JP2022133146A - Powder material, paste material, and manufacturing method of ceramic electronic component - Google Patents

Abstract

To provide a powder material capable of maintaining a continuity rate of an internal electrode layer while suppressing occurrence of cracking, a paste material, and a manufacturing method of a ceramic electronic component.SOLUTION: A powder material contains a Ni powder, a S source and a Sn source. The quantity of oxygen (O) in the Ni powder is 2 mass% or more with respect to Ni, the quantity of S with respect to Ni is 0.2 mass% or more, and 0.042≤S/Sn weight ratio≤5.5 and 0.39≤O/Sn weight ratio≤40 are satisfied.SELECTED DRAWING: Figure 5

Description

The present invention relates to powder materials, paste materials, and methods of manufacturing ceramic electronic components.

Ceramic electronic components such as laminated ceramic capacitors are produced by printing a metal paste made of a metal material such as nickel (Ni) on a dielectric green sheet made mainly of dielectric materials such as barium titanate, laminating and crimping. , cutting, binder removal, firing, external electrode coating, and the like. In order to meet the market demand for small-sized and large-capacity ceramic electronic components, there is a demand for thinning and high lamination of internal electrode layers as well as thinning of dielectric layers.

JP 2007-258646 A JP 2014-5491 A

In order to reduce the thickness of the internal electrodes, it is required to minimize the physical size of the metal powder particles before firing (see, for example, Patent Document 1). However, when base metal fine particles such as Ni are used, the amount of surface oxidation increases as the diameter is reduced. In particular, when the surface oxide film is 2 mass % or more, the progress of binder removal due to surface oxygen cannot be ignored, and binder removal cracks frequently occur, which can be a problem.

It is known to add sulfur (S) to suppress the reduction of surface oxygen (see, for example, Patent Document 2). However, when the amount of added S increases, cracks occur because rapid contraction occurs when S desorbs. In addition, the combustion reaction of S increases the degree of reduction in the atmosphere, accelerates the grain growth of the common material and dielectric, and deteriorates the continuity of the internal electrodes.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a powder material, a paste material, and a method for manufacturing a ceramic electronic component that can maintain the continuity of internal electrode layers while suppressing the occurrence of cracks. With the goal.

A powder material according to the present invention includes a Ni powder containing Sn and an S source, the amount of oxygen (O) in the Ni powder is 2 mass% or more relative to Ni, and 0.042 ≤ S / Sn weight ratio ≤ 5.5 and 0.39 ≤ O/Sn weight ratio ≤ 40.

In the above powder material, the oxygen in the Ni powder may be oxygen in the surface oxide of the Ni powder.

In the powder material, the amount of S to Ni may be 0.2 mass % or more.

In the above powder material, the Ni powder may have an average particle size of 0.01 μm to 0.2 μm.

The paste material according to the present invention includes a Ni powder containing Sn and an S source, the amount of oxygen (O) in the Ni powder is 2 mass% or more relative to Ni, and 0.042 ≤ S / Sn weight ratio ≤ 5.5 and 0.39 ≤ O/Sn weight ratio ≤ 40.

In the above paste material, the oxygen in the Ni powder may be oxygen in the surface oxide of the Ni powder.

In the above paste material, the amount of S relative to Ni may be 0.2 mass % or more.

In the above paste material, the Ni powder may have an average particle size of 0.01 μm to 0.2 μm.

A method for manufacturing a ceramic electronic component according to the present invention comprises forming an internal electrode pattern containing Ni powder containing Sn and an S source on a dielectric green sheet containing ceramic material powder and an organic binder, thereby forming a laminate unit. , forming a laminate by laminating the lamination units, and firing the laminate, wherein the amount of oxygen (O) in the Ni powder is 2 mass relative to Ni % or more, 0.042≦S/Sn weight ratio≦5.5, and 0.39≦O/Sn weight ratio≦40.

In the method for manufacturing a ceramic electronic component, the oxygen in the Ni powder may be oxygen in a surface oxide of the Ni powder.

