JPH0454577B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is applicable to printed wiring boards, hybrid ICs,
The present invention relates to metal core epoxy resin copper-clad laminates with good heat dissipation properties used for circuit boards and LSI mounting boards. [Prior art] Conventionally, epoxy resin, glass cloth-based epoxy resin prepreg, polyimide resin, glass cloth-based polyimide resin prepreg, polyimide film with double-sided adhesive, etc. have been applied on a metal core such as an aluminum plate, anodized aluminum plate, or copper plate. A metal core copper clad laminate is manufactured by bonding copper foil through an insulating resin layer. To improve the adhesion between the metal core and the insulation layer,
Various studies have been made. For example, Research and Practical Application Report Vol. 18 No. 12 (1969)
describes that the adhesion between the aluminum surface and the insulating resin layer can be increased by mechanically polishing the aluminum plate and then subjecting it to a chromic acid treatment. In addition, in 1982-25826, a method of alumite treatment of aluminum plates was proposed;
55-12754 proposes a method of etching an aluminum plate with an alkali or treating a copper plate with an acetic acid system, and Japanese Patent Publication No. 56-17227 proposes a method of mechanically roughening a metal plate. [Problems to be Solved by the Invention] These metal core epoxy resin copper-clad laminates are required to have heat resistance properties after being subjected to various treatments. For example, solder heat resistance after moisture absorption treatment, etc. When the metal plate is treated as described above, the adhesion between the metal plate and the epoxy resin is good under normal conditions, but in the solder heat resistance test after the severe moisture absorption treatment, separation occurs between the metal and the epoxy resin. There are cases. The purpose of the present inventors is to improve the adhesive strength so that when an epoxy resin layer is used as an insulating layer, no peeling occurs between the metal plate and the epoxy resin in a soldering heat resistance test after moisture absorption treatment. Therefore, various surface treatments for metal plates were investigated, and the present invention was arrived at. [Means for solving the problem] The method for producing a metal core epoxy resin copper-clad laminate of the present invention includes mechanically polishing a metal plate, applying an amino-based silane coupling agent solution, and drying the solvent. After that, a copper foil is placed on the treated surface with an epoxy resin layer interposed therebetween and cured under heat and pressure. Next, the present invention will be explained in more detail. Metal plates used in the present invention include aluminum plates, alumite plates, copper plates, silicon steel plates,
Examples include galvanized steel plates, iron-nickel 42 alloy plates, amber plates, and clad plates made by bonding these metal plates together. Aluminum plates are preferred because of their excellent heat dissipation and ease of workability. Methods for mechanically polishing metal plates include sanding with abrasive paper, polishing cloth, etc., brush polishing,
ball polishing, sandplast, liquid honing,
There are methods such as shot blasting. After the adhesive surface of the metal plate is mechanically roughened by such a method, the remaining abrasive powder and metal powder are thoroughly washed away. The amino-based silane coupling agents used in the present invention include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, and N-β(aminoethyltrimethoxysilane). )γ
-aminopropylmethyldimethoxysilane, p-
Examples include aminophenyltrimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Preferred is γ-aminopropyltriethoxysilane. These amino-based silane coupling agents have a concentration of 0.01 to 5.0% by weight, preferably 0.1 to 5.0% by weight.
