JPS587462B2 - Manufacturing method of coating sheet and copper clad laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel thermosetting cyanate ester-coated sheet in which a thermosetting modified polyethylene resin sheet is coated with a cyanate ester resin composition, and a laminate using the sheet. This manufacturing method provides a laminate that has particularly excellent adhesive strength with 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 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 had been removed by etching was gray or blackish-gray, and the electrical properties 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 sheet (hereinafter simply referred to as a sheet) in which a thermosetting modified polyethylene resin sheet (hereinafter simply referred to as a sheet) is coated with a cyanate ester resin composition.
This is a method for producing a copper-clad laminate, characterized in that the cyanate ester coated sheet (referred to as a cyanate ester coated sheet), the base material, and the copper foil are layered and laminated and molded.

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

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 (-O-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-reacted products 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 method for manufacturing the covering sheet of the present invention includes: Any ordinary coating method may be used, such as dipping the composite sheet into a cyanate ester resin composition diluted with an appropriate solvent, or using a roll coater, or drying at a temperature below the softening point of the modified polyethylene resin. Do it at temperature.

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. .

The coating amount of the cyanate ester resin composition is 1 to 100 g, preferably 3 to 60 g per 1 m on one side of the composite sheet.
g range.

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.

The cyanate ester coated sheet of the present invention is obtained in the manner described above.

This covering sheet is extremely useful as a laminate material for manufacturing copper-clad laminates when combined with a base material and copper foil.

Next, a method for manufacturing a laminate using the cyanate ester-covered sheet of the present invention will be explained.

First, the base material of the present invention is glass cloth surface-treated with various coupling agents such as epoxysilane, aminosilane, and organic titanate; glass paper, and organic fiber cloth with excellent heat resistance such as fully aromatic nylon cloth. Yes, also
Copper foil is ordinary copper foil for laminated boards.

Next, an example of the arrangement for manufacturing a laminate in which the cyanate ester coated sheet of the present invention, a base material, and copper foil are laminated will be explained based on the drawings.

Figure 1 shows an example in which a base material 3 is layered between double-sided sialic acid ester coated sheets 2, 2, and copper foils 1, 1 are layered on the outside of both sheets.
The figure shows an example in which base materials 23, 23 and copper foils 21, 21 are arranged on both sides of a double-sided coating sheet 220.

Fig. 3 shows a case where a plurality of combinations of the inner layers shown in Fig. 1 or Fig. 2 are used, and the thickness can be freely adjusted. (corresponding to 44 in the figure) to other laminated materials, such as epoxy resin prepreg,
This is an example of a hardened substrate.

1 to 4 are arrangement 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: temperature 120 to 250°C, preferably 150 to 200°C, pressure 5 to 200 kg/cm2,
Preferably at 10-50 kg/cm2 for 0.2-8 hours,
Preferably 0.5 to 3 hours, and further 2 hours if necessary.
Post-curing may be carried out at a temperature of 00-250°C.

By carrying out the method of the present invention described in detail above, a copper-clad laminate can be obtained that has the excellent dielectric properties and moisture resistance of polyethylene resin, has a good appearance, and has the adhesive strength of copper foil and is stiff. It will be done.

Examples and comparative examples are shown below.

Example 1 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 were added to 120 to 1 parts by weight of dicumyl peroxide.
After kneading in a heated roll at 30°C, the mixture was processed into a sheet to obtain a sheet (2) with a thickness of 0.28 mm.

This sheet (2) was thermocompressed onto a glass cloth (2) treated with organic titanate to obtain a composite sheet (2) having a resin content of 58 wt%.

Add 2 to 75 parts by weight of methyl ethyl ketone to the sheet ■ mentioned above.
・2-bis(4-cyanatophenyl)propane 20
parts by weight, 5 parts by weight of bis(4-maleimidophenyl)methane, and 0.2 parts by weight of zinc octylate were impregnated with a cyanate ester solution and dried at 120°C for 10 minutes to obtain a cyanate ester-coated sheet. (Amount of adhesion: 18g/m
2) ■ was obtained.

These ■, ■, and ■ are shown in Figure 443 and 44, respectively.
, 42, and laminated and molded 4 sheets of ■ at a temperature of 200℃ and a pressure of 30kg/cm2 for 2 hours to a thickness of 1.6m.
A copper-clad laminate with a diameter of m was obtained.

Table 1 shows the physical properties of this laminate.

Example 2 70 parts by weight of high-density polyethylene, 25 parts by weight of perchloropentacyclododecane, and 3.5 parts by weight of ammonium trioxide were kneaded in a heated roll at 120 to 130°C, and processed into a sheet with a thickness of 0. A sheet ■ of .24 mm was obtained.

On this sheet ■, 60 parts by weight of acetone and a prepolymer of 2,2-bis(4-cyanatophenyl)propane (
A cyanate ester-coated sheet (adhering amount: 55
g/m2)■ was obtained.

Six sets of the thus obtained cyanate ester-coated sheets (■) and epoxy silane-treated glass cloths (corresponding to numbers 32 and 33 in FIG. 3) were used at a temperature of 1.
Laminated molding was carried out for 2 hours at 80°C and a pressure of 50kg/cm2.
A copper-clad laminate with a thickness of 1.6 mm was obtained.

Table 1 shows the physical properties of this laminate. Example 3 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-butyl dicumyl peroxide in a heated roll at 110 to 120°C. , it was processed into a sheet shape to obtain a sheet (■) with a thickness of 0.3 mm.

Add 2,2-bis(
It was impregnated with a cyanate ester solution in which 5 parts by weight of 4-cyanatophenyl)propane was dissolved and dried at 80°C for 10 minutes to form a cyanate ester-coated sheet (adhesion amount: 3
．． 2g/m2)■ was obtained.

On the other hand, the above-mentioned sheet (■) was thermocompressed onto a glass cloth treated with organic titanate to obtain a composite sheet (2) with a resin content of 60 wt%, and five sheets of this (■) were stacked at a temperature of 170°C and a pressure of 10 kg/cm2. Laminated and molded for 2 hours to a thickness of 1.3m.
A laminated plate ■* of m was obtained.

A cyanate ester-coated sheet ■ is placed on the surface of this laminated board ■※, and a copper foil is placed on top of it at a temperature of 170℃ and a pressure
Molding was carried out for 2 hours at 10 kg/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 Example 20 Sheet (1) and glass cloth (2) were press-molded in the same manner as in Example 2 to obtain a copper-clad laminate having a thickness of 1.6 mm.

Table 1 shows the physical properties of this laminate. *JIS K-69
According to 12.

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]

FIGS. 1 to 4 show examples of the arrangement of laminates in the production of laminates using the coating sheet of the present invention. The numbers in the figure are 1, 21, 31, 41: copper foil, 2, 22, 32, 42:
Double-sided coating sheet, 3, 23, 33, 43: Base material, 44:
Laminated material is shown.

Claims (1)

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