JP2734019B2 - Production of copper-plated long paper products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a novel method for producing a long copper-plated long-sized paper product, which is pure water copper containing no corrosive elements such as halogens. The film is formed and has excellent conductivity, so copper or nickel can be used as it is or as necessary.
It is preferably used for various applications such as antistatic materials, electromagnetic wave shielding materials, and conductive materials such as resistors by plating other metals.

[Conventional technology and its problems]

BACKGROUND ART Generally, paper products manufactured using inorganic fibrous materials such as glass, ceramics, and carbon are widely used as reinforcing materials for FRP (fiber reinforced plastics). Recently, a metal layer has been formed on these paper products to impart antistatic properties and electromagnetic wave shielding properties, but their use is expanding.

Generally, as a method of forming a copper film on the surface of an electrically insulating article, there are an electroless plating method, a vapor deposition method, a conductive coating method, a molten metal spraying method, and the like.

Electroless plating is an excellent method because it is the most common and allows low-temperature plating. But glass,
It is difficult to directly deposit plating on ceramics and the like, and in the case of nonwoven fabrics and the like, a binder resin for papermaking is usually used. Therefore, when performing electroless copper plating on a paper product such as a nonwoven fabric, pretreatment is essential, but there is a problem that these resin binders are dissolved in a processing solution for normal pretreatment, and When an epoxy resin or the like is used as a binder resin or a resin for surface treatment, there is a problem that deposition of a plating layer is insufficient.

The vapor deposition method requires special equipment for vapor deposition, and depending on the type of article, requires a pretreatment for improving adhesiveness. The application of the conductive paint drastically lost the properties of the paper product. Although there is a molten metal spraying method, a low melting point metal is usually used, and is not used for copper or the like.

Further, it is known that when copper formate is applied to an article and heat-treated in a non-oxidizing atmosphere, an article having a copper film adhered thereto can be obtained. However, there is no conventional example of copper-plated paper by this method, and there is no method suitable for mass production,
It has not been put to practical use.

Therefore, at present, as a paper having a metal layer, only a material obtained by spraying and coating aluminum having a relatively low melting point has been put to practical use.

[Means for solving the problem]

In view of the above circumstances, the present invention has been completed as a result of intensive studies on a method for economically producing a copper-plated paper by a simple method.

That is, the present invention is a method for continuously copper plating a paper having a resin layer on its surface, wherein copper formate is continuously disposed on the paper, and then the copper formate disposed paper is continuously disposed. Non-oxidizing atmosphere or under reduced pressure, it is introduced into a heating device maintained at a temperature of 165 ° C. or more and a temperature not higher than the deformation deterioration temperature of the paper, and after holding for a predetermined time, the paper is continuously taken out. A method for producing a copper-plated paper product, wherein the resin layer comprises a hydroxyl group (-OH), a carboxyl group (-
COOH), carbonyl group (> CO), amino group (—NH ₂ ,> N
H), at least one selected from the group consisting of a cyano group (-CN), an ester bond (-COO-), an amide bond (-CONH-), a urea bond (-NHCONH-), and a urethane bond (-NHCOO-). A thermosetting resin or a thermoplastic resin having a functional group or a bonding group of
It is 0.005 g or more per 1 cm ^{2, and} the arrangement of copper formate in the paper is performed by continuously immersing the long paper in a solution in which copper formate is dissolved or a solution in which copper formate powder is dispersed. Or after continuously applying the solution to the long papermaking product, temperature
This is a method for producing a copper-plated long paper-made product comprising a step of drying at 110 ° C. or lower and a plurality of the paper-made products being stacked.

 Hereinafter, the present invention will be described.

The papermaking product of the present invention is glass fiber, alumina, silica, rock wool, other inorganic fibrous materials, woven fabrics, nonwoven fabrics, papers, and the like using plate-like materials, and particularly long nonwoven fabrics. Paper is preferable because it fully utilizes the features of the present invention.

