JP2003283123A - Laminated substrate and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated substrate in which adhesion between a resin layer and a metal layer is secured even if the substrate is maintained at high temperature for a long time, and to provide a method of manufacturing the same. <P>SOLUTION: A composite layer 2 is inserted between a resin layer 1 and a metal layer 3, wherein the composite layer 2 is formed by dispersing a metal filler in a resin and bonding the particles of the metal filler between each other by melting. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible printed circuit (FPC).
Circuit) and automatic tape bonding (TA
B: Tape Automatic Bonding)
For example, the present invention relates to a laminated substrate and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, with the miniaturization of electronic equipment and the increase in density of printed wiring boards due to higher speeds, resin materials having a small dielectric constant and a high insulation resistance value have been attracting attention as materials for the boards. For example, a copper-polyimide substrate in which at least one surface of a polyimide resin film layer is coated with copper as a metal layer is widely applied as a laminated substrate having excellent heat resistance.

Here, as a method for laminating a metal layer on a film-shaped resin layer, for example, a laminating method in which a resin layer and a metal layer are attached with an adhesive or the like is known. However, the laminated substrate adhered with an adhesive has a problem of poor heat resistance. In addition, there is a problem that the electrical insulation is deteriorated due to the interposition of the adhesive layer between the resin layer and the metal layer. Therefore, without interposing an adhesive layer on the resin layer surface, a sputtering method, an ion plating method,
Many means for directly forming a metal layer by vapor deposition, electroless plating, or a combination of these techniques have been proposed, and among these, electroless plating is widely applied.

The electroless plating method is a method in which the surface of the resin layer is made hydrophilic by using a reducing agent or a reagent such as acid or base, a catalyst is added thereto, and then electroless plating is performed to form a metal coating. (See Japanese Patent Application Laid-Open No. 5-114779). However, in this method, it is difficult to uniformly apply the catalyst over a wide area, and there is a risk that pinholes may be generated during plating. Here, in order to suppress the generation of pinholes during plating, it is common practice to perform dry plating such as a sputtering method before wet plating. For example, JP-A-10-25
In Japanese Patent No. 6700, a base metal layer is formed on the surface of a resin layer by dry plating using at least one selected from nickel, copper-nickel alloy, chromium, and chromium oxide, and further a copper coating is formed by dry plating. After forming a metal coating such as the above, a means for forming a copper conductor layer on this upper surface by electrolytic plating or electroless plating has been proposed. According to this means, it is possible to form a metal layer with few pinholes on the surface of the resin layer. However,
Since a large number of steps including a vacuum process are required, the cost is increased, and the adhesion between the metal layer and the resin layer is weak, and especially when holding at high temperature for a long time, it is sufficient. There was a problem that good adhesiveness could not be obtained.

Therefore, JP-A-10-204646 proposes a means of interposing benzimidazole thiol on the surface of a plastic film, applying a catalyst thereon, and then performing electroless plating and electrolytic plating. ing. According to this means, it is possible to suppress the decrease in the adhesive strength even when kept at a high temperature of 150 ° C. for a long time. However, even with this means, the adhesion strength after the high temperature holding test could not exceed 1 kgf / cm, and there was still room for improvement.

By the way, a resin film is formed on a metal foil by applying and heating a dope of a resin precursor on the upper surface of the metal foil, which is a so-called casting method, which has excellent adhesiveness between the resin layer and the metal layer. It is known that a laminated substrate can be easily provided. However, this method has a problem in that the thickness of the metal layer is limited by the thickness of the metal foil used, so that it cannot be thinner than the metal layer obtained by the plating method. In recent years, a thin metal layer has been earnestly desired as the wiring density becomes narrower, but the laminated substrate formed by this casting method was not suitable for this purpose.

The present invention has been made in view of the above circumstances, and even when it is held for a long time under high temperature conditions,
It is an object of the present invention to provide a laminated substrate capable of ensuring the adhesiveness between the resin layer and the metal layer and a method for manufacturing the laminated substrate.