It is dissolved in a single or mixed solvent such as water, methanol, ethanol, toluene, xylene, etc. to a concentration of 1.0% by weight, and the solution is applied to the polished metal plate described above. As a coating method, spray coating, dipping coating, etc. are used. Thereafter, the solvent is removed by heating and drying. The temperature at this time is 50
The temperature range is preferably from ℃ to 250℃, more preferably
The temperature ranges from 80℃ to 200℃. Further, by applying reduced pressure, it is also possible to dry the solvent at room temperature or a temperature close to room temperature. The epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups on average per molecule, but examples include diglycidyl ether type epoxy resin of bisphenol A, butadiene diepoxide , 4,4′-di(1,2-
epoxyethyl) diphenyl ether, 4,4'-
Di(epoxyethyl) diphenyl, diglycidyl ether of resorcinol, diglycidyl ether of phloroglycin, triglycidyl ether of p-aminophenol, 1,3,5-tri(1,2-
epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol novolak, triglycidyl ether of trimethylolpropane, cresol novolak Polyglycidyl ether of glycerin, triglycidyl ether of glycerin, diglycidyl ether type epoxy resin of halogenated bisphenol A, polyglycidyl ether of halogenated phenol novolak, triglycidyl isocyanurate, vinyl cyclohexene dioxide, 3,4
-Alicyclic epoxy resins such as -epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, hydantoin epoxy resins, and the like. These epoxy resins are usually used in the form of an epoxy resin composition containing a curing agent, curing accelerator, etc., and may be used either dissolved in a solvent or in a solvent-free form. As the curing agent, an amine curing agent, an acid anhydride curing agent, a phenol curing agent, a polyamide resin curing agent, an imidazole curing agent, etc. are used.
Particularly preferred is dicyandiamide. As the epoxy resin layer in the present invention, a prepreg obtained by impregnating a base material with an epoxy resin varnish and drying the solvent may be used, or an epoxy resin composition containing a filler or the like may be used. Alternatively, only the epoxy resin composition may be used since it does not contain a base material or filler. Base materials include glass cloth, glass paper, paper,
Quartz fiber cloth, aromatic polyamide fiber cloth, etc. can be used. Further, as the filler, it is possible to use powders such as beryllia, boron nitride, magnesia, alumina, and silica. The copper foil used in the present invention is generally an electrolytic copper foil, but it is also possible to use a rolled copper foil. When the epoxy resin layer is prepreg, the required number of prepregs are layered on one or both sides of a metal plate treated with an amino-based silane coupling agent, and then copper foil is layered on the outside, and the metal core is cured by heating and pressure. An epoxy resin copper-clad laminate is obtained. If the epoxy resin layer is an epoxy resin composition alone or an epoxy resin composition containing a filler, apply these varnishes to the adhesive surface of copper foil or the adhesive surface of a metal plate treated with an amino-based silane coupling agent. A metal core epoxy resin copper-clad laminate can be obtained by applying the resin to one or both of them, then drying them, overlapping them, and curing them under heat and pressure. The metal core epoxy resin copper-clad laminate obtained by the present invention has excellent adhesive strength between the metal plate and the epoxy resin under normal conditions as well as solder heat resistance after moisture absorption treatment. The present invention will be described in detail below using examples. However, the present invention is not limited to the following examples. [Examples] Example 1 This example relates to an aluminum core single-sided copper-clad laminate using an epoxy resin prepreg for the epoxy resin layer. The adhesive side of the 1.0mm thick aluminum plate,
After sanding in the vertical and horizontal directions using 1200-grit abrasive paper, it was thoroughly washed with water. This aluminum plate
0.3% of γ-aminopropyltriethoxysilane
After being immersed in the aqueous solution for 1 minute, it was dried at 120°C for 30 minutes. 3.0 parts by weight of dicyandiamide was added to a solution in which 100 parts by weight of bisphenol A type epoxy resin manufactured by Yuka Ciel Co., Ltd., trade name Epicote 1001 (softening point: 70°C, epoxy equivalent: 490 g/eq.) was uniformly dissolved in 24 parts by weight of methyl ethyl ketone. Add a solution dissolved in 45 parts by weight of ethylene glycol monomethyl ether,
Furthermore, benzyldimethylamine is added as a curing accelerator.
Epoxy resin varnish A with a resin content of 60% by weight was prepared by adding 0.2 parts by weight. After impregnating Nittobo glass cloth G-7010-BZ-2 (thickness 0.1 mm) with this epoxy resin varnish A, dry coating was applied at a coating temperature of 160°C and a coating speed of 3 m/min to remove the solvent. A prepreg with a resin content of 45% by weight was obtained. These two prepregs were stacked on the aluminum plate treated with the aminosilane coupling agent after polishing, and on top of that, an electrolytic copper foil (TAI treated, 35 μm thick) manufactured by Furukawa Circuits Oil Co., Ltd. was stacked.
