JP2002260954A - Ceramic green body and manufacturing of ceramic electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ceramic green body such as a green chip where defects cannot be easily generated in structure after burning. SOLUTION: The ceramic green body (42) has a ceramic green sheet (10a) containing a first bonding agent, and a metal film (22) formed in a specific pattern on the surface of the ceramic green sheet via a bonding layer (24) containing a second bonding agent. When thermal decomposition temperature in the first bonding agent is set to T1 deg.C, and that in the second one is set to T2 deg.C, the relation expression of T1-T2<20 is met, and the bonding layer containing the second bonding agent is composed by a compound that is not changed into carbon in the thermal decomposition process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ceramic green body and a method for manufacturing a ceramic electronic component using the ceramic green body.

[0002]

2. Description of the Related Art A multilayer ceramic capacitor as an example of a ceramic electronic component generally includes a green chip (element body before firing) obtained by alternately laminating a plurality of dielectric layer pastes and internal electrode layer pastes. It is manufactured by firing.

As a method for obtaining a green chip, a ceramic green sheet is formed on a carrier film using a dielectric layer paste by a doctor blade method or the like, and an internal electrode layer paste is printed thereon in a predetermined pattern. A method of peeling and laminating these one by one (sheet method) is known. Also known is a method of printing a plurality of dielectric layer pastes and internal electrode layer pastes alternately on a carrier film by using, for example, a screen printing method, and then peeling the carrier film (printing method).

In each of these sheet methods and printing methods, an internal electrode pattern is formed by printing using a paste for an internal electrode layer. Therefore, the internal method depends on the particle size of raw metal particles or the thickness of a screen. There was a limit to the thickness of the electrode.

Therefore, without using the internal electrode layer paste,
Instead, a method (transfer method) of using a metal film formed on a carrier film by various thin film forming methods and transferring it to the surface of a ceramic green sheet as an internal electrode pattern has been proposed.

On the other hand, since it is difficult to transfer a metal film having little adhesiveness to the surface of a ceramic green sheet having a low binder content without defects, it is difficult to transfer a metal film through an adhesive layer. It is formed on the surface of the ceramic green sheet.

[0007]

As described above, the multilayer ceramic capacitor obtained by firing the green chips manufactured by various methods has the disadvantage that the ceramic and the metal are simultaneously fired at the sintering temperature of the ceramic. In some cases, structural defects such as lamination and cracks were generated inside the capacitor.

In the literature: "New Keras 3, Multilayer Ceramic Capacitor (Gakudensha)", the binder (binder) contained in the ceramic green sheet is rapidly decomposed in the binder removal step performed before firing. It is shown that this causes a structural defect inside the capacitor (see pages 57 to 58 of the same document). It is also disclosed that in order to avoid rapid decomposition of the binder, it is effective to make the heating rate as slow as possible.

It is an object of the present invention to provide a ceramic green body such as a green chip which is less likely to cause structural defects after firing, and a method for manufacturing a ceramic electronic component such as a multilayer ceramic capacitor using the same.

[0010]

Means for Solving the Problems The present inventors use a ceramic green body obtained by transferring a metal film of a predetermined pattern onto the surface of a ceramic green sheet via an adhesive layer to obtain a ceramic electronic device such as a multilayer ceramic capacitor. When manufacturing a component, the binder contained in the ceramic green sheet and the binder contained in the adhesive layer interposed between the ceramic green sheet and the metal film are made of a specific resin, so that the inside of the electronic component is Has been found to be able to reduce structural defects.

That is, the ceramic green body according to the present invention is formed in a predetermined pattern on a ceramic green sheet containing a first binder and an adhesive layer containing a second binder on the surface of the ceramic green sheet. When the first binder is T1 ° C. and the second binder is T2 ° C., the thermal decomposition temperature of each binder is T1-T1.
The adhesive layer containing the second binder, which satisfies the relational expression of T2 <20, is made of a compound that does not become carbon in the thermal decomposition process.

In the method for manufacturing a ceramic electronic component according to the present invention, a metal film is formed in a predetermined pattern on a surface of a ceramic green sheet containing a first binder via an adhesive layer containing a second binder. The thermal decomposition temperature of the binder is
When the binder is T1 ° C. and the second binder is T2 ° C., T
A step of performing a binder removal process on a pre-fired element body having a ceramic green body that satisfies the relational expression of 1-T2 <20 and in which the adhesive layer containing the second binder is formed of a compound that does not become carbon in a thermal decomposition process. And firing the element body before firing after the binder removal.

In this specification, the thermal decomposition temperatures (T1, T
2) means that, using thermogravimetric analysis (TG), the second binder component is heated to 600 ° C. at a heating rate of 10 ° C./min in the atmosphere of the atmosphere, and the weight is reduced from the initial weight of 100 to 0%.
It means the temperature at the time when it becomes (zero). Compounds that do not become carbon during the pyrolysis process include
Examples include a high molecular weight organic compound containing a large amount of unsaturated bonds (-C = C-) and (-C−C-), and an organic compound other than an aromatic compound.

The element body before firing only needs to have the ceramic green body, and may be constituted by a single layer of the ceramic green body. Alternatively, the ceramic green body may be formed of another ceramic green body. It may be constituted by a laminate obtained by laminating together with a body and / or other ceramic green sheets. When a multilayer ceramic electronic component such as a multilayer ceramic capacitor is manufactured, the element body before firing is formed of the multilayer body.

Preferably, the binder removal treatment is performed in a
The heating is performed at a heating rate of 300 ° C./hour, a holding temperature of 150 to 400 ° C., and a holding time of 0.5 to 24 hours.

