectric constant inorganic filler) is not particularly limited as long as it is an inorganic filler capable of setting the relative dielectric constant of the entire low dielectric constant layer to 10 or less. As the low dielectric constant inorganic filler, CaO. (Mg, Zn) O.SiO ₂ ceramics {for example, (Ca, Sr, Ba) O.MgO.SiO ₂ ceramics, CaO.MgO. (Si, Sn, Ti , Zr) O ₂ ceramics, etc.}. Among these, CaO. (Mg, Zn) O.SiO ₂ ceramics is preferable. Only one type of low dielectric constant filler may be used, or two or more types may be used in combination.

Among the above-mentioned various low dielectric constant inorganic fillers, CaO. (Mg, Zn) O.SiO ₂ -based ceramics are preferable. Furthermore, the composition formula (1) [xCaO.yM ¹ O.zSiO ₂ ] = 100 mol%), an inorganic filler mainly composed of an alkaline earth metal element-containing filler that satisfies the following conditions (1) and (2) is preferable.

Condition (1): M ¹ in the composition formula (1) is at least one of Mg and Zn.
Condition (2): x, y and z in the composition formula (1) have values corresponding to the case where the respective correlations are represented using a triangular diagram, such as side AB, side BC in FIG. Side CD and Side DA (Point A is x = 25, y = 0, z = 75, Point B is x = 5, y = 35, z = 60, Point C is x = 30, y = 40, z = 30 And the point D is x = 65, y = 0, z = 35.) However, the side AB, the side BC, the side CD, and the side DA are all included in the region. is there.

X in the composition formula (1) represents a ratio of CaO when the total of CaO, M ¹ O, and SiO ₂ contained in the alkaline earth metal element-containing filler is 100 mol%. This x is 5 to 65 mol%, preferably 10 to 55 mol%, more preferably 10 to 45 mol%. In this range, the sinterability is particularly good.

  In addition, CaO in the composition formula (1) may be partially substituted by SrO and / or BaO, or may not be substituted. In the case of substitution, this substitution amount is usually 25 mol% or less of the total of SrO and BaO when the total of CaO, SrO and BaO is 100 mol%. Within this range, the alkaline earth metal element-containing filler can be dissolved in the crystal, increasing the amount of crystal and keeping the dielectric loss small. Among these, when only SrO is contained, when the total of CaO and SrO is 100 mol%, SrO is preferably more than 0 mol% and 25 mol% or less, more than 0 mol% and more than 20 mol% % Or less is preferable. Furthermore, when only BaO is contained, when the total of CaO and BaO is 100 mol%, BaO is preferably more than 0 mol% and not more than 25 mol%, more than 0 mol% and not more than 15 mol%. Is preferred.

Furthermore, y in the composition formula (1) represents a ratio of M ¹ O when the total of CaO, M ¹ O, and SiO ₂ contained in the alkaline earth metal element-containing filler is 100 mol%. . This y is 0-40 mol%, 5-35 mol% is preferable and 10-35 mol% is more preferable. In this range, the sinterability is particularly good.
M ¹ in the composition formula (1) is at least one of Mg and Zn. That is, the alkaline earth metal element-containing filler may contain only MgO, may contain only ZnO, or may contain both MgO and ZnO. Among these, only MgO or MgO and ZnO are preferable, and only MgO is more preferable.

Further, z in the composition formula (1) represents the proportion of SiO ₂ in the case where the total of CaO and ^{M 1} O and SiO ₂ contained in the alkaline earth metal element-containing filler is 100 mol%. This z is 30 to 75 mol%, preferably 35 to 70 mol%, more preferably 35 to 65 mol%. In this range, the sinterability is particularly good.

SiO ₂ in the composition formula (1) may be substituted with at least one of SnO ₂ , TiO _2, and ZrO ₂ , or may not be substituted. In the case of substitution, when the total of SiO ₂ , SnO ₂ , TiO ₂ and ZrO ₂ is 100 mol%, the total of SnO ₂ , TiO ₂ and ZrO ₂ is 10 mol% or less. Within this range, the dielectric loss can be kept sufficiently low.

  Furthermore, this alkaline earth metal element-containing filler may or may not contain other metal elements in addition to the above elements. When other metal elements are contained, examples of the metal elements include Al, Fe, Ti, Mn, and Co. These may contain only 1 type and may contain 2 or more types.

Further, the alkaline earth metal element-containing filler is usually present dispersed in the matrix of the glass. The alkaline earth metal element-containing filler itself usually has a crystalline phase and an amorphous phase. Among these, as the crystal phase, diopside {(Diopside), composition example CaMg [Si ₂ O ₆ ]}, akermanite {(Akermanite), composition example Ca ₂ MgSi ₂ O ₇ }, merwinite {(Merwinite), composition example Ca ₃ Mg (SiO ₄ ) ₂ }}, cristobalite {(Cristobalite), composition example SiO ₂ }, forsterite {(Forsterite), composition example (Mg ₂ [SiO ₄ ])}, wollastonite {(Wollastonite), Composition Example (Ca ₃ [Si ₃ O ₉ ])}, Monticellite {(Monticellite), Composition Example (CaMgSiO ₄ )}, Enstatite {(enstatite), Composition Example (MgSiO ₃ )}, Quartz {(Quartz), Composition example Si _2} and tridymite {(Trydimite), preferably it has at least one of composition example SiO _2}. Among these, at least one of diopside, wollastonite, akermanite, forsterite, enstatite and merwinite is preferable, and among diopside, wollastonite, akermanite, forsterite and enstatite At least one is more preferable.
Further, these crystal phases are preferably main crystal phases. That is, for example, these crystal phases have a total of 50% by mass or more (more preferably 60% by mass or more and may be 100% by mass) when the entire alkaline earth metal element-containing filler is 100% by mass. It is preferable to contain. In this range, the low temperature sinterability is particularly excellent.

