JP5540450B2 - Conductive paste composition for internal electrode, multilayer ceramic electronic component using the same, and manufacturing method thereof - Google Patents

Description

  The present invention relates to an internal electrode conductive paste composition excellent in dispersibility, printability, and adhesion to a dielectric sheet, a multilayer ceramic electronic component using the same, and a method for producing the same.

  A screen printing method is generally used in the process of forming the internal electrode of the multilayer ceramic capacitor (MLCC). Recently, a gravure printing method is being used to improve productivity.

  Gravure printing is a type of intaglio printing, which uses an intaglio made by applying photographic technology to print, and fills the recessed portions of the image with ink, and the rest of the ink is doctor. ) To remove and print.

  However, when the internal electrode layer of the multilayer ceramic capacitor is formed using the gravure printing method, there is a possibility that a scattering phenomenon may occur on the sheet due to the physical properties of the paste.

  In addition, ethyl cellulose resin used in the production of gravure paste is excellent in printability, but has a glass transition temperature (Tg) of 130 ° C. or higher, and has an adhesive force at a temperature lower than that. Lower.

  For this reason, there is a problem that delamination occurs between the dielectric sheet and the internal electrode layer in a product that requires high lamination, such as an ultra-high capacity multilayer ceramic capacitor.

  An object of the present invention is to provide a conductive paste composition for internal electrodes that is excellent in dispersibility, printability, and adhesion to a dielectric sheet, a multilayer ceramic electronic component using the same, and a method for producing the same.

  In one embodiment of the present invention, an internal electrode conductive paste composition comprising 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and 4 to 20 parts by weight of a binder resin having a molecular weight of 150,000 or less. I will provide a.

  The viscosity of the conductive paste composition for internal electrodes may be 2.0 Pa · s or less.

  The conductive metal powder may be one or more selected from the group consisting of silver (Ag), lead (Pb), platinum (Pt), nickel (Ni), and copper (Cu).

  The binder resin may be polyvinyl butyral.

  The conductive metal powder may have a particle size of 50 to 300 nm.

  The internal electrode conductive paste composition may further include a rosin ester resin.

  The rosin ester resin may have a content of 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder.

  In another embodiment of the present invention, a ceramic body on which a dielectric layer is laminated, and 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and a molecular weight of 150,000 are formed on the dielectric layer. An internal electrode layer formed of a conductive paste composition for internal electrodes containing 4 to 20 parts by weight of the following binder resin, an external electrode formed outside the ceramic body and electrically connected to the internal electrodes; A multilayer ceramic electronic component comprising:

  On the other hand, in still another embodiment of the present invention, the internal electrode conductive material includes 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and 4 to 20 parts by weight of binder resin having a molecular weight of 150,000 or less. A step of preparing a conductive paste composition, a step of forming an internal electrode layer with the conductive paste composition on a plurality of green sheets, and a green sheet on which the internal electrode layer is formed are laminated to form a laminate. There is provided a method for manufacturing a multilayer ceramic electronic component, comprising: a step; a step of manufacturing a green chip using the multilayer body; and a step of baking the green chip to manufacture a ceramic body.

  The conductive paste composition for internal electrodes according to the present invention is excellent in dispersibility and printability, and has an effect of preventing the occurrence of scattering in the printing process.

  In addition, in the lamination, pressure bonding, and cutting processes, the strength characteristics of the film itself are excellent as well as the adhesive strength with the dielectric sheet, and there is an effect that no delamination occurs.

1 is a schematic perspective view illustrating a multilayer ceramic capacitor according to an embodiment of the present invention. It is sectional drawing cut | disconnected along AA 'of FIG. It is a manufacturing process figure which manufactures the multilayer ceramic capacitor by other embodiment of this invention.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the accompanying drawings.

  However, the embodiments of the present invention can be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. Accordingly, the shape and size of the elements in the drawings may be exaggerated for clear explanation, and the elements indicated by the same reference numerals in the drawings are the same elements.

