JPS587461B2 - Manufacturing method of coated composite sheet and copper clad laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel thermosetting cyanate ester-coated composite sheet in which a sheet of thermosetting modified polyethylene resin fused to a base material is coated with a cyanate ester resin composition; and a method for manufacturing a laminate using the sheet,
The object of the present invention is to provide 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 thermosetting 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 adhesion to copper foil is insufficient, and if a large amount of crosslinking agent is used to increase the adhesion to copper foil, The surface of the substrate from which the foil was removed by etching was 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 cyanate ester-coated composite comprising a sheet (hereinafter referred to as composite sheet) in which a thermosetting modified polyethylene resin is fused to a base material and coated with a cyanate ester resin composition. This is a method for manufacturing a copper-clad laminate, which comprises laminating and molding a sheet (hereinafter referred to as a cyanate ester-coated composite sheet) and the cyanate ester-coated composite sheet and copper foil.

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 is a completely aromatic nylon cloth such as glass cloth or glass paper that has been surface-treated with various camping 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.

Furthermore, depending on the method of fusing and arranging the composite sheet with the base material, there are various types of composite sheets, such as homogeneous ones, those where the base material is unevenly distributed on one side of the composite sheet, those where the base material is unevenly distributed on both surfaces, and those where the base material is unevenly distributed only in the middle part. Manufactured in various shapes depending on the purpose.

The cyanate ester resin composition of the present invention is a thermosetting resin composition containing cyanate esters, and preferably has one or more cyanate groups (-0-C≡N) in the molecule. Organic compounds containing two or more maleimide groups, cyanate ester resin compositions such as prepolymers thereof, mixtures or pre-reaction products of these with organic compounds containing one or more maleimide groups, preferably two or more maleimide groups in the molecule. , or a thermosetting resin composition typified by a mixture with an epoxy resin or a pre-reacted product.

Specific examples include dicyanatobenzene, bis(cyanatophenyl) ether, bis(cyanatophenyl)propane, polycyanated phenol novolak, halogenated bis(cyanatophenyl)propane, etc. Cyanate ester resin compositions such as polymers, mixtures or pre-reactants of these with maleimides such as bis(maleimidophenyl)methane, bis(maleimidophenyl)ether, maleimidophenyl dimaleimidophenylmethane, or bisphenol A
These include mixtures or preliminary reactants with epoxy resins such as type epoxy resins, halogenated bisphenol A type epoxy resins, and phenol novolac type epoxy resins.

The coated composite sheet of the present invention may be manufactured by any conventional coating method such as dipping the composite sheet in a cyanate ester resin composition diluted with an appropriate solvent, using a roll coater, or the like. , drying is performed at a temperature below the softening point of the modified polyethylene resin.

In addition, it is sufficient that the coating is applied to the surface that will be bonded to the copper foil.
Although it is not necessarily necessary that both sides be coated, it is preferable that both sides be coated when used in a through-hole laminate or the like.

The coating amount of the cyanate ester resin composition is 1 to 100 g, preferably 3 to 6 g per 1 m2 of one side of the composite sheet.
It is in the range of 0g.

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.

In the manner described above, the cyanate ester-coated composite sheet of the present invention is obtained.

This coated composite sheet is extremely useful as a prepreg for manufacturing copper-clad laminates in combination with copper foil.

Next, a method for producing a laminate using the cyanate ester-coated composite sheet of the present invention will be explained.

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 a double-sided cyanate ester coated composite sheet 2, 2, and Fig. 2 shows a portion corresponding to the intermediate layer in Fig. 1 (23 in Fig. 2). This is an example in which a material other than the cyanate ester-coated composite sheet of the present invention is used, 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 an excellent 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 peroxide were added to 120 to 1 parts by weight.
After being cross-wired in a hot roll at 30° C., it was processed into a sheet shape, and then thermocompression bonded to a glass cloth treated with organic titanate to obtain a composite sheet A-1 having a resin content of 60 wt%.

To the thus obtained A-1, 95 parts by weight of acetone and 2
- Impregnated with a cyanate ester resin solution in which 5 parts by weight of 2-bis(4-cyanatophenyl)propane was dissolved and dried at 80°C for 10 minutes to form a cyanate ester-coated composite sheet (adhering amount: 3. 6g/m2) B-1 was obtained.

Five sheets of A-1 were stacked, one sheet of B-1 was placed on top of that, and copper foil was further layered, and lamination molding was performed at a temperature of 180°C and a pressure of 50 kg/cm2 for 2 hours to form a single-sided copper-clad sheet with a thickness of 1.6 mm. A laminate was obtained.

Table 1 shows the physical properties of this laminate. Example 2 After kneading 70 parts by weight of low density polyethylene, 25 parts by weight of perchloropentacyclododecane, 5 parts by weight of antimony trioxide, and 2.1 parts by weight of t-butylcumyl peroxide in a heated roll at 110 to 120°C. A composite sheet A-2 having a resin content of 54 wt% was obtained by melt-coating a glass cloth treated with epoxy silane.

To the thus obtained A-2, add 2 to 60 parts by weight of acetone.
・Impregnated with a cyanate ester resin solution in which 40 parts by weight of 2-bis(4-cyanatophenyl)propane prepolymer (number average molecular weight 500 to 550) was dissolved,
It was dried at 0° C. for 5 minutes to obtain a cyanate ester-coated composite sheet B-2 (adhering amount: 63 g/m 2 ).

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
After being cross-wired in a 30° C. hot roll, it was processed into a sheet and was thermocompression bonded 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 were added 75 parts by weight of methyl ethyl ketone, 20 parts by weight of 2,2-bis(4-cyanatophenyl)propane, 5 parts by weight of bis(4-maleimidophenyl)methane, and 0.2 parts by weight of zinc octylate. It was impregnated with a cyanate ester-maleimide resin solution in which parts by weight were dissolved, and dried at 120°C for 10 minutes to form a cyanate ester-maleimide coated composite sheet B-3 (adhesion amount: 21 g/m2).
) was obtained.

Layer 4 sheets of A-3, place one sheet of B-3 on each side, then layer copper foil, and heat at 200℃ and 10kg/cm2 pressure.
Time lamination molding was performed 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.

*From the physical properties shown in Table 1 according to JIS K-6912, 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 on which the coated composite sheet of the present invention is arranged, and Figure 2 shows a double-sided copper-clad laminate in which the coated composite sheet of the present invention is combined with another laminate. It is an example of arrangement of the laminated materials of a laminated board. The numbers in the figure are 1, 21: double-sided coated composite sheet, 2, 22: copper foil, 23
: It is a laminated material.

Claims (1)

[Scope of Claims] 1. A thermosetting cyanate ester-coated composite sheet comprising a sheet of a heat-curable modified polyethylene resin fused to a base material and coated with a cyanate ester resin composition. 2. A method for producing a copper-clad laminate, comprising laminating and molding the cyanate ester-coated composite sheet and copper foil.