Moreover, it is preferable that each of these crystal phases is a crystal phase deposited in the alkaline earth metal element-containing filler obtained in advance. That is, the low dielectric constant layer can be obtained by mixing a low dielectric constant inorganic filler mainly containing an alkaline earth metal element-containing filler obtained in advance with the low dielectric constant layer-constituting glass and firing. That is, it is not necessary to precipitate a predetermined crystal phase while finely controlling the temperature of the firing process from CaO.M ¹ O.SiO ₂ glass, and the cost of the low dielectric constant inorganic filler itself can be greatly suppressed.

In addition, the low dielectric constant layer can contain a low dielectric constant inorganic filler containing the alkaline earth metal element-containing filler as a main component, so that the dielectric loss can be suppressed even when the glass content is small. Furthermore, since the excellent dielectric properties can be exhibited while suppressing the content of the low dielectric constant layer-constituting glass to a low level, an excellent multilayer ceramic component can be obtained at a low cost.
When x is 15 to 65 mol%, y is 0 to 35 mol%, and z is 35 to 75 mol%, the relative dielectric constant at 10 GHz is 5 to 10. In particular, a low dielectric constant layer having a small dielectric loss (that is, for example, 5 × 10 ⁻⁴ to 50 × 10 ⁻⁴ ) can be obtained. That is, as shown in FIG. 2, side AE, side EF, side FD and side DA (point E is x = 15, y = 35, z = 50, point F is x = 35, y = 30, z = 35 This is a case where the x, y, and z are included in the region surrounded by (the side AE, the side EF, the side FD, and the side DA are all included in the region).

  The alkaline earth metal element-containing filler is a main component contained in the low dielectric constant inorganic filler. The content of the alkaline earth metal element-containing filler in the low dielectric constant inorganic filler is not particularly limited, but usually exceeds 50 mass% when the entire low dielectric constant inorganic filler is 100 mass%. The content is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, all the low dielectric constant inorganic fillers may be alkaline earth metal element-containing fillers (that is, the alkaline earth metal element-containing filler is 100% by mass). If the alkaline earth metal element-containing filler is 50% by mass or less, the low-temperature sinterability tends to decrease.

  Furthermore, in the low dielectric constant layer, as the low dielectric constant inorganic filler, in addition to the alkaline earth metal element-containing filler, other low dielectric constant inorganic fillers may be contained, and other low dielectric constant inorganic fillers may be contained. You don't have to. Examples of other low dielectric constant inorganic fillers include alumina fillers made of alumina, various fillers made of calcium titanate, mullite, cordierite, talc, and the like. These may use only 1 type and may use 2 or more types together. Among these, an alumina filler is preferable. These other low dielectric constant inorganic fillers can be contained in a range mainly composed of the alkaline earth metal element-containing filler (that is, 50% by mass or less of the entire low dielectric constant inorganic filler).

In this low dielectric constant layer, the relative dielectric constant at 10 GHz by the parallel conductor plate type dielectric resonator method according to JIS R1641 can be made 15 or less. Furthermore, the relative dielectric constant can be 12 or less, and particularly 10 or less. However, the relative dielectric constant is usually 5 or more. Further, the dielectric loss at 10 GHz according to the same method can be set to 100 × 10 ⁻⁴ or less (usually 5 × 10 ⁻⁴ or more). Furthermore, the dielectric loss can be 50 × 10 ⁻⁴ or less (usually 5 × 10 ⁻⁴ or more), 45 × 10 ⁻⁴ or less, particularly 40 × 10 ⁻⁴ or less. In particular, it can be 35 × 10 ⁻⁴ or less.

The “high dielectric constant layer” is a layer containing a high dielectric constant layer-constituting glass and an inorganic filler (hereinafter also simply referred to as “high dielectric constant inorganic filler”) and having a relative dielectric constant of 30 or more.
As the “glass” (high dielectric constant layer-constituting glass), the low dielectric constant layer constituting glass can be applied as it is. However, both glasses may be completely the same glass or different glasses within the same composition system.

The content of the high dielectric constant layer constituting glass in the high dielectric constant layer (volume ratio of the high dielectric constant layer constituting glass when the entire high dielectric constant layer is 100% by volume) is not particularly limited, but is 5 to 45 volumes. % Is preferable, 5-35 volume% is more preferable, and 10-30 volume% is still more preferable. If it is this range, it can sinter at low temperature of 850-1050 degreeC, and also can obtain especially high Q value.
Further, by adjusting the content of the high dielectric constant layer-constituting glass within the above range, the dielectric properties of the high dielectric constant layer, particularly ε _r and τ _f can be adjusted. epsilon _r can be increased with a decrease in the content of the high dielectric constant layer construction glass can be reduced with increasing content of the high dielectric constant layer construction glass. The absolute value of tau _f can greatly with the decrease of the content of the high dielectric constant layer construction glass can be reduced with increasing content of the high dielectric constant layer construction glass.

  The difference between the content of the low dielectric constant layer-constituting glass in the low dielectric constant layer and the content of the high dielectric constant layer-constituting glass in the high dielectric constant layer is 15% by volume or less (more preferably 0 ˜12% by volume, more preferably 0˜10% by volume). If it is this range, it can bake, without generating the big level | step difference by the difference in the allocation between different materials.

The “inorganic filler” (high dielectric constant inorganic filler) is not particularly limited as long as it is an inorganic filler capable of setting the relative dielectric constant of the entire high dielectric constant layer to 30 or more. Examples of the high dielectric constant inorganic filler include BaO · TiO ₂ · REO _3/2 · BiO _3/2 ceramics, barium titanate ceramics, and strontium titanate ceramics. Among these, BaO · TiO ₂ · REO _3/2 · BiO _3/2 ceramics are preferable. This is because when this ceramic is used, it is difficult to cause a problem due to firing. These high dielectric constant inorganic fillers may be used alone or in combination of two or more. _Further, BaO · rare earth element RE contained in the _{TiO 2 ·} REO _{3/2 · BiO} 3/2 ceramics is not particularly limited, for example, Nd, Sm, Gd, La, be used Ce and Pr, etc. it can. Among these, Nd, Sm and Gd are preferable. This is because the absolute value of τ _f can be brought close to 0 while maintaining a high ε _r and Q value. These REs may be used alone or in combination of two or more.