  The conductive paste composition for internal electrodes according to an embodiment of the present invention comprises 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and 4 to 20 parts by weight of a binder resin having a molecular weight of 150,000 or less. Including.

  Hereinafter, each component of the conductive paste composition for internal electrodes according to an embodiment of the present invention will be described more specifically.

  The conductive metal powder is not particularly limited, and examples thereof include silver (Ag), lead (Pb), platinum (Pt), nickel (Ni), and copper (Cu). These may be used alone or in combination of two or more. May be used.

  The conductive metal powder may have various particle sizes according to the embodiment of the present invention, and may have a particle size of, for example, 50 to 300 nm.

  The binder resin has a molecular weight of 150,000 or less after dispersion, and may contain 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder.

  In particular, the binder resin may be a polyvinyl butyral resin.

  According to an embodiment of the present invention, excellent phase stability of the paste can be obtained by adjusting the molecular weight after dispersion of the binder resin added to the paste composition, in particular, the polyvinyl butyral resin, to 150,000 or less. .

  After the paste is manufactured, it may take up to several months before it proceeds to the printing process, so the phase stability of the paste after dispersion is important.

  Therefore, in order to ensure the phase stability of the paste after dispersion, one embodiment of the present invention is characterized in that the final molecular weight after dispersion of the polyvinyl butyral resin is controlled in order to realize low viscosity.

  Since the molecular weight of the polyvinyl butyral resin is reduced by a dispersion process performed in a 3-roll mill, a bead mill, a high-pressure disperser, or the like used in the paste manufacturing process, the paste viscosity is determined by the final molecular weight after dispersion. become.

  Therefore, according to one embodiment of the present invention, by adjusting the molecular weight after dispersion of the polyvinyl butyral resin to 150,000 or less, particularly 50,000 to 150,000, the paste viscosity is suitable for printing. It becomes possible to implement 0 Pa · s or less.

  The paste viscosity suitable for the printing is particularly preferably in the range of 0.5 to 2.0 Pa · s.

  The conductive paste composition for internal electrodes according to an embodiment of the present invention is not particularly limited in its printing method, but is suitable for, for example, a gravure printing method.

  Further, when the average molecular weight of the polyvinyl butyral resin is adjusted to 150,000 or less as described above, it is possible to control the scattering phenomenon and to prevent the phenomenon that the paste is scattered on the dielectric sheet during printing.

  In addition, the paste manufactured by controlling the average molecular weight of the polyvinyl butyral resin has excellent adhesion to the dielectric sheet in the lamination step after printing, and is excellent in alignment by preventing electrode displacement. An electrode is obtained.

  Therefore, when the internal electrode layer is formed using the paste composition according to an embodiment of the present invention, a gap is formed between the internal electrode and the dielectric sheet and inside the internal electrode layer, even in the case of high lamination, and cracks are generated. It is possible to obtain an effect that does not cause a peeling failure such as the occurrence of.

  After dispersion of the paste, the average molecular weight of the polyvinyl butyral resin can be compared by gel permeation chromatography after the paste is centrifuged at a high speed and the floating resin is gel permeation chromatography.

  In addition, since it is advantageous for the phase stability of the paste to add a certain amount or more of the binder resin, the internal electrode conductive paste composition according to an embodiment of the present invention is based on 100 parts by weight of the conductive metal powder. You may include 4-20 weight part of binder resins.

  When the content of the binder resin is less than 4 parts by weight, the resin content is insufficient compared to the total specific surface area of the conductive metal powder and ceramic powder added to the paste, realizing excellent dispersibility and printability. Can not.

  On the other hand, if the content of the binder resin exceeds 20 parts by weight, there is a high possibility that residual carbon remains during the calcination and firing processes, which may deteriorate the characteristics of the multilayer ceramic electronic component.

  In addition, since the content of the conductive metal powder in the paste is relatively reduced, there is a risk of reducing electrode connectivity and coverage after firing.