[0008]

As a result of intensive studies by the present inventors in order to solve such problems, as a result, a mixed layer made of a resin material and a metal material is provided between the resin layer and the metal layer. It was found that the adhesiveness between the resin layer and the metal layer is improved by forming the above, and the present invention has been completed. The present inventors have also found that by imparting conductivity to the mixed layer, a thin metal layer can be easily formed on the upper surface of the mixed layer by electrolytic plating.

The laminated board of the present invention is a laminated board in which a metal layer is laminated on at least one surface of a resin layer, wherein a metal material and a resin material are mixed between the resin layer and the metal layer. It is characterized in that a layer is formed. Here, in the laminated substrate of the present invention, the mixed layer has conductivity and has a volume resistivity of 1 × 10 ⁻¹ Ωcm.
It is preferably less than. In the laminated substrate of the present invention, the mixed layer has a structure in which 5 to 95% by weight of a metal filler as the metal material is dispersed in the resin material, and the particle diameter of the metal filler is 200 nm or less. Is preferred.

Further, in the laminated substrate of the present invention, the mixed layer preferably has a mesh structure in which the metal fillers are fused. Further, in the laminated substrate of the present invention, the mixed layer may have a structure in which the resin material is filled in the pores of a porous metal layer as the metal material. Further, in the laminated substrate of the present invention, it is preferable that the resin material forming the mixed layer is made of an insulating resin.

Further, in the laminated substrate of the present invention, it is preferable that the resin material forming the mixed layer is made of the same material as the resin layer. The method for producing a laminated substrate of the present invention is a method for producing a laminated substrate in which a metal layer is laminated on at least one surface of a resin layer, which comprises a resin material and a metal material laminated on at least one surface of the resin layer. It is characterized in that a metal layer is laminated on the upper surface of the mixed layer.

Here, in the method for manufacturing a laminated substrate of the present invention, it is preferable that the metal layers are laminated by electrolytic plating. Further, in the method for producing a laminated substrate of the present invention, it is preferable that the mixed layer is laminated on the upper surface of the resin layer whose surface is hydrophilized. Furthermore, in the method for manufacturing a laminated substrate of the present invention, the resin material forming the resin layer and the mixed layer is not melted, and the metal material forming the mixed layer is subjected to heat treatment at a melting temperature, It is preferable to include a step of fusing the metal materials.

Further, in the method for manufacturing a laminated substrate of the present invention, it is preferable that the resin material forming the mixed layer is formed of an insulating resin. Further, in the method for manufacturing a laminated substrate of the present invention, it is preferable that the resin material forming the mixed layer is formed of the same material as the resin layer. According to the laminated substrate of the present invention, since the mixed layer made of the resin material and the metal material is formed between the resin layer and the metal layer, the resin material in the mixed layer and the resin layer are bonded, and , The metal material in the mixed layer and the metal layer come to adhere to each other. Therefore, it becomes possible to secure the adhesiveness between the resin layer and the metal layer even when it is held for a long time under high temperature conditions.

Further, according to the laminated substrate of the present invention, by imparting conductivity to the mixed layer, the electroplating method is directly used on the upper surface of the mixed layer without applying conductivity treatment to the upper surface of the mixed layer. Therefore, it is possible to reduce the labor and cost involved in the metal layer forming process. Further, according to the laminated substrate of the present invention, the metal fillers that are the metal materials that form the mixed layer are fused together, and the metal filler has a mesh structure, thereby forming a metal material that forms the mixed layer. Since the entanglement with the resin material becomes large, the strength of the mixed layer can be improved and the conductivity in the mixed layer can be further improved.

Further, according to the laminated substrate of the present invention, by forming the resin material and the resin layer forming the mixed layer from the same material, the adhesiveness between the resin layer and the mixed layer can be further improved. It will be possible. According to the method for manufacturing a laminated board of the present invention, the laminated board of the present invention can be easily realized. Further, according to the method for manufacturing a laminated substrate of the present invention, the metal layer can be formed thin by laminating the metal layer by the electrolytic plating method.