Among these BaO · TiO ₂ · REO _3/2 · BiO ₃ / _2- based ceramics, the high dielectric constant inorganic filler has a composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] ( However, RE is a rare earth metal element, and a, b, c, and d represent molar ratios, and a + b + c + d = 1)), each of a to d is 0.09 ≦ a ≦ 0. More preferably, the main component is a rare earth metal element-containing filler that satisfies 16, 0.54 ≦ b ≦ 0.62, 0.20 ≦ c ≦ 0.34, and 0 ≦ d ≦ 0.10.

Further, the a in the composition formula (3) is preferably 0.10 ≦ a ≦ 0.15, and more preferably 0.11 ≦ a ≦ 0.15. In this range sinterability is good, the absolute value of tau _f is particularly small. The b is preferably 0.55 ≦ b ≦ 0.61 and more preferably 0.56 ≦ b ≦ 0.59. Q values of the high dielectric constant layer This range is particularly large, the absolute value of tau _f is particularly small. Furthermore, c is preferably 0.24 ≦ c ≦ 0.33, and more preferably 0.24 ≦ c ≦ 0.32. Within this range, the sinterability is good and the Q value is particularly large. The d is preferably 0.02 ≦ d ≦ 0.08, and more preferably 0.04 ≦ d ≦ 0.07. In this range, _εr is particularly large.

In this high dielectric constant layer, ε _{r at} a measurement frequency of 1 to 5 GHz by the parallel conductor plate type dielectric resonator method can be 30 or more, particularly 40 or more, and further 50 to 70. Similarly, the measured Q value, resonance frequency f, and product f · Q can be set to 1500 GHz or more, further 2000 GHz or more, and particularly 2500 GHz or more. Furthermore, the absolute value of τ _f (temperature range; 25 to 80 ° C.) measured in the same manner can be 40 ppm / ° C. or less, further 30 ppm / ° C. or less, and particularly 20 ppm / ° C. or less.

Further, in the present multilayer ceramic component, the lamination of the low dielectric constant layer and the high dielectric constant layer may be a lamination in which both layers are in direct contact or may be a lamination through other layers. Usually, they are laminated in direct contact. However, the ratio of the area in direct contact is not particularly limited. For example, the main surface area of both layers facing each other (the main surface of the low dielectric constant layer and the main surface of the high dielectric constant layer) has a smaller main surface area. In this layer, the contact area with other layers (low dielectric constant layer or high dielectric constant layer) is 5% or more (preferably 25% or more, or 100% may be sufficient) with respect to the total area of the main surface. When an intervening layer is provided between the low dielectric constant layer and the high dielectric constant layer, the intervening layer is usually a layer having a thickness of 30 μm or less. Examples of the intervening layer include a conductor layer and other ceramic layers (a low dielectric constant layer that is not of the same composition system, a high dielectric constant layer that is not of the same composition system, and the like).
The “laminated portion” is a portion that includes at least a low dielectric constant layer and a high dielectric constant layer and is laminated adjacently. This multilayer part may be a part of the multilayer ceramic component or the entire multilayer ceramic component.

  The multilayer ceramic component of the present invention can include other portions besides the low dielectric constant layer and the high dielectric constant layer. As another part, a conductor layer is mentioned. The conductor layer can be disposed on the surface of the low dielectric constant layer and / or the surface of the high dielectric constant layer. The conductor metal constituting the conductor layer is not particularly limited, and a metal that can exhibit conductivity in the field of electronic components, an alloy thereof, and the like can be used. Examples of such conductive metals include Ag, Cu, Au, and the like, and alloys thereof. That is, for example, as the conductor layer, a conductor layer containing 80% by mass or more (more preferably 90% by mass or 100% by mass) of Ag when the entire conductor layer is 100% by mass can be used. .

  The “multilayer ceramic component” of the present invention includes a multilayer ceramic component integrally including a capacitor and / or resonator and an inductor, a multilayer ceramic component integrally including a capacitor and / or resonator, an inductor and a balun, and ceramic. Examples thereof include a multilayer ceramic component integrally provided with a capacitor in a substrate, a multilayer ceramic component integrally provided with a resonator in a ceramic substrate, and the like. Capacitors and resonators require high dielectric constant materials for miniaturization. In contrast, inductors and the like require a low dielectric constant material in order to reduce stray capacitance and adjust characteristic impedance. Therefore, in order to provide them integrally, it is necessary to use two or more kinds of dielectric materials having different dielectric characteristics in the multilayer ceramic component.

A specific example of the multilayer ceramic component of the present invention will be described with reference to FIG.
FIG. 3 is an exploded perspective view showing an example of the multilayer ceramic component (100) of the present invention. The multilayer ceramic component (100) is a filter that integrally has a balun function. That is, the lower balun part (B1) composed of three low dielectric constant layers (fired and integrated) laminated through various conductors, and the four layers of high dielectrics laminated through various conductors An upper balun consisting of a filter part (F) consisting of a dielectric layer (fired and integrated) and four low dielectric constant layers (fired and integrated) laminated via various conductors Part (B2). Each of these parts is laminated and molded in an unfired stage and then fired integrally.

  The lower balun portion (B1) includes a low dielectric constant layer (11) including an external connection conductor (111, not shown) and a ground conductor (112), and a low dielectric constant including a resonator conductor (121). A layer (12) and a low dielectric constant layer (13) including a resonator conductor (131) are laminated.

  Further, the filter section (F) includes a high dielectric constant layer (14) including a grounding conductor (141), a high dielectric constant layer (15) including a capacitor conductor (151 and 152), and a resonator inductance combined conductor. A high dielectric constant layer (16) including (161 and 163) and a resonator conductor (162) and a high dielectric constant layer (17) including a grounding conductor (171) are laminated.

