JPH01168865A - Production of article coated with copper film - 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] [Industrial Application Field] The present invention relates to polyimide, wholly aromatic polyamide, polyamideimide, PPS (polyphenylene sulfide),
This article relates to a new method for forming a copper coating on articles such as films, sheets, molded articles, fibers, cloth, paper, powder, etc. made of ultra-heat-resistant resin such as polybenzimidazole, and includes articles on which a copper coating is formed using this manufacturing method. Copper is firmly attached without any special pre-treatment, and it does not contain any corrosive elements such as halogens, so it can be used as is or with copper or other metals plated. It is suitably used as a base for electrical, adhesive, and various other uses.

[Conventional technology and its problems]

The method for forming a copper coating on super heat-resistant resin articles is as follows:
Examples include electroless plating, vapor deposition, pressure welding, and bonding with adhesives.

The electroless plating method is the most common and excellent method, but it usually requires special pretreatment depending on the resin used, and has the disadvantage that the process is complicated. .

The vapor deposition method requires special equipment for vapor deposition, making it difficult to manufacture large products, and depending on the type of ceramic, pretreatment is required to improve adhesiveness. Furthermore, although pressure bonding methods and bonding with adhesives are used as appropriate, there are cases where pressure bonding is not possible, the shape of the molded product is limited, and when adhesives are used, the adhesive layer becomes thicker.
This method has the disadvantage that the physical properties of the adhesive layer deteriorate the physical properties of the resulting product.

[Means for solving problems]

In view of the above circumstances, the present invention was completed as a result of studies on a method of providing an economical and high-quality material with a copper film formed thereon by a simple method.

That is, in the present invention, a desired part of an ultra-heat-resistant resin article,
After applying a mixed solution containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components, the deformation deterioration temperature of the super heat-resistant resin article is at 165°C or higher in a non-oxidizing atmosphere. This is a method for producing a copper film-forming article, which is characterized by heating to the following temperature.

The present invention will be explained below.

The super heat-resistant resin articles of the present invention are trapezoidal articles such as films, sheets, molded bodies, fibers, cloth, paper, and powder. Specific examples of super heat-resistant resins include polyimide, wholly aromatic polyamide, polyamideimide, PPS (polyphenylene sulfide), and polybenzimidazole.

A mixed solution (hereinafter referred to as treatment solution) containing as essential components a copper compound selected from copper hydroxide or organic acid copper of the present invention and a polyhydric alcohol, which is used to form a copper film on the above resin. The copper compound to be used is copper hydroxide or a copper salt of an organic acid, and these are not particularly limited, but preferably a compound that easily separates from the surface without carbonizing at the temperature used for forming the copper film. Select as appropriate, taking into consideration price and availability. Specifically, formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, capric acid,
Copper salts of monocarboxylic acids such as lauric acid, stearic acid, naphthenic acid, benzoic acid, oleic acid, acrylic acid, methacrylic acid, crotonic acid, pentenoic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline acids, copper salts of polycarboxylic acids such as succinic acid, azelaic acid, brassic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, maleic acid; furthermore, esters and amides of mono- or polycarboxylic acids, etc. Also included are copper salts of hydroxyl groups such as glycolic acid and amino acids such as glutamic acid.

Polyhydric alcohol is a compound containing two or more hydroxyl groups, and although it is not particularly limited, it has good wettability with the surface of the molded product and is suitable for use at the temperature used for copper film formation. A compound that can be easily released from the surface without carbonization is preferred. Specifically, ethylene glycol, propylene glycol, butanediol, bentanediol, hexanediol, 1.5-hexadiene-3°4-diol, 2.6-octadiene-4,5-
Diol, glycerin, 1.2.3-butanetriol, 1.2.3-pentanetriol, pentamethylglycerin, erythritol, pentaerythritol, atonite, arabite, diethylene glycol, triethylene glycol, dipropylene glycol, other polyalkylenes Glycols, even jetanolamine,
Examples include triethanolamine.

The treatment liquid of the present invention is prepared by mixing the above-described copper hydroxide or organic acid copper with a polyhydric alcohol. The composition ratio of copper hydroxide or organic acid copper and polyhydric alcohol in the treatment liquid is not particularly limited as long as a uniformly mixed solution can be prepared, but if more copper hydroxide or organic acid copper is used, It is preferable to use copper hydroxide or organic acid copper.
It is used in a range of 70% by weight, preferably 20 to 60% by weight, and is kneaded uniformly at room temperature or under heating.

In addition, when preparing the treatment liquid of the present invention, additives other than those mentioned above may be used in combination as appropriate, and these include organic acids, amines, organic solvents, surfactants, and salts of copper and other metals. , polyvinyl alcohol, etc.

The above treatment liquid is applied to the desired part of the ultra-heat-resistant resin article by printing, brush coating, dibbing, spray coating, barcoding, roll coating, or other application methods in an inert atmosphere. The copper film-formed article of the present invention is manufactured by heat treatment.