  In order to ensure printability and dispersibility, the binder resin added must be 4 parts by weight or more with respect to 100 parts by weight of the conductive metal powder.

  Therefore, the binder resin in one embodiment of the present invention preferably has a content of 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder.

  However, if the amount of the high molecular weight binder resin, especially polyvinyl butyral resin (molecular weight 250,000-400,000) is large, a viscosity of 2.0 Pa · s or less suitable for printing cannot be realized and added. If the amount is small, problems arise in dispersibility and printability.

  On the other hand, in one embodiment of the present invention, even when the content is the above, the molecular weight of the binder resin is adjusted to 150,000 or less, so that a viscosity of 2.0 Pa · s or less suitable for printing can be realized.

  The internal electrode conductive paste composition may further include a rosin ester resin.

  By further including the rosin ester resin, it is possible to improve the viscosity stability of the internal electrode conductive paste composition and the adhesion or adhesion with the dielectric sheet.

  The rosin ester resin may have a content of 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder.

  When the amount of the rosin ester resin is less than 4 parts by weight, the effect of improving the viscosity stability and the adhesion to the dielectric sheet is reduced. When the amount exceeds 20 parts by weight, the content of the conductive metal powder in the paste is reduced. There is a problem that it becomes relatively decreased.

  Meanwhile, the internal electrode conductive paste composition according to an embodiment of the present invention includes 40 to 100 parts by weight of ceramic powder with respect to 100 parts by weight of conductive metal powder.

The ceramic powder is added to control sintering shrinkage of the conductive metal powder, and is not particularly limited as long as it is generally used. For example, there is barium titanate (BaTiO ₃ ). .

  Other than that, the solvent and the like contained in the internal electrode conductive paste composition are not particularly limited as long as they are used in the manufacture of pastes.

  That is, as a solvent for the conductive paste composition for internal electrodes, for example, terpineol, dihydroterpineol, butyl carbitol, kerosene or the like may be used.

  FIG. 1 is a schematic perspective view illustrating a multilayer ceramic capacitor according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view taken along line AA ′ of FIG.

  Referring to FIGS. 1 and 2, a multilayer ceramic electronic component, particularly a multilayer ceramic capacitor 100 according to another embodiment of the present invention is formed on a ceramic body 110 having a dielectric layer 111 stacked thereon and the dielectric layer 111. An internal electrode layer 130a formed of a conductive paste composition for internal electrodes, comprising 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and 4 to 20 parts by weight of binder resin having a molecular weight of 150,000 or less, 130b, and external electrodes 120a and 120b formed outside the ceramic body 110 and electrically connected to the internal electrodes.

  The ceramic body 110 is obtained by laminating a plurality of ceramic dielectric layers 111 and sintering them, and adjacent dielectric layers are integrated.

The ceramic dielectric layer 111 may be made of a ceramic material having a high dielectric constant, but is not limited thereto. For example, barium titanate (BaTiO ₃ ) -based material, lead composite perovskite-based material, or strontium titanate (SrTiO 3). ₃ ) A system material or the like may be used.

  The internal electrode layers 130a and 130b are formed between the one dielectric layer in the process of laminating the plurality of dielectric layers, and are sintered to form the inside of the ceramic body via the one dielectric layer. It is formed.

  One ends of the internal electrode layers 130a and 130b are alternately exposed on both side surfaces of the ceramic body.

  One ends of the internal electrode layers 130a and 130b exposed on the side surfaces of the ceramic body are electrically connected to the external electrodes 120a and 120b, respectively.

  The internal electrodes 130a and 130b are formed of an internal electrode paste composition according to an embodiment of the present invention.

  Specific components and contents of the internal electrode paste composition according to the embodiment of the present invention are as described above.

  The internal electrode paste composition according to an embodiment of the present invention is excellent in dispersibility and printability. When an internal electrode layer is formed using the internal electrode paste composition, the adhesive strength with a dielectric sheet is excellent, and thus a peeling failure occurs. The effect that does not.