  The upper balun part (B2) includes a low dielectric constant layer (18) including a connection conductor (181) for connecting the resonator inductance electrode (163) and the resonator conductor (191), and the resonator A low dielectric constant layer (19) including a conductor (191), a low dielectric constant layer (20) including a resonator conductor (201), and a low dielectric constant layer (21) including a grounding conductor (211) are stacked. Being done.

  In addition, the dotted line shown in FIG. 3 shows the electrical connection between each conductor. That is, the grounding conductor (112) and the resonator conductor (121) of the lower balun part (B1), the grounding conductor (211) and the resonator conductor (201) of the upper balun part (B2), and the upper balun. The connection conductor (181) and the resonator conductor (191) of the portion (B2) are connected by a through-hole conductor (not shown). The resonator conductor (131) in the lower balun section (B1) and the resonator conductor (191) in the upper balun section (B2) and the resonator inductance combined conductor (163) in the filter section (F) and the upper balun. The connection conductor (181) of the part (B2) is connected to each other by external conductors (not shown) formed outside the multilayer ceramic component.

[2] Manufacturing method of multilayer ceramic component (1)
The production method of the present invention comprises an unfired low dielectric constant sheet production process, an unfired high dielectric constant sheet production process, an unfired conductor layer forming process, a lamination process, and a firing process.
The above-mentioned “unfired low dielectric constant sheet manufacturing process” is a process for forming a mixture obtained by mixing a glass having a predetermined composition and an inorganic filler containing an alkaline earth metal element-containing filler as a main component to form an unfired low dielectric sheet. This is a step of forming a dielectric sheet.

The above “glass” contains at least each element of Ba, Zn, B and Si, and when the total oxide equivalent amount of each element is 100 mass%, Ba is 25 to 55 mass% in terms of BaO, Zn Is 5 to 30% by mass in terms of ZnO, B is 15 to 35% by mass in terms of B ₂ O ₃ , and Si is 5 to 30% by mass in terms of SiO ₂ . For this glass, the same low dielectric constant layer-constituting glass in the multilayer ceramic component can be applied as it is.

  Moreover, the low dielectric constant layer-constituting glass to be used is usually in a powder form. The particle size and the like of the low dielectric constant layer-constituting glass powder are not particularly limited, but the center particle size is 0.1 to 3.0 μm (more preferably 0.1 to 2.0 μm, still more preferably 0.1 to 1). 0.5 μm). Within this range, the low temperature sintering property is more excellent.

The above “inorganic filler” represents the following condition (1) and condition (2) when represented by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%). It is an inorganic filler whose main component is a filler containing an alkaline earth metal element to be filled.
Condition (1): M ¹ in the above composition formula is at least one of Mg and Zn.
Condition (2): x, y, and z in the above composition formula are values corresponding to the cases where the respective correlations are represented using a triangular diagram, such as side AB, side BC, side CD in FIG. Side DA (point A is x = 25, y = 0, z = 75, point B is x = 5, y = 35, z = 60, point C is x = 30, y = 40, z = 30 and point D Is in the region surrounded by x = 65, y = 0, z = 35) (however, side AB, side BC, side CD and side DA are all included in the region).
About this inorganic filler, the same low dielectric constant inorganic filler in the said multilayer ceramic component can be applied as it is.

Among these inorganic fillers, the method for producing the alkaline earth metal element-containing filler is not particularly limited, but after calcining at 1000 to 1300 ° C. after mixing the oxide, carbonate and / or hydroxide of each metal element. It is preferable to obtain a calcined product and then pulverize the calcined product.
That is, each metal element is all the predetermined elements to be included in the inorganic filler, such as Ca, Mg, Zn, Si, Sr, Ba, Sn, Ti, Zr, Al, Fe, Ti, Mn, and Co. Of these, at least Ca and Si. Each element may be a compound other than an oxide, carbonate and hydroxide (for example, chloride), but usually an oxide, carbonate and / or hydroxide is used. When two or more oxides, carbonates and hydroxides of each element are present, only one of them may be used, or two or more may be used in combination. In addition, each compound may contain only one of the above elements or two or more.

The calcining means heating the mixture obtained by the above mixing at a calcining temperature of 1000 to 1300 ° C. The calcining temperature is preferably 1100 to 1300 ° C, particularly preferably 1150 to 1250 ° C. If the calcining temperature is less than 1000 ° C., it is difficult to sufficiently precipitate the alkaline earth metal element-containing filler, and if it exceeds 1300 ° C., the resulting calcined product tends to be pulverized. The calcining time is not particularly limited, but is usually 1 hour or longer (preferably 2 to 5 hours, usually 8 hours or shorter).
Furthermore, by this calcination, the alkaline earth metal element-containing filler is a crystal of at least one of diopside, akermanite, merwinite, cristobalite, forsterite, wollastonite, monticite, enstatite, quartz and tridymite. It may have a phase (particularly a main crystal phase). Among these, at least one of diopside, wollastonite, akermanite, forsterite, enstatite and merwinite is preferable, and among diopside, wollastonite, akermanite, forsterite and enstatite At least one is more preferable.

The alkaline earth metal element-containing filler may be obtained by any method. That is, for example, it can be obtained by precipitating an alkaline earth metal element-containing filler from the glass as a crystal phase while finely controlling the heating temperature of the glass containing the predetermined element. This method is very costly. On the other hand, the alkaline earth metal element-containing filler can be obtained very simply by the calcination, and a desired filler can be obtained at low cost. Further, the obtained alkaline earth metal element-containing filler is excellent in wettability with glass, in particular wettability with BaO.ZnO.B ₂ O ₃ .SiO ₂ glass, and even at a low glass amount, it has a low temperature. Can be sintered. Furthermore, the obtained alkaline earth metal element-containing filler can be fired without greatly changing the crystal phase of the main crystal phase even in the final firing with glass.

