JPS58107335A - Manufacture of copper plated laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing a copper-clad laminate.

Conventionally, copper-clad laminates are produced by applying adhesive to an unsaturated resin-impregnated base material (a base material such as paper impregnated with unsaturated resin) that serves as the core layer in a copper foil roughening furnace, and heating it. It is manufactured by stacking B-stage adhesive-coated copper foils and heating and curing them. In this case, semi-curing (B-staging) of the adhesive
Since a long heat drying zone is required, a large production space is required, and the required energy is also large, which poses a problem from the viewpoint of energy conservation. Moreover, when producing the resin-impregnated base material for the core layer, impregnating the base material with the resin is complicated, and the thickness accuracy of the core layer of the resin-impregnated base material is insufficient.

The present invention was made in view of the above circumstances, and it provides a sheet material containing an unsaturated polyester resin that is semi-cured by irradiation with at least one of light and electron beams.
The copper foils are stacked and integrated via an adhesive layer that has become semi-cured by irradiation with at least one of light and electron beams, and then subjected to at least one of electron beam irradiation, light irradiation, and heating. The gist of this method is to completely cure the unsaturated polyester resin-containing sheet and the adhesive layer to obtain a copper-clad laminate.

That is, the present invention does not B-stage the adhesive layer by heating, but B-stages it by light irradiation or electron beam irradiation.
- Since it is staged, it becomes possible to cure quickly, reduce the manufacturing space, and improve productivity. In addition, the core layer is not a resin-impregnated base material but a sheet-like body that can be formed in one step by extrusion molding, etc. This eliminates the need for rolling and resin impregnation processes, and improves the thickness accuracy of the core layer. Become.

Next, the present invention will be explained in detail.

A copper-clad laminate is manufactured using this invention, for example, according to the following embodiments.

■ Apply an adhesive to the rough side of the steel foil, create a sheet containing unsaturated polyester resin by extrusion molding, and irradiate the adhesive layer and the sheet with electron beams to make it into a B-stage. Then, they are stacked and pressed together to integrate them, and then irradiated with an electron beam to completely cure them.

In this case, it is not necessary to incorporate a photosensitizer and a thermal polymerization initiator into the unsaturated polyester resin-containing sheet and the adhesive. By the way, when electron beam irradiation is performed in air, the resin inside that is not in contact with the air is cured, but the resin on the surface that is in contact with the air remains uncured due to polymerization inhibition by ozone generated in large quantities by electron beam irradiation. become a state. Therefore, in the above embodiment, after electron beam irradiation,
When the adhesive-coated copper foil and the unsaturated polyester resin-containing sheet are overlapped, the resin inside each is in a semi-hardened state, but since the surface is unhardened, it is easy to fuse and integrate them. Become. When the stacked materials are further irradiated with electron beams and completely cured, the resin layer to be cured is quickly removed from the air by the cured adhesive and the copper foil on the surface, so the ozone No inhibition of polymerization occurs. In this way, when electron beam irradiation is used, the adhesive and the unsaturated polyester resin-containing sheet are cured in a desirable manner, so that the adhesiveness between the copper foil and the adhesive layer, and between the adhesive layer and the core layer is improved. It gets expensive. Therefore, the punching properties of the resulting copper-clad laminate are good (no delamination occurs during punching). In addition, the resin cures faster (curing time on the order of seconds), resulting in high productivity.

Energy and space savings can be realized. Further, since no heat is applied, there is an advantage that oxidation of the copper foil and deformation such as deterioration and warping of the substrate do not occur.

■ In the aspect of (■) above, B-staging involves light irradiation,
For example, ultraviolet irradiation is performed, and complete curing is performed by electron beam irradiation.

Instead of expensive electron beam irradiation using irradiation equipment, performing B-stage and -di conversion using inexpensive ultraviolet irradiation reduces the initial investment.
It has the advantage of being easy to adopt because equipment depreciation costs can be reduced. In this case, since B-staging is performed by ultraviolet irradiation, it is necessary to mix a photosensitizer with the adhesive and the unsaturated polyester resin-containing sheet (a thermal polymerization initiator is not required).