Further, according to the method for manufacturing a laminated substrate of the present invention, the adhesiveness between the resin layer and the mixed layer is further improved by forming the mixed layer on the upper surface of the resin layer whose surface is hydrophilized. It becomes possible. Further, according to the method for manufacturing a laminated substrate of the present invention, the resin material forming the mixed layer is formed of the same material as the resin layer, so that the adhesion between the resin layer and the mixed layer can be further improved. It will be possible.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view showing one structural example of the laminated substrate in the present invention. The laminated substrate 10 according to the present embodiment has a structure in which a composite layer (mixed layer) 2 formed by mixing a resin material and a metal material and a metal layer 3 are sequentially laminated on the upper surface of a resin film (resin layer) 1. Have.

The resin film 1 may be any insulating resin film, for example, PET resin, phenol resin,
Examples include aramid resin and polyimide resin. Here, when laminating a copper thin film as the metal layer 3, a polyimide resin having the same linear expansion coefficient and high heat resistance is most suitable. The thickness of the resin film 1 is not particularly limited, but the thickness usually used for electronic substrates is 30 to 200.
Those having a thickness of μm are preferably used.

The composite layer 2 has a structure in which a metal filler as a metal material is dispersed in a resin material, the metal fillers are fused and the metal material exists in a mesh form. The composite layer 2 is electrically conductive and has a volume resistivity of 1 × 10 ⁻¹ Ωcm or less. Here, the volume resistivity of the composite layer 2 is 1 ×
Composite layer 2 if greater than 10 ^-1 Ωcm
It is not preferable because the ratio of the metal material in the inside is small, the adhesiveness between the composite layer 2 and the metal layer 3 becomes insufficient, and it becomes difficult to directly perform electroplating on the composite layer 2.

The thickness of the composite layer 2 is preferably thin, preferably 0.01 to 5.0 μm, and more preferably 0.01 to 3.0 μm. Composite layer
The type of metal filler constituting 2 is not particularly limited,
For example, materials such as copper, nickel, silver and chrome can be used. Here, in order to fuse the metal fillers to form a mesh structure, the resin materials forming the resin film 1 and the composite layer 2 are melted by heating at a temperature at which they are not decomposed or deteriorated. It is necessary to form the metal filler from a material having a low melting point.

The form of the metal filler is not particularly limited, and examples thereof include spherical, acicular, and polyhedral shapes. Furthermore, the particle size of the metal filler is 200 nm or less,
It is more preferably 100 nm or less, and the proportion of the metal filler in the resin material is 5 to 95% by weight, and further preferably 30 to 95% by weight. Here, when the particle diameter of the metal filler is 200 nm or more, the in-plane uniformity of the plated metal layer formed on the composite layer 2 is deteriorated, and the effect of lowering the melting point of the metal filler is not significant, so that the metal filler is This is not preferable because the fusion temperature between them increases. Further, when the proportion of the metal filler is less than 5% by weight, not only the adhesiveness with the metal layer 3 becomes insufficient, but also the conductivity of the composite layer 2 becomes insufficient, and the upper surface of the composite layer 2 is directly electroplated. It will be difficult to apply. On the other hand, if the proportion of the metal filler exceeds 95% by weight, the adhesiveness with the resin film 1 becomes insufficient, which is not preferable.

The resin material constituting the composite layer 2 is
Any insulating resin may be used, and examples thereof include PET resin, phenol resin, epoxy resin, aramid resin, and polyimide resin. Here, considering the adhesiveness to the resin film 1, it is preferable to use the same material as the resin film 1. For example, when a polyimide resin is used as the resin film 1, it is most preferable that the resin material forming the composite layer 2 is also a polyimide resin.

The metal layer 3 is not particularly limited, but copper having high conductivity and low cost is most preferable. This metal layer 3
Is not particularly limited, but when used as a high-density printed circuit board, it is preferable to make it as thin as possible, preferably 0.1 to 30 μm, and more preferably 0.1 to 1 μm.
The thickness is preferably 5 μm. Next, a method of manufacturing the laminated substrate 10 according to this embodiment will be described. FIG. 2 is a cross-sectional view showing one manufacturing process of the laminated substrate in this embodiment.