As a method for forming a resin layer on the above-mentioned paper products, any method can be used as long as it is generally used as a sizing agent or a binder for producing these paper products. Therefore, if a sizing agent or a binder is used, it can be usually used as it is as a paper product on which the resin layer of the present invention is formed. In the case of forming a resin layer, both a thermosetting resin and a thermoplastic resin can be used as long as a liquid or solvent solution can be produced. From the point of adhesion of copper plating, hydroxyl group (-OH), carboxyl group (-COOH), carbonyl group (> CO), amino group (-
NH ₂ ,> NH), cyano group (-CN), ester bond (-COO
-), Amide bond (-CONH-), urea bond (-NHCONH)
-) And those having one or more functional groups or bonding groups selected from the group consisting of a urethane bond (-NHCOO-). Preferred resins are specifically urea resin, melamine resin, phenol resin, diallyl phthalate resin, unsaturated polyester resin, polyisocyanate resin, epoxy resin, polyamine-bismaleimide resin,
Ordinary thermosetting resins such as polymaleimide-epoxy resin, polymaleimide-isocyanate resin and cyanato resin; polyvinyl alcohol, polyvinyl acetate, ethylene-vinyl acetate copolymer, low to non-crystalline polyester for hot melt adhesives Resin and polyamide resin, acrylonitrile-butadiene-styrene copolymer, styrene
Acrylate copolymer, nylon-6, nylon-66,
Thermoplastic resins such as nylon-6 / 66 and other polyamide resins, and crystalline polyester resins such as polybutylene terephthalate and polyethylene terephthalate.

The copper formate of the present invention is generally cupric formate, and includes anhydrous copper formate, copper formate tetrahydrate, and mixtures thereof.

In the present invention, copper formate is usually added to the paper having the resin layer described above in an amount of usually not less than 0.005 g / cm ² , and preferably not more than 0.005 g / cm ² .
01~0.1g / cm ² was placed, it continuously non-oxidizing atmosphere or reduced pressure, is introduced into the heating apparatus which is maintained at a predetermined temperature above the temperature 165 ° C., a temperature between 130 ° C. ~ the predetermined temperature 1deg /
By raising and holding at a speed of not less than one minute, metallic copper generated by thermal decomposition of copper formate is deposited on the papermaking product.

As the heating equipment, infrared radiation, electron beam, radiation heating such as microwave, electric furnace, oven, oil heating, heating steam heating, and other means appropriately used,
It is a continuous heater with an introduction part, a heating part, and a take-out part for the article to be heated.Depending on the resin used for the paper product, the heat treatment temperature and the degradation or decomposition temperature of the resin may approach each other. It is preferable that the variation of the set temperature is small. The heating is performed at a heating rate of 1 to 50 ° C./min.
The heating time is 20 ° C./min and the heating time is 3 hours or less, preferably 1 to 60 minutes. If the heating rate is less than 1 ° C./min, the resulting plated film tends to be non-uniform or the adhesive strength tends to be inferior, and the amount of copper powder generated is undesirably large. In addition, fastness does not cause any problem in the case of one sheet of copper-plated paper or when a plurality of sheets are introduced without being in close contact with each other, but when a plurality of sheets are introduced in close contact with each other, the rate of temperature rise is low. If the speed is too high, copper plating is also formed on the contact portion of the papermaking product, and the contact portion may be undesirably adhered.

Non-oxidizing atmosphere can be obtained by a known method such as N ₂ , Ar, CO ₂ , CO, H
By introducing a gas such as ( ₂₎ , reducing the volume of the heating part of the papermaking product and reducing the opening area of the inlet and outlet to the heating part, the copper formate decomposition gas atmosphere without using inert gas The method of holding is exemplified. In addition, a method of sealing the introduction part and the take-out part of the article to be plated with a roll or the like, a method of storing the entire apparatus in a decompression chamber or a box, and arranging a decompression chamber for the introduction part and the take-out part of the molded article to be plated, etc. The degree of reduced pressure is preferably 400 Torr or less, particularly preferably 200 Torr or less.

In addition, as a method of previously disposing copper formate on a paper product,
A method of using copper formate powder and uniformly arranging the same on a paper having a resin layer. The paper formate is placed on the paper on which copper formate is arranged as described above, and the copper formate powder is placed between the two papers. A powder placement method such as a method of sandwiching the powder can be used. However, a method of dissolving copper formate in a solvent having a relatively low boiling point that does not substantially react with copper formate or using a solution in which powder is uniformly dispersed,
It is suitable in terms of handling and formation of a more uniform coating film.
Suitable solvents include water, alcohols, aliphatic hydrocarbons,
Aromatic hydrocarbons, and others preferably having a boiling point of 200 ° C. or lower are exemplified.In particular, in the case of anhydrous copper formate, water-free organic solvents such as heptane, hexane, cyclohexane, octane, propanol, and butanol It is preferable to use a dispersion solution obtained by kneading, for example, heptanol, benzene, toluene, xylene and the like and copper formate fine powder. The method of application is, for example, other application means such as brush coating, depiping, spray coating, bar coating, roll coating, printing, etc., and drying is not more than the decomposition start temperature of copper formate, usually 130 ° C. or less, especially 110 ° C. or less. Heat or dry under reduced pressure.