Preferably, the method further comprises a step of cutting the element body before firing before the binder removal processing.

[0017] Preferably, the metal film is formed on the surface of the ceramic green sheet with an adhesive force of 50 g or more.

In this specification, the adhesive force of the metal film is determined by bonding a lead wire (φ1.2 mm) to the surface of the metal film using an instant adhesive, and attaching the lead wire to a tensile tester (trade name:
MODEL1311D, AIKOH ENGINEER
ING Co., Ltd.) and only the metal film portion has a pulling speed of:
It means a load applied when the metal film is peeled off from the ceramic green sheet in the process of being pulled at 2 mm / min.

Preferably, the content of the second binder in the adhesive layer is 50 to 100% by weight.

Preferably, the thickness of the adhesive layer is 0.1 to
10 μm.

[0021] Preferably, the content of the first binder in the ceramic green sheet is 1 to 25% by weight.

Preferably, the metal film contains a base metal.

The ceramic green body according to the present invention is, for example, a metal film in which a metal film is formed in a predetermined pattern on the surface of a substrate, and an adhesive layer containing a second binder is formed on the surface of the metal film. Contacting the adhesive layer side of the transfer member with a ceramic green sheet containing a first binder; separating the substrate from the ceramic green sheet; and forming the predetermined pattern on the surface of the ceramic green sheet via the adhesive layer. And a step of transferring the metal film.

The metal film transfer member that can be used for producing the ceramic green body according to the present invention is, for example,
Forming a metal film in a predetermined pattern on the surface of the base,
Forming an adhesive layer containing a second binder on the surface of the metal film.

The method for forming the adhesive layer is not particularly limited, and examples thereof include electrodeposition coating, spray coating, and printing. However, from the viewpoint of being able to form only on the surface of the metal film, it is preferable to form by the electrodeposition coating method.

[0026]

In the ceramic green body according to the present invention, the thermal decomposition temperature (T1) of the first binder contained in the ceramic green sheet and the thermal decomposition temperature (T2) of the second binder contained in the adhesive layer are specified. To satisfy the relational expression of
Moreover, the adhesive layer containing the second binder is made of a compound that does not become carbon during the thermal decomposition process.

For this reason, even if the ceramic green body is used to remove the binder, non-lamination between the ceramic and the metal film is less likely to occur, and a structure such as delamination is formed inside the fired ceramic electronic component. There is little risk of defects. As a result, the ceramic electronic component manufactured using the ceramic green body of the present invention does not cause deterioration of various characteristics such as electric characteristics, physical characteristics and durability characteristics.

In the present invention, by forming the metal film on the surface of the ceramic green sheet with an adhesive force of 50 g or more, the metal film is securely fixed to the surface of the ceramic green sheet. In this case, there is little possibility that the metal film is displaced or peeled off.

Accordingly, there is little risk of short-circuit failure which may occur due to displacement of the metal film and non-lamination which may occur due to peeling of the metal film. As a result, structural defects inside the ceramic electronic component after firing are prevented. .

The ceramic electronic component is not particularly limited, and may be, for example, a multilayer ceramic capacitor, a piezoelectric element,
Examples include chip inductors, chip varistors, chip thermistors, chip resistors, and other surface mount (SMD) chip-type electronic components.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the drawings. 1 is a partially cutaway cross-sectional view of the multilayer ceramic capacitor according to the present embodiment, FIG. 2 is a plan view of the multilayer ceramic capacitor of FIG. 1, and FIG. 3 is a ceramic green body used in the process of manufacturing the capacitors shown in FIGS. FIG. 4 is a cross-sectional view taken along line IV-IV in FIG.
5 is a perspective view of a member for transferring a metal film used in a process of manufacturing a ceramic green body, FIG. 6 is a cross-sectional view taken along the line VI-VI of FIG. 5, and FIGS. 7A to 7F are ceramic green sheets. FIG. 8 is a process chart showing an example of a method for transferring a metal film to a substrate.
(A) and FIG. 8 (B) are perspective views of the ceramic green body used in the process of manufacturing the capacitor shown in FIGS. 1 and 2.

In this embodiment, the structure of a multilayer ceramic capacitor as an example of a ceramic electronic component, the structure of a ceramic green body used for manufacturing the multilayer ceramic capacitor, a method of manufacturing the same, and a multilayer ceramic capacitor using the ceramic green body The method of manufacturing the capacitor will be described in this order.

[0033] Multilayer Ceramic Capacitor As shown in FIG. 1 and FIG. 2, the multilayer ceramic capacitor 2 according to the present embodiment has a capacitor element body 4, a first terminal electrode 6, and a second terminal electrode 8. The capacitor body 4 includes a dielectric layer 10, a first internal electrode layer 12,
It has an internal electrode layer 14, and has a multilayer structure in which first internal electrode layers 12 and second internal electrode layers 14 are alternately stacked between dielectric layers 10. One end of each first internal electrode layer 12 is
It is electrically connected to the inside of the first terminal electrode 6 formed outside the first end 4a of the capacitor body 4.
One end of each second internal electrode layer 14 is connected to a second terminal electrode 8 formed outside the second end 4 b of the capacitor body 4.
Is electrically connected to the inside.

In this embodiment, the internal electrode layers 12 and 14
Is formed by transferring a metal film 22 (see FIGS. 3 and 4) to a ceramic green sheet, and is made of the same material as the metal film 22, but has a thickness corresponding to the horizontal shrinkage due to firing. Thicker than

The material of the dielectric layer 10 is not particularly limited.
For example, it is composed of a dielectric material such as calcium titanate, strontium titanate and / or barium titanate. The thickness of each dielectric layer 10 is not particularly limited, but is generally several μm to several hundred μm.