In the method for manufacturing a ceramic electronic component, the amount of S relative to Ni may be 0.2 mass % or more.

In the method for manufacturing a ceramic electronic component, the Ni powder may have an average particle size of 0.01 μm to 0.2 μm.

According to the present invention, it is possible to provide a powder material, a paste material, and a method of manufacturing a ceramic electronic component that can maintain the continuity of internal electrode layers while suppressing the occurrence of cracks.

1 is a partial cross-sectional perspective view of a laminated ceramic capacitor; FIG. FIG. 2 is a cross-sectional view taken along the line AA of FIG. 1; FIG. 2 is a cross-sectional view taken along line BB of FIG. 1; It is a figure which illustrates the flow of the manufacturing method of a laminated ceramic capacitor. (a) and (b) are figures which illustrate a lamination process.

Hereinafter, embodiments will be described with reference to the drawings.

(embodiment)
FIG. 1 is a partial cross-sectional perspective view of a laminated ceramic capacitor 100 according to an embodiment. FIG. 2 is a cross-sectional view taken along line AA of FIG. 3 is a cross-sectional view taken along line BB of FIG. 1. FIG. As illustrated in FIGS. 1 to 3, a multilayer ceramic capacitor 100 includes a multilayer chip 10 having a substantially rectangular parallelepiped shape, and external electrodes 20a and 20b provided on either of the two opposing end surfaces of the multilayer chip 10. . Of the four surfaces of the laminated chip 10 other than the two end surfaces, two surfaces other than the top surface and the bottom surface in the stacking direction are referred to as side surfaces. The external electrodes 20a and 20b extend on the upper surface, lower surface and two side surfaces of the laminated chip 10 in the lamination direction. However, the external electrodes 20a and 20b are separated from each other.

The laminated chip 10 has a structure in which dielectric layers 11 containing a ceramic material functioning as a dielectric and internal electrode layers 12 containing Ni (nickel) as a main component are alternately laminated. The edge of each internal electrode layer 12 is alternately exposed to the end face provided with the external electrode 20a of the laminated chip 10 and the end face provided with the external electrode 20b. Thereby, each internal electrode layer 12 is alternately connected to the external electrode 20a and the external electrode 20b. As a result, the multilayer ceramic capacitor 100 has a configuration in which a plurality of dielectric layers 11 are laminated with internal electrode layers 12 interposed therebetween. In the laminated body of the dielectric layers 11 and the internal electrode layers 12 , the internal electrode layer 12 is arranged as the outermost layer in the lamination direction, and the upper and lower surfaces of the laminated body are covered with the cover layer 13 . The cover layer 13 is mainly composed of a ceramic material. For example, the material of the cover layer 13 is the same as the main component of the dielectric layer 11 and the ceramic material.

The size of the multilayer ceramic capacitor 100 is, for example, length 0.25 mm, width 0.125 mm, and height 0.125 mm, or length 0.4 mm, width 0.2 mm, height 0.2 mm, or length 0.6 mm, 0.3 mm wide and 0.3 mm high; or 1.0 mm long, 0.5 mm wide and 0.5 mm high; or 3.2 mm long, 1.6 mm wide and 0.5 mm high. 1.6 mm in height, or 4.5 mm in length, 3.2 mm in width and 2.5 mm in height, but are not limited to these sizes.

The dielectric layer 11 is mainly composed of, for example, a ceramic material having a perovskite structure represented by the general formula _ABO3 . Note that the perovskite structure contains ABO _3-α deviating from the stoichiometric composition. For example, the ceramic materials include BaTiO ₃ (barium titanate), CaZrO ₃ (calcium zirconate), CaTiO ₃ (calcium titanate), SrTiO ₃ (strontium titanate), and Ba _1-xy forming a perovskite structure. Ca _x Sr _y Ti _1-z Zr _z O ₃ (0≦x≦1, 0≦y≦1, 0≦z≦1) and the like can be used. The thickness of each dielectric layer 11 is, for example, 0.05 μm or more and 5 μm or less, or 0.1 μm or more and 3 μm or less, or 0.2 μm or more and 1 μm or less.

