KR100645629B1 - Dielectric multi-layered coating powder and composite dielectric material using the same - Google Patents

Abstract

The present invention relates to a dielectric multilayer coating powder, a composite dielectric material using the same, and a use thereof, wherein the oxide powder is coated with a metal component, and optionally a magnetic component is coated thereon, and then the oxide component is coated again. .

In the case of the composite material using the dielectric multilayer coating powder according to the present invention, it is possible to achieve the dielectric constant improvement and the dielectric loss reduction of the composite at the same time can be applied to a multifunctional composite module, a built-in passive device, a radio wave absorber, a material for removing noise. .

Dielectrics, Multi-Layer Coating Powders, Composite Dielectric Materials, Oxides, Metals, Magnetic Materials

Description

Dielectric multi-layered coating powder and composite dielectric material using the same

1 is a view showing a composite dielectric material for a capacitor according to the prior art.

2 is a cross-sectional view showing the layer structure of the dielectric multilayer coating powder according to an embodiment of the present invention.

3 is a cross-sectional view showing the layer structure of the dielectric multilayer coating powder according to another embodiment of the present invention.

※ Explanation of code about main part of drawing ※

100: composite dielectric material 200, 300: dielectric multilayer coating powder

10: dielectric filler 20: resin

30: oxide powder 40: metal coating layer

40: oxide coating layer 50: magnetic coating layer

The present invention relates to a dielectric multilayer coating powder, a composite dielectric material using the same and its use. More specifically, the present invention relates to a dielectric multilayer coating powder, a composite dielectric material using the same, and a use thereof, by which a metal component, optionally a magnetic substance component, and an oxide component are sequentially coated on an oxide powder to simultaneously achieve improved dielectric constant and lower dielectric loss. will be.

Portable information and communication devices such as mobile phones require more data transmission and various multimedia support functions in the future. Accordingly, the trend of miniaturization, high density, and modularization of electronic components is inevitably progressing.

Printed Circuit Boards (PCBs) used to serve as simple wiring boards in the past, but with the development of embedded passive device (EPD) technology, which allows passive devices to be embedded inside the board, it has been developed as a functional module board. In order to cope with high-performance and high-density functional substrates, development of EPD materials with excellent characteristics is urgently needed.

Currently, passive devices are mostly mounted on the surface of printed circuit boards in the form of discrete components, accounting for 50% of the board area. In particular, the high connection distance between the devices at high frequencies cause electrical parasitic components to reduce the electrical performance of the product and the number of connections through the solder is also causing problems in the reliability of the product.

Embedded Passive Device (EPD) is a technology proposed to solve this problem and integrates the existing discrete passive devices into the multilayer PCB from the surface area of the substrate. By using this method, the area occupied by passive devices can be reduced, thereby increasing the chip mounting density and shortening the connection length between devices, thereby improving electrical performance. The use of built-in passive elements in printed circuit boards simplifies board fabrication, reduces unwanted parasitic inductance and cross talk in terms of cost reduction and technology, and reduces component cost and package. The cost can be reduced and the process cost can be reduced.

In particular, in the case of a de-coupling capacitor, which is widely used for power supply of an IC, noise removal, etc., a large number of passive components are used, for example, a mobile phone, and occupy the largest area of a PCB board. have. Therefore, there is a strong need to embed these decoupling capacitors inside the substrate. In order to embed a capacitor inside a substrate, a substrate material applicable to a high dielectric constant PCB process is required. However, the FR-4, which is widely used as a PCB material, has a very low dielectric constant of about 4, which is not suitable for embedding a capacitor. Therefore, a ceramic-epoxy composite material containing a dielectric having a high dielectric constant as a filler has been developed as a material for a capacitor.

In this regard, as shown in FIG. 1, in the case of the ceramic-epoxy composite 100 for a capacitor according to the prior art, the ceramic dielectric filler 10 is used as a composite type dispersed in the epoxy resin 20. have. Here, BaTiO ₃ powder is mainly used as the dielectric filler 10.

