JP2745678B2 - Production of copper-plated long paper products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel method for producing a long paper product which is plated with copper, and a pure copper film containing no corrosive element such as halogen at all. Since it is formed and has excellent conductivity, it can be used as it is or plated with copper, nickel, or other metals as needed or used as a conductive material such as an antistatic material, an electromagnetic wave shielding material, or a resistor. It is suitable for use.

[Prior art and its problems] Normally, papermaking products manufactured using inorganic fibrous materials such as glass, ceramics, and carbon are widely used as reinforcing materials for FRP. 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.

In general, 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, application of a conductive paint, 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. In addition, when electroless copper plating is applied to a paper product such as a nonwoven fabric, a pretreatment is essential, but a problem that a generally used resin binder for papermaking is dissolved by a processing solution for a normal pretreatment. In addition, 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 have been no examples in which a paper product is copper-plated by this method, and the bonding strength of the copper film is insufficient due to processing conditions and other factors, and there is no method suitable for mass production, and the method 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 uses a resin-treated paper-making product, which is continuously heated in a non-oxidizing atmosphere or under reduced pressure at a temperature of 165
C. or higher and introduced into a heating device maintained at a temperature not higher than the deformation deterioration temperature of the papermaking product, and copper formate was heated to a temperature of 130 ° C to 1 ° C.
Continuously introduced into the heater so as to raise the temperature up to 65 ° C. at a rate of 1 deg./min or more, and after keeping both for a predetermined time at an interval of 5 cm or less, take out the paper continuously. A method for producing a copper-plated paper product comprising: a resin for treating a resin, wherein a hydroxyl group (-OH), a carboxyl group (-COO
H), carbonyl group (> CO), amino group (—NH ₂ ,> N
H), a cyano group (-CN), an ester bond (-COO-), an amide bond (-CONH-), a urea bond (-NH-CONH-), and a urethane bond (-NHCOO-). Being a thermosetting resin or a thermoplastic resin having one or more functional groups or bonding groups, and further comprising a supply amount of the copper formate which is 0.001 g / cm ² or more per a total surface area of the papermaking product. This is a method for producing plated long paper products.

 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.

In addition, the resin treatment of the above-mentioned paper products is not particularly limited as long as it is generally used as a sizing agent or a binder for producing these paper products, and further, when the obtained paper products are subjected to surface treatment. Any of thermosetting resins and thermoplastic resins can be used as long as they can produce a liquid or solvent solution. However, from the viewpoint of the adhesion of copper plating, hydroxyl groups (-OH), carboxyl groups (-COOH ), Carbonyl group (> CO), amino group (—NH ₂ ,> NH), cyano group (—CN), ester bond (—COO—), amide bond (—CONH—), urea bond (—NHCONH—) And a compound having at least one functional group or a bonding group selected from the group consisting of and 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, polymaleimide-epoxy resin, polymaleimide-isocyanate resin , Ordinary thermosetting resins such as cyanate resin; polyvinyl alcohol, polyvinyl acetate, ethylene-vinyl acetate copolymer,
Low to non-crystalline polyester resin and polyamide resin for hot melt adhesive, acrylonitrile-butadiene-
Styrene copolymer, styrene-acrylate copolymer,
Thermoplastic resins such as nylon-6, nylon-66, 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 usually cupric formate, and includes anhydrous copper formate, copper formate tetrahydrate, and mixtures thereof. In the present invention, anhydrous copper formate is particularly preferred.

In the present invention, the above-described resin-treated paper and copper formate are simultaneously or separately continuously and continuously placed in a non-oxidizing atmosphere or under reduced pressure in a heating device maintained at a predetermined temperature of 165 ° C. or higher. And holding them at intervals of 5 cm or less for a predetermined time to deposit metallic copper produced by thermal decomposition of copper formate on the papermaking product. At this time, the temperature of copper formate is 130-165 ℃
The temperature is raised at a rate of 1 deg / min or more.

As the heating device, infrared radiation, electron beam, radiation heating such as microwave, electric furnace, oven, oil heating, pressurized steam heating, nichrome wire, and other means are appropriately used, the heating of the article to be heated It is a continuous heater with an introduction part, a heating part, and a take-out part. Depending on the resin used for the papermaking product, the heat treatment temperature may be close to the degradation or decomposition temperature of the resin. It should be good. The heating unit is preferably a heating plate system, and the heating rate of the papermaking product is not particularly limited. However, copper formate has a heating rate of 130 to 165 ° C and a heating rate of 1 to 1 ° C.
It is preferable to raise the temperature at 50 ° C / min, particularly 2 to 35 ° C / min.
The paper and copper formate are kept at an interval of 5 cm or less, particularly at an interval of 2 cm or less, and the heating and holding time is 3 hours or less, preferably 1 to 60 minutes. If the rate of temperature rise of copper formate is less than 1 ° C./min, the resulting plating film is likely to be non-uniform, or the adhesive strength tends to be inferior, and the amount of copper powder generated is also unfavorable. Although the plating rate of copper having a high temperature rising rate is high, it is not preferable because the plating film tends to be non-uniform.

