JPH0775771A - Reusing method of waste copper-plated laminate substrate as resource - Google Patents

Abstract

PURPOSE:To reuse a waste copper-plated laminate substrate as a resource by separating copper from the substrate component to recover. CONSTITUTION:Copper is separated from another component by cutting the waste copper-plated laminate substrate and bringing into collision with each other in floating state while keeping heated state. The waste copper plated laminate substrate is cut so as to be capable of treating in a conical cyclone 3 and the cut copper plated laminate substrates 2 are supplied into the conical cyclone 3 with a heated gas and are brought into collision with each other to easily and efficiently separate into copper foil 5, fiber 6 and resin 4.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a waste copper clad laminate,
The present invention relates to a method of recovering by separating and recovering copper and a base material component. The separated and recovered copper can be reused as a copper raw material, and the base material component can be reused as a filler for various synthetic resin molded articles such as automobile parts and thermosetting synthetic resin laminates.
The copper-clad laminate referred to in the present invention includes a printed wiring board obtained by subjecting the copper-clad laminate to circuit processing.

[0002]

2. Description of the Related Art In a manufacturing process of a copper-clad laminate itself and a manufacturing process of a printed wiring board obtained by processing the copper-clad laminate, defective products and cutting ear scraps generated by the processing of the product are generated. , Waste materials containing copper are generated. These waste materials are collected by a professional disposal company of industrial wastes, the copper content is recovered by various methods, and the residuals are disposed of as industrial wastes.

The following methods are generally known as methods for recovering copper from waste materials containing copper.

[0004] The first is to dissolve copper contained in a waste material with an iron chloride solution, to put a steel material in the solution, and to use the difference in ionization tendency between iron and copper to precipitate copper on the steel material. This is a substitution method of regenerating an iron chloride solution.

The second method is an electrolytic treatment method in which copper contained in a waste material containing copper is dissolved in a copper chloride solution, and this is electrolytically treated to deposit copper on the cathode (see JP-A-2-254188). ).

The third method is a method of immersing a waste material containing copper in a copper chloride solution to dissolve the copper, exposing the resulting solution to a high temperature atmosphere, and separating and recovering the copper as an oxide.

No. 4 is a direct combustion method in which a waste material containing copper is directly roasted at a specific temperature and with a reduced supply of air, and then crushed to classify copper (JP-A-2- 887
25 publication).

[0008]

[Problems to be Solved by the Invention] In recent years, due to the worsening of transportation conditions due to the increase of industrial waste, treatment treatment, lack of capacity, and stricter legal regulation, the treatment cost has soared sharply, causing a serious social problem. Is becoming. As measures against this, it is strongly desired socially to suppress the generation of industrial waste, reduce the amount of the waste, and develop technologies for recycling. However, each of the above methods has various problems as described below.

The substitution method with an iron chloride solution has a low quality because the recovered copper contains a large amount of iron, and the residue after dissolution of the copper foil must be incinerated or landfilled as industrial waste. .

The electrolytic treatment method using a copper chloride solution requires an environmental measure for chlorine gas generation at the same time at the anode, requires labor for peeling and collecting the deposited copper from the cathode, and requires a large amount of capital investment. Become. Further, although the electrodeposited copper has a relatively high purity, it also requires a small amount of cost for refining when it is reused because it contains trace components in the solution. The residue after dissolution of copper shall be incinerated or landfilled as industrial waste, as in the replacement method.

A method of recovering copper as an oxide by dipping a waste material containing copper into a copper chloride solution to dissolve the copper, exposing the resulting solution to a high temperature atmosphere, to obtain copper oxide of high purity, Although it is a very effective method economically and in terms of environmental measures, the equipment cost is relatively high and the problem of waste material disposal of the residue after copper melting is the same as the former two.

The direct combustion method has an advantage that a large amount of waste materials can be treated at a relatively low cost at one time, but the efficiency of recovering copper is extremely poor, and the bromine, phosphorus-based and other flame retardants contained in the waste materials are added to the resin. When the post-treatment of the contained substances, the material of the combustion furnace, and the treatment of the remaining materials of the combustion products are taken into consideration, the treatment cost is increased.

In view of the above points, the present invention is capable of safely and economically treating a waste copper clad laminate having environmental problems and separating copper foil as high-purity copper. It also provides a method by which residues can be recovered in a reusable form.

[0014]

DISCLOSURE OF THE INVENTION According to the present invention, a waste copper clad laminate is cut and kept in a heated state and collided with each other in a floating state to separate copper and other components. It is a characteristic method for recycling a waste copper-clad laminate.

