JPH01168866A - Production of article coated with copper film - Google Patents

Abstract

PURPOSE:To form a copper film having an excellent adhesive property with a simple means by applying a liq. mixture of copper hydroxide or the copper salt of an org. acid and a polyhydric alcohol on an article of a thermoplastic resin having a heat-deflection temp. higher than a specified value, and heating the article in a specified temp. range in a nonoxidizing atmosphere. CONSTITUTION:A liq. mixture contg. copper hydroxide or a copper compd. selected from the copper compds. of an org. acid and a polyhydric alcohol as the essential components is applied on the desired part of an article of the thermoplastic resin having >=165 deg.C heat-deflection temp. under a low load. The article is then heated in a nonoxidizing atmosphere to a temp. higher than 165 deg.C and lower than the deflection temp. of the article, and kept at that temp. For example, a liq. mixture consisting of 100 parts of copper hydroxide and 200 parts of glycerin is applied in 60mu thickness on one side of a molded article consisting of glass fiber-reinforced meta-xylenediamine and nylon MXD from adipic acid. The molded article is then heated to 180 deg.C in 30min in a gaseous N2 atmosphere, and kept at that temp. for 60min.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel method for forming a copper coating on a thermoplastic resin article having a heat distortion temperature of 165° C. or higher under low load. Copper film-formed articles manufactured using this manufacturing method have copper firmly attached to them without any special pretreatment.
Moreover, since it does not contain any corrosive elements such as halogens, it can be used as is or by plating with copper or other metals to produce films, sheets, molded products, fibers, cloth, powders, and various other forms. It is suitable for use in articles for use.

[Conventional technology and its problems]

Methods for forming a copper coating on a thermoplastic resin article, such as a molded article, include electroless plating, vapor deposition, pressure welding, bonding with an adhesive, and the like.

The electroless plating method is the most common and excellent method, but it usually requires pretreatment depending on the thermoplastic resin used, and has the disadvantage that the process is complicated. . In addition, there is a method of using a molded article made from a composition that is pre-blended with a diene rubber or the like in order to omit a pretreatment step, but this often results in deterioration of the inherent performance of the thermoplastic resin. Furthermore, in the case of a molded article containing a filler such as glass fiber, this method has the disadvantage that good adhesion cannot be obtained if the filler is exposed on the surface of the molded article.

The vapor deposition method requires special equipment for vapor deposition, making it difficult to manufacture large products, and depending on the type of resin, pretreatment is required to improve adhesiveness. Furthermore, although pressure bonding methods and bonding with adhesives are used as appropriate, they have drawbacks such as the shape of the molded product being limited and the adhesive layer becoming thick.

[Means for solving problems]

In view of the above circumstances, the present invention was completed as a result of research into a method of providing an economical and high-quality copper film-coated material using a simple method.

That is, in the present invention, the heat distortion temperature under low load is 165°C.
After applying a liquid mixture containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components to a desired part of the above thermoplastic resin article, the mixture is heated to 165°C in a non-oxidizing atmosphere. The above is a method for producing a copper film-formed article, which is characterized by heating and holding the thermoplastic resin article at a temperature below the thermal deformation temperature under a low load.

The present invention will be explained below.

The thermoplastic resin articles of the present invention having a heat deformation temperature of 165°C or higher under low load include films, sheets, molded articles formed by injection molding, compression molding, and other means, fibers, cloth, powder, etc. It is a trapezoidal molded body.

Specific thermoplastic resins include nylon-6, nylon-66, nylon-6/66, nylon-11, nylon-3, MXD6 and MXD6/10 derived from meta-xylylene diamine and aliphatic dicarboxylic acids. General-purpose engineering plastics such as crystalline polyester resins such as polyamide resins, polybutylene terephthalate, and polyethylene terephthalate; wholly aromatic polyesters whose main monomers are P-hydroxybenzoic acid, phthalic acid, and bisphenol, and polyethylene terephthalate, etc. Engineering plastics such as grafted aromatic polyester liquid crystal polymers, polyetherimide, polysulfone, polysulfone, polyethersulfone, polyetheretherketone, and polyphenylene ether, as well as fibers, minerals, and other filler reinforcements of these polymers, etc. Among these, those having the above-described heat distortion temperature of 190° C. or higher are preferable, and those having a heat distortion temperature of 210° C. or higher are particularly preferable because they allow a wider range of processing conditions for forming a copper film.

A mixed solution (hereinafter referred to as treatment The copper compound used in the liquid (referred to as "liquid") is copper hydroxide or a copper salt of an organic acid, and is not particularly limited, but preferably a compound that is easily released from the surface at the temperature used for forming the copper film. , to be selected appropriately taking into consideration price and availability. Specifically, formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, capric acid, lauric acid, stearic acid, naphthenic acid, benzoic acid, oleic acid, acrylic acid, methacrylic acid, crotonic acid, pentenoic acid, etc. Copper salts of monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, azelaic acid, brassylic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, maleic acid, etc. Copper salts of polycarboxylic acids: In addition, copper salts of mono- or polycarboxylic acid esters, amides, etc., hydroxyl groups such as glycolic acid, amino acids such as glutamic acid, etc.
Can be mentioned.

