JPH04206994A - Fabrication of multilayer ceramic composite board - Google Patents

Abstract

PURPOSE:To obtain high heat shock resistance even upon absorption of moisture by etching the copper foil of a ceramic compound, copper-laminated, layered board to form a circuit pattern and after treating the etching exposed surface of ceramic spray fused layer with silane coupling agent, a multi-layer attachment prepeg is placed on this copper foil and a copper-laminated, layered board or a copper foil is attached to create multiple layers. CONSTITUTION:A ceramic compound, copper-laminated, layered board with an alumina spray fused layer 2 and a copper foil 1 are used on both sides of a glass fabric based resin base 3 and after applying an etching resist to the copper foil 1, a circuit pattern is formed through etching and the etching resist is removed. Next, this ceramic compound, copper-laminated, layered board is dipped into a y-glycydoxy propyl trimethoxy silane methanol solution and after drying, the surface of the alumina spray fused layer exposed by etching are treated with silane coupling agent. After that, a copper foil 4 is layered on top of the ceramic compound, copper-laminated, layered board's copper foil 1, which forms the circuit pattern, using an epoxy-resin prepeg for multi- layer attachment, is thermal-pressure molded, and attached to form a multi-layer structure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a ceramic composite multilayer board with excellent thermal shock resistance using a ceramic composite copper clad laminate.

[Prior Art] Recently, with the progress of miniaturization and higher performance of electronic devices, the printed circuit boards and wiring boards used therein are becoming more dense by increasing the number of layers or shortening the circuit width.

Conventional methods for producing multilayer boards have mainly used glass cloth-based one-piece poxy resin copper-clad laminates or glass cloth-based polyimide resin copper-clad laminates, and the copper of these copper-clad laminates is used as the inner layer. After forming a circuit pattern by etching, a single-sided copper-clad laminate or copper foil is bonded to it via a multilayer adhesive prepreg, and then aligned with the inner layer circuit pattern using reference holes. A method is used in which the circuit pattern on the outer layer is formed by

However, there is a growing demand for multi-layered boards with higher multilayers and higher densities, and in response to these demands, glass cloth (copper clad made of Epoquin resin or glass cloth-based polyimide resin) has become stronger. In the conventional manufacturing method of multilayer boards using laminates, there are large variations in the method or dimensional changes of copper-clad laminates during the etching, multilayer pressing, and solder resist forming processes in the multilayer process. However, the position of the circuit pattern between each layer tends to be misaligned, which reduces the manufacturing yield of the multilayer board and does not necessarily improve productivity. There is a strong demand for a method for manufacturing multilayer boards.In addition, surface mounting of components on substrates is progressing, and in order to ensure reliability of connection with components,
There is also an increasing demand for a method that can manufacture a multilayer board with high reliability of connection to components using a copper-clad laminate having a substrate with low thermal expansion.

On the other hand, as a copper-clad laminate with improved dimensional stability and low thermal expansion, a ceramic composite copper-clad laminate has been proposed (Japanese Unexamined Patent Publication No. 152742/1983). This is a material in which a ceramic sprayed layer is provided between a copper foil and a reinforced plastic layer such as a glass cloth-based epoxy resin or a glass cloth-based polyimide resin. Since it has a ceramic sprayed layer in contact with the copper foil, it has a lower coefficient of thermal expansion and better voltage resistance than conventional copper-clad laminates. In addition, the copper foil peel strength and surface hardness are also good.

Furthermore, unlike conventional ceramic substrates, drilling process similar to that of copper-clad laminates using glass cloth-based epoxy resin, etc.
It has the feature that construction methods such as through-hole formation are possible.

[Problems to be Solved by the Invention] When a multilayer board is produced using the above-mentioned ceramic composite copper-clad laminate, dimensional changes in the multilayering process are significantly reduced due to the low coefficient of thermal expansion. Furthermore, since the coefficient of thermal expansion of the board itself is lowered, the reliability of connection with components is greatly improved.

When a ceramic composite copper-clad laminate is applied to a multilayer board in this way, various properties are improved. However, the thermal shock resistance, especially the thermal shock resistance upon moisture absorption, is not improved. That is, the interface between the prepreg layer used for multilayer adhesion and the ceramic layer exposed by etching tends to peel off due to thermal shock caused by the solder dip during moisture absorption. Therefore, in order to further improve the reliability when mounting components on a board, it is necessary to further improve the method to prevent interfacial peeling between the prepreg layer and the ceramic layer.

In order to solve these problems, the present invention provides a method for manufacturing a ceramic composite laminate that uses a ceramic composite copper-clad laminate to easily manufacture a ceramic composite laminate that has high thermal shock resistance even when moisture is absorbed. This is what we are trying to provide.

[Means for Solving the Problems] The present invention uses a ceramic composite copper-clad laminate having a ceramic sprayed layer between the copper foil and the reinforced plastic layer, and After etching to form a circuit pattern and treating the surface of the ceramic sprayed layer exposed by etching with a silane coupling agent, the circuit pattern is placed on the copper foil via a multilayer adhesive prepreg to form a copper-clad laminate. Alternatively, the present invention provides a method for producing a ceramic composite multilayer board, characterized in that the multilayered ceramic composite board is formed by bonding copper foil.

