JPS61255848A - Dielectric polyamide molded shape and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Summary The present invention relates to a novel conductive polyamide molded article and a method for producing the same.

Background of the Invention Conventionally, electroconductivity has been imparted to polyamide molded articles mainly through electroless metal forming. However, 1. Electroless metal forming has the major drawback that it is extremely complicated and requires a large number of processing steps including degreasing, chemical etching, sensitization, activation, and electroless metal + treatment. However, there is a drawback that the adhesion of the resulting metal film is poor. It has been disclosed that the latter of these drawbacks can be improved by devising pretreatment (Japanese Patent Application Laid-Open No. 161-1982, No. 32), blending silica into polyamide (Japanese Patent Application Laid-Open No. 158-236-1987), etc. However, no improvement has been made regarding the former.

On the other hand, it has been disclosed that conductivity can be imparted by coordinating a monovalent copper salt to the cyano group of a nitrile resin such as polyacrylic nitrile (Japanese Unexamined Patent Publication No. 56-11290
No. 9, Japanese Patent Publication No. 58-45263).

The present inventor conducted research with the aim of eliminating the drawbacks of the electroless Met+ method and forming a conductive film with excellent adhesion on polyamide molded products by a simple method, and developed the method using the above-mentioned nitrile resin. When tried, it was found that the monovalent copper salt was not coordinated to polyamide, and this method was not applicable. In order to achieve the above object, the inventor continued further intensive research.

As a result, the purpose was achieved by coordinating divalent steel ions after activating the amide group on the polyamide molded product, and reducing it to monovalent steel ions with a sulfur-containing reducing agent. It has been found that conductive polyanide molded products can be obtained.

The present invention was completed based on the above findings.

The present invention relates to a conductive polyamide molded product characterized in that a cuprous sulfide coating is closely formed on the surface of the polyamide molded product, and a polyamide molded product subjected to an activation treatment for amide groups to be made of divalent copper. A conductive polyamide molded article characterized by being treated with an ionic solution and then brought into contact with a sulfur-containing reducing agent to reduce copper ions to a monovalent one to form a cuprous sulfide coating on the surface of the polyamide molded article. Pertains to manufacturing method.

The conductive polyamide molded article of the present invention is one in which a cuprous sulfide coating is closely formed on the surface of the polyamide molded article. The thickness of the cuprous sulfide coating in the present invention is not particularly limited, but is usually 0. OI ~ 50μ solution. The cuprous sulfide coating has extremely excellent adhesion and is also excellent in cold resistance and heat resistance. Furthermore, since the cuprous sulfide coating uniformly covers the surface of the polyamide molded product, its conductivity is extremely stable.

The conductive polyamide molded article of the present invention is manufactured, for example, as follows.

The polyamide molded article in the present invention is, for example, a film, fiber, cloth, rectangular parallelepiped, cylindrical, These are molded bodies of various shapes such as spherical shapes. Further, the molded product may have a multilayer structure of a resin other than borianide and polyamide, or a mixture thereof.

First, a polyamide molded article is subjected to an amide group activation treatment. This activation treatment weakens the strong hydrogen bonds existing between amide groups and allows divalent steel ions to coordinate. This activation treatment involves the following: 1. Potassium iodide, sodium iodide, lithium iodide, potassium bromide, 1. thorium bromide, lithium bromide, etc. halogen compounds,
and 00 phenol) MEC 00 phenol, Barak 0
Preferably, at least one phenolic compound such as lophenol and bovine sirenol is used. Particularly preferred among these are a combination of halogen and a halogen compound, or a phenol compound. In addition, this activation process
To the above, it is preferable to immerse the polyamide molded article in an aqueous solution of at least one of an IS halide compound and a phenolic compound. The concentration of the aqueous solution at this time varies depending on the type of drug used and is not constant. 5
It is appropriate to set the concentration to about w*a14. Also,
In the case of Metafreel, usually 0,005~Q,5v
It is appropriate to set the concentration to tal/J. Although the treatment temperature is not particularly limited, it is usually appropriate to set it at about 5 to 50°C. Further, the processing time also varies and is not constant, but in the above case, it is usually appropriate to set it to about 1 second to 10 hours.

If the amide group is not activated, coordination of divalent copper ions does not occur, so a sulfided No. 1 steel coating is not formed. Therefore, during this activation treatment, a part of the polyamide molded product is dipped in a treatment solution or a part of the polyamide molded product is immersed in a mass. By doing so, it is possible to easily form a cuprous sulfide coating only on desired portions. For example, it is easy to form a cuprous sulfide coating only on one side of the film, or to form the coating only on the side of the molded body that requires conductivity.

Incidentally, prior to the activation treatment of the amide group, if necessary, a conventional degreasing treatment may be performed.

Next, 1. The polyamide molded product subjected to the above activation treatment is treated with a divalent steel ion solution, and then contacted with a sulfur-containing reducing agent.◇ The treatment with the divalent steel ion solution is not particularly limited, but for example, Normally 0.2 #4 salts such as cupric nitrate, cupric sulfate, cupric acetate, cupric chloride, etc. O1~l Q pal
This is preferably carried out by immersion in an aqueous solution of about 1 to 5 mol/l of O, preferably 1 to 5 mol/l, at a temperature of about 5 to 50°C for about 1 second to 5 hours, preferably 2 minutes to 1 hour. .