The components of the present invention have been described above. Here, the production method of the present invention will be described with specific examples.

1 and 2 are conceptual views of the apparatus for producing a copper-plated paper product of the present invention.

In FIG. 1, a paper-made product [10] wound on a roll
The copper formate powder [1] is uniformly arranged, passed through a roll, and introduced into a plating chamber [A] having a hot plate type heating device. Here, the temperature of the paper is rapidly increased, and the copper formate disposed on the paper is decomposed to form a copper layer and copper powder on the surface of the paper. Then, it is introduced into the post-treatment tank [C], where the by-produced copper powder is removed, rust prevention treatment and the like are performed as appropriate. The copper-plated product exiting the post-treatment tank C is appropriately dried or the like and wound into a roll. In the plating chamber A, copper formate is decomposed to generate gases such as CO, CO ₂ , H ₂ , and H ₂ O. These gases are post-processed so as not to be exhausted into the environment.

FIG. 2 shows the apparatus of FIG. 1 in which a copper formate impregnation tank [B
1] and a drying chamber [B2] for impregnated paper products. The papermaking product [10] wound on the roll is a copper formate impregnation tank B1.
After being impregnated with the copper formate solution, the mixture is introduced into the drying chamber B2 and heated to a temperature of 130 ° C. or lower to remove the solvent. Then, it is introduced into the plating chamber A and treated in the same manner as in FIG. In the method shown in FIG. 2, the solvent gas generated in the drying chamber B2 is cooled by a cooler to become a liquid, which is circulated and used as a solvent in a copper formate powder dissolving tank. The gas from the plating chamber A and the cooler is subjected to post-treatment such as incineration as in the case of FIG.

By the above method, a copper-plated paper product is obtained in which a copper film is formed on the surface of the paper product, and a part of copper powder generated from copper formate which did not participate in the film formation was generated. The copper powder is easily removed by blowing air or water on the paper, by sucking air, or by other means. The removed copper-plated paper is subjected to a known rust prevention treatment as necessary, and is further subjected to a known copper, nickel, gold, or other electroless plating or electroplating of a metal as appropriate. . In addition, by-products of copper powder have a demerit at first glance, but have an effect of isolating between the plated papers, and can process a plurality of papers at the same time, resulting in a significant improvement in productivity. This is a great advantage from the point of view.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Parts in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 100 parts of anhydrous copper formate powder and 50 parts of butyl alcohol were kneaded to obtain a dispersion solution in which the anhydrous copper formate powder was uniformly dispersed (hereinafter referred to as treatment liquid 1).

A glass nonwoven fabric produced using an epoxy resin as a binder was used as the resin-treated paper.

According to the process shown in FIG. 2, a copper-plated article subjected to a rust-proof treatment under the following conditions was produced, and this copper-plated article was tested. In addition, the obtained copper-plated paper was cut into 15 cm squares, and this was integrated with an unsaturated polyester resin to a thickness of 3 m.
A molded plate of m was manufactured, and the electrical characteristics of the molded plate were measured.

 The results are shown below.

-Copper plating conditions; Copper formate impregnation tank [B1]: Using treatment liquid 1, impregnation was performed at room temperature under the conditions of an average impregnation time of 20 seconds.

. Drying room [B2]: Heated to a maximum temperature of 120 ° C. and dried under the condition of a residence time of 20 seconds. The adhesion amount of copper formate anhydride powder is 0.05 g / cm ²
Met.

. Plating chamber [A]: The hot platen temperature was set to 230 ° C, and the residence time was 120 seconds.

. Post-treatment tank [C]: Using an aqueous solution containing a rust preventive (benzotriazole, surfactant) at room temperature, spray cleaning and rust preventive treatment were simultaneously performed.

Performance of copper-plated paper; Copper film: A film having a thickness of 0.2 to 0.5 μm, the initial appearance was a pure copper color, and there was no change in appearance even after storage for 100 days in a room.

. Electrical characteristics: sheet resistance 0.2Ω / □. · Electrical characteristics of the unsaturated polyester resin molded plate; Electrical characteristics: sheet resistance 0.8Ω / □. . Electromagnetic wave shielding properties: There was an electric field shielding effect of 50 to 60 dB at 30 MHz to 300 MHz.

Example 2 The copper plated article obtained in Example 1 was subjected to electro nickel plating. This electroplated nickel-plated product is cut into 15 cm squares, and this is integrated with the unsaturated polyester resin to obtain a thickness.
A molded plate of 3 mm was manufactured, and the electrical characteristics of the molded plate were measured.