As illustrated in FIG. 2, the area where the internal electrode layer 12 connected to the external electrode 20a and the internal electrode layer 12 connected to the external electrode 20b face each other is the area that produces the capacitance in the multilayer ceramic capacitor 100. . Therefore, a region that produces the electric capacitance is called a capacitance region 14 . That is, the capacitance region 14 is a region where adjacent internal electrode layers 12 connected to different external electrodes face each other.

A region in which the internal electrode layers 12 connected to the external electrode 20a face each other without interposing the internal electrode layers 12 connected to the external electrode 20b is called an end margin 15 . The end margin 15 is also a region where the internal electrode layers 12 connected to the external electrode 20b face each other without interposing the internal electrode layers 12 connected to the external electrode 20a. That is, the end margin 15 is a region where the internal electrode layers 12 connected to the same external electrode face each other without interposing the internal electrode layers 12 connected to different external electrodes. The end margin 15 is a region that does not produce capacitance.

As exemplified in FIG. 3 , in the laminated chip 10 , regions from two side surfaces of the laminated chip 10 to the internal electrode layers 12 are called side margins 16 . That is, the side margin 16 is a region provided so as to cover the end portions of the plurality of internal electrode layers 12 laminated in the laminated structure extending to the two side surfaces. The side margin 16 is also a region that does not generate capacitance.

The dielectric layer 11 is formed by firing a dielectric material containing ceramic material powder, an organic binder, and the like. The internal electrode layers 12 are formed by firing a powder material containing Ni powder and a paste material containing a common material. In order to make the internal electrode layers 12 thinner, it is required to minimize the physical size of the Ni powder particles for forming the internal electrode layers 12 . However, reducing the Ni powder size increases the surface area. As the surface area increases, the absolute amount of surface oxide film on the Ni powder increases. In the Ni powder, when the amount of oxygen (O) with respect to Ni is 2 mass% or more, the oxygen accelerates the oxidation of the binder of the dielectric material, thereby promoting binder removal and frequent occurrence of binder removal cracks, which poses a problem. obtain. Binder removal cracks are cracks caused by shrinkage caused by accelerated binder removal. The amount of oxygen to Ni is the weight ratio of oxygen when Ni+O is 100 mass %.

Therefore, it is known to add sulfur (S) to the paste material in order to suppress the reduction of the Ni powder. However, when the amount of S added to Ni increases, rapid contraction occurs when S desorbs, and cracks occur. In addition, the combustion reaction of S increases the degree of reduction in the atmosphere, accelerates grain growth of the common material and ceramic material powder, and may deteriorate the continuity of the internal electrode layers 12 .

Therefore, in the present embodiment, a powder material or a paste material that can maintain the continuity of the internal electrode layers 12 while suppressing the occurrence of cracks is used.

First, a method for manufacturing the multilayer ceramic capacitor 100 will be described. FIG. 4 is a diagram illustrating the flow of the manufacturing method of the multilayer ceramic capacitor 100. As shown in FIG.

(Raw material powder preparation process)
First, a dielectric material for forming the dielectric layer 11 is prepared. The A-site and B-site elements contained in the dielectric layer 11 are usually contained in the dielectric layer 11 in the form of sintered particles of _ABO3 . For example, BaTiO ₃ is a tetragonal compound with a perovskite structure and exhibits a high dielectric constant. This BaTiO ₃ can generally be obtained by reacting a titanium raw material such as titanium dioxide with a barium raw material such as barium carbonate to synthesize barium titanate. Various methods are conventionally known for synthesizing the main component ceramic of the dielectric layer 11, such as a solid phase method, a sol-gel method, and a hydrothermal method. Any of these can be employed in the present embodiment.