Contact treatment with a sulfur-containing reducing agent is not particularly limited, but
For example, sulfur-containing reducing agents such as sodium thiosulfate, sodium sulfite, sodium sulfide, potassium thiosulfate, potassium sulfite/potassium sulfide, etc. are usually 0.01 to IO#1σl.
/ l, preferably 0.1 to 5 mar/ll
to an aqueous solution of IO to 100°C, preferably 40 to 80°C.
at a temperature of 10 minutes to 1 week, preferably 1 to 24
It is best to do this by soaking for a period of time.

The treatment with a divalent copper ion solution and the contact treatment with a sulfur-containing reducing agent may be carried out using separate containers, but the treatment solution after the former treatment is not removed in particular and is placed in the same container. It is more preferable to further add the latter treatment solution and carry out the latter treatment continuously. These treatments are suitably carried out by stirring or shaking as appropriate.

By treatment with a divalent steel ion solution and then contact treatment with a sulfur-containing reducing agent, the divalent steel ions are coordinated to the amide group, and then the ions are reduced to monovalent and at the same time sulfur is bonded. As a result, a cuprous sulfide coating having metallic luster is formed in close contact with the surface of the ryanide molded product. The thickness of the cuprous sulfide coating depends on the concentration of the cupric salt in the former treatment (see above) and is usually about 0.01 to 50 μm.

In this way, the conductive polyanidite molded article of the present invention can be manufactured and obtained.

The present invention provides the following remarkable effects.

(1) Surface rfIK sulfide a of various polyamide moldings
il#! A film can be formed in close contact extremely easily, and a novel conductive polyamide molded product that has never been obtained before can be obtained.

(2) The adhesion of the sulfide No. 1 steel coating is extremely excellent.
(3) The cuprous sulfide coating uniformly covers the surface of the polyanid molded product, so its conductivity is extremely stable. Regarding conductivity itself, while uncoated polyamide molded products usually exhibit an electrical resistance of about 1011 Ω·1, the conductive polyamide molded products of the present invention usually have an electrical resistance of about 10 4 Ω·1 or less. This results in excellent conductivity.

(4) The cuprous sulfide coating also has excellent cold resistance and heat resistance.

1911 The present invention will be described in detail below with reference to Examples.

Example 1 Disc-shaped film of polyanide-6 (thickness: 50 p m
, diameter near 11), iodine 2.5 f (10vtm
e1% potassium iodide 3.3F (20pptMIa/
) was dissolved in distilled water for about 20 seconds at room temperature to activate the amide groups, and the hair was washed with running water for about 30 minutes. Cupric nitrate solution 20
ml<0.4flal/It> for a few minutes at room temperature, then soaked in 20xl of sodium thiosulfate solution (0.4pm/It) for a few minutes at room temperature.
al/l) was added, left at room temperature for several minutes, heated at 63°C, shaken for 3 hours, washed with water, and dried to form a No. 1 steel sulfide film with a metallic luster on the leading edge that adhered to both sides of the film. A conductive boria three-dimensional film of the present invention was obtained.

The surface resistivity value of this conductive film was determined by the DC power four-point method using a "R4328J Milliohmmeter" manufactured by Hewlett-Packard Rose Card Co., Ltd. 11 decided 2
．． It was 0x102Ω.

Further, the close layer properties of this conductive film on which cuprous sulfide was applied were evaluated by the adhesion rate using the following cross-cutting test method, and it was found that the adhesion was 100%, indicating that the adhesion was extremely excellent.

Measurement of 0 adhesion rate: After making 11 score lines that reach the film surface in a matrix pattern at 1-fi intervals vertically and horizontally on the conductive surface of the conductive film to be tested, place 1.0 in width on the score lines. ~t
, 5aII% ``Menji Inter Tape'' manufactured by Chiban Co., Ltd.) was attached to an adhesive tape having a length of 3 to 5cIl, and then the tape was peeled off at once in a direction of 90 to 180° with respect to the film surface. The ratio of the number of pieces remaining without peeling off the sulfide No. 1 steel coating out of 100 pieces of the base plate is expressed as a percentage. All these operations should be performed at room temperature.

In addition, this conductive film xI! Photoelectron spectroscopy (ES)
CA) (Takasu Seisakusho Co., Ltd.'s "EscA750" and a data processing device (-ESCAPAC760) were used to conduct a surface analysis, and the peak of the 1st IR sulfide was confirmed.Also, the peak of the 1st IR of sulfide was confirmed. The peak disappears,
The large shift in the peak of the anidocarbonyl carbon, especially the subpeak, suggests that cuprous sulfide is coordinated on the anido group. The analysis results are shown in Table 1. The units of numerical values in Table 1 are eV.