In the method for manufacturing a ceramic composite multilayer board of the present invention, a ceramic composite copper-clad laminate is used.

A ceramic composite copper-clad laminate has a ceramic sprayed layer between a copper foil and a reinforced plastic layer.

The thickness of the copper foil for the ceramic composite copper clad laminate is 18μ.
Preferably, the thickness is from m to 105 μm.

The reinforced plastic layer is usually made of glass cloth-based epoxy resin or glass cloth-based (4 polyimide resin is preferred.The thickness of the reinforced plastic layer is 0.05 mm.
~1.6 mm is preferred.

The +3 qualities of the ceramic sprayed layer between the copper foil and the reinforced plastic layer include alumina, mullite, spinel,
Titania, zircon, silica, Zugerai l-, magnesia, zirconia, and calcia are preferably used. Among these, alumina is particularly suitable from the viewpoint of heat dissipation, and cordierite is particularly suitable from the viewpoint of drill workability. The thickness of the ceramic sprayed layer is:
The thickness is preferably 15 μm to 200 μm.

Such a ceramic composite copper-clad laminate can be formed by thermally spraying ceramic onto a copper foil surface to form a ceramic sprayed layer, and then hot-pressing a reinforced plastic layer on the ceramic sprayed layer -L.

In the present invention, the ceramic composite copper clad laminate described in 1. is used, and after etching the copper foil of the ceramic composite copper clad laminate to form a circuit pattern, the surface of the ceramic sprayed layer exposed by the etching is etched with silane. Treat with coupling agent.

The surface of the ceramic sprayed layer exposed by etching can be treated with a silane coupling agent. It is also possible to treat the surface exposed by etching the ceramic sprayed layer by treating the entire surface with a silane coupling agent. Specifically, for example, a method of etching the copper foil on the surface of a ceramic composite copper-clad laminate to form a circuit pattern, and then immersing the ceramic composite copper-clad laminate in a silane coupling agent solution and then drying the circuit pattern. A method in which a silane coupling agent solution is applied to the surface of a ceramic composite copper-clad laminate with a circuit pattern formed thereon by applying a silane coupling agent solution using a brush, a sponge roller, etc., and then dried. One method is to apply it with a spray.

-7= As a silane coupling agent, vinyltrichlorosilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-benzylaminopropyltrimethoxysilane (β-me I xy) silane, γ-glyside Xypropyl trime 1-xysilane, N-β (aminoethyl)-γ
-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-chloropropyltrimethoxysilane.

These silane coupling agents can be used after being diluted with a solvent if necessary. As a solvent for diluting the silane coupling agent, water, methanol, ethanol, etc., or a mixture thereof can be used.

The surface of the ceramic sprayed layer is treated with a silane coupling agent, for example, when using a γ-crisitoxypropyltrimethoxysilane solution, the ceramic composite copper-clad laminate is immersed in this solution for 3 minutes and then heated for 50 minutes. ．． It is preferable to dry at 0 O 0 C for 30 minutes to 5 hours.

After the surface of the ceramic sprayed layer exposed by etching is treated with a silane coupling agent, the ceramic sprayed layer treated with the silane coupling agent is brought into contact with the multilayer adhesive prepreg. , a copper foil with a circuit pattern formed thereon, which is then multilayered by adhering a copper clad laminate or copper foil through a multilayer adhesive prepreg;
Ceramic composite multilayer plates can be manufactured.

A method for bonding a copper clad laminate or copper foil via a multilayer adhesive prepreg is to sequentially laminate a multilayer adhesive prepreg, a copper clad laminate, or a copper foil on a copper foil on which a circuit pattern has been formed. A method of bonding by hot-pressing molding is preferred.

As the prepreg for multilayer adhesion, those used for the multilayering of ordinary multilayer boards can be suitably used. Specifically, for example, a glass cloth base epoxy resin prepreg or a glass cloth base polyimide resin prepreg may be mentioned. The thickness of the prepreg for multilayer adhesive is 0.
．． 05 mm to 02 mm is preferable.

The thickness of the copper foil to be bonded is preferably 5 μm to 70 μm.

It is preferable to form a circuit pattern on the bonded copper foil or the copper foil of a copper-clad laminate by etching the circuit pattern by properly aligning it with the circuit pattern on the inner layer using reference holes or the like.

[Function] The ceramic sprayed layer of the ceramic composite copper-clad laminate is formed on the copper foil surface by thermal spraying, and therefore is a porous layer with a porosity of 7 to 20% by volume.