However, for this general composite form, the dielectric constant of the composite is highly dependent on the dielectric constant of the resin component (eg, epoxy). In general, the dielectric constant of a composite in which a BaTiO ₃ dielectric powder having a relative dielectric constant of about 3000 and an epoxy having a dielectric constant of about 4 is mixed at a volume ratio of about 40:60 is difficult to have a value of 20 to 50 or more.

In order to solve these drawbacks, the dielectric constant can be increased by increasing the amount of the dielectric powder, but it is difficult to add more than 40% by volume in order to satisfy the peel strength with the Cu electrode for use as a substrate material. .

On the other hand, increasing the dielectric constant of the polymer resin is a viable alternative, but considering the compatibility with other materials, transition temperature (Tg), reliability criteria, it is also difficult to apply a new resin.

In addition, even when the metal powder is used instead of the dielectric powder, the dielectric constant can be increased, but the dielectric loss is increased, so it is not significant for practical use.

Therefore, in the present invention, as a result of extensive research to solve the above problems, it is possible to achieve the dielectric constant improvement and the dielectric loss reduction of the composite simultaneously by multi-coating the oxide powder with a metal component and optionally a magnetic component. With this in mind, the present invention has been completed.

Accordingly, an object of the present invention is to provide a dielectric multi-layer coating powder that can achieve a dielectric constant improvement and a dielectric loss reduction of the composite at the same time using a variety of functional powder.                         

Another object of the present invention is to provide a composite dielectric material using the dielectric multilayer coating powder.

Still another object of the present invention is to provide a use of the dielectric multilayer coating powder.

According to a first aspect of the present invention for achieving the above and other objects:

There is provided a dielectric multilayer coating powder comprising an oxide powder having an average particle diameter of 0.1 to 10 µm, a metal coating layer coated while being in contact with the oxide powder, and an oxide coating layer coated while being in contact with the metal coating layer. At this time, the thickness of the metal coating layer and the oxide coating layer is 0.005 ~ 2㎛, respectively, the oxide is Al, Ba, Si, Mg, Mn, Zr, Ni, Pb, Ti, Ca, Sr, Fe, Mn, Zn, Cr Is an oxide of a metal selected from the group consisting of Cu, Y and combinations thereof, wherein the metal is from the group consisting of silver, gold, platinum, palladium, copper, nickel, iron, aluminum, molybdenum, tungsten, alloys and mixtures thereof Is selected. The dielectric multilayer coating powder may be dispersed in a resin and used as a composite dielectric material. The composite dielectric material may also be used in a passive element or a composite module.

According to a second aspect of the present invention for achieving the above and other objects:

An oxide powder having an average particle diameter of 0.1 to 10 µm, a metal coating layer coated while being in contact with the oxide powder, a magnetic coating layer coated while being in contact with the metal coating layer, and an oxide coating layer coated while being in contact with the magnetic coating layer A dielectric multi-layer coating powder is provided. In this case, the thickness of the metal coating layer, oxide coating layer and magnetic coating layer is 0.005 ~ 2㎛, respectively, the oxide is Al, Ba, Si, Mg, Mn, Zr, Ni, Pb, Ti, Ca, Sr, Fe, Mn, Oxide of a metal selected from the group consisting of Zn, Cr, Cu, Y and combinations thereof, the metal being silver, gold, platinum, palladium, copper, nickel, iron, aluminum, molybdenum, tungsten, alloys and mixtures thereof The magnetic body is selected from the group consisting of Mn-Zn-based ferrite, Ni-Zn-based ferrite, Mn-Mg-Zn-based ferrite, Ni-Cu-Zn-based ferrite, Fe ₂ O ₃ and Fe ₃ O ₄ Is selected. The dielectric multilayer coating powder may be used as a radio wave absorber, a material for removing noise.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

As described above, in the present invention, by coating a metal component and a magnetic component selectively on the oxide powder and coating the oxide component on the oxide powder again, the dielectric multilayer coating powder capable of simultaneously improving the dielectric constant and decreasing the dielectric loss of the composite, using the same A composite dielectric material and its use are provided.

2 and 3 show the layer structure of the dielectric multilayer coating powder according to one embodiment of the first and second surfaces of the present invention, respectively.