A predetermined additive compound is added to the obtained ceramic material powder according to the purpose. Additive compounds include magnesium (Mg), manganese (Mn), vanadium (V), chromium (Cr), rare earth elements (yttrium (Y), samarium (Sm), europium (Eu), gadolinium (Gd), terbium ( Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb)) oxides, or cobalt (Co), nickel (Ni), lithium (Li), boron (B), an oxide containing sodium (Na), potassium (K) or silicon (Si), or a glass containing cobalt, nickel, lithium, boron, sodium, potassium or silicon.

For example, a ceramic material powder is wet mixed with a compound containing an additive compound, dried and pulverized to prepare a ceramic material powder. For example, the ceramic material powder obtained as described above may be pulverized to adjust the particle size, or combined with a classification process to adjust the particle size. A dielectric material is obtained by the above steps.

(Lamination process)
Next, an organic binder such as polyvinyl butyral (PVB) resin, an organic solvent such as ethanol or toluene, and a plasticizer are added to the obtained dielectric material and wet-mixed. Using the obtained slurry, the dielectric green sheet 52 is coated on the substrate 51 by, for example, a die coater method or a doctor blade method, and dried. The base material 51 is, for example, a PET (polyethylene terephthalate) film.

Next, as illustrated in FIG. 5A, internal electrode patterns 53 are formed by printing a paste material for forming internal electrode layers 12 on dielectric green sheets 52 . In FIG. 5A, as an example, four layers of internal electrode patterns 53 are formed on a dielectric green sheet 52 at predetermined intervals. A dielectric green sheet 52 having an internal electrode pattern 53 formed thereon is used as a lamination unit. The paste material may contain ceramic particles as a common material. Although the main component of the ceramic particles is not particularly limited, it is preferably the same as the main component ceramic of the dielectric layer 11 . For example, BaTiO ₃ having an average particle size of 50 nm or less may be uniformly dispersed.

Next, while peeling the dielectric green sheet 52 from the substrate 51, lamination units are laminated as illustrated in FIG. 5(b). Next, a predetermined number (for example, 2 to 10 layers) of cover sheets are laminated on the upper and lower sides of the laminate obtained by laminating the lamination units, and are thermocompressed to obtain a chip having a predetermined chip size (for example, 1.0 mm×0.5 mm). 5 mm). In the example of FIG. 5(b), the cut is made along the dotted line. The cover sheet may have the same composition as the dielectric green sheet 52, or may have a different additive compound.

(Baking process)
After removing the binder from the ceramic laminate thus obtained in an N ₂ atmosphere, a metal paste that serves as a base layer for the external electrodes 20a and 20b is applied by a dipping method, and the oxygen partial pressure is 10 ⁻⁵ to 10 ⁻⁸ . Firing at 1100 to 1300° C. for 10 minutes to 2 hours in a reducing atmosphere of atm. Thus, the laminated ceramic capacitor 100 is obtained.

(Reoxidation treatment step)
After that, reoxidation treatment may be performed at 600° C. to 1000° C. in an N ₂ gas atmosphere.

(Plating process)
After that, metal coating such as Cu, Ni, and Sn may be applied to the external electrodes 20a and 20b by plating. Through the steps described above, the multilayer ceramic capacitor 100 can be manufactured.

(Composition of paste material)
In the present embodiment, the thickness of the internal electrode layers 12 is reduced in order to increase the lamination of the internal electrode layers 12 . For example, the thickness of each internal electrode layer 12 is 1 μm or less, 0.4 μm or less, and 0.2 μm or less. In order to make the internal electrode layers 12 thinner, a small-diameter Ni powder is used as the Ni powder contained in the paste material for forming the internal electrode layers 12 . For example, the Ni powder has an average particle size of 0.01 μm to 0.2 μm, 0.03 μm to 0.15 μm, or 0.05 μm to 0.11 μm.