First, the resin material forming the composite layer 2 is dissolved in a solvent, and a predetermined amount of the metal filler forming the composite layer 2 is dispersed in the solvent to prepare a dispersion liquid in advance. Here, the surface of the resin film 1 may be chemically or physically treated for the purpose of improving the adhesiveness between the resin film 1 and the composite layer 2. As the chemical hydrophilic treatment, the resin is a basic aqueous solution such as sodium hydroxide or potassium hydroxide, an acidic aqueous solution such as hydrochloric acid or sulfuric acid, a reducing aqueous solution such as hydrazine or formalin, or an oxidizing agent such as hydrogen peroxide solution. Examples include a method of immersing in an aqueous solution and performing heat treatment. Further, examples of the physical hydrophilic treatment include oxygen plasma treatment.

Next, this dispersion is applied to the upper surface of the resin film 1 and dried by heating, so that the composite layer 2 is laminated on the upper surface of the resin film 1 as shown in FIG. Subsequently, the resin material forming the resin film 1 and the composite layer 2 is not melted, and the resin film 1 on which the composite layer 2 is laminated is heated at a temperature at which only the metal filler forming the composite layer 2 is melted. . At this time, the metal fillers composing the composite layer 2 are fused to form a structure in which the metal fillers are present in the composite layer 2 in a mesh shape.

By laminating the metal layer 3 on the upper surface of the composite layer 2, as shown in FIG. 1, the composite layer 2 and the metal layer 3 are laminated on the upper surface of the resin film 1 in this order. Complete 10. The method for laminating the metal layer on the composite layer 2 is not particularly limited, and examples thereof include dry plating methods such as sputtering method, ion plating method and vapor deposition method, and wet plating methods such as electroless plating and electrolytic plating. Can be mentioned. In particular, when the composite layer 2 is provided with conductivity, the electroplating method can be directly used on the upper surface of the composite layer 2 without performing the conductivity providing process.

Here, the method of forming the composite layer 2 on the upper surface of the resin film 1 is not limited to the above-mentioned method. For example, a resin precursor is dissolved in a solvent, and a predetermined amount of a metal filler is dispersed in the solvent. Alternatively, the dispersion may be applied on the upper surface of the resin film 1, the solvent may be removed, and then the resin precursor may be heat-cured to form the dispersion. At this time, when the resin precursor is a solution, it is also possible to directly disperse the metal filler in the resin precursor solution and heat-cur it without using a solvent. For example, when using a polyimide resin that is insoluble in a general-purpose solvent, the metal filler may be directly dispersed in a polyamic acid solution that is a polyimide precursor.

As another method for forming the composite layer 2 on the upper surface of the resin film 1, the composite layer 2 is formed by using a metal oxide filler or metal salt filler having a particle size of 200 nm or less, preferably 100 nm or less as a metal precursor. You may choose to do this. The metal oxide filler is not particularly limited as long as it is a material that can be reduced by a method that does not chemically or thermally affect the resin forming the resin film 1 and the composite layer 2, and examples thereof include cuprous oxide, and second oxide. Examples thereof include copper, nickel oxide, chromium oxide, silver oxide, copper nitrate, copper sulfate, copper acetate, silver acetate and the like. The use of this metal oxide filler is preferable because unnecessary salts do not remain in the composite layer 2.

For example, in order to form the composite layer 2 using a metal oxide filler or a metal salt filler as a metal precursor, first, the metal oxide filler or the metal salt filler is dispersed in a solution of a resin or a resin precursor. Then, this dispersion is applied to the upper surface of the resin film 1. Next, the solvent is dried or the resin precursor is cured, and the metal oxide filler is reduced. The reduction of the metal oxide filler or the metal salt filler may be performed before or after the solvent drying process or the heat curing process of the resin precursor, or may be performed simultaneously with these processes. Further, the reduction of the metal oxide filler or the metal salt filler may be carried out by previously mixing a reducing agent in the dispersion liquid and performing heat reduction, or by reducing with a reducing gas such as hydrogen gas or carbon monoxide gas. You may perform by making it contact.