(2) In the embodiment (2) above, B-staging is carried out by ultraviolet irradiation and complete curing is carried out by heating.

In this case, it is necessary to blend both a photosensitizer and a thermal polymerization initiator into the adhesive and the sheet containing the unsaturated polyester resin.

In the above embodiments (1) to (2), the effect of B-staging by ultraviolet rays or electron beam irradiation and the effect of improving thickness accuracy by forming the core layer with a sheet-like material can be obtained in common.

In addition, to describe the unsaturated polyester resin-containing sheet material in more detail, the unsaturated polyester resin-containing sheet material contains unsaturated polyester resin,
The material used is one in which fillers, reinforcing materials, etc. are mixed, kneaded with a mixer such as a kneader or roll, and then formed into a sheet using an extruder or calender roll. The unsaturated polyester resin was prepared by suitably blending a photosensitizer, a thermal polymerization initiator, a thermal polymerization inhibitor, a crosslinking agent, etc. with the unsaturated polyester according to the embodiments 1 to 2 above. things are used. Here, the unsaturated polyester includes, for example, α, β-unsaturated dibasic acids such as maleic anhydride and fumaric acid, and if necessary, some of these acids such as phthalic anhydride, inphthalic acid, terephthalic acid,
Those substituted with saturated dibasic acids such as tetrachloroheptalic anhydride, tetrabromophthalic anhydride, het acid, succinic acid, adipic acid, and ethylene glycol, prohylene glycol, butanediol, neopentyl glycol, diethylene glycol Glycols such as , xylylene/glycol, and hydrogenated bisphenol A are heat-polymerized such that the molar ratio of acid component to glycol component is approximately 1:1. As a photosensitizer,
For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether.

Pensoin inoglobil ether, benzophenone, 8
-Methylbenzophenone, 2,4-dimethylbenzophenone, chloranthraquinone, methylanthraquinone,
Diphenyl disulfide and anthraquinone are used. However, some unsaturated polyester resins start polymerization upon light irradiation even without a photosensitizer (those using itaconic acid or itaconic anhydride as part of the unsaturated dibasic acid, those using cinnamon-based polyvinyl alcohol, etc.) There is also a book that partially esterifies it with acid, and there is no need to use a photosensitizer when using such a product. Examples of the thermal polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, dicumyl peroxide, cyclohexanone peroxide, 2,
5-dimethyl-2°5-di(tert-butylperoxy)-hexa/ is used. As a thermal polymerization inhibitor,
For example, hydroquinone, hydroquinone monomethyl ether, LerL-7' tylcatechol, benzoquinone, diphenylbenzoquino/, methoxyphenol,
G-tert'-7' tilcresol is used. As the crosslinking agent, for example, vinyl-P-phenylpenshade, allylurea, acrylic, lylamide, phenylmaleimide, triallyl cyanurate, diallyl phthalate prepolymer, and vinyl ester resin are used. In this case, a liquid crosslinking agent may be used in combination. Examples of liquid crosslinking agents include styrene.

Chlorstyrene, divinylbenzene, vinyltoluene,
Examples include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.

Moreover, as the copper foil, a commercially available steel foil for copper-clad laminates is used.

As an adhesive for bonding steel foil, oligomers and monomers having acrylic or methacrylic groups, and
Depending on the aspect of ~■, a resin composition formed by appropriately blending a photosensitizer, a thermal polymerization initiator, a filler, etc., or a prepreg etc. in which a base material such as glass cloth is impregnated with the resin composition is used. .

Since the present invention manufactures a copper-clad laminate as described above, the resin can be cured quickly, productivity can be improved, and the manufacturing space can be reduced.

Furthermore, since the core layer is constituted by a sheet-like body that can be formed by extrusion molding or the like, manufacturing can be simplified and the dimensional accuracy of the core layer can be improved. In addition, in this invention, the sheet-shaped body and the copper foil are stacked and integrated via an adhesive layer and are completely cured in that state, so that the process can be operated continuously from the beginning to the end.