The “mixing” is a step of mixing glass and an inorganic filler. When this mixing is performed, the glass and the inorganic filler are usually in a powder form. Further, a binder, a solvent, a plasticizer, and / or other additives can be further mixed.
Examples of the binder include acrylic resin, polyvinyl butyral resin, cellulose derivative, polyamide, polypeptide, polyimide, polystyrene, and polyvinyl alcohol. A binder may use only 1 type and may use 2 or more types together. Examples of the solvent include aromatic solvents such as toluene and xylene, ketones such as methyl ethyl ketone and acetone, and alcohols such as ethanol, butanol, isopropanol, and butyl carbitol. Only 1 type may be used for a solvent and it may use 2 or more types together.
Furthermore, a plasticizer and various additives may be contained. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, diethyl phthalate, butyl benzyl phthalate, 2-ethylhexyl phthalate, dioctyl adipate, and 2-ethylhexyl adipate. Only one type of plasticizer may be used, or two or more types may be used in combination. Furthermore, examples of the additive include a colorant, a leveling agent, an antifoaming agent, and a dispersing agent. Only one type of additive may be used, or two or more types may be used in combination.

  The “molding” is to form a mixture containing glass and inorganic filler obtained by the above mixing into a sheet form. Although a shaping | molding method is not specifically limited, It can shape | mold by methods, such as a doctor blade method and a slip cast method. Thereafter, the sheet-like molded body can be further dried to remove the solvent.

The above-mentioned “unfired high dielectric constant sheet manufacturing process” is a method for forming an unfired high dielectric constant by molding a mixture obtained by mixing glass having a predetermined composition and an inorganic filler containing a rare earth metal element-containing filler as a main component. This is a step of forming a sheet.
As the “glass”, the glass used in the unfired low dielectric constant sheet production process can be applied as it is. However, as long as it is within the above glass range, the unfired low dielectric constant sheet constituting glass and the unfired high dielectric constant sheet constituting glass may be the same or different.

The “inorganic filler” has the composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, and a, b, c, and d have a molar ratio of And a rare earth metal element-containing filler that satisfies the following condition (3) when expressed as a + b + c + d = 1.
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10.
About this inorganic filler, the same high dielectric constant inorganic filler in the said multilayer ceramic component can be applied as it is.
For the “mixing” and the “molding”, the respective steps in the unfired low dielectric constant sheet manufacturing process can be applied as they are.

The “unfired conductor layer forming step” is a step of forming an unfired conductor layer containing Ag on the surface of the unfired low dielectric constant sheet and / or the unfired high dielectric constant sheet.
The method for forming the unfired conductor layer is not particularly limited. For example, an unfired conductor layer slurry containing Ag powder, a binder, a solvent, and the like is prepared, and the unfired conductor layer slurry is used as an unfired low dielectric constant sheet and / or Alternatively, it can be formed by screen printing on the surface of an unfired high dielectric constant sheet. Further, the unfired conductor layer may be only one of the front and back surfaces of the unfired low dielectric constant sheet, or may be both surfaces. Moreover, a part of each surface may be covered, and the whole may be covered. The same applies to the surface of the unfired high dielectric constant sheet.
Further, the unsintered conductor layer contains Ag. The content of Ag is not particularly limited, but Ag is 80% by mass or more (more preferably 90% by mass or 100% by mass) when the entire conductor layer after firing is 100% by mass. It is preferable that it is a thing. The green conductor layer may contain other metals in addition to Ag. Examples of other metals include Cu and Au. These may use only 1 type and may use 2 or more types together.

  The “lamination step” is a step of manufacturing an unfired laminated body by laminating an unfired low dielectric constant sheet and an unfired high dielectric constant sheet after the unfired conductor layer forming step. This lamination method is not particularly limited, and heating may be performed or may not be performed. Further, it may be pressurized or not pressurized. Among these, thermocompression bonding is preferable.

  The “firing step” is a step of firing the unfired laminate at 800 to 1050 ° C. The firing temperature is preferably 800 to 950 ° C, and more preferably 850 to 950 ° C. If it is less than 800 degreeC, it may become difficult to sinter a laminated ceramic component sufficiently densely. On the other hand, although it can be fired at a high temperature exceeding 1050 ° C., simultaneous firing with a low melting point conductor tends to be difficult. The firing atmosphere is not particularly limited, and an air atmosphere, an inert atmosphere, a reducing atmosphere, a wet atmosphere, or the like can be used.

  In this manufacturing method, other steps besides the unfired low dielectric constant sheet manufacturing step, the unfired high dielectric constant sheet manufacturing step, the unfired conductor layer forming step, the laminating step, and the firing step are performed. Can be provided. As another process, a degreasing process is mentioned, for example. That is, when a binder, a plasticizer, etc. are contained in an unbaked low low dielectric constant sheet and / or an unbaked high dielectric constant sheet, a degreasing process can be performed before a baking process. Although the heating temperature of a degreasing process is not specifically limited, For example, it can be 150-500 degreeC. Moreover, the heating atmosphere in a degreasing process is not specifically limited, The atmosphere similar to the said baking atmosphere can be used. In addition, this degreasing process may be performed continuously with a baking process, and may be performed by another process.

[3] Manufacturing method of multilayer ceramic component (2)
Another manufacturing method of the present invention includes an unsintered low dielectric constant sheet manufacturing process, an unsintered high dielectric sheet manufacturing process, a laminating process, and a firing process.
Each process in the manufacturing method can be applied as it is to the “unfired low dielectric constant sheet manufacturing process”, the “unfired high dielectric sheet manufacturing process”, and the “baking process”.
In the “laminating step”, an unsintered low dielectric constant sheet and an unsintered high dielectric constant sheet are laminated so that a predetermined position and a predetermined number of sheets are laminated, and an uncontaining Ag containing Ag is interposed between the laminated layers. In this process, a fired laminated body is manufactured by printing a fired conductor layer. The method for forming the unfired conductor layer in this step is not particularly limited, but the method in the unfired conductor layer forming step in the production method can be used as it is.