Although the material of the terminal electrodes 6 and 8 is not particularly limited, copper, a copper alloy, nickel or a nickel alloy is usually used, but silver or an alloy of silver and palladium can also be used. The thickness of the terminal electrodes 6 and 8 is not particularly limited, but is usually about 10 to 50 μm.

The shape and size of the multilayer ceramic capacitor 2 may be appropriately determined according to the purpose and application. When the monolithic ceramic capacitor 2 has a rectangular parallelepiped shape, it usually has a vertical length (0.6 to 5.6 mm, preferably 0.6 to 3.2 m).
m) × width (0.3 to 5.0 mm, preferably 0.3 to 5.0 mm)
1.6 mm) x thickness (0.3 to 1.9 mm, preferably 0.3 to 1.6 mm).

A ceramic green body used for manufacturing the multilayer ceramic capacitor 2 according to the present embodiment will be described.

As shown in FIGS. 3 and 4, the ceramic green body 42 according to the present embodiment has a ceramic green sheet 10a. Ceramic green sheet 1
On the surface of Oa, a metal film 22 having a predetermined pattern is formed via an adhesive layer 24.

The ceramic green sheet 10a is made of the first
It contains a binder and a dielectric material.

The first binder may be an organic solvent-soluble system, a water-soluble system or a water-alcohol-soluble system. Examples of the organic solvent-soluble binder include ethyl cellulose, polyvinyl butyral, and acrylic resin. Examples of the water-soluble or water-alcohol-soluble binder include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, and a water-soluble acrylic resin.

When the thermal decomposition temperature of the first binder is T1 (° C.), T1 is preferably 600 ° C. or lower, more preferably 500 ° C. or lower. Note that the lower limit of T1 is preferably 200 ° C. The method for measuring the thermal decomposition temperature is as described above.

Ceramic green sheet 1 of first binder
The content with respect to 0a is preferably 1 to 25% by weight, more preferably 5 to 12.5% by weight.

The dielectric material is appropriately selected from composite oxides and various compounds to be oxides, for example, carbonates, nitrates, hydroxides, organometallic compounds, and the like, and can be used by appropriately mixing.

Ceramic green sheet 1 of dielectric material
The content with respect to 0a is preferably 70 to 99% by weight,
More preferably, it is 80 to 95% by weight.

The thickness of the ceramic green sheet 10a is preferably 0.5 to 30 μm, more preferably 0.5 μm to 30 μm.
5 to 10 μm.

The composition of the metal film 22 is not particularly limited, but is preferably a metal such as Ag, Cu, Pd, or Ni, or an alloy thereof. When the metal film 22 is formed by electroplating or electroless plating, elements such as P, B, S, and C may be further contained. Thickness D of metal film 22
1 (see FIG. 4) is preferably about 0.1 to 5 μm, more preferably about 0.1 to 1.5 μm. Metal film 22
May be composed of a single layer, or may be composed of two or more layers having different compositions.

The adhesive layer 24 contains a second binder.

In the present invention, the adhesive layer 24 containing the second binder is used.
Is composed of a compound that does not become carbon during the thermal decomposition process. If the adhesive layer 24 containing the second binder is made of a compound that becomes carbon in the course of thermal decomposition, the carbon causes non-lamination between the metal film 22 and the ceramic green sheet 10a. ,
After firing, a structural defect inside the capacitor occurs.

Examples of the compound that does not become carbon during the thermal decomposition process include, for example, a high molecular weight organic compound containing a large amount of unsaturated bonds (—C ＝ C—) and (—C≡C—) in its structure, Organic compounds other than aromatic compounds are exemplified. Examples of such a compound include organic solvent-soluble systems such as ethyl cellulose and polyvinyl butyral; water-soluble systems or water-alcohol-soluble systems such as methyl cellulose and hydroxyethyl cellulose;
There is no particular limitation as long as it satisfies the scope of the present invention.

When the thermal decomposition temperature of the second binder is T2 (° C.), T2 is preferably less than 600 ° C., more preferably 500 ° C. or less. Note that the lower limit of T2 is preferably 200 ° C. The method for measuring the thermal decomposition temperature is as described above.

The content of the second binder in the adhesive layer 24 is preferably 50 to 100% by weight, more preferably 6 to 100% by weight.
7 to 100% by weight.

The adhesive layer 24 may contain a plasticizer and other additives. In particular, by including a plasticizer, the metal film 2 for the ceramic green sheet 10a can be formed.
2 can be adjusted. Examples of the plasticizer include phthalic esters and ethanolamine. The content of the additive in the adhesive layer 24 is preferably about 0 to 50% by weight.

The adhesive layer 24 is preferably as thin as the metal film 22 and uniform. Specific thickness D2
(See FIG. 4) is preferably 0.1 to 10 μm, more preferably 0.1 to 1 μm.

In the present invention, the thermal decomposition temperature T1 of the first binder and the thermal decomposition temperature T2 of the second binder are T1-
The relational expression of T2 <20 is satisfied. By satisfying such a relational expression, non-lamination does not occur between the ceramic green sheet 10a and the metal film 22, and the possibility of causing structural defects such as delamination inside the fired capacitor is reduced.