Further, as another method of forming the composite layer 2, this structure is preliminarily synthesized by utilizing the self-holding property of the structure in which the metal fillers are fused and the metal fillers are present in a mesh shape. Alternatively, this structure may be formed by impregnating a resin. Specifically, first, a structure is prepared in which the metal fillers are fused and the metal fillers are present in a mesh shape. Next, a solution of a resin or a resin precursor is applied on the upper surface of the resin film 1, and a structure prepared in advance is attached to the solution,
By heating, the solvent is volatilized or the resin precursor is cured. At this time, if the resin precursor is a solution, it is not necessary to use a solvent.

Further, the step of fusing the metal filler constituting the composite layer 2 is not limited to this, and the process of laminating the composite layer 2 on the upper surface of the resin film 1, that is, the dispersion liquid in which the resin material is dispersed is used. In the process of heating and drying or the process of curing the resin precursor, by adjusting the fusion temperature of the metal filler to the required heating temperature, the lamination of the composite layer 2 and the fusion between the metal fillers can be realized at the same time. Good. At this time, the particle size is 200
It is known that the melting point of metal fine particles of nm, preferably 100 nm or less is significantly lower than that of the bulk material. Since this melting point depends on the particle diameter, the melting point can be controlled by controlling the particle diameter of the metal filler. It is also possible to adjust.

According to the laminated substrate 10 of this embodiment, the composite layer 2 formed by mixing the resin material and the metal material is formed between the resin film 1 and the metal layer 3, so that the composite layer 2 The resin material and the resin film 1 adhere to each other, and the metal material in the composite layer 2 adheres to the metal layer 3. Therefore, it becomes possible to secure the adhesiveness between the resin film 1 and the metal layer 3 even when it is held for a long time under high temperature conditions.

Further, according to the laminated substrate 10 of this embodiment, since the composite layer 2 is provided with the conductivity, the composite layer 2 is directly provided on the top surface of the composite layer 2 without performing the conductivity providing process on the top surface of the composite layer 2. An electrolytic plating method can be used. Therefore, it is possible to reduce the labor and cost required for forming the metal layer 3. Furthermore, according to the laminated substrate 10 of the present embodiment, the composite layer 2 is formed by fusing the metal fillers, which are the metal materials forming the composite layer 2, to form a mesh-like structure. The entanglement between the metal material and the resin material is increased. Therefore, composite layer 2
It is possible to improve the strength of the composite layer and further improve the conductivity of the composite layer 2.

In the laminated substrate 10 of the present embodiment, the composite layer 2 has a structure in which a metal filler as a resin material is dispersed in the resin material. However, in the composite layer 2, the resin material and the metal material are mixed. However, the present invention is not limited to this, and for example, the pores of the porous metal film may be filled with a resin material.

[0035]

EXAMPLES Next, the effects of the present invention will be verified by the following examples. (Invention Example 1) First, 10.0 g of bis (4-aminophenyl) ether and 10.9 g of pyromellitic dianhydride are dissolved in 100 g of N-methylpyrrolidone (NMP), and the mixture is stirred at room temperature for 1 hour. Therefore, NM of polyamic acid
A P solution was obtained.

Next, this polyamic acid NMP solution 5
In g, 5 g of cupric oxide nanoparticles having an average particle diameter of 30 nm (manufactured by CI Kasei Co., Ltd.) was added as a metal filler, and a stirring mode was used with a stirring defoaming machine (HM-500, manufactured by Keyence Corporation). The dispersion treatment was performed under the conditions of 10 minutes and 5 minutes in the defoaming mode. As the metal filler, the particle size of copper oxide was measured using a laser scattering particle size distribution meter (LA-920) manufactured by Horiba, Ltd.

Next, this dispersion was applied as a resin film onto a polyimide film (Kapton film manufactured by Toray DuPont Co., Ltd., film thickness 50 μm) cut into a size of 3 × 3 cm, and 350 ° C. in a hydrogen atmosphere. A reduction treatment was performed for 1 hour under the temperature condition of 1 to form a composite layer on the polyimide film in which copper nanoparticles and polyimide were mixed. Here, the obtained composite layer had conductivity, and the volume resistivity was 4 × 10 ⁻⁵ Ωcm. The volume resistivity of the composite layer was obtained by using a resistivity meter Lorester GP (manufactured by Mitsubishi Chemical Corporation).

