JPS60228678A - Formation of metallic film on surface of high molecular material - Google Patents

Abstract

PURPOSE:To stick very easily and firmly a metallic film to the surface of a high molecular material by coating the surface of the material with a polymer or an oligomer contg. nitrogen and by carrying out chemical plating. CONSTITUTION:The surface of the high molecular material such as PE, polyamide or PVC is coated with the polymer or the oligomer contg. nitrogen such as allylamine or vinylpyridine by dipping the high molecular material in the soln. of the coating material or by other method. The amount of the coating material used is 0.1-2.0pts.wt., especially 0.5-1.5pts.wt. (expressed in terms of solid matter) per 100pts.wt. high molecular material. A noble metal such as pd as a catalyst is stuck to the coated surface of the high molecular material by about 0.01-0.2g/m<2> ordinary, and a metallic film, for example, of Ni, Co, Ag or the like is formed by chemical plating as usual.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a metal film on the surface of a polymeric material.

Conventionally, it is widely known that a metal coating is formed on the surface of a polymeric material by chemical plating, but in this case, the adhesion of the metal coating to the surface of the polymeric material is poor, and the metal coating may peel off during use. Or.

It has drawbacks such as poor conductivity.

The present inventors have conducted various studies to overcome the above-mentioned drawbacks found in the prior art. As a result, the present inventors formed a film of a nitrogen-containing polymer or oligomer on the surface of a polymeric material in advance, and then applied chemical plating treatment to the surface of the polymeric material. The present inventors have discovered that the object can be achieved by applying the following methods, and have completed the present invention.

That is, according to the present invention, there is provided a method for forming a metal film on the surface of a polymeric material, which is characterized in that the surface of the polymeric material is coated with a nitrogen-containing polymer or oligomer in advance, and then subjected to chemical plating treatment. Ru.

The coating material used to coat the surface of the polymeric material in the present invention is a nitrogen-containing polymer or oligomer. In this coating material, nitrogen is contained in various forms, such as amine bonds, imine bonds, amide bonds, imide bonds, urethane bonds, and 21-helical bonds. In this case, nitrogen may be contained in either the main chain or the side chain of the polymer or oligomer. The nitrogen content is
In the coating material, it is at least 5% by weight, usually about 10 to 15% by weight, calculated as nitrogen atoms (N).

Polymers or oligomers used as coating materials in the present invention include various conventionally known polymers, such as those shown below.

(1) Oligomers, homopolymers and copolymers of nitrogen-containing polymers shown below.

Allylamine, vinylpyridine, aminostyrene, vinylpyrrole, N-vinylpyrrolidone, N-vinylcarbazole N,N-dimethylacrylamide, acrylonitrile,
Dimethylaminopropylmethacrylamide etc.

(2) Oligomers, homopolymers and copolymers of amino acids.

(3) Polypeptides such as gelatin, albumin, and casein, and nitrogen-containing natural polymers such as chitin and x1-san.

(4) Oligomers, homopolymers, and copolymers of nitrogen-containing cyclic monomers such as ethyleneimine, oxazolines, and oxazolidines.

(5) Oligomers and polymers having urethane bonds such as urethane resins.

(6) Melamine resin, urea resin, etc.

To carry out the present invention, first, the surface of a polymeric material is coated using the nitrogen-containing coating material described above. In this case, the shape of the polymeric material is arbitrary, and includes, for example, a fibrous shape, a film shape, a plate shape, a cylindrical shape, and the like. In addition, as the polymer material, various conventionally known polymer materials are used, such as polyolefins such as polyethylene, polypropylene, and polystyrene, as well as polyester, polyamide (nylon), polyacrylonitrile, polyvinylidene chloride, and polychloride. Vinyl, polyvinyl acetate, polysulfone, acrylic resin, phenolic resin, two-handed plastic coherence natural rubber, urethane rubber, etc.

There are rubber, silicone rubber, acrylic rubber, etc.
Natural fibers such as cotton, silk, and wool, cupro, acetate,
There are regenerated cellulose such as rayon.