In the present invention, the first binder and the first binder are so formed that the metal film 22 is formed with an adhesive force of preferably 50 g or more, more preferably 60 g or more, to the ceramic green sheet 10 a via the adhesive layer 24. 2 Select binder. If the adhesive force is less than 50 g, the metal film 22 cannot be securely fixed to the surface of the ceramic green sheet, and the metal film 22 may be displaced or peeled off when the ceramic green body is laminated. There is a possibility that short-circuit failure may occur due to the displacement of the metal film 22, and non-lamination may occur due to peeling of the metal film 22.

A method for manufacturing the ceramic green body An example of a method for manufacturing the ceramic green body 42 according to this embodiment will be described.

The ceramic green body 42 shown in FIGS. 3 and 4 uses, for example, the metal film transfer member 30 shown in FIGS. 5 and 6 and the ceramic green sheet 10a shown in FIG. It can be manufactured as follows.

As shown in FIGS. 5 and 6, the metal film transfer member 30 according to the present embodiment has a base 20. On the surface of the base 20, a patterned metal film 22 is formed. An adhesive layer 24 is formed on the surface of the metal film 22.

The substrate 20 is a conductive substrate such as a metal plate or a metal foil, an insulating substrate such as polyethylene terephthalate or polypropylene, or a conductive thin film formed or laminated on the surface of the insulating substrate so as not to be substantially peeled off. Although any of composite substrates may be used, a conductive substrate is employed in the present embodiment, and the back surface is insulated and coated. It is desirable that the surface roughness of the base 20 be sufficiently smaller than the thickness of the metal film to be formed. The thickness of the base 20 may be about 10 to 100 μm.

The composition and thickness of the metal film 22 are as described above. The composition and thickness of the adhesive layer 24 are also as described above.

The metal film transfer member 30 according to the present embodiment
Is manufactured, for example, through the following steps.

First, for example, as shown in FIG.
A plating resist layer 60 having an opening 62 having a desired pattern is formed on the surface of the base 20. The plating resist layer 60 may be formed by a printing method such as a screen printing method. Alternatively, a photosensitive dry film may be attached to the surface of the substrate 20 and then exposed through a metal mask and then developed. It may be formed using a lithographic method. The material of the plating resist layer 60 may be appropriately selected according to the type of plating solution used to form the metal film 22. The thickness of the plating resist layer 60 is 1 to 30 μm.
m.

Next, as shown in FIG.
Opening 62 of plating resist layer 60 formed on the surface of
Next, the metal film 22 is formed by a wet film forming method such as electroplating or electroless plating.

As a plating bath when the metal film 22 is formed by the electroplating method, for example, when a nickel metal film is formed, a so-called Watt bath containing nickel sulfate, nickel chloride, and boric acid as main components, nickel sulfamate Sulfamic acid baths containing nickel bromide and boric acid as the main components, and copper pyrophosphate and potassium pyrophosphate as the main components when forming copper metal films are widely used. A plating bath can be used. Also,
In addition to the above main components, additives such as a stress adjusting agent, a surfactant, and a leveling agent may be included.

As the plating bath for forming the metal film 22 by the electroless plating method, for example, in the case of a nickel alloy film, a nickel-phosphorus type bath using sodium phosphinate as a reducing agent, sodium borohydride A nickel-boron type bath using dimethylamine borane or the like as a reducing agent may be used. However, when used as an electrode of a multilayer ceramic electronic component, a reaction with ceramic during sintering is taken into consideration. It is desirable to select a bath having a small amount of eutectoid such as B and B.

Next, as shown in FIG.
The adhesive layer 24 is laminated on the surface of the metal film 22 formed on the substrate 0.

In order to form the adhesive layer 24 on the surface of the metal film 22, for example, the base 2 on which the metal film 22 is formed
0 is immersed in the solution containing the second binder.

Next, as shown in FIG. 7D, the plating resist layer 60 is peeled off. As a result, a metal film 22 having a predetermined pattern is formed on the surface of the base 20, and the metal film 2 is formed.
2 is a metal film transfer member 3 having an adhesive layer 24 formed on its surface.
0 is obtained.

The ceramic green sheet 10a according to the present embodiment shown in FIG. 7E is manufactured, for example, through the following steps.

First, a dielectric paste is prepared. The dielectric paste is composed of an organic solvent-based paste obtained by kneading a dielectric material and an organic vehicle, or a water-soluble solvent-based paste.

The dielectric material is as described above. The organic vehicle is obtained by dissolving a binder (first binder) in an organic solvent, and the binder is as described above. The organic solvent is not particularly limited, terpineol, butyl carbitol, acetone,
Examples include toluene. As the water-soluble solvent used for the water-soluble solvent-based paste, a solvent in which a water-soluble binder, a dispersant, and the like are dissolved in water is used. The aqueous binder (first binder) is as described above.

The content of the organic vehicle in the above-mentioned dielectric paste is not particularly limited, and is usually a content, for example, about 1 to 5% by weight of a binder (first binder) and about 10 to 5% by weight of a solvent.
It may be about 50% by weight. In the dielectric paste,
If necessary, additives selected from various dispersants, plasticizers, glass frit, insulators and the like may be contained.

Using this dielectric paste, a ceramic green sheet 10a shown in FIG. 7E is formed on a carrier film (not shown) so as to be peelable by a doctor blade method or the like.

In the following description, the metal film transfer member 3
8 and the ceramic green sheet 10a, FIG.
The case where the first ceramic green body 42a shown in (A) is manufactured by a direct transfer method will be exemplified.