Next, 80 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 180 g of sulfuric acid were dissolved in 1 liter of purified water to prepare an electrolytic plating bath. Then, the polyimide film having the composite layer formed on the upper surface is immersed in this electrolytic plating bath, and electrolytic copper plating is performed at room temperature at a current density of 3 A / dm ² to form a metal layer having a thickness of 7
A copper thin film layer of μm was formed to complete the laminated substrate. With respect to the obtained laminated plate, a heat resistance test was carried out by holding it at 150 ° C. for 24 hours in the air, and then the heat resistant adhesion strength was evaluated. As a result, the strength was 1.3 kgf / cm. The adhesion strength was determined as peeling strength according to JIS C6481 (180 degree peel). (Invention Example 2) First, 5 g of cupric oxide nanoparticles having an average particle diameter of 30 nm (manufactured by CI Kasei Co., Ltd.) were added to 5 g of diethylene glycol (boiling point: 249 ° C.), and the same method as in Invention Example 1 was performed. Dispersion processing was performed. As the metal filler, the particle size of copper oxide was measured by the same method as in Inventive Example 1.

Next, this dispersion was applied onto a slide glass so as to have a length of 2 cm, a width of 1 cm and a thickness of 10 μm. Next, this slide glass was put into a firing furnace, the inside of the furnace was deaerated with a vacuum pump, and then hydrogen gas was caused to flow at a flow rate of 1 liter / min. Next, the temperature of the firing furnace was raised from room temperature to 250 ° C. over 1 hour, and after reaching 250 ° C., heating was further performed at this temperature for 1 hour. By this heat treatment, diethylene glycol volatilizes.

Then, the slide glass was cooled to obtain a porous copper thin film in which copper particles were fused to each other and were present in a mesh shape on the slide glass. Here, the porous copper thin film has a porous structure with a pore diameter of 300 nm and a thickness of 1 μm.
It was m. The pore size on the surface of the porous copper thin film is
Using Hitachi SEM (S-4700),
The sample surface O _S plasma coating process (about 3n
m) and then observed under the condition of an acceleration voltage of 2 kv.

Then, as a resin film, 3 × 3 cm
On a polyimide film cut into a size of, a NMP solution of a polyamic acid obtained by the same method as in Invention Example 1 was applied, and a porous copper thin film was stuck thereon, and a porous copper thin film and a polyimide film were formed. To form a laminate. Next, this laminate is subjected to a heat treatment at a temperature of 350 ° C. for 1 hour in a nitrogen atmosphere to imidize the polyamic acid to form a mixture of porous copper and polyimide on the polyimide film. . Here, the thickness of this composite layer was 3 μm. The composite layer had conductivity and had a volume resistivity of 1 × 10 ⁻⁵ Ωcm. The volume resistivity of the composite layer was measured by the same method as in Inventive Example 1.

Then, on the upper surface of this composite layer, an electrolytic plating method similar to that of the first example of the present invention was used to form a metal layer.
A copper thin film having a thickness of 7 μm was formed to complete the laminated substrate.
In the obtained laminated board, it was placed in the atmosphere at 150 ° C. for 24 hours.
When a heat resistance test for holding for a time was performed and then the heat resistance adhesion strength was evaluated, the strength was 1.4 kgf / cm. The adhesion strength was measured by the same method as in Inventive Example 1. (Comparative Example) First, in 9.7 g of a polyamide solution prepared in the same manner as in Inventive Example 1, as a metal filler, an average particle size of
A composite layer obtained by mixing copper and polyimide on a polyimide film in the same manner as in Inventive Example 1 except that 0.3 g of cupric oxide nanoparticles (manufactured by CI Kasei Co., Ltd.) having 0 nm are dispersed. Was formed. Here, the proportion of copper in this composite layer was 2.4% by weight, and the film thickness was 2 μm.

Then, a pretreatment agent for electroless plating (MSC-27, MSS-27, M) is formed on the upper surface of the composite layer.
SA-27, MSP-27, manufactured by Uemura Kogyo Co., Ltd.) was used for pretreatment of electroless plating. Then, 10 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 30 g of ethylenediaminetetraacetic acid disodium salt (manufactured by Wako Pure Chemical Industries, Ltd.), and formalin solution (manufactured by Wako Pure Chemical Industries, Ltd.) 5 ml was dissolved in 1 liter of pure water to form an electroless plating solution.