The method of making the heating equipment a non-oxidizing atmosphere is known,
By introducing gas such as N ₂ , Ar, CO ₂ , CO, H ₂ , reducing the volume of the heating section of the papermaking product and reducing the opening area of the inlet and outlet to the heating section, the inert gas An example is a method of maintaining a copper formate decomposition gas atmosphere without using a gas. 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 pressure reduction degree is 4000 Torr or less, preferably 200 Torr or less, especially 30 Torr
The following is preferred.

In addition, the amount of copper formate introduced was 0.00
1 g / cm ² or more, preferably I to range 0.002~0.1g / cm ^2, introduction method include a method of introducing a copper formate arranged on a continuous belt. As a method of disposing copper formate on the belt, a solution in which copper formate is dissolved or a powder is uniformly dispersed in a solvent having a relatively low boiling point that does not substantially react with copper formate is prepared, and this is applied to a continuous belt. , A method of drying, preferred solvents include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, and other suitable boiling point 110 ° C
The following are exemplified, especially in the case of anhydrous copper formate,
Water-free organic solvents such as heptane, hexane,
It is preferable to use a dispersion solution obtained by kneading fine powder of copper formate with cyclohexane, octane, propanol, butanol, heptanol, benzene, toluene, xylene and the like. Examples of the application method include other application methods such as brush coating, depiping, spray coating, bar coating, roll coating, and printing.Drying is performed by heating at a temperature not higher than the decomposition start temperature of copper formate, particularly 110 ° C. or lower. Dry under reduced pressure.

The components of the present invention have been described above, and the manufacturing method of the present invention will now be described by way of example.

FIG. 1 is a conceptual diagram of an apparatus for manufacturing a double-sided copper-plated product of the present invention, and FIG. 2 is an example of a heating method in a reduced-pressure plating chamber.

The production apparatus shown in FIG. 1 is capable of reducing the pressure with vacuum rolls (V1 to V4 '), and heat-treats the article (10) to be plated and the copper formate adhesion belt at an interval of 5 cm or less. It comprises a vacuum plating chamber (A) for plating, peripheral equipment for attaching copper formate to a belt (20) around the belt and supplying the belt to the vacuum plating chamber A, and a post-treatment tank (C) for plated paper. In FIG. 1, a long paper product (10) is introduced into a vacuum plating chamber A via a vacuum roll (V1), where it is heated to a predetermined temperature by a far-infrared heater (H3). In addition, a copper formate solution is applied by an application roll (C1, C1 '), and a heater (H
1, H1 ') dried copper formate coated belt (21,21') is likewise reduced pressure plating chamber A via vacuum rolls (V3, V3 ').
And the above-mentioned papermaking material 10 between the heaters (H2, H2 ').
And is moved and held at a predetermined interval. During this time, the copper formate is heated to a predetermined temperature by the heaters H2 and H2 ', evaporates and decomposes on the paper to become a reductive decomposition gas with copper, and the copper forms a film on the paper. The obtained copper-plated product (11) exits from the reduced-pressure plating chamber A via a vacuum roll (V2), is treated in a post-treatment tank (C), and is dried to obtain a desired copper-plated product. On the other hand, the copper formate supply belts 21 and 21 'exit from the vacuum plating chamber A via the vacuum rolls (V4 and V4'), where the copper powder and the like adhering to the surface are appropriately removed and cleaned, and formic acid is removed. The copper formate liquid in the copper coating tanks (B1, B1 ') is applied by coating rolls (C1, C1') and dried. The solvent vapor generated by the drying is guided to a cooler, cooled and made into a liquid, and then uniformly mixed with the copper formate powder (1) in the copper formate liquid preparation tank (B) to be coated with a copper formate coating tank B1. , B1 '.

FIG. 2 shows an example in which the temperature of the papermaking product 10 in the above-mentioned vacuum plating chamber is kept higher than that of the copper formate powder.
The heating wire is inserted into the gap between the copper formate coated belt 21 and the papermaking product 10.