First, as shown in FIG. 7E, a metal film transfer member 30 shown in FIGS. 5 and 6 is formed on the surface of a ceramic green sheet 10a formed on a carrier film (not shown) so as to be peelable. Are laminated so as to be in contact with each other, and both are preferably at a temperature of 30 to 150 ° C., more preferably 50 to 120 ° C., and preferably 0.01 to 10 MPa, more preferably 0.01 to 1 M.
Heat and pressurize at a pressure of Pa. As a result, the metal film 22 having the predetermined pattern adheres favorably to the surface of the ceramic green sheet 10a by the action of the adhesive layer 24.

Next, as shown in FIG.
0 to peel off the ceramic green sheet 10a
The metal film 22 (= 12a) is transferred to the surface of FIG.
A first ceramic green body 42a shown in (A), that is, a first ceramic green body 42a in which a metal film pattern 12a to be the first internal electrode layer 12 (see FIG. 1) is formed on the surface of the ceramic green sheet 10a is obtained. Can be

The second ceramic green body 42b shown in FIG.
A second ceramic green body 42b in which a metal film pattern 14a to be the second internal electrode layer 14 (see FIG. 1) is formed on the surface of a can be obtained in the same manner.

Method of Manufacturing Multilayer Ceramic Capacitor An example of a method of manufacturing the multilayer ceramic capacitor 2 according to this embodiment will be described. The multilayer ceramic capacitor 2
A first ceramic green body 42a shown in FIG.
It is manufactured as follows using the second ceramic green body 42b shown in FIG.

First, a plurality of the first ceramic green bodies 42a and the second ceramic green bodies 42b are laminated together with the ceramic green sheets 10a on which no pattern is formed, if necessary, and cut along the cutting lines 16. To get a green chip.

Next, binder removal processing and firing processing are performed on the green chip.

The binder removal treatment of the green chip is performed before the firing, and in particular, a metal film (the internal electrode 1 after the firing) is used.
2, 14) contains a base metal such as Ni or a Ni alloy, and in an air atmosphere, the rate of temperature rise is 5 to 300.
° C / hour, more preferably 10 to 100 ° C / hour, and the holding temperature is 150 to 400 ° C, more preferably 200 to 30 ° C.
0 ° C, holding time 0.5 to 24 hours, more preferably 5 to 24 hours.
To 20 hours.

The firing atmosphere of the green chip may be appropriately determined according to the type of the metal film. In the case where a base metal such as Ni or a Ni alloy is included, the oxygen partial pressure of the firing atmosphere is reduced by 1%.
0 ^{- 7} is preferably a to 10 ^-3 Pa. If the oxygen partial pressure is too low, the metal of the metal film will be abnormally sintered and will be interrupted. If the oxygen partial pressure is too high, the metal film will tend to be oxidized. The holding temperature during firing is 1100 to 140
It is 0 degreeC, More preferably, it is 1200-1380 degreeC. If the holding temperature is too low, densification will be insufficient, and if the holding temperature is too high, the electrode will be interrupted due to abnormal sintering of the metal of the metal film or the diffusion of the internal electrode material will tend to deteriorate the capacitance temperature characteristics.

Other firing conditions include a heating rate of 50 to 500 ° C./hour, more preferably 200 to 300 ° C.
° C / hour, the temperature holding time is 0.5-8 hours, more preferably 1-3 hours, the cooling rate is 50-500 ° C / hour, more preferably 200-300 ° C / hour, and the firing atmosphere is a reducing atmosphere. It is desirable to use, for example, a mixed gas of nitrogen gas and hydrogen gas as the atmosphere gas after humidification.

When firing in a reducing atmosphere, it is desirable to anneal the sintered body of the capacitor chip. In the above-described binder removal processing, firing and annealing steps, for example, a wetter or the like can be used to humidify the nitrogen gas or the mixed gas. The water temperature in this case is desirably 5 to 75 ° C.

As described above, the capacitor body 4 shown in FIGS. 1 and 2 is obtained. By forming terminal electrodes 6 and 8 at both ends of the obtained capacitor body 4,
The multilayer ceramic capacitor 2 is obtained.

The ceramic green body 4 according to the present embodiment
In No. 2, the thermal decomposition temperature (T1) of the first binder included in the ceramic green sheet 10a and the thermal decomposition temperature (T2) of the second binder included in the adhesive layer 24 satisfy a specific relational expression. And the adhesive layer 24 containing the second binder is made of a compound that does not become carbon during the thermal decomposition process.

Therefore, the ceramic green body 42
Even when the binder is removed by using the method, non-lamination between the ceramic and the metal film is less likely to occur, and structural defects such as delamination are less likely to occur inside the laminated ceramic capacitor 2 after firing.
As a result, the manufactured multilayer ceramic capacitor 2
It does not cause deterioration of various characteristics such as electric characteristics, physical characteristics and durability characteristics.

Further, by forming the metal film 22 on the surface of the ceramic green sheet 10a with an adhesive force of preferably 50 g or more, more preferably 60 g or more, the metal film 22 is securely fixed to the surface of the ceramic green sheet 10a. Therefore, when the ceramic green bodies 42 are stacked, the metal film 22 is less likely to be displaced or peeled off.

Therefore, there is little possibility that short-circuit failure which may occur due to displacement of the metal film 22 or non-lamination which may occur due to peeling of the metal film 22 may occur. As a result, structural defects inside the multilayer ceramic capacitor 2 after firing may occur. Is prevented.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and can be implemented in various modes without departing from the gist of the present invention. Of course.