As shown in FIG. 1, the waste copper-clad laminate is heated and crushed by cutting the waste copper-clad laminate in a conical cyclone 3 to an extent such that it can be processed, and the waste copper cut from the shooter 1 is cut. The laminated copper plate 2 is fed into the cyclone 3 having a conical shape together with the heated gas, and the cut waste copper laminated copper plates 2 are made to collide with each other, so that the copper 5, the fiber 6 and the resin 4 can be easily and efficiently. Can be well separated. Although the heating temperature varies slightly depending on the material of the substrate, it is preferably about 300 to 500 ° C. The copper-clad laminate to be treated may be supplied to the cyclone without being heated and heated by the heated gas, but if the pre-heated copper-clad laminate is supplied to the cyclone together with the heated gas, it is treated. The time is short, which is preferable.

When the temperature is lower than 300 ° C., the copper foil does not come off (the reason is explained in the section of action), and when the temperature is higher than 500 ° C., there is a risk that the resin component is decomposed to generate a flammable gas and ignite, and The resin carbonizes.

Air can be used as the gas, and the blower 8
The air is heated by the heater 7 and sent to the cyclone 3. The copper-clad laminate 2 supplied from the shooter 1
By being heated by air in the cyclone and colliding with each other, the copper foil 5, fibers 6 and resin 4 are separated and discharged. The copper foil separates into granules and the resin powders and separates from the fibers. Depending on the material of the base material, especially the resin material, flammable gas may be generated during processing. When treating such a material, nitrogen gas is sent from the nitrogen gas supply source 10 as a gas to reduce the oxygen partial pressure to avoid danger.

[0018]

In the copper-clad laminate, the peel strength of the copper foil becomes smaller as the temperature of the laminate rises. FIG. 2 shows the temperature characteristics of the peel strength of the copper foil for the glass cloth-based epoxy resin copper-clad laminate. When the heated copper-clad laminate is cooled, the peel strength of the copper foil returns to its original value. The temperature characteristics of the peel strength of copper foil show almost the same changes for the paper-based epoxy resin copper-clad laminate and the paper-based phenol resin copper-clad laminate.

From the graph of FIG. 2, it can be seen that the copper foil is easily peeled off when heated to about 300.degree. Therefore, when the copper-clad laminate is made to collide with another copper-clad laminate while being heated to 300 ° C. or more, the copper peeling occurs due to the impact. By the heating, the binding force of the resin itself is weakened, the binding with the base fiber is weakened, and they are separated by the impact of mutual collision and separated.

Next, after holding the glass cloth base material epoxy resin copper clad laminate at each temperature of 20 to 500 ° C. for 10 minutes,
I peeled off the copper foil and checked its quality. The result is shown in FIG. At 200 ° C. or less, the resin of the substrate is peeled off while remaining attached to the copper foil, resulting in poor quality. The grade is 200
It can be seen that the temperature is improved from 0 ° C to 300 ° C, and only the copper foil is peeled off at 300 ° C.

[0021]

EXAMPLES The present invention will now be described with reference to examples. Example 1 The thickness of a copper foil cut into a size of 3 cm square has a thickness of 35 μm.
The waste material of the paper cloth base material phenol resin copper clad laminate of m is heated to 300 ° C. in advance, and nitrogen gas and compressed air are heated to 300 ° C. and sent by using the conical cyclone shown in FIG. The waste materials were rotated at high speed for 10 minutes. As a result, the waste material of the laminated plate is copper foil, and the particle size is 5 to 200 μm.
Separated into resin powder and carbonized paper. Copper is granular and can be separated from other components by sieving and has a purity of 9
It was 9.9% or more.

Example 2 A copper foil having a thickness of 35 μ was cut into a size of 3 cm square.
m glass cloth base material epoxy resin copper clad laminate waste material,
Preheat to 300 ° C and use the conical cyclone shown in Fig. 1 to 300 ° C in nitrogen and air gas atmosphere.
Compressed air was forcibly sent for 10 minutes to cause the waste materials to collide at high speed. As a result, the waste material of the laminated plate is copper and the grain size is 5
Separated into resin powder of ˜200 μm and glass single fiber with a maximum length of 30 mm. Copper was in the form of granules, which could be separated from other components by sieving, and the purity was 99.9% or more.

20 parts by weight of the separated glass fiber was kneaded with 100 parts by weight of polypropylene resin and heat-molded to prepare a test piece. The tensile strength, bending strength and heat distortion temperature of this test piece were examined. The results are shown in Table 1.
Commonly used filler (talc) for comparison
The results are also shown in Table 1. As for the test method, tensile strength is JISK7113, bending strength is JISK7203,
The heat distortion temperature was based on JISK7207.