The method for coating the polymer material with the coating material may be any method as long as it can coat the surface of the polymer material with the coating material in a layered manner, and various conventionally known methods may be employed. Such coating methods include, for example, coating by dipping in a coating material solution, spray coating with this coating material solution, and 3- pretreatment (chromic acid treatment,
(sand etching treatment, light irradiation treatment, plasma irradiation, etc.)
After that, in addition to simple coating methods such as applying a coating material solution, nitrogen-containing monomers are applied to the surface of the polymer material and irradiated with radiation, ultraviolet rays, lasers, etc., or subjected to plasma, heat, etc. , a method of graft polymerizing a nitrogen-containing monomer onto the surface of a polymer material, etc. The coating amount of the coating material on the polymeric material is preferably the amount to form a monomolecular film, but generally 0.1 to 2.0 parts by weight in terms of solids per 1.00 parts by weight of the polymeric material. Preferably 0.5-1.
5 parts by weight.

Next, the surface of the polymeric material coated with the nitrogen-containing polymer or oligomer as described above is subjected to chemical plating treatment by a conventional method. In this case, the chemical plating treatment involves, for example, contacting with a solution containing noble metal ions to adhere and bond the noble metal to form a noble metal layer. This noble metal layer exhibits a catalytic effect when the metal ions contained therein are deposited on the surface of the polymeric material from the subsequent chemical plating solution. In this case, the precious metals include palladium,
Platinum, gold, etc. are used, but palladium is preferred. This solution containing noble metal ions can be prepared according to conventionally known methods, for example, by dissolving a soluble salt of a noble metal, such as a halide, in water in the presence of a solubilizing agent such as hydrochloric acid. . The amount of noble metal deposited on the surface of the polymer material is 0.1 g/back, usually about 0.01 to 0.2 g/post. The surface of the polymer material that has been surface-treated with the solution containing noble metal ions is washed with water and subjected to the next chemical plating treatment.

As the chemical plating solution used in the present invention, various conventionally known ones can be employed. In addition, various metals may be added to the plating solution to form a metal film on the surface of the polymeric material, such as Nl, Cot Ag+ LFe, Cu, Zn, etc. It will be done. In addition to these individual metals, alloys such as Ni-Co, Nj'J, Nj. Fe.

Although it can be made of Co-W, Co-Fe, etc., when forming an alloy film, a plurality of metal salts may be added to the plating solution as desired. Chemical plating solutions generally contain metal salts, reducing agents, complexing agents, buffering agents,
Contains stabilizers, etc. In this case, sodium hypophosphite, 1-lium borohydride, aminoborane, formalin, etc. are used as reducing agents, and as complexing agents and buffers, formic acid, acetic acid, succinic acid, citric acid, etc. are used. , tartaric acid, malic acid, glycine, ethylenediamine, EDTA, triethanolamine, sodium/potassium tartrate, etc. are employed.

A typical composition of the chemical plating solution is, for example, Nj.

Metal salt such as Co 10-200g/Q, hypophosphite 0.
3-50g/Q, pH buffer 5-300g/Q
Preferably,
To such a plating solution, 5 to 200 g/Q of glycine can be further added as an auxiliary additive.

In addition, other plating solutions include metal salt 10-20h/Q
, potassium sulfur tartrate 10~ioOg/Q,
Or EDTA10-120g/Q, alkali hydroxide 1
Monthly 0-60g/fl, alkali carbonate 5-50g/Q,
Examples include formalin 10 to 200mQ, and copper is a typical plating metal. Chemical plating treatment is usually performed at a temperature of 20 to 95
Performed at °C.

In the present invention, as described above, since the surface of the polymeric material is coated with a nitrogen-containing polymer or oligomer to make it suitable for chemical plating, a metal film is formed on the surface by chemical plating. is extremely easy to obtain, and the resulting metal coating strongly adheres to the surface of the polymeric material.

In the case of the present invention, not only fresh chemical plating solution but also used chemical plating waste solution can be used as the chemical plating solution. times) after
It can be used as a chemical plating solution in the present invention by adding a complexing agent and a reducing agent. According to the present invention, metal can be efficiently deposited in the form of a film on the surface of a polymer material even from such chemical plating waste liquid or etching waste liquid, so that the desired metal film can be formed at a significantly low cost. It can be formed on the surface of molecular materials.

71 The polymer material having a metal film on the surface obtained by the present invention exhibits metallic luster and has electrical conductivity, and is used in various fields.

The polymeric material having a metal coating obtained by the present invention is applied as an electromagnetic shielding material in the form of conductive fibers, films, sheets, containers, etc.