For example, in the above-described embodiment, the electrode pattern 12 is formed on the surface of the ceramic green sheet 10a.
Although a direct transfer method is employed as a method for forming a,
The present invention is not limited to this, and an indirect transfer method in which the electrode pattern 12a is formed indirectly via one or more intermediate media may be employed. The electrode pattern 12a is not directly transferred to the surface of the ceramic green sheet 10a, but is temporarily transferred to an intermediate medium (not shown) having a high strength such as paper, and the electrode pattern 12a is used to transfer the electrode pattern By using the indirect transfer method for transferring the pattern 12a, more complete transfer of the electrode pattern 12a becomes possible.

Further, in the above-described embodiment, a multilayer ceramic capacitor is exemplified as the ceramic electronic component. However, the present invention is not limited to this, and a single-layer ceramic capacitor manufactured by a single layer of the ceramic green body of the present invention. May be used.

[0094]

EXAMPLES Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.

Example 1 Production of Metal Film Transfer Member First, a metal film transfer member was produced as described below.

A stainless plate was prepared as a substrate. Next, after insulating the entire surface of one surface of the substrate, a plating resist was formed on the other surface of the substrate to form a pattern having a predetermined shape having an opening. As a pretreatment for the stainless steel plate, alkaline electrolytic degreasing and hydrochloric acid pickling were performed, and then the plate was immersed in a stripping solution (Nikka Non-Tack, manufactured by Nihon Kagaku Sangyo) for 1 minute to perform an easy stripping process.

Next, the substrate on which the plating resist of the predetermined pattern was formed on one surface was immersed in a nickel sulfamate plating bath to form a nickel plating film in the opening of the plating resist. When the thickness of the nickel plating film was measured using a fluorescent X-ray film thickness meter, the average was 0.5 μm.
m.

The nickel sulfamate plating bath
Composition: nickel sulfamate: 300 g / L, bromide
Nickel: 5 g / L, boric acid: 30 g / L, and naph
Sodium tarin disulfonate (stress reducing agent): 0.5
g / L. Plating process is temperature
50 ° C., pH 4.5, cathode current density 0.5 A / dm² To
For 6 minutes.

Next, the stainless steel plate on which the nickel plating film of the predetermined pattern is formed is set in advance to a solid concentration of 1%.
% Was immersed for 1 second in a solution in which the adhesive layer component was dissolved in toluene, so that the adhesive layer was formed on the surface of the nickel plating film. The appearance of the adhesive layer was transparent and exhibited an interference color over the entire surface. The thickness was determined from the increase in weight to be 0.6 μm. The composition of the adhesive layer was composed of an acrylic resin A (pyrolysis temperature T2 = 400 ° C.) as the second binder: 67% by weight and a phthalate ester plasticizer: 33% by weight.

Next, only the plating resist was removed to obtain a metal film transfer member.

Preparation of Ceramic Green Body Next, a plurality of ceramic green bodies were prepared using the obtained metal film transfer member.

The adhesive layer side of the obtained metal film transfer member was
Overlaid on a 4 μm thick ceramic green sheet formed on a PET film,
After heating and pressing for a-1 minute, the stainless steel plate was separated from the surface of the ceramic green sheet to obtain a ceramic green body.

The composition of the ceramic green sheet is an acrylic resin (the thermal decomposition temperature T) as the first binder.
1 = 410 ° C.): 5 parts by weight, barium titanate: 90 parts by weight, and plasticizer: 5 parts by weight. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

The metal film was satisfactorily transferred onto the ceramic green sheet without transfer failure. When the adhesion of the nickel plating film to the ceramic green sheet was examined, it was as good as 150 g. The adhesive strength of the nickel plating film is determined by bonding a lead wire (φ1.2 mm) to the surface of the nickel plating film using an instant adhesive, and attaching the lead wire to a tensile tester (trade name: MODEL1311).
D, manufactured by AIKOH ENGINEERING Co., Ltd.), and only the nickel-plated film portion is pulled at a speed of 2 mm /
The load applied when the metal film was peeled off from the ceramic green sheet in the process of pulling in minutes.

The thermal decomposition temperatures (T1, T2) of the first and second binders were determined by thermogravimetric analysis (TG) up to 600 ° C. at a rate of 10 ° C./min. The first and second binder components were heated to a temperature at which the weight became 0 (zero) from the initial weight of 100.

Preparation of Fired Ceramic Body Ten ceramic green bodies thus obtained were laminated and pressed to obtain a green chip, and then subjected to binder removal treatment and firing to obtain a fired ceramic body. The binder removal process
In an air atmosphere, the temperature was raised at a rate of 50 ° C./hour, the holding temperature was 250 ° C., and the holding time was 10 hours. The firing was performed in a humidified N ₂ + H ₂ mixed gas atmosphere at a temperature rising rate of 300 ° C./hour and a holding temperature of 125 ° C.
The test was performed under the conditions of 0 ° C., holding time: 5 hours, and cooling rate: 300 ° C./hour. A wetter with a water temperature of 35 ° C. was used for humidifying the atmosphere gas during firing.

The occurrence rate of delamination was 0%.

The incidence of delamination was determined by polishing the side surfaces of 100 ceramic fired bodies and observing the entire polished surface with an optical microscope. As a result, the number of fired bodies in which no delamination was observed was 100. This is the divided value.

Table 1 shows the results. The presence or absence of carbon during the thermal decomposition process of the adhesive layer containing the second binder is determined by
It was determined by the following method. That is, the presence or absence of carbon is determined by using a thermogravimetric analysis (TG) to heat the adhesive layer component containing the second binder up to 600 ° C. at a heating rate of 10 ° C./min in the air atmosphere, And visually confirmed.