Although the method for producing the copper-plated paper product of the present invention has been described with reference to the drawings, the present invention naturally covers the above-described method except that the paper product and copper formate are separately held at predetermined intervals in a heating device. It is not limited to the drawings. For example, when plating on only one side is sufficient, supply copper formate to the lower side in a horizontal arrangement; instead of applying copper formate to the copper formate supply belt and drying it, electrostatic coating of powder , Powder application and pressure bonding, etc .; a method of changing the supply belt to one with surface irregularities or a wire mesh, heat-resistant resin cloth, etc .; further, reversing the introduction and movement direction of the copper formate supply belt; The arrangement is horizontal; copper formate powder is used, and the whole system is a reduced pressure system.

In addition, the copper-plated paper product produced as described above is subjected to a known rust prevention treatment as necessary, and further, a known copper,
Nickel, gold, or other metals are used by appropriately performing electroless plating or electrolytic plating.

〔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 A dispersion in which 100 parts of anhydrous copper formate powder and 50 parts of butyl alcohol were kneaded to uniformly disperse the anhydrous copper formate powder (hereinafter referred to as “dispersion liquid”).
Treatment liquid 1) was obtained.

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

The treatment liquid 1 was applied to one side of a predetermined aluminum film and dried to obtain a copper formate supply belt.

The above-mentioned paper and copper formate supply belt are held in a container that can be decompressed, and a supply / removal unit is provided, so that the paper and the copper formate supply belt can be transported to the center of a set of heating plates and to the left and right of the paper. Using the placed apparatus, the paper and the copper formate supply belt were continuously supplied onto a heating plate, taken out, and formed into a copper-plated paper on both sides.

The length of the heating area of the heating plate is 40 cm, the pressure in the vessel is 0.1 to 1 Torr, the temperature of the heating plate is 230 ° C., the introduction speed of the papermaking material is 5 cm / min, and the speed of the copper formate supply belt is 1.3 cm / min. The amount of adhesion was 0.013 g / cm ² , the distance between the paper and copper formate was 20 mm, and the rate of temperature rise of copper formate was 16 ° C./min between 130 and 165 ° C.

After finishing the plating of the predetermined length of paper, stop the decompression,
The container was opened, allowed to cool to room temperature, and the copper-plated paper was taken out.

The thickness of this copper film is 0.5 to 1.0 μm, and the surface resistance is 0.
It was 1Ω / □.

Example 2 In Example 1, copper plating was performed in the same manner as in Example 1, except that an animina-silica nonwoven fabric manufactured using an epoxy resin as a binder was used as a resin-treated paper, a single copper formate supply belt was used, and the belt was horizontally arranged. A paper was produced.

The resulting copper-plated paper has a thickness of 0.5 to 1.0 μm on one side,
The surface resistance had a copper film of 0.1Ω / □.

[Action and Effect of the Invention]

According to the production method of the present invention as described above, it has conventionally been difficult to form a copper film having excellent adhesion by electroless plating or the like unless a special pretreatment is performed. A molded article in which a copper film having excellent adhesiveness is formed on an object can be manufactured.

The copper-plated layer of this copper-plated paper is made of copper, nickel, chromium, by electroplating, electroless plating, or other means.
Since silver, gold, and other platings can be easily and uniformly made, they are preferably used as they are or as inexpensive undercoating treatments of these plated products.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an apparatus for producing a double-sided copper-plated paper product of the present invention, and FIG. 2 is another example of a heating method in a reduced-pressure plating chamber.

Claims (3)

(57) [Claims] (1) A resin-treated paper product is continuously placed in a non-oxidizing atmosphere or under reduced pressure in a heating apparatus maintained at a temperature of 165 ° C. or more and a deformation deterioration temperature of the paper material. At the same time, introduce copper formate to a temperature between 130 ° C and 165 ° C.
Copper plating which is continuously introduced into the heater so as to raise the temperature at a rate of 1 deg./min or more, and the two are kept for a predetermined time at an interval of 5 cm or less, and then the paper is continuously taken out. Method of producing a finished paper product. 2. The method according to claim 1, wherein the resin for resin treatment is a hydroxyl group (—OH),
A carboxyl group (-COOH), a carbonyl group (> CO), amino group (-NH _2,> NH), cyano group (-CN), an ester bond (-COO-), an amide bond (-CONH-), urea bond The copper-plated papermaking according to claim 1, which is a thermosetting resin or a thermoplastic resin having one or more functional groups or bonding groups selected from the group consisting of (-NHCONH-) and a urethane bond (-NHCOO-). Method of manufacturing a product. 3. The method according to claim 1, wherein the supply amount of the copper formate is 0.001 g / cm ² or more based on the total surface area of the paper product.