  This method is different in that the green conductor in the above method is formed in the lamination step. That is, in the above method, the unfired conductor layer is formed in advance on the surface of each unfired low dielectric constant sheet and unfired high dielectric constant sheet, and in the lamination step, the unfired low dielectric constant sheet on which the unfired conductor layer is formed. And an unfired high dielectric constant sheet are laminated together. On the other hand, this method is a method of forming an unfired conductor layer at a necessary site each time an unfired low dielectric constant sheet and an unfired high dielectric constant sheet are laminated in the laminating step.

Hereinafter, the present invention will be described specifically by way of examples.
[1] Multilayer ceramic component (1) Low dielectric constant layer-constituting glass and high dielectric constant layer-constituting glass Commercial glass powders G1 and G2 adjusted to the mass ratios shown in Table 1 were prepared.
G1 and G2 are glasses that are not of the same composition system in the present invention. That is, when the elements contained in G1 are integrated in the descending order of the oxide equivalent contents shown in Table 1, the element types integrated up to over 70% by mass are “Ba, B, Zn and Si”. It is. On the other hand, when G2 is accumulated in the same manner, the element species accumulated until it exceeds 70 mass% is “B, Zn, and Si”. Although the three elements “B, Zn, and Si” are common, G1 and G2 do not have the same composition system because “Ba” is not common. Table 1 also shows the glass transition temperature and the center particle size of each glass.

(2) Preparation of low dielectric constant inorganic filler Each commercially available CaCO ₃ powder (purity; 99% or more), MgO powder (purity; 99.6%) and SiO ₂ powder (purity; 99% or more) It measured so that each of the coefficient x, y, and z contained in Formula (1) might become the value shown in Table 2. Thereafter, each powder was wet-mixed using ethanol as a medium. Next, the obtained mixed powder was calcined at 1200 ° C. for 2 hours in an air atmosphere. Thereafter, a dispersant, a binder, and ethanol were added to the calcined product and pulverized using a ball mill to obtain four types of slurry-like low dielectric constant inorganic fillers.

(3) Production of unfired low dielectric constant sheet The glass prepared in (1) above and each low dielectric constant inorganic filler obtained in (2) above were mixed at a volume ratio shown in Table 2 to obtain Using the mixed slurry, unfired low dielectric constant sheets (Experimental Examples L1 to L4) having a thickness of 120 μm were prepared by a doctor blade method.

(4) Manufacture of test piece for single characteristic evaluation of low dielectric constant layer and characteristic evaluation The mixed slurry obtained in the above (3) is dried and granulated, and using a φ19 mm mold at 20 MPa It was formed into a cylindrical shape by uniaxial pressing. Subsequently, a CIP (cold isostatic pressing) process was performed at a pressure of 150 MPa, and the obtained molded body was fired at 880 to 940 ° C. for 2 hours in an air atmosphere to obtain porcelains (Experimental Examples L1 to L4). .
Both ends of the obtained cylindrical porcelain (L1 to L4) are polished, and each of the polished porcelains is subjected to a relative dielectric constant at a measurement frequency of 10 GHz by a parallel conductor plate type dielectric resonator method according to JIS R1641. The rate and dielectric loss were measured. The results are also shown in Table 1. X-ray diffraction measurement was performed on the polished surface of each porcelain to identify the main crystal phase. The crystal phases recognized as a result are also shown in Table 1.

(5) Preparation of high dielectric constant inorganic filler Commercially available BaCO ₃ powder (purity; 99.9%), TiO ₂ powder (purity; 99.9%), Nd ₂ O ₃ powder (purity; 99.9%) and Bi ₂ O ₃ powder (purity: 99.9%) is used as a raw material, blended so that each of the coefficients a, b, c and d included in the composition formula (3) has the values shown in Table 3, and a mixer After 20 to 30 minutes of dry mixing, the mixture was pulverized with a vibration mill. As cobblestones, alumina balls were used, and the grinding time was 4 hours. Thereafter, the obtained mixed powder was calcined at 1100 ° C. for 2 hours in an air atmosphere, and then the obtained calcined product was pulverized by a ball mill to obtain four types of high dielectric constant inorganic fillers.

(6) Production of unfired high dielectric constant sheet The glass prepared in the above (1) and each high dielectric constant inorganic filler obtained in the above (5) were mixed at a ratio shown in Table 3 and obtained. Using the mixed slurry, an unfired high dielectric constant sheet (Experimental Examples H1 to H4) having a thickness of 120 μm was prepared by a doctor blade method.

(7) Manufacture of test piece for single characteristic evaluation of high dielectric constant layer, and characteristic evaluation The mixed slurry obtained in the above (6) is dried and granulated, and the resulting granulated powder is pressed ( The molded article was molded into a cylindrical molded article having a diameter of 19 mm and a height of 8 mm by molding pressure (98 MPa), and then fired at a temperature of 930 to 1050 ° C. for 2 hours in an air atmosphere to give porcelain (Experimental Examples H1 to H4). Obtained.
Thereafter, both end surfaces of the obtained cylindrical porcelain (H1 to H4) are polished, and each polished porcelain is measured in accordance with JIS R1641 by a parallel conductor plate type dielectric resonator method, with a measurement frequency of 1 to 5 GHz. Ε _r , Q value and τ _f (temperature range; 25 to 80 ° C.) were measured. The results are also shown in Table 3. The Q value is represented by the product (f · Q) of the resonance frequency (f) at the time of measurement and the measured value of the Q value.

(8) Manufacture of multilayer ceramic component The unfired low dielectric constant sheet having a thickness of 120 μm obtained in (3) above is cut into a length of 150 mm and a width of 130 mm, and the unfired high dielectric constant sheet obtained in (6) above. Are cut into a length of 150 mm and a width of 130 mm, and each of the combinations shown in Table 4 is used. From the bottom, three layers of unfired low dielectric constant sheet—one unfired high dielectric constant sheet—one unfired low dielectric constant sheet 4 layers Thus, each of the 8 unfired sheets was laminated and thermocompression bonded to obtain an unfired laminate. Next, the obtained unfired laminated body was cut into a length of 2 mm and a width of 3 mm, and fired at 900 ° C. for 2 hours in an air atmosphere to obtain laminated ceramic parts P1 to P5.