Therefore, when a prepreg for multilayer adhesive is bonded to this, the resin of the prepreg is impregnated into the pores. Furthermore, the surface of the ceramic sprayed layer exposed by etching the copper foil and bonded to the prepreg for multilayer adhesive is a rough surface with fine irregularities, to which the assembled surface of the copper foil is directly transferred. Because the ceramic sprayed layer is impregnated with resin and the surface of the ceramic sprayed layer is a finely rough surface that can exert an anchoring effect, the adhesion between ceramic and resin, which are originally dissimilar abrasive materials, is extremely low. Despite this, the ceramic composite multilayer board has high adhesion between the ceramic sprayed layer and the multilayer adhesive prepreg. However, when it absorbs moisture, its adhesion deteriorates.

Therefore, in the present invention, the surface of the ceramic sprayed layer exposed by etching, that is, the surface of the ceramic sprayed layer to be bonded to the prepreg for multilayer adhesive, is treated with a silane coupling agent, so that the silane coupling agent can bond between the ceramic and the prepreg. By utilizing the bonding effect between the resins, we have achieved a significant improvement in the adhesion between the ceramic sprayed layer and the multilayer adhesive prepreg. Therefore, the thermal shock resistance of the resulting ceramic composite multilayer board upon moisture absorption is improved, and peeling of the interface between the ceramic sprayed layer and the multilayer adhesive prepreg due to the solder dip upon moisture absorption is prevented.

[Example] Hereinafter, the present invention will be further explained with reference to Examples.

Example].

A ceramic composite multilayer plate having the laminated structure shown in FIG. 1 was manufactured. That is, plate thickness 0, 4. Ceramic composite copper clad laminate (MCL-CE-67,1-1) with a 100 μm thick alumina sprayed layer 2 and a 35 μm thick copper foil 1 on both sides of a glass cloth base material epoxy resin base 3 of 100 mm thick.
An etching resist was formed on the copper foil 1 using a copper foil (manufactured by Rikkasei Kogyo), and after etching was performed to form a circuit pattern, the etching resist was removed. Next, this ceramic composite copper-clad laminate was immersed in a 3% methanol solution of γ-glycidoxypropyltrimethoxysilane (A-187, manufactured by Nippon Unicar) for 2 minutes, air-dried for 10 minutes, and then dried at 70°C for 2 minutes. After drying for a while, the surface of the alumina sprayed layer exposed by etching was treated with a silane coupling agent. Next, on the copper foil 1 on which the circuit pattern of this ceramic composite copper-clad laminate was formed, a prepreg for multilayer adhesive made of epoxy resin (Hitachi Chemical Co., Ltd.) was applied.
Copper foil 4 (thickness: 18 μm) was laminated with a copper foil 4 (thickness: 18 μm) interposed in a layer (manufactured by Co., Ltd.) 5, followed by hot-press molding and adhesion to form a multilayer ceramic composite board.

The copper foil on the surface of the resulting ceramic composite four-layer board was etched over the entire surface. Four similar products were manufactured, put into a pressure soldering tester, subjected to moisture absorption treatment for 1, 2, and 3.4 hours under the conditions of 121°, 012 atm, and then dipped in a soldering bath at 260°C. No blistering caused by delamination n1 was observed in the four-layer ceramic composite board.

Comparative Example 1 A ceramic composite 4-layer board was prepared with the same configuration as in Example and treated with a silane coupling agent, and the same test was conducted, and it was found that no blistering occurred after 1 hour of pressure-packing treatment. However, in the case where the process was carried out for 2 hours or more, the interface between the prepreg layer and the ceramic layer was blistered 11 years after dipping into the solder bath.

[Effects of the Invention] According to the method for producing a ceramic composite multilayer board of the present invention, a ceramic composite copper-clad laminate is used to produce a ceramic composite that has excellent dimensional stability, a low coefficient of thermal expansion, and excellent thermal shock resistance when absorbing moisture. It is possible to obtain a multilayer board, and it is possible to meet the demands for higher multilayers and higher densities of multilayer boards, which are expected to become more demanding in the future.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing the laminated structure of a four-layer ceramic composite plate manufactured in an example of the present invention. Explanation of symbols] Copper 2 Alumina sprayed layer 3 Glass cloth 7i! ; 4,1 epoxy resin base 4 Copper foil 5 Prepreg for multilayer adhesive

Claims (3)

[Claims] 1. Using a ceramic composite copper clad laminate having a ceramic sprayed layer between the copper foil and the reinforced plastic layer, the copper foil of this ceramic composite copper clad laminate is etched to form a circuit pattern, and the ceramic sprayed exposed by the etching is After the surface of the layer is treated with a silane coupling agent, a copper-clad laminate or copper foil is bonded onto the copper foil on which a circuit pattern is formed via a multilayer adhesive prepreg to form a multilayer. A method for manufacturing a ceramic composite multilayer board. 2. 2. The method for manufacturing a ceramic composite multilayer board according to claim 1, wherein the ceramic sprayed layer of the ceramic composite copper-clad laminate is a ceramic sprayed layer mainly composed of cordierite. 3. 2. The method for manufacturing a ceramic composite multilayer board according to claim 1, wherein the ceramic sprayed layer of the ceramic composite copper clad laminate is a ceramic sprayed layer mainly containing alumina.