Heat and pressure harden at 170℃ for 2 hours at a pressure of 40Kgf/ ^cm2 ,
An aluminum core epoxy resin copper-clad laminate was obtained. Table 1 shows the measurement results of the properties of this laminate.
In the 260℃ soldering heat resistance test under normal conditions and after moisture absorption treatment (boiling for 1 hour), there was no abnormality after floating for 5 minutes.
It has excellent adhesion between the aluminum plate and the resin, and has a high copper foil peel strength value. The drawing is a cross-sectional view of a metal core epoxy resin single-sided copper-clad laminate manufactured by the manufacturing method of the present invention, in which 1 is a copper foil, 2 is an epoxy resin layer, 3 is a treated surface of a metal plate treated with an amino-based silane coupling agent after polishing, and 4 is a metal plate. Example 2 This example relates to an aluminum core single-sided copper-clad laminate in which an epoxy resin structure is used alone in the epoxy resin layer. Epoxy resin varnish A prepared in Example 1 was applied onto the roughened surface of electrolytic copper foil (TAI treated, thickness 35 μm) using an applicator and dried at 160° C. for 10 minutes. The resin thickness after drying was 50 μm. After polishing this epoxy resin-coated copper foil in the same manner as in Example 1, it was stacked on an aluminum plate treated with an aminosilane coupling agent, and then heated at a pressure of 40 kgf/cm ² .
Heat and pressure curing was performed at 170° C. for 2 hours to obtain an aluminum core epoxy resin single-sided copper-clad laminate. Table 1 shows the measurement results of the properties of this laminate.
In the 260℃ soldering heat resistance test under normal conditions and after moisture absorption treatment (boiling for 1 hour), there was no abnormality after floating for 5 minutes.
It has excellent adhesion between the aluminum plate and the resin, and has a high copper foil peel strength value. Comparative Example 1 An aluminum core epoxy resin copper-clad laminate was produced in the same manner as in Example 1 except that the aluminum plate was used without treatment. The properties are shown in Table 1, and in both the solder resistance heat test under normal conditions and after moisture absorption treatment (boiling for 1 hour), peeling occurred at the interface between the aluminum plate and the epoxy resin after floating for 1 minute. Comparative Example 2 An aluminum core epoxy resin copper-clad laminate was produced in the same manner as in Example 1, except that the aluminum plate was only subjected to polishing treatment (without silane coupling agent treatment). The characteristics are shown in Table 1. In the normal soldering heat resistance test, peeling occurred at the interface between the aluminum plate and the epoxy resin after 3 minutes of floating, and in the soldering heat resistance test after moisture absorption treatment (1 hour of boiling), after 1 minute of floating. , peeling occurred at the interface between the aluminum plate and the epoxy resin. Comparative Example 3 An aluminum core epoxy resin copper-clad laminate was produced in the same manner as in Example 1, except that the aluminum plate was not subjected to polishing treatment but only treated with a silane coupling agent. The properties are shown in Table 1, and in the solder heat resistance tests under normal conditions and after moisture absorption treatment (boiling for 1 hour), peeling occurred at the interface between the aluminum plate and the epoxy resin after floating for 1 minute. Example 3 The aluminum portion of the aluminum core epoxy resin copper-clad laminate produced in Example 1 was shaved off to a thickness of 70 μm. In order to measure the adhesive strength between aluminum and epoxy resin, we measured the peeling strength of aluminum foil in accordance with JIS-C-6481 and found a value of 2.2 kgf/cm, which is an extremely high adhesive strength. Ta. Comparative Example 4 The adhesive side of a 1.0 mm thick copper plate was electrolytically roughened in a copper sulfate bath, and the surface was further immersed in a 0.3% aqueous solution of γ-aminopropyltriethoxysilane for 1 minute, and then dried at 120°C for 30 minutes. did. Using this copper plate, a copper core epoxy resin copper-clad laminate was produced in the same manner as in Example 1. As a result of measuring its characteristics, there was no abnormality after a normal 5-minute float, but in a soldering heat resistance test with moisture absorption treatment (boiling for 1 hour), peeling occurred at the interface between the copper plate and the epoxy resin after a 1-minute float. In addition, using this copper core epoxy resin copper clad laminate, the thickness of the copper plate was increased in the same manner as in Example 3.