(9) Evaluation of multilayer ceramic component The presence or absence of a crack was confirmed by the image which expanded each center grinding | polishing surface of the obtained multilayer ceramic components P1-P5 1000 times with the scanning electron microscope. As a result, the multilayer ceramic parts in which no crack was found were indicated with “◎” in the crack column of Table 4. On the other hand, the multilayer ceramic parts in which cracks were found are indicated by “x” in the crack column of Table 4.
Furthermore, the presence or absence of delamination was confirmed by an image obtained by enlarging the central polished surface of the multilayer ceramic parts P1 to P5 by 1000 times with a scanning electron microscope. As a result, the multilayer ceramic parts in which no delamination was found were indicated by “◎” in the delamination column of Table 4. In addition, for the laminated ceramic parts in which delamination was observed but the delamination was slightly less than 5 μm at the end and there was no problem in use, “Δ” was shown in the delamination column of Table 4. Further, for the multilayer ceramic parts in which delamination of 5 μm or more was found, “x” was shown in the delamination column of Table 4.

表４中の「＊」は本発明の範囲外であることを示す。

“*” In Table 4 indicates that it is outside the scope of the present invention.

(10) Effects of Examples From L1 to L4 in Table 2 above and H1 to H4 in Table 3 above, the unfired low dielectric constant sheet and the unfired high dielectric constant sheet are both intended dielectrics when fired alone. The properties and sinterability were shown.
On the other hand, from Table 4, both delamination and cracking were recognized in P5 in which the glass constituting the low dielectric constant layer and the high dielectric constant layer was different. On the other hand, in P1 to P4, since the glass used in the low dielectric constant layer and the high dielectric constant layer has the same composition system, there is no occurrence of cracks. However, in P4, the difference between the glass content of the low dielectric constant layer and the glass content of the high dielectric constant layer (glass content difference) is as large as 16% by volume, so that delamination does not become a problem in use. Slightly observed at the end. On the other hand, in P1 to P3, this glass content difference was as small as 3 to 4% by volume, and a very good laminated state was obtained.

  The present invention is widely used in the field of electronic components. In particular, it is suitable as various electronic components used in the microwave band and the millimeter wave band. The various electronic components include a multilayer ceramic component integrally including a capacitor and / or a resonator and an inductor, a multilayer ceramic component integrally including a capacitor and / or a resonator, an inductor and a balun, and a capacitor in a ceramic substrate. Monolithic ceramic parts integrally comprising a ceramic substrate, monolithic ceramic parts integrally comprising a resonator in a ceramic substrate, various balanced output filters, balanced output LC filters, balanced output dielectric filters, balanced output SAW filters, etc. Can be mentioned. Furthermore, individual components such as a duplexer, a resonator, an LC device, a coupler, a diplexer, a diode, a dielectric antenna, and a ceramic capacitor can be mentioned. Furthermore, it includes at least one of a general-purpose board, a board such as a functional board in which various functional parts are embedded (LTCC multilayer device, etc.), a package such as MPU and SAW, and these individual parts, boards, and packages. Examples include modules. In addition, these electronic components include mobile communication devices, mobile communication base station devices, satellite communication devices, satellite communication base station devices, satellite broadcast devices that use various microwave band and / or millimeter wave band radio waves, It can be used for a wireless LAN device, a Bluetooth (registered trademark) device, and the like.

It is a triangular figure which shows the correlation of the coefficient x, y, and z regarding an alkaline-earth metal element containing filler. It is a triangular figure which shows the preferable range of the correlation of the coefficient x, y, and z regarding an alkaline-earth metal element containing filler. The dotted line range represents the same range as in FIG. 1 is a schematic exploded perspective view showing an example of a multilayer ceramic component of the present invention.

Explanation of symbols

100; multilayer ceramic parts,
B1; lower balun part,
B2; upper balun part,
F; filter part,
11, 12, 13, 18, 19, 20, 21; low dielectric constant layer,
14, 15, 16, 17; high dielectric constant layer,
112, 141, 171, 211; conductor for grounding,
121, 131, 162, 191, 201; conductor for resonator,
151, 152; conductors for capacitors,
161, 163: resonator inductance combined conductor,
181: a conductor for connection.

Claims (11)