 The results are shown below.

・ Electric nickel plating conditions: Bath composition: Nickel sulfate 300g /. Nickel hydrochloride 65g /. Boric acid 45g /. . Conditions: temperature 45 ° C. Time 20 minutes. Current density 2A / dm ^2.・ Performance of electro-nickel plated paper. . Nickel film: 10μ coating. . Electrical characteristics: Sheet resistance 0.06Ω / □. · Electrical characteristics of the unsaturated polyester resin molded plate; Electrical characteristics: sheet resistance 0.12Ω / □. . Electromagnetic wave shielding properties: There was an electric field shielding effect of 60 to 70 dB at 30 MHz to 300 MHz.

Example 3 Using a glass non-woven fabric produced using a urea resin as a binder as a resin-treated paper, a rust-proof copper-plated paper was produced according to the process shown in FIG. 1 under the following conditions. Tested. The results are shown below.

-Copper plating conditions; Spray copper formate powder: 100 mesh through anhydrous copper formate powder 0.1 on paper
Spray evenly at a rate of 0 g / cm ² .

. Plating chamber [A]: The hot platen temperature was set to 230 ° C, and the residence time was 240 seconds.

. Post-treatment tank [C]: Using an aqueous solution containing a rust preventive (benzotriazole, surfactant) at room temperature, spray cleaning and rust preventive treatment were simultaneously performed.

Performance of copper-plated paper; Copper film: A film having a thickness of 0.5 to 1.0 μm, the initial appearance was a pure copper color, and there was no change in the appearance even after storage for 100 days in a room.

. Electrical characteristics: sheet resistance 0.1Ω / □. Example 4 In the same manner as in Example 1, except that an alumina / silica nonwoven fabric produced using an epoxy resin as a binder was used as the resin-treated paper, a rust-proofed copper-plated paper was produced.

The resulting copper-plated paper had a copper coating of 0.2 to 0.5 μm and a sheet resistance of 0.2Ω / □.

[Action and Effect of the Invention]

According to the production method of the present invention as described above, it is possible to produce a copper-plated paper product that has not been commercialized conventionally with extremely high productivity.

This copper-plated paper has excellent adhesiveness of the copper film, and has good electrical properties as it is. The copper plating layer can easily and uniformly form copper, nickel, chromium, silver, gold, and other plating by electroplating, electroless plating, or other means. Therefore, it can be suitably used as it is or after plating, for various uses such as an antistatic material, an electromagnetic shielding material, and a conductive material such as a resistor.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 and FIG. 2 show a plating step according to the present invention. The symbols in the figure are respectively 1: copper formate powder, 10: papermaking, 11: copper plating paper, A: plating chamber, B1: copper formate impregnation tank, B2: drying chamber, C: post-treatment tank, H: 2 shows a heater.

Claims (5)

(57) [Claims] 1. A method of continuously copper-plating a paper having a resin layer on its surface, wherein copper formate is continuously disposed on the paper, and the copper formate-arranged paper is continuously non-plated. Copper, which is introduced into a heating device maintained at a temperature of 165 ° C. or higher and a temperature lower than the degradation temperature of the papermaking material under an oxidizing atmosphere or reduced pressure, and after holding for a predetermined time, continuously taking out the paperwork. Production of plated paper. 2. The method according to claim 1, wherein said resin layer comprises a hydroxyl group (-OH), a carboxyl group (-COOH), a carbonyl group (> CO), and an amino group (-
NH ₂ ,> NH), cyano group (-CN), ester bond (-COO
-), Amide bond (-CONH-), urea bond (-NHCONH)
2. The production of a copper-plated paper according to claim 1, which is a thermosetting resin or a thermoplastic resin having at least one functional group or bonding group selected from the group consisting of-) and a urethane bond (-NHCOO-). Law. 3. The amount of copper formate to be placed on said paper is 1c.
^{2. The} method for producing a copper-plated continuous paper according to claim 1, wherein the amount is 0.005 g or more per m2. 4. A method for disposing copper formate on the paper-making product by continuously dipping the long paper-making product in a solution in which copper formate is dissolved or a solution in which copper formate powder is dispersed, or 2. The method for producing a copper-plated long paper according to claim 1, wherein the step is carried out in a step of continuously applying the paper to the paper having a length and drying it at a temperature of 110 ° C. or lower. 5. The method for producing a copper-plated long paper according to claim 4, wherein a plurality of said papers are stacked.