JP2551490B2 - UV-curable aqueous resin-coated copper foil, UV-curable aqueous resin-coated copper clad laminate, their manufacturing method and their cured coating removal method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a copper-clad laminate used as a printed circuit board, a metal foil used in this copper-clad laminate, and a method for producing them.

The invention also relates to the use of these copper foils or copper clad laminates.

[Prior Art] The copper foil surface of a conventionally used copper clad laminate for a printed wiring board and the surface of the copper foil used for the copper foil are each formed by etching the copper foil to form a circuit. In the above, no particular protection of the surface was performed. Therefore, such a copper foil or a copper-clad laminate is scratched due to adhesion of foreign matter to the copper foil surface when the copper foil is processed into a copper-clad laminate or when the copper-clad laminate is processed into a circuit. , The drawback of easily causing a defect, the drawback of causing a defect due to discoloration,
Further, when handling a thin copper foil in particular, the foil itself has a drawback that it tends to wrinkle and break and become defective.

Conventionally, attempts have been made to prevent damage by laminating a polypropylene film on a copper foil, but it has a drawback that it is inconvenient and a decrease in workability cannot be avoided.

[Problems to be Solved by the Invention] The present invention is directed to a copper foil and a copper-clad laminate having a resin-cured coating capable of preventing scratches, adhesion of foreign matter, discoloration, etc. on the surface of the copper foil and being easily removable by water or the like. The purpose is to provide a plate.

Another object of the present invention is to provide a manufacturing method capable of easily manufacturing the above copper foil and copper clad laminate.

A further object of the present invention is to provide a method for easily removing the copper foil having the above-mentioned cured coating and the cured coating of the copper clad laminate.

[Means for Solving the Problems] As a result of intensive studies conducted by the present inventors in order to achieve the above object, the above object can be achieved by providing a cured film of an ultraviolet curable aqueous resin on the surface of a copper foil. Based on this finding, the present invention has been completed.

That is, the present invention provides a copper foil with an ultraviolet-curing aqueous resin, which is provided with a cured coating film that swells or dissolves in water obtained by curing an ultraviolet-curing aqueous resin on the surface of a copper foil.

The copper foil used in the present invention is preferably a copper foil such as an electrolytic copper foil or a rolled copper foil. In addition to this, an alloy foil of copper-zinc, copper-tin, or the like, or a copper-plated layer, a zinc-plated layer, a silver-plated layer, a gold-plated layer, a nickel-plated layer, a chrome-plated layer, or an alloy-plated layer of these on the copper foil surface A composite foil or the like having a thickness of several μm may also be used.

The thickness of these copper foils is not particularly limited, but those having a thickness of 1 to 100 μm are preferable from the viewpoint of handling and economical reasons.

Since the copper foil of the present invention is provided with a cured coating of an ultraviolet curable water-based resin, it is possible to prevent scratches and the like on the copper foil surface. Further, in the case of a thin copper foil, this cured coating prevents wrinkles and improves the handling property. The cured coating can be easily removed by swelling, desorption or dissolution within a few minutes with water, an acid aqueous solution or an alkaline aqueous solution. After removing the cured coating, the same fresh copper surface as before the coating is formed can be reproduced.

The UV-curable water-based resin used for forming the cured film is one that dissolves very well in water, can easily form a coating film, and has a high curing speed. As such a material, unsaturated polyamide ether, unsaturated polyamide ester, unsaturated polyamide alcohol and the like are preferably used, and unsaturated polyamide ether is particularly preferably used. Specifically MO
A base resin M580 containing a UV curing initiator, which is commercially available from NOCURE PTY. LTD. (Australia), is preferably used. This product is used by diluting it with water in any proportion and diluting it to an appropriate viscosity. When this coating film is irradiated with ultraviolet rays, it varies depending on the thickness of the coating film formed.
It is cured in a short time of seconds, and a protective film effective for preventing scratches, foreign matter adhesion, discoloration, etc. is formed. Since the cured coating film of the present invention is a cured coating film of an ultraviolet curable water-based resin, which is different from a usual ultraviolet cured resin coating film, even if it is a cured coating film, the coating film can be easily peeled off with water when used. The thickness of this cured coating is preferably 0.1 to 200 μm. Particularly preferably, it is 5 to 30 μm.