Example 2 The composition of the adhesive layer was changed to the acrylic resin A as the second binder.
(Pyrolysis temperature T2 = 400 ° C.): 100% by weight, acrylic resin as first binder (Pyrolysis temperature T2)
1 = 400 ° C) to obtain a ceramic green body and a ceramic fired body in the same manner as in Example 1. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

When the adhesive strength of the nickel plating film was examined using the obtained ceramic green body, it was as good as 60 g. The incidence of delamination was 5%. Table 1 shows the results.

Example 3 The composition of the adhesive layer was changed to acrylic resin B as the second binder.
(Thermal decomposition temperature T2 = 460 ° C.): A ceramic green body and a ceramic fired body were obtained in the same manner as in Example 2, except that the composition was 100% by weight. In this embodiment, T1
-T2 <20 was satisfied.

When the adhesion of the nickel plating film was examined using the obtained ceramic green body, it was as good as 100 g. The incidence of delamination was 5%.
Table 1 shows the results.

Example 4 The composition of the adhesive layer was 100% by weight of butyral resin C (pyrolysis temperature T2 = 490 ° C.) as the second binder, and acrylic resin (thermal Decomposition temperature T
1 = 450 ° C.), and a ceramic green body and a ceramic fired body were obtained in the same manner as in Example 1. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

When the adhesive strength of the nickel plating film was examined using the obtained ceramic green body, it was as good as 100 g. The incidence of delamination was 0%.
Table 1 shows the results.

Example 5 The composition of the adhesive layer was composed of a butyral resin C (pyrolysis temperature T2 = 490 ° C.) as a second binder: 67% by weight and a phthalate ester plasticizer: 33% by weight. Acrylic resin as first binder (pyrolysis temperature T1 = 400
C), a ceramic green body and a ceramic fired body were obtained in the same manner as in Example 1. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

When the adhesive strength of the nickel plating film was examined using the obtained ceramic green body, it was as good as 120 g. The incidence of delamination was 0%.
Table 1 shows the results.

Example 6 The composition of the adhesive layer was 100% by weight of butyral-based resin D (the thermal decomposition temperature T2 = 480 ° C.) as the second binder, and the composition of the acrylic resin (thermal Decomposition temperature T
1 = 400 ° C) to obtain a ceramic green body and a ceramic fired body in the same manner as in Example 1. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

When the adhesion of the nickel plating film was examined using the obtained ceramic green body, it was 50 g. The incidence of delamination was 10%. Table 1 shows the results.

The rate of delamination was 10%.
It is presumed that the metal film was slightly peeled off when the ceramic green bodies were laminated because the adhesion of the nickel plating film was slightly low at 50 g.

Example 7 The composition of the adhesive layer was composed of 100% by weight of ethylcellulose E as a second binder (thermal decomposition temperature T2 = 420 ° C.) and an acrylic resin as a first binder (thermal decomposition temperature). T
1 = 400 ° C) to obtain a ceramic green body and a ceramic fired body in the same manner as in Example 1. In the present embodiment, the relational expression of T1−T2 <20 was satisfied.

When the adhesive strength of the nickel plating film was examined using the obtained ceramic green body, it was as good as 70 g. The incidence of delamination was 5%. Table 1 shows the results.

Comparative Example 1 The composition of the adhesive layer was changed to an acrylic resin F as a second binder.
(Thermal decomposition temperature T2 = 380 ° C.): 80% by weight and phthalate plasticizer: 20% by weight, except that
In the same manner as in Example 1, a ceramic green body and a ceramic fired body were obtained.

In this example, the relational expression of T1−T2 <20 was not satisfied. The adhesion of the nickel plating film was examined using the obtained ceramic green body.
It was 0 g. The incidence of delamination was 90%. Table 1 shows the results.

The delamination rate is 90%.
The reason why T1 and T2 did not satisfy the above relational expression was that non-lamination occurred between the ceramic green sheet and the metal film, and the adhesion of the nickel plating film was 40 g. It is presumed that the metal film was peeled off when the ceramic green body was laminated due to the low value.

Comparative Example 2 The composition of the adhesive layer was changed to an acrylic resin F as a second binder.
(Thermal decomposition temperature T2 = 380 ° C.): 67% by weight and phthalate plasticizer: 33% by weight, and an acrylic resin as the first binder (Thermal decomposition temperature T1 = 400)
C), a ceramic green body and a ceramic fired body were obtained in the same manner as in Example 1.

In this example, the relational expression of T1-T2 <20 was not satisfied. Further, the adhesion of the nickel plating film was examined using the obtained ceramic green body.
It was 0 g. The rate of delamination was 70%. Table 1 shows the results.

The delamination rate was 70%.
The reason is that non-lamination occurs between the ceramic green sheet and the metal film because T1 and T2 did not satisfy the above relational expression, and as a result, when laminating the ceramic green body, It is presumed that the film was peeled off.

Comparative Example 3 The composition of the adhesive layer was composed of a phenolic resin G (pyrolysis temperature T2 = 600 ° C. or higher) as a second binder: 67% by weight and a phthalate ester plasticizer: 33% by weight. , An acrylic resin as the first binder (the thermal decomposition temperature T1 = 4
(00 ° C.), and a ceramic green body and a ceramic fired body were obtained in the same manner as in Example 1.