An attempt to reduce the diameter of the Ni powder increases the surface area of the Ni powder. Along with this, the absolute amount of the surface oxide film of the Ni powder increases. In this embodiment, Ni powder with an oxygen content of 2 mass % or more is used. As a result, Ni powder having a sufficiently small particle size can be used, and the continuity rate of the internal electrode layers 12 after firing can be maintained at a high value.

The paste material contains an S source in order to suppress binder oxidation due to oxygen contained in the Ni powder. As a result, reduction of the Ni powder is suppressed, binder oxidation is suppressed, and crack generation can be suppressed.

Also, the Ni powder contains a Sn source. An Sn source may be separately added to the Ni fine particles, or Ni—Sn alloy powder may be used as the Ni powder. By adding Sn, a stable sulfide containing Sn is formed with respect to Ni sulfide, so that the combustion reaction of S is suppressed and the rapid shrinkage due to the rapid desorption of S is suppressed. In addition, an increase in the reduction degree of the atmosphere is suppressed, and grain growth of the ceramic material powder and common material is suppressed. Thereby, the continuity rate of the internal electrode layers 12 can be maintained at a high value.

If the amount of Sn in the paste material is too small relative to the amount of S, the combustion reaction of S may not be sufficiently suppressed. Therefore, in the present embodiment, an upper limit is set for the S/Sn weight ratio. Specifically, the S/Sn weight ratio is ≤5.5.

If the amount of Sn relative to the amount of O in the paste material is too small, the progress of binder removal due to surface oxygen cannot be ignored, and binder removal cracks may occur. Therefore, in the present embodiment, an upper limit is set for the O/Sn weight ratio. Specifically, the O/Sn weight ratio is ≤40.

If the amount of Sn in the paste material is too large, a liquid phase appears in the internal electrode layers 12 during the firing process, causing the internal electrode layers 12 to become spherical, which may deteriorate the continuity of the internal electrode layers 12 . Therefore, in the present embodiment, a lower limit is set for the S/Sn weight ratio. Specifically, 0.042≦S/Sn weight ratio. Furthermore, a lower limit is set for the O/Sn weight ratio. Specifically, 0.39≦O/Sn weight ratio.

The paste material is obtained by adding an additive to a powder material containing Ni powder. At the time of the powder material, the amount of oxygen (O) in the Ni powder is 2 mass% or more with respect to Ni, 0.042 ≤ S / Sn weight ratio ≤ 5.5, and 0.39 ≤ O / Sn weight ratio ≤ 40 conditions may be satisfied. In this case, the paste material after adding the additive to the powder material may also satisfy the above conditions. If the above conditions are not satisfied at the time of the powder material, the above conditions may be satisfied by adjusting the components of additives added to the powder material.

From the viewpoint of reducing the diameter of the Ni powder, the oxygen content in the Ni powder is preferably 2 mass% or more, more preferably 2.5 mass% or more.

If the amount of oxygen in the Ni powder is too large, the progress of binder removal due to surface oxygen cannot be ignored, and binder removal cracks may occur. Therefore, it is preferable to set an upper limit for the amount of oxygen in the Ni powder. For example, the oxygen content in the Ni powder is preferably 5.5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.

If the amount of S with respect to Ni is small, there is a possibility that binder oxidation cannot be sufficiently suppressed. Therefore, it is preferable to set a lower limit on the amount of S with respect to Ni. For example, the amount of S to Ni is preferably 0.2 mass % or more, more preferably 0.3 mass % or more. The amount of S with respect to Ni is the weight ratio of S when Ni+S is 100 mass %.

If the amount of S with respect to Ni is too large, the amount of desorption of S may increase. Therefore, it is preferable to set an upper limit for the amount of S with respect to Ni. For example, the S content relative to Ni is preferably 0.6 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.4 mass% or less.

From the viewpoint of sufficiently suppressing the combustion reaction of S, the S/Sn weight ratio is preferably 5.5 or less, more preferably 5 or less.

From the viewpoint of suppressing the occurrence of binder removal cracks, the O/Sn weight ratio is preferably 40 or less, more preferably 30 or less.