Next, electroless plating is carried out under the conditions of pH 12.5 and liquid temperature of 60 ° C. to form a conductive layer, and then electrolytic plating is carried out under the same conditions as in Inventive Example 1, and copper is deposited on the upper surface of the conductive layer. The plated layer was thickened to form a copper thin film of 7 μm in total, and the laminated substrate was completed. With respect to the obtained laminated plate, a heat resistance test was carried out by holding it at 150 ° C. for 24 hours in the air, and then the heat resistant adhesion strength was evaluated.
Its strength was 0.1 kgf / cm.

As described above, from the results of Examples 1 and 2 of the present invention and Comparative Example, in the present invention in which the composite layer in which the resin material and the metal material are mixed is sandwiched between the resin film and the metal layer. In the laminated substrate, it was confirmed that the adhesiveness between the resin film and the metal layer could be secured even when the laminated substrate was kept under high temperature conditions for a long time.

[0046]

As described above, according to the laminated substrate of the present invention, since the mixed layer made of the resin material and the metal material is sandwiched between the resin layer and the metal layer, the high temperature condition is satisfied. Even when it is held for a long time, it becomes possible to secure the adhesiveness between the resin layer and the metal layer. Further, by imparting conductivity to the mixed layer, it becomes possible to reduce the labor and cost involved in the film forming process of the metal layer. According to the method for manufacturing a laminated board of the present invention, the laminated board of the present invention can be easily realized.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing one structural example of a laminated substrate of the present invention.

FIG. 2 is a cross-sectional view showing one manufacturing process of the laminated substrate of the present invention.

[Explanation of symbols]

1 Resin film (resin layer) 2 Composite layer (mixed layer) 3 metal layers 10 Laminated board

Claims (13)

[Claims] 1. A laminated substrate in which a metal layer is laminated on at least one surface of a resin layer, wherein a mixed layer made of a metal material and a resin material is formed between the resin layer and the metal layer. A laminated substrate characterized by being. 2. The mixed layer is electrically conductive and has a volume of
Resistivity is 1 × 10 ^-1Characterized by less than Ωcm
The laminated substrate according to claim 1. 3. The mixed layer has a structure in which 5 to 95% by weight of a metal filler as the metal material is dispersed in the resin material, and the particle diameter of the metal filler is 200 nm.
The following is the laminated substrate according to claim 1 or 2. 4. The laminated substrate according to claim 3, wherein the mixed layer has a mesh structure in which the metal fillers are fused to each other. 5. The laminated substrate according to claim 1, wherein the mixed layer has a structure in which a hole of a porous metal layer as the metal material is filled with the resin material. 6. The resin material forming the mixed layer,
An insulating resin is used, and it is characterized by the above-mentioned.
The laminated substrate according to any one of 1. 7. The resin material forming the mixed layer,
7. The laminated substrate according to claim 1, wherein the laminated substrate is made of the same material as the resin layer. 8. A method of manufacturing a laminated substrate, in which a metal layer is laminated on at least one surface of a resin layer, wherein a mixed layer made of a resin material and a metal material is laminated on at least one surface of the resin layer. A method for manufacturing a laminated substrate, which comprises laminating metal layers. 9. The method for manufacturing a laminated substrate according to claim 8, wherein the metal layer is laminated by an electrolytic plating method. 10. The method for producing a laminated substrate according to claim 8, wherein the mixed layer is laminated on the upper surface of the resin layer whose surface is hydrophilized. 11. The resin material forming the resin layer and the mixed layer is not melted, and the metal material forming the mixed layer is heat-treated at a melting temperature to fuse the metal materials. The method for manufacturing a laminated substrate according to claim 8, further comprising: 12. The method of manufacturing a laminated substrate according to claim 8, wherein the resin material forming the mixed layer is formed of an insulating resin. 13. The method of manufacturing a laminated substrate according to claim 8, wherein the resin material forming the mixed layer is formed of the same material as the resin layer.