  FIG. 3 is a manufacturing process diagram for manufacturing a multilayer ceramic capacitor according to another embodiment of the present invention.

  Referring to FIG. 3, a method for manufacturing a multilayer ceramic electronic component, particularly a multilayer ceramic capacitor according to another embodiment of the present invention, includes 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and a molecular weight of 150,000 or less. Preparing an internal electrode conductive paste composition containing 4 to 20 parts by weight of a binder resin, forming an internal electrode layer with the conductive paste composition on a plurality of green sheets, and forming the internal electrode layer And laminating the green sheets to form a laminate, producing a green chip using the laminate, and firing the green chip to produce a ceramic body.

  First, an internal electrode conductive paste composition containing 100 parts by weight of conductive metal powder, 40 to 100 parts by weight of ceramic powder, and 4 to 20 parts by weight of a binder resin having a molecular weight of 150,000 or less can be prepared. .

  Thereafter, a multilayer ceramic electronic component is manufactured using the conductive paste. Here, a manufacturing process of the multilayer ceramic capacitor 100 will be described as an example.

  First, a plurality of green sheets can be prepared (a).

  The ceramic green sheet can be produced by mixing ceramic powder, a binder, and a solvent to produce a slurry, and then making the slurry into a sheet having a thickness of several μm by a doctor blade method.

  Also, the internal electrode layers 130a and 130b can be formed on the green sheet using the internal electrode conductive paste (b).

  The internal electrode conductive paste is a conductive paste according to an embodiment of the present invention, and the first and second internal electrode patterns can be formed by a gravure printing method.

  When the internal electrode layers 130a and 130b are thus formed, a green body can be separated from the carrier film, and then a plurality of green sheets can be stacked and stacked to form a laminate (c). .

  Subsequently, the green sheet laminate is pressure-bonded at high temperature and high pressure (d), and the pressed sheet laminate is cut into a predetermined size (e) by a cutting process, thereby producing a green chip. (F).

  Thereafter, the ceramic body 110 is manufactured by calcination, firing and polishing, and the multilayer ceramic electronic component, particularly the multilayer ceramic capacitor 100 can be completed by the external electrodes 120a and 120b and the plating step.

  Therefore, in the multilayer ceramic capacitor 100 according to an embodiment of the present invention, the internal electrode layers 130a and 130b are formed using the conductive paste composition, so that peeling defects between the internal electrode layer and the dielectric layer are reduced. Thus, an effect of improving the reliability of the multilayer ceramic capacitor 100 can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

[Example 1 to Example 10]
In Examples 1 to 10 according to an embodiment of the present invention, the particle size of nickel powder is 100 nm, 200 nm, and 300 nm, respectively, and 4 to 8 parts by weight of polyvinyl butyral resin content is mixed with 100 parts by weight of nickel powder. Then, barium titanate (BaTiO ₃ ) was mixed as a ceramic powder to prepare a conductive paste composition for internal electrodes.

  Specific contents are as shown in Table 1 below.

  Using the conductive paste composition, a multilayer ceramic electronic component, particularly a multilayer ceramic capacitor, according to an embodiment of the present invention was manufactured for each example.

  In particular, the molecular weight of the polyvinyl butyral resin in Examples 1 to 10 was adjusted to 150,000 or less according to an embodiment of the present invention.

[Comparative Examples 1 to 5]
Comparative Examples 1 to 5 were the same as the above Examples except that the molecular weight of the polyvinyl butyral resin was more than 150,000 compared to Examples 1 to 10.

  A multilayer ceramic capacitor was prepared using the pastes according to Examples 1 to 10 and Comparative Examples 1 to 5, and the content of polyvinyl butyral resin and the viscosity depending on the average molecular weight, presence or absence of scattering, adhesive force, printability, laminateability and peeling. The presence or absence of occurrence was measured and listed in Table 1 below.

  As can be seen from the results of Table 1 above, in Examples 1 to 10 of the present invention, the paste viscosity is 2.0 Pa · s or less suitable for printing, and no scattering or peeling after cutting occurs at the time of applying the paste. Excellent effect is obtained.