[0024]

[Table 1] ───────────────────────────── Item Unit Glass fiber kneaded product Talc kneaded product ──────── ───────────────────── Tensile strength MPa 45 40 ───────────────────────── ───── Bending strength MPa 60 50 ─────────────────────────────Heat deformation temperature ℃ 140 135 135───── ────────────────────────

Next, the epoxy resin (bisphenol A
Type: 90 parts by weight of epoxy equivalent 480), 2 parts by weight of dicyandiamide and 0.15 parts by weight of 2-ethyl-4-methylimidazole to a cresol novolac type epoxy resin (epoxy equivalent of 190), and diluted with a solvent to prepare a resin. Resin varnish A having a content of 60% was obtained. In this resin varnish A,
100 parts by weight of resin powder obtained by treating the waste copper clad laminate was mixed. This is designated as resin varnish B.

The resin varnish A was applied to a glass cloth (WE-18K-RB84 manufactured by Nitto Boseki Co., Ltd.) with a resin content of 42-4.
The glass cloth prepreg was impregnated and dried to 5% to obtain a glass cloth prepreg. Further, the resin varnish B was impregnated into a glass nonwoven fabric base material so that the solid content of the varnish was 90%, and dried to obtain a glass nonwoven fabric prepreg.

Glass cloth prepregs are arranged on the upper and lower surface layers,
With a configuration in which a glass non-woven fabric prepreg is used as an intermediate layer, a copper foil having a thickness of 35 μm is laid on the outside of the glass fabric prepreg and heated and pressed for 90 minutes at a molding temperature of 170 ° C. and a pressure of 4 MPa,
A double-sided copper-clad laminate having a thickness of 1.6 mm was obtained.

The bending strength of the obtained laminated plate was 450 in the vertical direction.
MPa, horizontal: 320 MPa, water absorption is D-24 / 2
3: 0.06%, dielectric constant of 1 MHz, Accepted state: 4.
4%, D-48 / 50: 4.4, Pressure cooker 2.1 atm 121 ° C. Solder heat resistance test after treatment (260
In a solder bath at ℃ for 20 seconds), there was no more than that.

Next, in place of the resin powder, a non-woven fabric prepreg was obtained by using a resin varnish containing 100 parts by weight of aluminum hydroxide (Hidilite H3211). A tension laminate was obtained.

The bending strength of the obtained laminate was 400: length.
MPa, horizontal: 290 MPa, water absorption is D-24 / 2
3: 0.08%, dielectric constant of 1 MHz, Accepted state: 4.
6%, D-48 / 50: 4.5, Pressure cooker 2.1 atmosphere, Solder heat resistance test after treatment at 121 ° C (260
In a solder bath at ℃ for 20 seconds), pressure cooker 2 hours, one of 5 test pieces produced measling, 3 hours 5 out of 5 test pieces produced measling, 4 hours out of 5 test pieces One had measling and four had blisters.

[0031]

EFFECTS OF THE INVENTION According to the present invention, copper contained in a waste copper-clad laminate having a problem in terms of environmental safety, glass fiber and resin can be separated and recovered at low cost. The obtained copper can be recycled into various industrial fields as various copper raw materials after being recovered as high-grade molten metal. Further, the glass filament can be directly used as a filler for thermoplastics and thermosetting plastics, and can also be utilized as a raw material for various kinds of glass, which is extremely effective in industry such as suppressing the generation of industrial waste and recycling.

[Brief description of drawings]

1 is a schematic diagram of an apparatus for carrying out the present invention.

FIG. 2 is a graph showing changes in copper foil peeling strength with heating temperature.

FIG. 3 is a graph showing changes in copper quality depending on heating temperature.

[Explanation of symbols]

 1 Shooter 2 Waste copper clad laminate 3 Cyclone 4 Resin powder 5 Copper 6 Glass fiber 7 Heater 8 Blower

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teruo Teshima 1150 Gozamiya, Shimodate City, Ibaraki Prefecture Goseimiya Plant, Hitachi Chemical Co., Ltd. (72) Minor Morita 1500 Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Shimodate Factory of Industrial Co., Ltd.

Claims (2)

[Claims] 1. A waste copper-clad laminate, characterized in that the waste copper-clad laminate is cut and kept in a heated state and collided with each other in a floating state to separate copper and other components. Plate recycling method. 2. A waste copper-clad laminate is cut into a cone-shaped cyclone to such an extent that it can be processed, and is sent into a cone-shaped cyclone together with heated gas to produce a cut waste copper-clad laminate. A method for recycling a waste copper-clad laminate, which is characterized by colliding with each other to separate copper and other components.