According to the first aspect of the present invention, the dielectric multilayer coating powder 200 is an oxide powder 30 having an average particle diameter of 0.1 to 10㎛, a metal coating layer 40 coated while contacting the oxide powder 30, And an oxide coating layer 50 coated while being in contact with the metal coating layer 40.

Oxide powder 30 used in the present invention is made of Al, Ba, Si, Mg, Mn, Zr, Ni, Pb, Ti, Ca, Sr, Fe, Mn, Zn, Cr, Cu, Y and combinations thereof Oxide of a metal selected from the group.

The average particle diameter of the oxide powder 30 is preferably 0.1 to 10㎛. If the average particle diameter is less than 0.1 mu m, it is difficult to obtain high dielectric properties, and the particles of the oxide powder are agglomerated to form a nonuniform mixture, and thus there is a difficulty in handling. On the other hand, if the average particle diameter exceeds 10 mu m, the dielectric properties are good, but the pattern is difficult to fabricate, and thus it is difficult to apply to a smooth substrate having a thin thickness.

The production method of the oxide powder 30 is not particularly limited as long as it is a method known in the art can be used all.

The method for producing an oxide powder having a composition represented by ABO ₃ among the above-described oxides will be described below by way of example, but is not particularly limited thereto.

First, an organic polymer compound is adsorbed to the carbonate powder of element A to obtain an organic polymer adsorbed carbonate powder. In this case, a slurry in which the carbonate powder of element A is dispersed in an organic polymer compound solution is prepared, and then, the solvent contained in the solution is removed from the slurry by drying or the like, whereby the organic polymer compound is adsorbed on the surface. It is preferred to produce a polymer adsorbent carbonate powder. Thereafter, as needed, heat treatment is performed on the organic polymer-adsorbed carbonate powder.

Next, the organic polymer compound adsorbed carbonate powder and the oxide powder of element B are mixed to obtain a mixed powder. And the process of calcining this mixed powder is performed, and the raw material powder for dielectric ceramics is obtained by this.

According to this manufacturing method, since the organic polymer adsorption carbonate powder is used as the carbonate powder of element A, sintering and particle growth of the carbonate powder of element A in the calcination step are suppressed. Therefore, calcination can proceed in a state where the carbonate of element A and the oxide of element B are uniformly dispersed while maintaining the fine state of the carbonate powder of element A. As a result, the ABO _{3 type} of fine particles and excellent composition uniformity Oxide powder can be obtained.

The amount of adsorption of the organic polymer compound described above is not particularly limited. However, if the amount of adsorption is too small, a predetermined effect is not obtained. On the contrary, if the amount of adsorption is too large, the heat treatment profile is precisely used to sufficiently decompose the organic material. There is a risk of causing an increase in production costs, such as the need for control. In consideration of this, the adsorption amount of the organic polymer compound is preferably selected in the range of 0.1 to 5.0% by weight, preferably 0.3 to 2.0% by weight. The molecular weight of the said organic high molecular compound is typically in the range of 1000-100000. Moreover, it is preferable that the said organic high molecular compound has at least 1 functional group among a carboxyl group, a vinyl group, an acryl group, and an epoxy group. If the molecular weight of the organic polymer compound is in the above-described range and it is provided with the above-described functional group, the organic polymer compound can be efficiently adsorbed to the carbonate powder, and more effectively suppress the sintering and particle growth of the carbonate powder in the calcination step. Can be.

For example, in the case of obtaining a dielectric material powder of the _three-based BaTiO, usually of BaCO ₃ powder is used as the carbonate powder of the element A, a powder of TiO ₂ is used as the oxide powder of the element B, the BaCO ₃ powder It is preferable that silver specific surface area is 10 m <2> / g or more. It is because the effect by the above-mentioned organic high molecular compound is exhibited more remarkably by making a specific surface area more than 10 m <2> / g. Preferably, the specific surface area of the BaCO ₃ powder is 10 to 80 m 2 / g, more preferably 10 to 40 m 2 / g.

The metal component used in the metal coating layer 40 is selected from the group consisting of silver, gold, platinum, palladium, copper, nickel, iron, aluminum, molybdenum, tungsten, alloys and mixtures thereof.