From the viewpoint of suppressing the appearance of the liquid phase in the internal electrode layers 12, the S/Sn weight ratio is preferably 0.042 or more, more preferably 0.08 or more. Also, the O/Sn weight ratio is preferably 0.39 or more, more preferably 0.6 or more.

From the viewpoint of suppressing the combustion reaction of S, the amount of Sn to Ni is preferably 0.065 mass % or more, more preferably 0.1 mass % or more. From the viewpoint of suppressing the appearance of the liquid phase in the internal electrode layers 12 during the firing process, the amount of Sn to Ni is preferably 11 mass % or less, more preferably 6 mass % or less.

According to the manufacturing method according to the present embodiment, since the paste material described above is used, it is possible to maintain the continuity of the internal electrode layers while suppressing the occurrence of cracks.

In addition, in each of the above-described embodiments, a laminated ceramic capacitor has been described as an example of a ceramic electronic component, but the present invention is not limited to this. For example, other electronic components such as varistors and thermistors may be used.

Hereinafter, multilayer ceramic capacitors according to the embodiments were produced and their characteristics were examined.

(Examples 1-20 and Comparative Examples 1-31)
Additives were added to the barium titanate powder, and the mixture was sufficiently wet-mixed and pulverized in a ball mill to obtain a dielectric material. A butyral-based organic binder and toluene and ethyl alcohol as solvents were added to the dielectric material, and a dielectric green sheet was coated on a PET substrate by a doctor blade method.

Next, an internal electrode pattern was formed on the dielectric green sheet by printing a conductive metal paste. Regarding the Ni powder contained in the conductive metal paste, the surface oxide film amount was adjusted according to the synthesis conditions. Moreover, the amount of S and the amount of Sn were also adjusted by adding an S-containing dispersant and a Sn-containing organometallic complex solution in the paste preparation stage. In Example 1, the surface oxygen content relative to Ni was 2.30 mass%, the S content relative to Ni was 0.41 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 4.0 mass%. 056 and the O/Sn weight ratio was 22.755. In Example 2, the surface oxygen content relative to Ni was 2.56 mass%, the S content relative to Ni was 0.34 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 3.0 mass%. 364 and the O/Sn weight ratio was 25.328. In Example 3, the surface oxygen content relative to Ni was 3.98 mass%, the S content relative to Ni was 0.25 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 2.0 mass%. 473 and the O/Sn weight ratio was 39.376. In Example 4, the surface oxygen content relative to Ni was 2.50 mass%, the S content relative to Ni was 0.55 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 5.5 mass%. 441 and the O/Sn weight ratio was 24.734. In Example 5, the surface oxygen content relative to Ni was 3.71 mass%, the S content relative to Ni was 0.47 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 4.0 mass%. 670 and the O/Sn weight ratio was 36.705. In Example 6, the surface oxygen content relative to Ni was 2.30 mass%, the S content relative to Ni was 0.41 mass%, the Sn content relative to Ni was 5.89 mass%, and the S/Sn weight ratio was 0.30 mass%. 070 and the O/Sn weight ratio was 0.391. In Example 7, the surface oxygen content relative to Ni was 2.56 mass%, the S content relative to Ni was 0.34 mass%, the Sn content relative to Ni was 5.89 mass%, and the S/Sn weight ratio was 0.56 mass%. 058 and the O/Sn weight ratio was 0.435. In Example 8, the surface oxygen content relative to Ni was 3.98 mass%, the S content relative to Ni was 0.25 mass%, the Sn content relative to Ni was 5.89 mass%, and the S/Sn weight ratio was 0.98 mass%. 042 and the O/Sn weight ratio was 0.676. In Example 9, the surface oxygen content relative to Ni was 2.50 mass%, the S content relative to Ni was 0.55 mass%, the Sn content relative to Ni was 5.89 mass%, and the S/Sn weight ratio was 0.5 mass%. 093 and the O/Sn weight ratio was 0.425. In Example 10, the surface oxygen content relative to Ni was 3.71 mass%, the S content relative to Ni was 0.47 mass%, the Sn content relative to Ni was 5.89 mass%, and the S/Sn weight ratio was 0.1 mass%. 080 and the O/Sn weight ratio was 0.630. In Example 11, the surface oxygen content relative to Ni was 2.50 mass%, the S content relative to Ni was 0.13 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 1.0 mass%. 286 and the O/Sn weight ratio was 24.734. In Example 12, the surface oxygen content relative to Ni was 3.00 mass%, the S content relative to Ni was 0.01 mass%, the Sn content relative to Ni was 0.10 mass%, and the S/Sn weight ratio was 0.01 mass%. 099 and the O/Sn weight ratio was 29.681. Comparative Examples 1 to 31 are shown in Table 1.