Table 1 Also, when this conductive film was observed using a scanning electron microscope (manufactured by JEOL Ltd. r7'-1oo),
It was found that a cuprous sulfide coating having a thickness of 0.2 to 0.3 μm was formed in uniform and close contact. A scanning electron micrograph (magnification: 30,000 times) is shown in FIG.

Furthermore, the cold resistance of this conductive film was tested using liquid nitrogen (-17
The heat resistance was determined by measuring the front deposition rate after immersion in boiling water (100℃) for 1 hour, and by measuring the front deposition rate after immersion in boiling water (100℃) for 1 hour. As a result of the investigation, it was found that the adhesion rate was 100% in all cases, and it was found to be excellent in cold resistance and heat resistance.

Example 2 A disc-shaped film of boria trido-6 as a raw material with a thickness of 1
A conductive polyamide film of the present invention was obtained in the same manner as in Example 1, except that a film having a diameter of 50 μm was used.

The surface resistivity value of this conductive film was measured in the same manner as in Example 1 and was found to be 6.4×10 2 Ω. In addition, when the adhesion rate was investigated by measuring the adhesion rate, it was found that the adhesion rate was 10.
It was 0%.

Furthermore, this conductive film was inspected using a scanning electron microscope in the same manner as in Example 1. Scanning electron micrographs are shown in Figures 2-2. FIG. 2 (30,000x magnification) shows the surface of an untreated polyamide-6 film. Figure 3 (30,000x magnification) shows the surface of the conductive film obtained in this example.The surface is almost as smooth as that in Figure 2, and the cuprous sulfide coating is uniform. It can be seen that they are formed in close contact. Figure 4 (4200x magnification) shows the cross section of the conductive film obtained in this example, with a thickness of about 5.
It can be seen that the cuprous sulfide coating with a thickness of μm is uniformly and tightly formed.

Example 3 A disc-shaped film of raw material polyamide-6 with a thickness of 5
A conductive polyamide film of the present invention was obtained in the same manner as in Example 1 of another company using μm polyamide film.
The resistance was measured using a DC power supply two-point method using a 3.8 x 10 3 multimeter.

Example: As a disc-shaped film of borianide-6 as a raw material, the thickness is 1
Use a 50μ solution and activate the amide group to 0.0
A conductive polyanide film of the present invention was obtained in the same manner as in Example 1, except that the hair was soaked in an aqueous solution of 5 tnol/l of metafureryl.

The surface resistivity value of this conductive film was measured in the same manner as in Example 1 and was found to be 6.5×10 2 Ω. In addition, when the adhesion rate was investigated by measuring the adhesion rate, it was found that the adhesion rate was 10.
It was 0%.

Examples 5 to 7 Conductive polyamide films of the present invention were obtained in the same manner as in Example 1, except that the polyamide disk film shown in Table 2 was used as the raw material.Measured in the same manner as in Example 1. The surface resistivity value and adhesion rate are also listed in Table 2.

2nd. The hair (surface diameter = 71) was immersed in the iodine solution described in Example 1 at room temperature for about 20 seconds, subjected to amide group activation treatment, washed with running water for about 39 minutes, and then air-dried. Immerse it in 20 sl (0.4 mal/I) of cupric nitrate solution for several minutes at room temperature,
Then add 20 ml of sodium thiosulfate solution (0-4""
/j), leave it at room temperature for a few minutes, and heat it to 63℃.
After shaking for a while, washing with water and drying, a conductive polyanide woven fabric of the present invention having a blue metallic luster was obtained. The surface resistivity values measured in the same manner as in Example 1 are shown in Table 3. A thin film was formed. Using this film, polyanide-6 thin-0 supported on PE porous film was prepared in the same manner as in Example 1.
A copper coating was closely formed on 7 sides to obtain an electrically conductive polyamide-polyethylene multilayer film of the present invention. - The surface resistivity value of this conductive film was measured in the same manner as in Example 3 and was found to be 1.7×10' Ω.

[Brief explanation of the drawing]

FIG. 1 shows a scanning electron micrograph (magnification: 30,000 times) of the conductive polyamide film of the present invention obtained in Example 1. FIG. 2 shows a scanning electron micrograph (30,000x magnification) of an untreated polyamide-6 film. Figures 5 and 4 are scanning electron micrographs of the conductive polyamide film of the present invention obtained in Example 2 (magnification of Figure 3 is 300
00 times, and 4200 times in Fig. 4). (The above) ・、、;・' Figure 1 Figure 2 - 9 ≧ 5゛mi,゛, l, 7S ゛,:,゛Figure 3 Figure 4

Claims (3)

[Claims] (1) A conductive polyamide molded article characterized in that a cuprous sulfide coating is closely formed on the surface of the polyamide molded article. (2) A polyamide molded product that has been subjected to activation treatment for amide groups is treated with a divalent copper ion solution, and then brought into contact with a sulfur-containing reducing agent to reduce the copper ions to monovalent one and coat the surface of the polyamide molded product. A method for producing a conductive polyamide molded article, which comprises closely forming a cuprous sulfide coating. (3) The production method according to claim 2, wherein the activation treatment of the amide group is performed using at least one of a halogen, a halogen compound, and a phenol compound.