The thickness of the metal coating layer 40 is preferably 0.005 ~ 2㎛. When the thickness of the metal coating layer is less than 0.005 μm, the metal coating layer may be easily oxidized by the oxide components above and below the coating layer, and thus, it may be difficult to exhibit the unique characteristics of the metal. On the other hand, when the thickness of the metal coating layer exceeds 2㎛ the possibility of cracking in the coating layer is increased due to the stress at the joint surface due to the lattice constant difference between the oxide and the metal and the stress due to the difference in the thermal expansion coefficient of the dissimilar material. There is a disadvantage that the properties of the composite deteriorate.

The method of coating the metal coating layer 40 on the oxide powder 30 is not particularly limited as long as it is known in the art and can be used.

For example, in the case of forming a metal coating layer on an oxide powder such as barium titanate, an aqueous solution of salts constituting the metal layer (eg, NiCl ₂ , NiSO ₄ , Ni (CH ₃ COO) _{2 in the} Ni metal layer coating) Oxide powders such as barium titanate, reducing agents such as N ₂ H ₄ to reduce these metal components, reaction regulators such as NaOH, etc. are added together to control the reaction in the solution, and then Ni (OH) ₂ and The same gel is coated. The desired metal coating film can be formed by heat-treating the metal gel-coated powder at a suitable temperature in a reducing atmosphere.

In addition, the metal coating layer may be formed on the surface of the oxide powder by using an electroless plating method, a method of depositing a metal component, a rice method using a solution chemical route in the above solution, or the like.

On the other hand, the oxide component used in the oxide coating layer 50 has a composition represented by the formula ABO ₃ , as described above in the oxide powder, where A is at least one element of Ba, Ca, Sr and Mg, B is at least one element of Ti and Zr.

The thickness of the oxide coating layer 50 is preferably 0.005 ~ 2㎛. If the thickness of the oxide coating layer is less than 0.005㎛ there is a disadvantage that it is difficult to exhibit the unique characteristics of the oxide. On the other hand, when the thickness of the oxide coating layer exceeds 2㎛ the possibility of cracking in the coating layer is increased due to the stress at the joint surface due to the lattice constant difference between the oxide and the metal and the stress due to the difference in thermal expansion coefficient of the dissimilar material. There is a disadvantage that the properties of the composite deteriorate.

The method of coating the oxide coating layer 50 on the metal coating layer 40 is not particularly limited as long as it is known in the art and can be used.

For example, an oxide coating layer may be formed on the surface of the metal coating layer by using a sol-gel method, hetero-coagulation method, hydrolysis of alkoxide, or the like.

As described above, the dielectric multilayer coating powder 200 composed of the oxide powder 30-the metal coating layer 40-the oxide coating layer 50 according to the first aspect of the present invention is a metal contained in the metal coating layer 40. At the same time, the dielectric loss and percolation are increased while the conductivity is prevented.

The dielectric multilayer coating powder 200 not only has the characteristics described above, but also disperses in a resin to give excellent flame retardancy and mechanical strength when used as a composite dielectric material used in embedded passive devices or functional composite module substrates.

Here, the content of the dielectric multilayer coating powder in the composite dielectric material is 5 to 60% by volume, preferably 30 to 50% by volume. When the content of the dielectric multilayer coating powder is less than 5 parts by weight, it is not possible to obtain the effect of improving the dielectric constant and decreasing the dielectric loss of the composite. If the content is more than 50% by volume, the fluidity is very bad during press molding, and a compact molding is not obtained. However, the optimum content of the dielectric multilayer coating powder can be appropriately adjusted according to the shape of the substrate pattern.

On the other hand, the resin used in the composite dielectric material is not particularly limited, but may be an organic polymer resin, a thermosetting resin, a thermoplastic resin, or a resin in combination thereof.

As said organic polymer resin, in the resin composition which consists of 1 type (s) or 2 or more types of resin whose weight average absolute molecular weight is 1000 or more, the sum of the number of atoms of a carbon atom and a hydrogen atom becomes 99% or more, and a part between resin molecules Or a heat resistant low dielectric polymer material in which all are chemically bonded to each other. By using the organic polymer resin having such a structure, a composite dielectric material having a high dielectric constant? In the high frequency band can be obtained.