470 layers of dielectric green sheets on which internal electrode patterns were formed were laminated and fired in a reducing atmosphere. The shape of the laminated chip after firing was 1.0 mm×0.5 mm×0.5 mm. The thickness of the dielectric layer was 0.5 μm. The thickness of the internal electrode layer was 0.4 μm.

(analysis)
For each of Examples 1 to 12 and Comparative Examples 1 to 31, 200 samples were examined for cracks. For Examples 1 to 12 and Comparative Examples 1 to 31, when the crack generation frequency exceeds 1%, it is determined that the crack determination is rejected (x), and when the crack generation frequency is 1% or less, the crack determination is made. It was determined to be pass (0).

For each of Examples 1 to 12 and Comparative Examples 1 to 31, 200 samples were examined for continuity of internal electrode layers. For Examples 1 to 12 and Comparative Examples 1 to 31, the average continuity rate of the internal electrode layer was calculated by observing the cross-sectional polished surface near the center of the chip with a SEM (scanning electron microscope) (magnification: 2000, average of 4 fields). If the average continuity rate is less than 70%, the continuity rate determination is determined to be unsatisfactory (x). When the average continuity rate was 80% or more, the continuity rate determination was judged to be pass (◯).

In Comparative Examples 1 to 3, the continuous rate judgment was judged to be unacceptable (x). It is considered that this is because the Ni powder with a small surface area (large average particle size) was used so that the amount of oxygen in the Ni powder was less than 2 mass % with respect to Ni.

In Comparative Examples 4 to 6, the continuous rate judgment was judged to be pass (◯). It is considered that this is because the Ni powder with a large surface area (small average particle size) was used so that the amount of oxygen in the Ni powder was 2 mass % or more with respect to Ni. However, the crack determination was determined to be unacceptable (x). It is considered that this is because the amount of oxygen increased and the binder removal was promoted, resulting in binder removal cracks.

Also in Comparative Examples 7 to 11, the crack judgment was judged to be unacceptable (x). This is because although the amount of S to Ni is 0.2 mass% or more, since Sn was not added, the combustion reaction of S was not suppressed, and rapid shrinkage occurred due to rapid desorption of S. Conceivable.

Also in Comparative Examples 12 to 15, the crack judgment was judged to be unacceptable (x). This is because although the amount of S relative to Ni is 0.2 mass% or more, the amount of Sn added is small, so the S/Sn weight ratio does not become ≤ 5.5, the combustion reaction of S is not suppressed, and the rapid addition of S This is thought to be due to the sudden contraction caused by the desorption.

Also in Comparative Examples 16 to 20, the crack judgment was judged to be unacceptable (x). This is because although the amount of S with respect to Ni is 0.2 mass% or more, the amount of Sn added is small, so the O/Sn weight ratio does not become ≤ 40, and the progress of binder removal due to surface oxygen cannot be ignored, and binder removal cracks occur. This is thought to be due to the occurrence of

In Comparative Examples 21 to 24, the crack determination was determined as pass (◯). It is considered that this is because the combustion reaction of S was suppressed due to the increased amount of Sn added. However, the continuous rate determination was determined to be unacceptable (x). This is because the amount of Sn added was too large, the weight ratio of 0.042≦S/Sn was not satisfied, and the weight ratio of 0.39≦O/Sn was not obtained, and a liquid phase appeared during the firing process of the internal electrode layers 12. It is thought that it is from

Also in Comparative Example 25, the continuous rate determination was determined to be unacceptable (x). This is probably because the amount of Sn added was too large and the weight ratio of 0.39≦O/Sn was not satisfied, and a liquid phase appeared during the firing process of the internal electrode layers 12 .