Next, embodiments will be described based on the drawings. 1st
The figure is an explanatory view of one embodiment of the present invention, in which a sheet-like body 2 is continuously extruded from an extruder or calender roll l, and ultraviolet lamps 8' and 4 are applied to the front and back surfaces of this sheet-like body 2. The sheet-like body 2 is semi-cured into a B-stage state by irradiating ultraviolet rays. On the other hand, copper foils 6 are continuously pulled out from roll-wound copper foils 5 arranged above and below the sheet-like body 2, and adhesive varnish 8 is applied from an applicator roll 7 to the surfaces facing the sheet-like body 2. It is applied continuously and irradiated with ultraviolet rays from an ultraviolet lamp 4 to form a B-stage. Then, this B-staged adhesive-coated steel foil 6 is continuously stacked and integrated on the front and back surfaces of the B-staged sheet material 2 using a pressure roll 9,
This is passed through a curing zone 10 (consisting of an ultraviolet lamp, an electron beam irradiation device, a heat dryer, or a suitable combination of these) to the sheet material 2 and the adhesive layer 8a.
is completely cured to form a laminate, and cut into a predetermined size using a cutting machine 11. In this way, copper-clad laminates 12 as shown in FIG. 2 are continuously obtained. In Figure 2, 6
1 is a copper foil, 8a is an adhesive layer, and 18 is a core layer composed of a sheet-like body (FIG. 1) 2. This copper foil laminate 12 is excellent in that the thickness accuracy of the core layer is high. In addition, as an electron beam irradiation device, the accelerating voltage is 800 to 10
From cable connection type up to 00kV 1.5 to 9. QMV
There are many commercially available products (for example, the EPS series manufactured by Nissin High Voltage Co., Ltd.) up to and including integrated types, from which an appropriate one can be used.

[Brief explanation of the drawing]

Fig. 1 is an explanatory diagram of the first stage of this invention, and Fig. 2 is a structural diagram of a steel clad laminate obtained thereby.
Shape 8.4... Ultraviolet lamp 6... Copper foil 8...
・Adhesive varnish 8--Adhesive layer 9...Press roll 10...Curing zone 12...Steel-clad laminate 1
8... Core layer patent applicant Matsushita Electric Works Co., Ltd. Agent Takeshi Matsumoto Conclusion 1 Figure 2 ＼ 6 Figure 2 procedural amendment (voluntary) June 19, 1987 Mr. Commissioner of the Japan Patent Office 1, of the case Indication Showa SS Patent application No. 2 ossrs'Q$Z Name of the invention Manufacturing method for steel clad laminates 3 Relationship with the case of the person making the amendment Patent applicant address Address 1048 Kadoma, Kadoma City, Osaka Prefecture Name of the invention
Name (583) Matsushita Electric Works Co., Ltd. Address 530
Chiyoda Building 8, 2-4-17 Tenjinbashi, Kita-ku, Osaka
No floor 6, subject of amendment 7, contents of amendment (1) Specification s11 page 4! From line J13 to line Kame 5, the phrase "(consisting of an ultraviolet lamp, an electron beam irradiation device, or...)" is replaced with "(consisting of an electron beam irradiation device, a heat dryer, or an appropriate combination of these)". ``Naru)'' is corrected.

Claims (2)

[Claims] (1) Copper foil is placed on an unsaturated polyester resin-containing sheet material that has been semi-cured by irradiation with at least one of light and electron beams. The unsaturated polyester resin-containing sheet material and the adhesive layer are completely cured by applying at least one of electron beam irradiation, light irradiation, and heating to obtain a copper-clad laminate. A manufacturing method for copper-clad laminates characterized by: (2) The method for manufacturing a copper-clad laminate according to claim 1, wherein the unsaturated polyester resin-containing sheet is continuously formed using an extruder or a calender roll.