Specific examples of such organic polymer resins include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, high density polyethylene, low molecular weight polyethylene, ultra high molecular weight polyethylene, ethylene-propylene copolymers, and polypropylene. Mono- or copolymers of nonpolar α-olefins, such as polybutene, poly4-methylpentene copolymers (hereinafter also referred to as (co) polymers), butadiene, (Ball) of each monomer of conjugated diene such as isoprene, pentadiene, hexadiene, octadiene, phenylbutadiene and diphenylbutadiene Polymers, styrene, nuclear substituted styrenes, for example methylstyrene, dimethylstyrene, ethylstyrene, isopropylst yrene), chlorostyrene, α-substituted styrene such as α-methylstyrene, α-ethylstyrene, divinylbenzene, vinylcyclohexane, and the like of each monomer of a vinyl containing vinyl (vinylcyclohexane) Co) polymers and the like.

Besides, thermosetting resins such as vinyl ester resins, unsaturated polyester resins, maleimide resins, polycyanate resins of polyphenols, epoxy resins, phenol resins and vinyl benzyl compounds, for example polyetherimide , Thermoplastic resins such as polyether sulfone, polyacetal, dicyclopentadiene resin, and the like can be used.

It is preferable that the composite dielectric material of this invention is based on the following manufacturing methods.

First, a dielectric multilayer coating powder is obtained according to the method described above. Then, the dielectric multilayer coating powder and the resin are combined and mixed in predetermined amounts. In addition, although mixing is performed also by dry mixing, it is preferable to mix sufficiently in organic solvents, such as toluene and xylene, by a ball mill and a stirrer.

After molding the slurry into a predetermined shape on the substrate to be applied, it is cured for about 30 to 480 minutes at a temperature of 100 to 200 ℃.

The composite dielectric material of the present invention can be applied to a built-in passive element or a functional composite module substrate or the like as a film or in a molded form of a bulk shape or a predetermined shape, and in various forms such as lamination of a film shape.

The above-described composite dielectric material of the present invention and the substrate using the same can achieve both the dielectric constant improvement and the dielectric loss reduction of the composite.

According to the second aspect of the present invention, the dielectric multilayer coating powder 300 is an oxide powder 30 having an average particle diameter of 0.1 to 10㎛, a metal coating layer 40 coated while contacting the oxide powder 30, And a magnetic coating layer 60 coated while being in contact with the metal coating layer 40, and an oxide coating layer 50 coated while being in contact with the magnetic coating layer 60.

The oxide powder 30 and the metal coating layer 40 used in the present invention are as described above in the first surface.

On the other hand, the magnetic component used in the magnetic coating layer 60 is Mn-Zn-based ferrite, Ni-Zn-based ferrite, Mn-Mg-Zn-based ferrite, Ni-Cu-Zn-based ferrite, Fe ₂ O ₃ and Fe ₃ O ₄ is selected from the group consisting of.

The thickness of the magnetic coating layer 60 is preferably 0.005 ~ 2㎛. If the thickness of the magnetic coating layer is less than 0.005㎛ there is a disadvantage that it is difficult to exhibit the unique characteristics of the magnetic body. On the other hand, when the thickness of the magnetic coating layer exceeds 2㎛ the possibility of cracking in the coating layer is increased due to the stress at the joint surface due to the lattice constant difference of the dissimilar material and the stress due to the difference in thermal expansion coefficient of the dissimilar material, in which case the composite material There is a disadvantage that the characteristics of the deterioration.

The method of coating the magnetic coating layer 60 on the metal coating layer 40 is not particularly limited as long as it is known in the art and may be used.

For example, a magnetic coating layer may be formed on the surface of the metal coating layer using a process similar to that of forming a dielectric such as a sol-gel method, a method of adding a reducing agent to a metal chloride solution, or an alkoxide method. Can be.

On the other hand, the oxide component used in the oxide coating layer 50 is as described above.