The method of the present invention can also be applied as a method for forming a conductive film in the production of IC integrated circuits.

That is, according to the present invention, a coating material is applied in the form of a printing ink onto a plastic substrate in the desired image, and the coated surface is treated with a noble metal salt solution and then subjected to a chemical plating treatment. In this way, a metal coating is formed on the plastic substrate 2 where the coating material was applied.

Furthermore, the method of the present invention can be applied as a technique for producing piezoelectric elements and piezoelectric sensors. That is, according to the present invention, it is possible to form a conductive metal coating that is strongly adhered to the surface of a flexible sheet made of natural rubber, synthetic rubber, etc.; The conductivity of Nos. 1 to 1 changes depending on the pressure.

Furthermore, the method of the present invention can be applied as a technique for producing electrodes for electromyographs and electrocardiographs. That is, according to the present invention, a conductive metal film can be formed on the surface of the flexible polymer sheet 1, and such a polymer sheet can be easily attached to the film.

Next, the present invention will be explained in more detail with reference to Examples.

In addition, the volume resistivity and surface resistance shown below are
It was measured as follows.

Volume resistivity: 1. ．． 40g/c of 98cJ disc-shaped copper electrode
A clamping pressure of +# was applied, and the current A and voltage V during this time were measured, and based on the measured values, the volume resistivity in the thickness direction was calculated using the following formula.

Volume resistivity (0cm) 8 cm) Surface resistance: Create an electrode by bonding a copper plate to epoxy resin, and place the electrodes between the electrodes, the distance between the copper plate electrodes is 2cm, and the electrode size is 30m.
Under the condition of 1 cm, plated cloth (2.5 cm x 2.5
cm) with a clamping pressure of 3 kg, and the current A between the electrodes is
and the voltage V, and based on the measured values, calculate the surface resistance using the following formula.

Surface resistance (Ω/mouth) Example 1 As a sample, a polyester fiber sheet (2.5 cm x 2
．． 5 cm), and then convert it into a 4-vinylpyridine polymer (
After being immersed in a 0.1% methanol solution with a molecular weight of about 200,000 for 10 minutes, it was pulled out and dried. Next, this sample was immersed in a PdcQ2 solution with a concentration of 0.15 g/[ for 10 minutes, then pulled out, thoroughly washed with water to remove excess Pdcflz, and then immersed in a nickel plating bath at 75°C for 10 minutes. Chemical plating treatment was applied.

The obtained sample had a nickel coating firmly adhered to the fiber surface. In this sample, the amount of nickel deposited is 6.25 cn on the fiber area. (2.5cm x 2
．． 5 cm), and its volume resistivity (Ω· mark) was 420.

The composition of the nickel plating bath is as follows.

Nickel sulfate・6H20・・・・・・・・・25g
IQ Sodium Hypophosphite・・・・・・30gI
Q Malic acid・・・・・・・・・・・・・・・・・・
・30g/Q succinic acid・・・・・・・・・・・・・・・
・・・・・・16gIQpH・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・4.5 Example 2 The experiment was conducted in the same manner as in Example 1 except that the sample immersion time in the nickel plating bath was varied. . The relationship between the immersion time and the amount of nickel deposited and volume resistivity of the resulting sample is shown in the following table. - Table 1 11-Example 3 An experiment was conducted in the same manner as in Example 1 except that a copper plating solution was used instead of the nickel plating bath. Copper plating was performed at a plating temperature of 20° C. and a plating bath immersion time of 10 minutes. As a result, a sample of fiber with a rust adhesion of 18 mg/6.25 d was obtained, and its volume resistivity was 30 Ω·cm.

The composition of the steel plating solution is as follows.

Copper sulfate・・・・・・・・・・・・・・・25 g
/ QEDTA・・・・・・・・・・・・・・・
...60gIQ (chemical name: ethylenediamine-4-
Sodium acetate) 35% formalin 73.5mΩ/
Qp■・・・・・・・・・・・・Self・・・・・・・・・
-13 Example 4 An experiment was conducted in the same manner as in Example 1 except that various polymer fibers were used instead of the polyester fiber sheet. The results are shown in the table below.

12-Table-2 Example 5 In Example 1, a plastic sheet (
The experiment was conducted in the same manner except that a 2.5 cm x 2.5 CI11) was used. The adhesion of the metal coating formed on the sheet was investigated. The results are shown in the table below.