In this example, the relationship of T1−T2 <20 was satisfied. In addition, when the adhesive strength of the nickel plating film was examined using the obtained ceramic green body, 120 g was obtained.
Met. When the presence or absence of carbon was examined in the adhesive layer containing the second binder using thermogravimetric analysis (TG), soot-like carbon was visually observed. The incidence of delamination was 95%. Table 1 shows these results.
Shown in

The delamination rate was 95%
The reason for this was that non-lamination occurred between the ceramic layer and the metal film because the adhesive layer containing the second binder remained as carbon between the binder removal step and the firing step. It is estimated that

Comparative Example 4 The composition of the adhesive layer was changed to an acrylic resin H as a second binder.
(Thermolysis temperature T2 = 360 ° C.): 67% by weight and phthalate plasticizer: 33% by weight, an acrylic resin as the first binder (Thermolysis temperature T1 = 400)
C), a ceramic green body and a ceramic fired body were obtained in the same manner as in Example 1.

In this example, the relational expression of T1-T2 <20 was not satisfied. The adhesion of the nickel plating film was examined using the obtained ceramic green body.
00 g. The rate of delamination was 70%. Table 1 shows the results.

The rate of occurrence of delamination was 70%.
The reason is that non-lamination occurs between the ceramic green sheet and the metal film because T1 and T2 did not satisfy the above relational expression, and as a result, when laminating the ceramic green body, It is presumed that the film was peeled off.

Comparative Example 5 A ceramic green body and a ceramic green body were prepared in the same manner as in Example 1 except that an acrylic resin (pyrolysis temperature T1 = 400 ° C.) was used as the first binder without an intervening adhesive layer. A fired body was obtained.

When the adhesion of the nickel plating film was examined using the obtained ceramic green body, it was 30 g. The incidence of delamination was 95%. Table 1 shows the results.

The rate of delamination was 95%
It is highly probable that the metal film peeled off when the ceramic green body was laminated because the adhesive strength of the nickel plating film was as low as 30 g.

[0138]

[Table 1]

[0139]

As described above, according to the present invention, a ceramic green body such as a green chip which is less likely to cause a structural defect after firing, and a ceramic electronic component such as a multilayer ceramic capacitor using the same are manufactured. We can provide a method.

[Brief description of the drawings]

FIG. 1 is a partially cutaway sectional view of a multilayer ceramic capacitor according to the present embodiment.

FIG. 2 is a plan view of the multilayer ceramic capacitor of FIG.

FIG. 3 is a perspective view of a ceramic green body used in a process of manufacturing the capacitor shown in FIGS. 1 and 2.

FIG. 4 is a sectional view taken along the line IV-IV in FIG.

FIG. 5 is a perspective view of a metal film transfer member used in a process of manufacturing a ceramic green body.

FIG. 6 is a sectional view taken along the line VI-VI of FIG.

FIGS. 7A to 7F are process diagrams showing an example of a method for transferring a metal film to a ceramic green sheet.

FIGS. 8A and 8B are perspective views of a ceramic green body used in the process of manufacturing the capacitor shown in FIGS. 1 and 2. FIG.

[Explanation of symbols]

2 multilayer ceramic capacitor (ceramic electronic component) 4 capacitor element 6 first terminal electrode 8 second terminal electrode 10 dielectric layer 10a ceramic green sheet 12 first internal electrode layer 12a pattern 14th 2 Internal electrode layer 14a Pattern 20 Substrate 22 Metal film 24 Adhesive layer 30 Metal film transfer member 42 Ceramic green body 42a First ceramic green body 42b Second ceramic green body 60 Plating resist layer 62 … Aperture

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5E082 AA01 AB03 BC32 BC38 EE04 EE05 EE31 EE35 EE39 FG06 FG26 FG54 LL03 MM24 PP03 PP06 PP09 PP10

Claims (9)

[Claims] 1. A ceramic green sheet including a first binder, and a metal film formed in a predetermined pattern on a surface of the ceramic green sheet via an adhesive layer including a second binder. When the thermal decomposition temperature of the binder is T1 ° C. for the first binder and T2 ° C. for the second binder, the relational expression of T1−T2 <20 is satisfied, and the adhesive layer containing the second binder is A ceramic green body comprising a compound that does not become carbon during the thermal decomposition process. 2. The ceramic green body according to claim 1, wherein the metal film is formed on the surface of the ceramic green sheet with an adhesive force of 50 g or more. 3. The ceramic green body according to claim 1, wherein the content of the second binder in the adhesive layer is 50 to 100% by weight. 4. The ceramic green body according to claim 1, wherein said adhesive layer has a thickness of 0.1 to 10 μm. 5. The ceramic green sheet according to claim 1, wherein the content of the first binder is 1 to 25% by weight.
5. The ceramic green body according to any one of 4. 6. The metal film according to claim 1, wherein said metal film contains a base metal.
The ceramic green body according to any one of the above. 7. A metal film is formed in a predetermined pattern on a surface of a ceramic green sheet containing a first binder via an adhesive layer containing a second binder, and a thermal decomposition temperature of each of the binders is set to a first temperature. When the binder is T1 ° C. and the second binder is T2 ° C., the compound satisfies the relational expression of T1−T2 <20, and the adhesive layer containing the second binder does not become carbon in a thermal decomposition process. A method for producing a ceramic electronic component, comprising: a step of removing a binder from a pre-fired element body having a ceramic green body constituted; and a step of firing the pre-fired element body after the binder removal. 8. The method according to claim 1, wherein the binder removal treatment is performed at 5 to 300 ° C. /
The method for manufacturing a ceramic electronic component according to claim 7, wherein the heating is performed at a temperature rising rate of time, a holding temperature of 150 to 400 ° C., and a holding time of 0.5 to 24 hours. 9. The method for manufacturing a ceramic electronic component according to claim 8, further comprising a step of cutting the element body before firing before the binder removal treatment.