The method of coating the oxide coating layer 50 on the magnetic coating layer 60 is not particularly limited as long as it is known in the art and can be used.

For example, an oxide coating layer may be formed on the surface of the magnetic coating layer by using a sol-gel method, hetero-coagulation method, hydrolysis of alkoxide, or the like.

As described above, according to the second aspect of the present invention, the dielectric multilayer coating powder 300 including the oxide powder 30-the metal coating layer 40-the magnetic coating layer 60-the oxide coating layer 50 is formed of a metal coating layer ( In addition to improving the dielectric constant by the metal component contained in 40), not only can the dielectric loss and percolation occur, but also a sudden increase in conductivity can be prevented, and the magnetic component contained in the magnetic coating layer 60 can be prevented. By using the magnetic resonance phenomenon by absorbing a specific frequency component has a characteristic that can remove electromagnetic waves or noise. Therefore, by using such characteristics, the dielectric multilayer coating powder 300 may be utilized as a radio wave absorber, a noise removing material, and the like.

As described above, according to the present invention, by multi-coating an oxide powder with a metal component and optionally a magnetic component, etc., a dielectric multilayer coating powder and a composite dielectric material capable of simultaneously improving dielectric constant and decreasing dielectric loss of a composite can be obtained. Can be.

In addition, the dielectric multilayer coating powder according to the present invention not only improves the dielectric constant and decreases the dielectric loss of the composite, but also when used as a composite dielectric material dispersed in a resin and applied to a built-in passive element or a functional composite module substrate, excellent flame retardancy and It serves to impart mechanical strength. In addition, by absorbing a specific frequency component using a magnetic resonance phenomenon by the magnetic component contained in the magnetic coating layer of the coating layer of the dielectric multilayer coating powder exhibits a characteristic that can remove the electromagnetic wave or remove the noise, it is a radio wave absorber, noise There is an advantage that can be widely applied to a material for removal.

Claims (15)

A dielectric multilayer coating powder comprising an oxide powder having an average particle diameter of 0.1 to 10 µm, a metal coating layer coated while being in contact with the oxide powder, and an oxide coating layer coated while being in contact with the metal coating layer. An oxide powder having an average particle diameter of 0.1 to 10 µm, a metal coating layer coated while being in contact with the oxide powder, a magnetic coating layer coated while being in contact with the metal coating layer, and an oxide coating layer coated while being in contact with the magnetic coating layer Dielectric multilayer coating powder, characterized in that. The dielectric multilayer coating powder according to claim 1 or 2, wherein the metal coating layer has a thickness of 0.005 to 2 µm. The dielectric multilayer coating powder according to claim 1 or 2, wherein the oxide coating layer has a thickness of 0.005 to 2 µm. The dielectric multilayer coating powder of claim 2, wherein the magnetic coating layer has a thickness of 0.005 to 2 μm. The method of claim 1 or 2, wherein the oxide is Al, Ba, Si, Mg, Mn, Zr, Ni, Pb, Ti, Ca, Sr, Fe, Mn, Zn, Cr, Cu, Y and combinations thereof Dielectric multilayer coating powder, characterized in that the oxide of the metal selected from the group consisting of. 3. The dielectric multilayer of claim 1 or 2, wherein the metal is selected from the group consisting of silver, gold, platinum, palladium, copper, nickel, iron, aluminum, molybdenum, tungsten, alloys and mixtures thereof. Coating powder. According to claim 2, wherein the magnetic material is Mn-Zn-based ferrite, Ni-Zn-based ferrite, Mn-Mg-Zn-based ferrite, Ni-Cu-Zn-based ferrite, Fe ₂ O ₃ and Fe ₃ O ₄ Dielectric multilayer coating powder, characterized in that selected. A composite dielectric material in which the dielectric multilayer coating powder according to claim 1 is dispersed in a resin. 10. The composite dielectric material according to claim 9, wherein the composite dielectric material comprises 5 to 60% by volume of dielectric multilayer coating powder. The composite dielectric material according to claim 10, wherein the composite dielectric material comprises a dielectric multilayer coating powder of 30 to 50% by volume. delete delete delete delete

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