Further, the copper foil of the present invention can be stored for a long period of time because the discoloration is prevented by the formation of the coating as described above, and when the copper foil is wound and stored, the pattern on the rough surface side of the foil is glossy. It is also possible to prevent transfer to the surface side.

As a method for producing the copper foil of the present invention, a solution of an ultraviolet curable aqueous resin is applied to the surface of the copper foil to form a coating film, and then a cured coating film that swells or dissolves in water by irradiating with ultraviolet rays is formed. The forming method is preferably used. Moreover, you may employ | adopt the heat drying means which volatilizes water as needed. The application is performed using a spray, a roll coater, dipping or the like. The thickness of the coating film can be adjusted by appropriately changing the concentration of the resin solution. The UV-curable water-based resin is preferably applied as it is or diluted with water up to about 5 times by weight.

The present invention also provides a copper-clad laminate with an ultraviolet-curing aqueous resin, comprising a copper-clad laminate surface provided with a cured coating that swells or dissolves in water obtained by curing an ultraviolet-curing aqueous resin. Is.

The copper-clad laminate of the present invention prevents scratches on the copper foil surface during each step of producing a printed circuit board, and eliminates the need for a backing plate during drilling, which improves workability in producing a printed circuit board. It has the advantage of improving. Further, this cured coating can be easily removed with water, an aqueous acid solution or an aqueous alkali solution.

As the copper foil used for the copper-clad laminate, the cured film of the UV curable water-based resin, and the like, the same ones as those used for the copper foil can be used.

The copper clad laminate of the present invention can be produced, for example, by laminating and molding the above-mentioned UV-curable aqueous resin-coated copper foil and a thermosetting resin-impregnated base material. Lamination molding is usually performed by heating and pressing. In this case, there is an advantage that a release paper inserted between the copper foil and the hot plate at the time of molding is not necessarily required.

As the thermosetting resin-impregnated base material, a base material such as paper, glass cloth, or glass non-woven fabric impregnated with a thermosetting resin such as phenol resin, epoxy resin, unsaturated polyester resin, or polyimide resin is preferably used. To be

The copper-clad laminate of the present invention is also formed by applying a solution of an ultraviolet-curing aqueous resin on the surface of a copper foil of a copper-clad laminate having no conventional cured coating to form a coating film, and then irradiating it with ultraviolet rays. Then, it can also be produced by forming a cured film that swells or dissolves in water. The hardened film is formed in the same manner as in the case of the copper foil.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to this.

Example 1 M-580 (MONOCUR was formed on the glossy side of a 35 μm thick electrolytic copper foil.
E PTY.LTD. (Australia), UV curable aqueous resin containing UV curing initiator) 100 parts by weight dissolved in 40 parts by weight of water so that the coating amount becomes 10 g / m ² by roll coater method. To form a coating film, and then, using an ultraviolet irradiation device equipped with a high-pressure mercury lamp, irradiation was performed under the conditions of 80 W, 1 light, and 5 seconds to obtain a copper foil having a cured film with a thickness of 10 μm. .

When the obtained copper foil was washed with water, the cured film swelled after 30 seconds and could be easily peeled and removed.

The copper foil did not discolor even after 60 days in a normal temperature atmosphere and was excellent in storage stability.

Example 2 A cured film of an ultraviolet curable aqueous resin was formed on the copper foil surface of a commercially available paper-based phenolic resin copper-clad laminate in the same manner as in Example 1.

The copper clad laminate with a cured coating thus obtained could be punched without a patch plate.