  Furthermore, in the case of Examples 1-10 of this invention, it is understood that it is excellent in printability and lamination | stacking property, and it is excellent also in the adhesive force with a dielectric material sheet.

  On the other hand, in Comparative Examples 1-5, the result that a scattering generate | occur | produces at the time of application | coating, or printability became unsatisfactory because of high viscosity was obtained.

  From Table 1 above, when the internal electrode layer is formed using the conductive paste composition for internal electrodes according to one embodiment of the present invention, it has excellent dispersibility, printability and laminateability, and the dielectric sheet and It can be seen that since the adhesive force is excellent, the effect of preventing the occurrence of defective peeling after cutting is obtained.

  The present invention is not limited by the above-described embodiments and attached drawings, but is limited by the appended claims. Accordingly, it is obvious to those skilled in the art that various forms of substitution, modification, and change are possible without departing from the technical idea of the present invention described in the claims. This also belongs to the technical idea described in the appended claims.

100 Multilayer Ceramic Capacitor 110 Ceramic Body 111 Dielectric Layer
120a, 120b External electrode 130a, 130b Internal electrode layer

Claims (11)

100 parts by weight of conductive metal powder,
40 to 100 parts by weight of ceramic powder,
A molecular weight of 150,000 or less of polyvinyl butyral (Polyvinyl Butyral) 4~20 parts by weight seen including, viscosity is not more than 2.0 Pa · s,
A conductive paste composition for internal electrodes. The conductive metal powder is at least one selected from the group consisting of silver (Ag), lead (Pb), platinum (Pt), nickel (Ni), and copper (Cu). 2. The conductive paste composition for internal electrodes according to 1. The conductive paste composition for internal electrodes according to claim 1 or 2 , wherein the conductive metal powder has a particle size of 50 to 300 nm. The conductive paste composition for internal electrodes according to any one of claims 1 to 3 , wherein the conductive paste composition for internal electrodes further contains a rosin ester resin. The conductive paste composition for internal electrodes according to claim 4 , wherein the rosin ester resin has a content of 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder. A ceramic body on which a dielectric layer is laminated;
Wherein formed in the dielectric layer, a conductive metal powder 100 parts by weight, ceramic powder 40 to 100 parts by weight, and saw including a molecular weight of 150,000 or less of polyvinyl butyral (Polyvinyl Butyral) 4~20 parts by weight, viscosity of 2. An internal electrode layer formed of a conductive paste composition for internal electrodes that is 0 Pa · s or less ,
A multilayer ceramic electronic component comprising: an external electrode formed outside the ceramic body and electrically connected to the internal electrode. Conductive metal powder 100 parts by weight, ceramic powder 40 to 100 parts by weight, and saw including a molecular weight of 150,000 or less of polyvinyl butyral (Polyvinyl Butyral) 4~20 parts by weight, the internal electrodes viscosity of less 2.0 Pa · s Preparing a conductive paste composition for use;
Forming an internal electrode layer with the conductive paste composition on a plurality of green sheets;
Laminating a green sheet on which the internal electrode layer is formed to form a laminate;
Producing a green chip using the laminate;
And firing the green chip to produce a ceramic body. The conductive metal powder is at least one selected from the group consisting of silver (Ag), lead (Pb), platinum (Pt), nickel (Ni), and copper (Cu). A method for producing a multilayer ceramic electronic component according to claim 7 . The method for manufacturing a multilayer ceramic electronic component according to claim 7 or 8 , wherein the conductive metal powder has a particle size of 50 to 300 nm. The method for producing a multilayer ceramic electronic component according to claim 7, wherein the conductive paste composition for internal electrodes further contains a rosin ester resin. The method for producing a multilayer ceramic electronic component according to claim 10 , wherein the rosin ester resin has a content of 4 to 20 parts by weight with respect to 100 parts by weight of the conductive metal powder.

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