JPS587460B2 - Method for manufacturing coated composite sheets and copper-clad laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel thermosetting epoxy-coated composite sheet in which a thermosetting modified polyethylene resin is fused to a base material and coated with an epoxy resin composition. This is a method for producing a laminate using the present invention, and provides a laminate that has particularly excellent adhesion to copper foil and retains the electrical properties of the substrate surface from which the copper foil has been etched away.

A composite sheet obtained by fusing heat-curable modified polyethylene resin to a glass cloth base material and copper foil are layered and laminated to form a composite sheet that has the excellent dielectric properties and moisture resistance of polyethylene resin. Attempts have been made to produce copper clad laminates.

However, when ordinary thermosetting modified polyethylene resin is used, its adhesive strength with copper foil is insufficient, and in order to increase the adhesive strength with copper foil, for example, a large amount of crosslinking agent is used. The surface of the substrate from which the copper foil was removed by etching appeared gray or blackish-gray, and the electrical characteristics were completely impaired.

The present invention was completed as a result of intensive research into a method for manufacturing copper-clad laminates that greatly increases the adhesive strength with copper foil and does not impair the electrical properties of the substrate surface from which the copper foil has been removed by etching. .

That is, the present invention provides a thermosetting epoxy-coated composite sheet (hereinafter referred to as composite sheet) made by coating a sheet (hereinafter referred to as composite sheet) in which a thermosetting modified polyethylene resin is fused to a base material with an epoxy resin composition.
This is a method for producing a copper-clad laminate, characterized in that the epoxy-coated composite sheet (hereinafter referred to as an epoxy-coated composite sheet) and copper foil are layered and laminated.

The thermosetting modified polyethylene resin of the present invention is low-density to high-density polyethylene, t-butylcumyl peroxide, dicumyl peroxide, α・α
0.1 to 10 wt% of an organic peroxide such as '-bis(t-butylperoxy)-p-diisopropylbenzene,
Preferably 1 to 5 wt% is added, and flame retardants such as antimony compounds, halogenated compounds, phosphorus compounds, and combinations thereof are added as necessary, and stabilizers such as copper damage inhibitors and halogen absorbers are added. It is formed by appropriately adding agents, amines, acid anhydrides, epoxy resins, diallyl phthalate resins, inorganic fillers, pigments, dyes, etc.

The base material of the present invention includes glass cloth, glass paper, fully aromatic nylon cloth, etc. whose surface has been treated with various coupling agents such as epoxysilane, aminosilane, and organic titanate.

The base material and the thermosetting modified polyethylene resin are fused together by a method of pressing the resin processed into a sheet shape and the base material with a hot roll, a method of coating the resin with molten resin, or the like.

The state of fusion with the base material varies depending on the fusion method, such as homogeneous, base material unevenly distributed on one side, unevenly distributed on both surfaces, and unevenly distributed only in the middle. Manufactured according to purpose.

The epoxy resin composition of the present invention is an epoxy resin used for ordinary laminates, such as bisphenol A epoxy resin, halogenated bisphenol A epoxy resin, phenol novolaxy resin, aliphatic epoxy resin, alicyclic epoxy resin, etc. Examples include group epoxy resins, and may contain other resins, fillers, and the like.

Further, in the present invention, no catalyst may be used, or a curing catalyst such as an acid anhydride, an amine, or an imidazole may be added as necessary.

The method for manufacturing the epoxy-coated composite sheet of the present invention includes:
Any conventional coating method may be used, such as dipping the composite sheet into an epoxy resin composition diluted with an appropriate solvent or using a roll coater, and drying is carried out at a temperature below the softening point of the modified polyethylene resin.

It should be noted that the coating only needs to be applied to the side that will be bonded to the copper foil, and it is not necessary that both sides be coated, but when used for through-hole laminates, it is preferable that both sides be coated. .

Further, the coating amount of the epoxy resin composition is in the range of 1 to 100 g, preferably 5 to 50 g per 1 m 2 of one side of the composite sheet.

If it is less than 1g/m2, the coating will not be effective, and if it is less than 100g
/m2 is not preferable because the advantages of modified polyethylene resin, such as electrical properties, are almost completely lost.

As described above, the epoxy-coated composite sheet of the present invention is obtained.

The epoxy-coated composite sheet of the present invention is extremely useful as a prepreg for producing copper-clad laminates in combination with copper foil.

Next, the second invention, ie, the method for manufacturing a laminate using an epoxy-coated composite sheet, will be described.

The drawings show an example of the arrangement of laminated materials for manufacturing a laminated board according to the present invention.

Fig. 1 shows an example in which copper foils 1, 1 are layered on both sides of double-sided epoxy-coated composite sheets 2, 2, and Fig. 2 shows the middle layer of Fig. 1. This is an example in which 3 is a laminate material other than the epoxy-coated composite sheet of the present invention, such as a composite sheet, an epoxy resin prepreg, or a cured substrate.

Both FIG. 1 and FIG. 2 are layout examples for manufacturing double-sided copper-clad laminates, but of course single-sided copper-clad laminates, thin laminates, and thick plates can also be manufactured.