Example 3 The copper foil with a cured coating obtained in Example 1 and a prepreg impregnated with a glass cloth of an epoxy resin are laminated, a release paper is not provided between the copper foil and the hot plate, and 168 ° C., 100 kg. Laminate molding was performed at / cm ² to obtain an epoxy resin copper clad laminate.

The cured coating on the copper foil surface of this copper-clad laminate did not adhere to the hot plate side, and it was possible to perform laminate molding without using release paper.

When this copper-clad laminate was washed with water in the same manner as in Example 1, the cured coating could be easily peeled off.

EFFECTS OF THE INVENTION Since the copper foil with an ultraviolet-curing aqueous resin and the copper-clad laminate with an ultraviolet-curing aqueous resin of the present invention have a cured resin coating on the surface, scratches on the copper surface can be prevented and high-density circuit formation can be achieved. In, it is possible to prevent defects caused by adhesion of fine foreign matter.

This cured resin film can be easily removed with water, an acid aqueous solution, or an alkaline aqueous solution, and it does not prevent anything in the circuit processing step. In addition, the copper-clad laminate of the present invention has the advantage that it can be punched without a patch plate, and that it does not require a release paper during heating and pressing when producing a copper-clad laminate.

Furthermore, the production method of the present invention makes it possible to easily provide a copper foil and a copper-clad laminate having the above-mentioned excellent features.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takeshi Yamagishi, 1226 Shimoeden Shimodate, Shimodate, Ibaraki Japan Electrolysis Co., Ltd. Shimodate No.2 Factory (56) Reference JP-A-55-152573 (JP, A) JP-A- 62-136274 (JP, A) JP-A-52-60891 (JP, A) JP-B-50-11416 (JP, B1)

Claims (11)

(57) [Claims] 1. A copper foil with an ultraviolet-curable aqueous resin, comprising a copper foil having a cured coating film which swells or dissolves in water obtained by curing an ultraviolet-curable aqueous resin. 2. The copper foil with an ultraviolet curable water-based resin according to claim 1, wherein the thickness of the cured film is 0.1 to 200 μm. 3. The copper foil with an ultraviolet-curable aqueous resin according to claim 1, wherein the ultraviolet-curable aqueous resin is an unsaturated polyamide ether. 4. A UV-curable aqueous resin for coating a solution of a UV-curable aqueous resin on the surface of a copper foil to form a coating film, and then irradiating it with UV rays to form a cured film which swells or dissolves in water. Copper foil manufacturing method. 5. A method for removing a cured film, which comprises removing the cured film of the copper foil with an ultraviolet-curable aqueous resin according to claim 1, 2 or 3 by using water, an acid aqueous solution or an alkaline aqueous solution. 6. A copper-clad laminate with an ultraviolet-curable aqueous resin, comprising a copper foil of the copper-clad laminate provided with a cured film which swells or dissolves in water obtained by curing the ultraviolet-curable aqueous resin. 7. The copper-clad laminate with an ultraviolet-curing aqueous resin according to claim 6, wherein the cured coating has a thickness of 0.1 to 200 μm. 8. The copper-clad laminate with a UV-curable aqueous resin according to claim 6, wherein the UV-curable aqueous resin is an unsaturated polyamide ether. 9. A method for producing a copper-clad laminate with an ultraviolet-curing aqueous resin, comprising laminating and molding the copper foil with an ultraviolet-curing aqueous resin according to claim 1 and a thermosetting resin-impregnated base material. 10. A copper foil of a copper clad laminate is coated with a solution of an ultraviolet curable water-based resin to form a coating film, which is then irradiated with ultraviolet rays to form a cured coating film that swells or dissolves in water. Manufacturing method of copper clad laminate with UV curable water-based resin. 11. A method for removing a cured coating, which comprises removing the cured coating of the copper-clad laminate with an ultraviolet-curable aqueous resin according to claim 6, 7 or 8 using water, an acid aqueous solution or an alkaline aqueous solution.