I scraped it off until it was 70μm. As a result of measuring the peel strength of this copper, the value was 1.4 Kgf/cm, which was a lower value than the adhesive strength of Example 3. Example 4 Using the aluminum core epoxy resin copper-clad laminate produced in Example 2, the characteristics after moisture absorption treatment were measured. The results are shown in Table 2, and even after 4 hours of pressure test (PCT) treatment at 120°C, no peeling occurred between the aluminum core and the epoxy resin. Furthermore, after moisture absorption treatment (after 5 and 30 minutes of boiling), the above test piece was subjected to a soldering heat resistance test at 300°C, with no abnormalities observed even after floating for 1 minute, and the soldering heat resistance after moisture absorption was excellent. Comparative Examples 5 to 14 Various surface treatments shown in Table 2 were applied to the adhesive side of the aluminum plate. Using this aluminum plate, an aluminum core epoxy resin copper-clad laminate was produced in the same manner as in Example 2. Table 2 shows the properties of these laminates after moisture absorption treatment. In the conventional surface treatments (Comparative Examples 5 to 11), although some surface treatments showed no abnormality in the pressure test alone, the soldering heat resistance after the boiling moisture absorption treatment was significantly inferior. In addition, when epoxy-based, vinyl-based, or methacrylic-based silane coupling agents other than amino-based silane coupling agents are used (Comparative Examples 12 to 14), the soldering heat resistance after boiling moisture absorption treatment is still inferior. Ta. As explained above, in conventional surface treatment methods for metal plates, peeling occurs between the metal plate and the epoxy resin during the solder float treatment after moisture absorption treatment, whereas the mechanical treatment method of the present invention By treating with an amino-based silane coupling agent after polishing, the soldering heat resistance after moisture absorption treatment is significantly improved.

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〔Effect of the invention〕

As explained above, according to the manufacturing method of the present invention, it has excellent soldering heat resistance under normal conditions and after moisture absorption treatment, excellent adhesion between metal plates and epoxy resin, and high copper foil peel strength. Metal core epoxy resin copper-clad laminates can be produced, and their industrial value is great.

[Brief explanation of the drawing]

The drawing is a sectional view of a metal core epoxy resin single-sided copper-clad laminate manufactured by the manufacturing method of the present invention. Explanation of symbols: 1...Copper foil, 2...Epoxy resin layer, 3...Metal plate treated surface, 4...Metal plate.

Claims (1)

[Claims] 1. After mechanically polishing a metal plate, an amino-based silane coupling agent solution is applied, and after the solvent is dried, a copper foil is placed on the treated surface with an epoxy resin layer interposed therebetween. A method for producing a metal core epoxy resin copper-clad laminate, characterized by curing under heat and pressure. 2 The amino-based silane coupling agent is γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)
γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl)γ-aminopropylmethyldimethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, or a mixture thereof, Claim 1 A method for manufacturing a metal core epoxy resin copper-clad laminate described in Section 1. 3. The method for manufacturing a metal core epoxy resin copper-clad laminate according to claim 1, wherein the epoxy resin is a glass cloth base epoxy resin prepreg. 4. The method for manufacturing a metal core epoxy resin copper-clad laminate according to claim 1, wherein the epoxy resin layer is made of only epoxy resin. 5 The metal plate is an aluminum plate, an alumite plate,
The metal core epoxy resin copper-clad laminate described in claim 1, which is a copper plate, a silicon steel plate, a zinc steel plate, an iron-nickel 42 alloy plate, an amber plate, or a clad plate thereof. Production method.