The conditions for lamination molding are a temperature of 120 to 250°C, preferably 150 to 200°C, a pressure of 5 to 200 kg/cm2, preferably 10 to 50 kg/cm2, for 0.2 to 8 hours, preferably 0.5 to 3 hours. Yes, additional 200 if necessary
Post-curing may be carried out at a temperature of -250<0>C.

By implementing the method of the present invention as described above,
A copper-clad laminate can be obtained that has the excellent dielectric properties and moisture resistance of polyethylene resin, has excellent adhesion to copper foil, has a good appearance, and is sturdy.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Example 1 70 parts by weight of high-density polyethylene, 25 parts by weight of perchloropentacyclododecane, 5 parts by weight of antimony trioxide, and 3.5 parts by weight of dicumyl peroxa were kneaded in a heated roll at 120 to 130°C, and then kneaded into a sheet. A composite sheet A-1 having a resin content of 60 wt % was obtained by thermocompression bonding to a glass cloth treated with an organic titanate.

The thus obtained composite sheet A-1 was impregnated with an epoxy resin solution prepared by dissolving 5 parts by weight of polyethylene glycol diglycidyl ether (epoxy equivalent: 280-300) in 95 parts by weight of water, and dried at 110°C for 10 minutes. Then, epoxy-coated composite sheet (coating amount: 4.2 g/m2) B-
I got 1.

Five composite sheets A-1 were stacked, epoxy-coated composite sheets B-1 were placed on top of them, copper foil was further stacked, and the temperature was 180°C.
℃, pressure 50kg/cm2 for 2 hours, thickness 1
．． A 6 mm single-sided copper-clad laminate was obtained.

Table 1 shows the physical properties of this laminate.

Example 2 70 parts by weight of low density polyethylene, 25 parts by weight of perchloropentacyclododecane, 5 parts by weight of antimony trioxide, 2.1 parts by weight of t-butylcumyl peroxide, and 1 part by weight of t-butylcumyl peroxide.
After kneading in a heated roll at 10 to 120° C., the mixture was melt-coated onto a glass cloth treated with epoxy silane to obtain a composite sheet A-2 having a resin content of 54 wt%.

To the thus obtained A-2, brominated bisphenol A type epoxy resin (epoxy equivalent:
450-500) 35 parts by weight, 5 parts by weight of diaminodiphenylmethane, and 0.2 parts by weight of ethylmethylimidazole were impregnated with an epoxy resin solution, and heated to 80°C.
After drying for 7 minutes, an epoxy coated composite sheet (g/m2) B-2 was obtained.

Six sheets of this B-2 were stacked, copper foil was placed on both sides, and lamination molding was performed at a temperature of 170℃ and a pressure of 30kg/cm2 for 2 hours.
A copper-clad laminate with a thickness of 1.6 mm was obtained.

Table 1 shows the physical properties of this laminate.

Example 3 85 parts by weight of high-density polyethylene, 12 parts by weight of decabromodiphenyl ether, 3 parts by weight of antimony trioxide, and 0.85 parts by weight of dicumyl peroxide in 120-1 parts by weight
The mixture was kneaded in a heated roll at 30° C., processed into a sheet, and bonded under heat to a glass cloth treated with organic titanate to obtain a composite sheet A-3 having a resin content of 58 wt%.

To the thus obtained A-3, 75 parts by weight of acetone and bisphenol A type epoxy resin (epoxy equivalent: 450
~500) Impregnated with an epoxy resin solution in which 20 parts by weight and 5 parts by weight of chlorendecic anhydride were dissolved, and heated at 120°C.
, dry for 5 minutes to form an epoxy-coated composite sheet (coating amount:
24g/m2) B-3 was obtained.

Layer 4 sheets of A-3, place one sheet of R-3 on each side, and then layer copper foil on both sides at a temperature of 200℃ and a pressure of 10kg/
Lamination molding was carried out for 2 hours at cm2 to obtain a copper-clad laminate having a thickness of 1.6 mm.

Table 1 shows the physical properties of this laminate.

Comparative Example 1 A copper foil was layered on six sheets of A-1 of Example 1, and press molding was performed in the same manner as in Example 1 to obtain a copper-clad laminate having a thickness of 1.6 mm.

Table 1 shows the physical properties of this laminate.

*Based on JIS K-6912.

From the physical properties shown in Table 1, it is clear that the copper-clad laminate of the present invention improves the disadvantages of the modified polyethylene resin laminate without impairing its characteristics.

[Brief explanation of the drawing]

Figure 1 shows an example of the arrangement of laminates in a double-sided copper-clad laminate with the covering composite sheet of the present invention arranged, and Figure 2 shows a double-sided copper-clad laminate in which the covering composite sheet of the present invention is combined with other laminates. This is an example of the arrangement of laminated materials of plates. The numbers in the figure are 1 and 21: copper foil, 2 and 22: double-sided coated composite sheet, and 23: laminate material, respectively.

Claims (1)

[Scope of Claims] 1. A thermosetting epoxy-coated composite sheet comprising a sheet in which a thermosetting modified polyethylene resin is fused to a base material and coated with an epoxy resin composition. 2. A method for manufacturing a copper-clad laminate, which comprises laminating and molding the epoxy-coated composite sheet and copper foil.