JPH0221155B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrochloric acid-resistant copper-clad laminate in which a heat-resistant epoxy resin base material using aromatic amines as a curing agent and copper foil are laminated. Now, it is well known that the characteristics of a copper-clad laminate made of a glass epoxy resin base material and copper foil can be obtained by combining the base material and the curing agent used. When making general-purpose materials that do not require heat resistance, use a mixture of dicyandiamide (DICY) as a curing agent, benzyl dimethylamine (BDMA) as a curing accelerator, and methyl oxide, methyl cellosolve, etc. as a solvent. On the other hand, for the purpose of obtaining heat-resistant copper-clad laminates, halogenated bisphenol base materials are used, and as curing agents, metaphenylenediamine (MPD), diamino diphenylmethane (DDM), A series of aromatic amines have been used, such as diamino diphenyl sulfo (DDS) and 3,3'-dichlorodiaminodiphenylmethane. When using a laminate made by adhering copper foil to an epoxy resin base material for printed circuits, various properties are required such as adhesion of the copper foil to the base material, soldering heat resistance, cyanide resistance, and hydrochloric acid resistance. be done. By the way, in order to obtain heat-resistant copper-clad laminates using epoxy resin base materials, aromatic amines are often used as hardeners for the base material, but when such hardeners are used, they have poor hydrochloric acid resistance. A major drawback was that it required copper-clad laminates. One example is general-purpose copper obtained by laminating a rough surface of copper foil on a normal epoxy resin base material using dicyan diamide as a hardening agent, benzyl dimethylamine as an accelerator, and methyl cellosolve as a solvent. Resistance to hydrochloric acid of clad laminates (The peel strength of a copper clad laminate specimen with a circuit width of 0.8 mm was immersed in a reagent of hydrochloric acid:water = 1:1 for 1 hour at room temperature was determined, and this was expressed as a deterioration rate. ) has a relatively small deterioration of 3 to 5%, but when diamino diphenyl sulfone (aromatic amine) is used as a curing agent and boron trifluoride monomer is used as a heat-resistant brominated epoxy resin base material. When a copper-clad laminate is made using ethylamino as an accelerator and methyl ethyl ketone as a solvent, and the deterioration rate is determined in the same manner as above, the value is 30% or more. Application of the resin base material is severely restricted. The present invention can provide a copper-clad laminate with good hydrochloric acid resistance from a heat-resistant epoxy resin base material using an aromatic amine as a curing agent and a copper foil roughened surface or a copper foil subjected to a known chromate treatment on the surface. This is what I did. The present inventors have already discovered that Cu, Fe, Co,
A copper-clad laminate obtained by forming a thin film of a known heavy metal deactivator that acts with heavy metal ions such as Mn and Cr to form an inactive metal complex compound, and then bonding this to an epoxy resin base material. However, he discovered that it has good heat resistance, and published Japanese Patent Application No. 55595 (1983).
No. 170593), a heat-resistant epoxy resin using aromatic amines as a curing agent can be used to coat a thin film of such a heavy metal deactivator on its rough surface or on a copper foil formed on the rough surface. When bonded to the base material, a thermally or chemically stable metal complex is formed on the surface of the copper foil, preventing oxidation due to aging and improving the hydrochloric acid resistance of copper-clad laminates. Thinking that this might be the case, we formed a thin film of the above heavy metal deactivator on the rough surface of copper foil or one that had been subjected to known chromate treatment, and then bonded it to a heat-resistant epoxy resin base material using aromatic amines as a hardening agent. I made a copper-clad laminate using the same methods as described above, and measured its hydrochloric acid resistance.The results were as follows.
3-(N-salicyloyl)amine-1,2,4-
It was confirmed that the formation of a thin film of heavy metal deactivators such as triazole, N,N'bis-2-naphthoylhydrazine, and bis-3-methoxy derivatives was extremely effective. The present invention is based on the above experimental results,
Here you can see it completed. To further explain the present invention, in the present invention, in order to form a thin film of the heavy metal deactivator of the present invention on the rough surface of copper foil or on the surface of the rough surface treated with known chromate, the chemical immersing the copper foil in a liquid or spraying it with the chemical;
Alternatively, roller coating may be used, but the easiest method is dipping. The concentration of the heavy metal deactivator used does not need to be particularly limited, but
It is sufficient to simply dry the copper foil after a short treatment at room temperature using a compound in the range of 0.01 to 1.0%.Also, as a curing agent for heat-resistant epoxy resin, metaphenylenediamine, diamino diphenylmethane, diaminodiphenylsulfone, It can be applied when any known aromatic amine such as 3,3'-dichlorodiamino diphenylmethane is used. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples As a copper foil sample (A) A 32μ thick copper foil whose rough surface was electrolytically roughened in a known copper sulfate bath after being peeled off from a foil roll. (B) Copper foil with a thickness of 32 μm that has been subjected to chromate treatment on the rough surface of the copper foil peeled off from the foil roll using a known method. For sample (A), 3-(N
-salicyloyl)amino-1,2,4-triazole with 0.1% and 0.5% solutions and for sample (B) with 0.1% and 0.5% solutions of N,N'bis-2-naphthoylhydrazine. , in any case,
The copper foil was immersed in the solution for 1 minute at room temperature, pulled out and once dried at room temperature, and further dried for 3 minutes using a dryer maintained at 110 to 120°C. next,
The rough side of the copper foil treated in this way is layered with a glass/brominated epoxy resin base material using 3,3'-dichlorodiamino diphenylmethane as a hardening agent.
A 250 mm x 250 mm x 2 mm copper-clad laminate was prototyped using molding conditions of 155°C, pressure of 100 Kg/cm ² , and 30 minutes. Next, the peel strength and hydrochloric acid resistance of the laminate (a copper-clad laminate sample with a circuit width of 0.8 mm was tested with the reagent hydrochloric acid: water =
The peel strength after immersion in 1:1 solution for 1 hour at room temperature was determined and this was expressed as the deterioration rate) and the cyanogen deterioration resistance (a copper-clad laminate sample with a circuit width of 3.2 mm was immersed in a 10%
The deterioration rate of peel strength after being immersed in a KCN aqueous solution at 70°C for 30 minutes was determined, and a test similar to the above was also conducted on a prototype copper-clad laminate made from blank foil. The results are shown in the table below.

【table】

[Table] From the table, the rough surface of copper foil or the rough surface of copper foil treated with chromate is treated with the heavy metal deactivator solution of the present invention, and then the heat-resistant glass epoxy resin base material using aromatic amine as a hardening agent is used. It is clear that the bonded copper-clad laminate exhibits excellent hydrochloric acid resistance and can significantly expand the range of application of conventional heat-resistant epoxy resin substrates of this type. Also, although not stated, a copper-clad laminate obtained by bonding a rough surface of copper foil to a normal glass/epoxy resin base material using diaminodiphenylsulfone as a hardening agent also has hydrochloric acid resistance that is almost equivalent to the above. Ta.

Claims (1)

[Claims] 1. Heavy metal inactivation in which the heat-resistant epoxy resin base material surface using aromatic amines as a curing agent is treated with heavy metal ions to form an inactive metal complex compound on the roughened surface or the roughened surface that has been previously treated with chromate. A hydrochloric acid-resistant copper-clad laminate characterized by having a copper foil layer formed with a thin film of a hydrochloric acid.