Table 3 Example 6 A sheet of nickel-adhered polyester fiber sheet 1" (15 cm
5cm) and a plastic sheet (ABS resin) (vertical 1
It was attached to a surface measuring 5 cm x width 15 cm x thickness 0.2 cm).

Next, the shielding effect of this sheet was measured.

As measuring devices, an evaluator (TR17301) and a spectrum analyzer (TR4172) were used. The results are shown in Tables 4 and 5. For comparison, Tables 4 and 5 also show the measurement results for plastic sheets to which the nickel-attached polyester fiber sheet was not attached.

Table 4 (Electric field shielding effect) Table 5 (Magnetic field shielding effect) In Tables 4 and 5, the larger the numerical value, the better the shielding effect.

Example 7 Nickel deposition amount 1, 9 obtained in the same manner as Example 1
Ethylene/vinyl acetate copolymer resin (vinyl acetate content 33
% by weight) were stacked and pressed together by passing between cooling rolls. In this case, the softened film resin filled the fiber voids of the nickel-attached polyester fiber sheet, forming a composite film in which the nickel-attached polyester fibers were contained as a reinforcing material. This composite film can be heat-sealed to a resin film, an inorganic board, or a metal plate.

This composite film was applied to the surface of the ABS resin plate for 13 minutes under pressure.
A laminate was obtained by heat-sealing at 0°C. Next, the electromagnetic wave transmission loss of this laminate was measured using a rectangular waveguide for the 4 GHz band, and as a result, a measurement limit of 40 dB was obtained.

Example 8 An experiment was conducted in the same manner as in Example 1, except that various 0.1% polymer solutions were used as the coating material instead of the polyvinylpyridine solution. The results are shown in Table-6.

16- Table 6 +11...Comparative example 2...Example 1 Example 9 After sufficiently immersing a polyethylene film in a 4-vinylpyridine monomer solution to swell it, take it out from the solution. The film was placed on a glass plate and irradiated with ultraviolet light from a low-pressure mercury lamp at a distance of 1 cm for 24 hours to graft-polymerize 4-vinylpyridine on the surface of the polystyrene film.

This film was immersed in an O, 1.5 g IQ Pd (112) solution, and then nickel plated in the same manner as in Example 1. As a result, a nickel film was formed on the 4-vinylpyridine graft polymerization surface of the plastic film. Furthermore, in this case, when the copper net was placed on the film during ultraviolet irradiation, the irradiated area was well plated with nickel, and a nickel film was formed in the form of a net on the plastic.

Example 10 Polyurethane rubber sheets 1~ with a thickness of 0.2 mm were dissolved in a 10% methanol solution of 4-vinylpyridine monomer for 30 min.
After being immersed for a minute, it was taken out of the solution and δ due to Co-60 was removed.
Under radiation irradiation, LH-Rad irradiation was performed to graft-polymerize vinylpyridine on the C-I surface. next.

This Sea 1~ is PdC at a concentration of 0.15g/fl, (12
After being immersed in the solution, nickel plating was performed in the same manner as in Example 1, and a nickel film was formed on the surface of the urethane rubber sheet.

Example 11 In Example 2, 1.2 mg/6.25 cJ of nickel was deposited on the polyester fiber sheet 1, which had a volume resistivity of 600 Ω·cm, and silver was further deposited thereon.

In this case, the amount of silver deposited is 7. ]-mg/6.25cJ has a volume resistivity of 163Ω・cm and a deposited amount of silver of 13.
The one with 7mg/6.25o has a volume resistivity of 142Ω・
cm is shown.

The composition of the silver plating bath used for the above deposition is as follows.

Silver cyanide 1-lium...! b:/Q 1-lium cyanide...5g/Q 1-lium hydroxide
Rium...1.6. /(1hydrogenation is 1~
Lium...5g/QTemperature...70°C Patent applicant: Director of the Agency of Industrial Science and Technology Kawa 1) Yube Designated representative: Keiji Takahashi, Director of Product Science Research Institute, Agency of Industrial Science and Technology

Claims (1)

[Claims] (1) A method for forming a metal film on the surface of a polymeric material, which comprises coating the surface of the polymeric material in advance with a nitrogen-containing polymer or oligomer, and then subjecting the surface to chemical plating.