Also in Comparative Examples 26 and 27, the continuous rate determination was determined to be unacceptable (x). This is because the amount of Sn added was too large, the weight ratio of 0.042≦S/Sn was not satisfied, and the weight ratio of 0.39≦O/Sn was not obtained, and a liquid phase appeared during the firing process of the internal electrode layers 12. It is thought that it is from

Also in Comparative Examples 28 to 31, the continuous rate judgment was judged to be unacceptable (x). It is considered that this is because the amount of Sn added was too large and the weight ratio of 0.042≦S/Sn was not satisfied.

On the other hand, in none of Examples 1 to 12, the crack determination and the continuity rate determination were not judged to be unsatisfactory (x). This is because, in the paste material, the oxygen content of the Ni powder is 2 mass% or more with respect to Ni, 0.042 ≤ S / Sn weight ratio ≤ 5.5, and 0.39 ≤ O / Sn weight ratio ≤ 40 This is thought to be because

Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and variations can be made within the scope of the gist of the present invention described in the scope of claims. Change is possible.

REFERENCE SIGNS LIST 10 laminated chip 11 dielectric layer 12 internal electrode layer 13 cover layer 14 capacitance region 15 end margin 16 side margin 20a, 20b external electrode 51 substrate 52 dielectric green sheet 53 internal electrode pattern 100 laminated ceramic capacitor

Claims (12)

Ni powder containing Sn;
an S source;
The amount of oxygen (O) in the Ni powder is 2 mass% or more with respect to Ni,
0.042≦S/Sn weight ratio≦5.5,
A powder material characterized in that 0.39≦O/Sn weight ratio≦40. 2. The powder material according to claim 1, wherein the oxygen of said Ni powder is oxygen of the surface oxide of said Ni powder. 3. The powder material according to claim 1, wherein the amount of S to Ni is 0.2 mass % or more. The powder material according to any one of claims 1 to 3, wherein the Ni powder has an average particle size of 0.01 µm to 0.2 µm. Ni powder containing Sn;
an S source;
The amount of oxygen (O) in the Ni powder is 2 mass% or more with respect to Ni,
0.042≦S/Sn weight ratio≦5.5,
A paste material characterized in that 0.39≦O/Sn weight ratio≦40. 6. The paste material according to claim 5, wherein the oxygen in the Ni powder is oxygen in the surface oxide of the Ni powder. 7. The paste material according to claim 5, wherein the amount of S to Ni is 0.2 mass % or more. The paste material according to any one of claims 5 to 7, wherein the Ni powder has an average particle size of 0.01 µm to 0.2 µm. forming a lamination unit by forming an internal electrode pattern containing Ni powder containing Sn and an S source on a dielectric green sheet containing ceramic material powder and an organic binder;
forming a laminate by laminating the lamination units;
and firing the laminate,
The amount of oxygen (O) in the Ni powder is 2 mass% or more with respect to Ni,
0.042≦S/Sn weight ratio≦5.5,
A method for producing a ceramic electronic component, wherein 0.39≦O/Sn weight ratio≦40. 10. The method of manufacturing a ceramic electronic component according to claim 9, wherein the oxygen in the Ni powder is oxygen in the surface oxide of the Ni powder. 11. The method for producing a ceramic electronic component according to claim 9, wherein the amount of S to Ni is 0.2 mass % or more. 12. The method of manufacturing a ceramic electronic component according to claim 9, wherein the Ni powder has an average particle size of 0.01 [mu]m to 0.2 [mu]m.

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