A laminated portion in which a low dielectric constant layer containing glass and an inorganic filler and having a relative dielectric constant of 10 or less and a high dielectric constant layer containing glass and an inorganic filler and having a relative dielectric constant of 30 or more are provided. ,
A laminated ceramic component, wherein the glass constituting the low dielectric constant layer and the glass constituting the high dielectric constant layer are of the same composition system.   The multilayer ceramic component according to claim 1, wherein the glass constituting the low dielectric constant layer is 35% by volume or less with respect to the entire low dielectric constant layer.   The multilayer ceramic component according to claim 1 or 2, wherein the glass constituting the high dielectric constant layer is 45% by volume or less with respect to the entire high dielectric constant layer. Each of the glass constituting the low dielectric constant layer and the glass constituting the high dielectric constant layer contains at least each element of Ba, Zn, B, and Si. When the oxide equivalent total amount is 100% by mass, the Ba is 25 to 55% by mass in terms of BaO, the Zn is 5 to 30% by mass in terms of ZnO, and the B is 15 to 35 in terms of B ₂ O _3. The multilayer ceramic component according to any one of claims 1 to 3, wherein the multilayer ceramic component contains 5% by mass and 5-30% by mass of Si in terms of SiO ₂ . When the inorganic filler constituting the low dielectric constant layer is expressed by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%), the following conditions ( The multilayer ceramic component according to any one of claims 1 to 4, comprising an alkaline earth metal element-containing filler satisfying 1) and condition (2) as a main component.
Condition (1): M ¹ in the composition formula (1) is at least one of Mg and Zn.
Condition (2): x, y and z in the composition formula (1) have values corresponding to the case where the respective correlations are represented using a triangular diagram, such as side AB, side BC in FIG. Side CD and Side DA (Point A is x = 25, y = 0, z = 75, Point B is x = 5, y = 35, z = 60, Point C is x = 30, y = 40, z = 30 And the point D is x = 65, y = 0, z = 35.) However, the side AB, the side BC, the side CD, and the side DA are all included in the region. is there.   2. The alkaline earth metal element-containing filler has a crystalline phase of at least one of diopside, akermanite, merwinite, cristobalite, forsterite, wollastonite, monticite, enstatite, quartz and tridymite. The multilayer ceramic component according to any one of 1 to 5. The inorganic filler constituting the high dielectric constant layer has a composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, a, b , C and d represent a molar ratio, and a + b + c + d = 1)), the rare earth metal element-containing filler satisfying the following condition (3) as a main component is represented by any one of claims 1 to 6. The laminated ceramic component described.
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10. When at least each element of Ba, Zn, B, and Si is contained, and the total amount in terms of oxide of each element is 100% by mass, the Ba is 25 to 55% by mass in terms of BaO, and the Zn is in terms of ZnO 5 to 30% by mass, B containing 15 to 35% by mass in terms of B ₂ O ₃ , and Si containing 5 to 30% by mass in terms of SiO ₂ , respectively,
Alkaline earth metal element content satisfying the following condition (1) and condition (2) when represented by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%) An unfired low dielectric constant sheet manufacturing process for forming an unfired low dielectric constant sheet by molding a mixture obtained by mixing an inorganic filler mainly composed of a filler,
The glass and the composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, a, b, c and d represent a molar ratio, a + b + c + d = 1)) A non-fired high dielectric constant sheet formed by molding a mixture obtained by mixing an inorganic filler mainly composed of a rare earth metal element-containing filler satisfying the following condition (3) Unfired high dielectric constant sheet manufacturing process to form,
An unsintered conductor layer forming step of forming an unsintered conductor layer containing Ag on the surface of the unsintered low dielectric constant sheet and / or the unsintered high dielectric constant sheet;
A laminating step for producing an unfired laminate by laminating the unfired low dielectric constant sheet and the unfired high dielectric constant sheet after the unfired conductor layer forming step; and
A method for producing a multilayer ceramic component comprising: a firing step of firing the unfired laminate at 800 to 1050 ° C.
Condition (1): M ¹ in the above composition formula is at least one of Mg and Zn.
Condition (2): x, y, and z in the above composition formula are values corresponding to the cases where the respective correlations are represented using a triangular diagram, such as side AB, side BC, side CD in FIG. Side DA (point A is x = 25, y = 0, z = 75, point B is x = 5, y = 35, z = 60, point C is x = 30, y = 40, z = 30 and point D Is in the region surrounded by x = 65, y = 0, z = 35) (however, side AB, side BC, side CD and side DA are all included in the region).
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10. When at least each element of Ba, Zn, B, and Si is contained, and the total amount in terms of oxide of each element is 100% by mass, the Ba is 25 to 55% by mass in terms of BaO, and the Zn is in terms of ZnO 5 to 30% by mass, B containing 15 to 35% by mass in terms of B ₂ O ₃ , and Si containing 5 to 30% by mass in terms of SiO ₂ , respectively,
Alkaline earth metal element content satisfying the following condition (1) and condition (2) when represented by the composition formula (1) [xCaO · yM ¹ O · zSiO ₂ ] (where x + y + z = 100 mol%) An unfired low dielectric constant sheet manufacturing process for forming an unfired low dielectric constant sheet by molding a mixture obtained by mixing an inorganic filler mainly composed of a filler,
The glass and the composition formula (3) [aBaO · bTiO ₂ · cREO _3/2 · dBiO _3/2 ] (where RE is a rare earth metal element, a, b, c and d represent a molar ratio, a + b + c + d = 1)) A non-fired high dielectric constant sheet formed by molding a mixture obtained by mixing an inorganic filler mainly composed of a rare earth metal element-containing filler satisfying the following condition (3) Unfired high dielectric constant sheet manufacturing process to form,
The unfired low dielectric constant sheet and the unfired high dielectric constant sheet are laminated so that a predetermined position and a predetermined number of sheets are laminated, and an unfired conductor layer containing Ag is printed between the laminations. A laminating step for forming and producing a green laminate, and
A method for producing a multilayer ceramic component comprising: a firing step of firing the unfired laminate at 800 to 1050 ° C.
Condition (1): M ¹ in the above composition formula is at least one of Mg and Zn.
Condition (2): x, y, and z in the above composition formula are values corresponding to the cases where the respective correlations are represented using a triangular diagram, such as side AB, side BC, side CD in FIG. Side DA (point A is x = 25, y = 0, z = 75, point B is x = 5, y = 35, z = 60, point C is x = 30, y = 40, z = 30 and point D Is in the region surrounded by x = 65, y = 0, z = 35) (however, side AB, side BC, side CD and side DA are all included in the region).
Condition (3): a in the composition formula (3) is 0.09 ≦ a ≦ 0.16, b is 0.54 ≦ b ≦ 0.62, and c is 0.20 ≦ c ≦ 0. 34, d satisfies 0 ≦ d ≦ 0.10.   The alkaline earth metal element-containing filler is mixed with oxides, carbonates and / or hydroxides of the above metal elements, and calcined at 1000 to 1300 ° C. to obtain a calcined product. The manufacturing method of the multilayer ceramic component of Claim 8 or 9 obtained by grind | pulverizing.   9. The alkaline earth metal element-containing filler has a crystal phase of at least one of diopside, akermanite, merwinite, cristobalite, forsterite, wollastonite, monticite, enstatite, quartz and tridymite. The manufacturing method of the multilayer ceramic component in any one of thru | or 10.

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