The non-oxidizing atmosphere is N2. Ar, CO2, C
D, under a gas atmosphere such as N2, or simply covering the coated surface with a heat-resistant film such as Teflon.
By heating and maintaining an atmosphere of gas decomposed from the coating layer. In addition, the heating is carried out batchwise or continuously by selecting radiation heating such as infrared rays, electron beams, microwaves, electric furnaces, ovens, oil heating, pressurized steam, and other means depending on the temperature used, Usually heating rate
50-bHr, preferably 100-b A predetermined temperature, i.e., a temperature range from 165°C to below the deformation deterioration temperature of the ultra-heat-resistant resin article, preferably 170°C-
The temperature may be simply heated to a temperature range of 300°C, or the temperature may be maintained at the same temperature range for 3 hours or less, preferably from several minutes to 2 hours.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 100 parts of copper formate and 200 parts of glycerin were stirred and mixed to obtain a viscous blue treatment liquid (hereinafter referred to as treatment liquid 1).

This treatment solution 1 was applied to a polyimide film (with glossy surfaces on both sides).
Product name: Kapton, made by Azuma DuPont ■, thickness 30p
) to a thickness of 201 cm, the temperature was raised to 200° C. in 30 minutes in a nitrogen gas atmosphere from a cylinder, held at this temperature for 60 minutes, and then taken out.

A shiny copper film was uniformly adhered to the surface of the obtained polyimide film.

The thickness of this copper film is 0.3/a, and the volume resistance is 1. OX1
Peeling test result by 0-'Ω・11 Cellotape base test (cross cut test) is 100/100, boiling 2
Even after hours, there was no swelling or peeling.

Further, a glossy copper film with uniform adhesion was obtained in the same manner as above except that the coating thickness of treatment liquid 1 was 120 mm.

The thickness of this copper film is 3JA, and the volume resistance is 7. OX 10-
'Ω' mark: Peeling test result by Cellotape base cross-cut test (cross-cut test) was 100/100, and there was no swelling or peeling even after 2 hours of boiling.

Example 2 100 parts of copper hydroxide and 200 parts of glycerin were stirred and mixed to obtain a viscous blue treatment liquid (hereinafter referred to as treatment liquid 2).

A polyimide film having a glossy copper film uniformly adhered thereto was obtained in the same manner as in Example 1, except that this treatment solution 2 was applied to a thickness of 120 mm.

The thickness of this copper film is 6-1 volume resistance 5. OX 10-'
Ω mark, peel test result by Cellotape base test (cross cut test) was 100/100, and there was no swelling or peeling even after 2 hours of boiling.

Example 3 In Example 1, 10 parts of copper acetate was substituted for 100 parts of copper formate.
A processing solution (hereinafter referred to as solution 3) was obtained in the same manner except that 0 part was used, and a polyimide film with a glossy copper film uniformly adhered was obtained in the same manner except that this processing solution 3 was used.

Example 4 A treatment liquid (hereinafter referred to as treatment liquid 4) was obtained in the same manner as in Example 1, except that 200 parts of triethanolamine was used instead of 200 parts of glycerin; A polyimide film with a glossy copper film uniformly adhered was obtained.

Example 5 A treatment liquid (hereinafter referred to as treatment liquid 5) was obtained in the same manner as in Example 1, except that 200 parts of ethylene glycol was used instead of 200 parts of glycerin. A polyimide film with a glossy copper film uniformly adhered was obtained.

Example 6 In Example 1, instead of polyimide film, PP
Using a molded product S with a thickness of 3 mm, process liquid 1 was applied to a thickness of 120 mm.
A molded product with a copper film in close contact was obtained in the same manner except that it was coated with -.

The thickness of this copper film was 3A3, the peel test result by cross-cut test was 100/100, and there was no swelling or peeling even after 2 hours of boiling.

Example 7 In Example 6, 100 parts of copper hydroxide, 20 parts of glycerin
A treatment liquid (hereinafter referred to as treatment liquid 6) was obtained by stirring and mixing 0 parts of formic acid and 10 parts of formic acid, and a molded article with a copper film in close contact was obtained in the same manner except that this treatment liquid 6 was used.

Example 8 A molded article with a copper film adhered to it was obtained in the same manner as in Example 6 except that treatment liquid 3 was used.

[Operations and Effects of the Invention] According to the manufacturing method of the present invention as described above, conventionally, a copper film with excellent adhesion could be formed by electroless plating or the like only after special pretreatment. By using extremely simple methods, it is possible to easily obtain products with a copper film with excellent adhesion on ultra-heat-resistant products that have previously been difficult to produce. Alternative to copper foil adhesion,
It is suitable for use as a base treatment for welding, etc., for copper-clad films, copper-clad plates, and other uses, or as an electrically conductive and thermally conductive film, either as is or by forming an oxidation-resistant coating. .

Claims (1)

[Claims] After applying a mixed solution containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components to a desired part of an ultra-heat-resistant resin article, the mixture is heated to 165% in a non-oxidizing atmosphere.
A method for producing a copper film-forming article, which comprises heating at a temperature above .degree. C. and below the deformation deterioration temperature of the ultra-heat-resistant resin article.