In addition, 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 forming the copper film. Compounds that are easily released from the surface are 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, attonite, aravit,
Examples include diethylene glycol, triethylene glycol, dipropylene glycol, other polyalkylene glycols, jetanolamine, triethanolamine, and the like.

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 solution is not particularly limited as long as it can be adjusted to a uniform solution to form a uniform coating when applied. It is preferable to use a larger amount of copper or organic acid copper, and usually copper hydroxide or organic acid copper is used in a range of 10 to 70% by weight, preferably 2% by weight.
It is used in a range of 0 to 60% by weight, and is homogenized by kneading at room temperature or under heating.

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

The above treatment liquid is printed, brushed, dipping, spray coated, bar coded, roll coated, etc. on a desired part of a thermoplastic resin molded body whose heat deformation temperature under low load is 165°C or higher, and is applied in a batch or continuous manner. The copper film-formed article of the present invention is produced by heat treatment in an inert atmosphere.

The non-oxidizing atmosphere is N2. Ar, CO2, C
D, Ha or the like gas atmosphere, or simply covering the coated surface with a heat-resistant film and heating it to maintain an atmosphere of decomposed gas from the coated layer.

The heating may be carried out batchwise or continuously by selecting appropriate temperatures such as radiation heating such as infrared rays, electron beams, or microwaves, electric furnaces, ovens, oil heating, pressurized steam, or other means. Usually, heating is carried out at a heating rate of 50 to 100 bt/Hr, and from a predetermined temperature, i.e., 165°C, to the thermal deformation temperature under low load of the thermoplastic resin article, preferably from 170°C to the low load of the thermoplastic resin article. By maintaining the heat distortion temperature in the following range for 0 to 3 hours, preferably 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 A viscous blue treatment liquid (hereinafter referred to as treatment liquid 1) was obtained by stirring and mixing 100 parts of copper hydroxide and 200 parts of glycerin.

This treatment solution 1 was applied to one side of a 3 mm thick molded product of nylon MXD6 made from glass fiber reinforced metaxylylene diamine and adipic acid to a thickness of 60 mm. After coating with U, the temperature was raised to 180° C. in 30 minutes under a nitrogen gas atmosphere from a cylinder, and after being held at this temperature for 60 minutes, it was taken out.

The copper film was uniformly adhered to the surface of the obtained nylon MXD6 molded product.

The thickness of this copper film is 3-1 volume resistance 3X10-'Ω・mark,
The peel test result by cellotape base cross cut test was 100/IOQ.

Example 2 100 parts of copper formate and 100 parts of ethylene glycol were stirred and mixed to obtain a viscous blue treatment liquid (hereinafter referred to as treatment liquid 2).

A molded article of nylon MXD6 to which a shiny copper film was evenly adhered was obtained in the same manner as in Example 1, except that this treatment liquid 2 was used.

Example 3 A treatment liquid (hereinafter referred to as treatment liquid 3) was obtained in the same manner as in Example 1 except that 200 parts of triethanolamine was used instead of 200 parts of glycerin; In the same manner, a molded product of nylon MXD6 to which the copper film was uniformly adhered was obtained.

Examples 4 to 11 In Examples 1 to 3, polyarylate (trade name: U Polymer, manufactured by Unitika ■, hereinafter referred to as U Polymer), polysulfone (trade name: Udelboly) was used instead of the molded product of nylon MXD6. Sulfon, manufactured by Amoco Chemicals,
(hereinafter referred to as tlPsP), 20% by weight glass fiber reinforced polyether sulfone (manufactured by Mitsui Toatsu ■, hereinafter referred to as pEsp)
Molding of polyetherimide (trade name: Ultem, manufactured by General Electric ■, hereinafter referred to as Ultem), polyetheretherketone (trade name: Pictrex, manufactured by ICI, UK, hereinafter referred to as PEEK) The product was treated under the conditions listed in Table 1 to obtain a molded product in which a copper film was uniformly formed.

The results are shown in Table 1.

In addition, treatment liquid 4 in Table 1 was obtained by stirring and mixing 100 parts of copper formate and 200 parts of glycerin, and treatment liquid 5 was obtained by stirring and mixing 100 parts of copper acetate and 200 parts of glycerin. This is what I got.

Further, the appearance of the copper film is based on visual observation, and ◯ indicates the formation of a uniformly adhered copper film.

[Operation and effects of the invention]

According to the manufacturing method of the present invention as described above, a molded article on which a copper film with excellent adhesion is formed can be easily obtained by extremely simple means. It can be used as a base treatment for vacuum evaporation, as a substitute for copper foil adhesion, as a base for welding, for copper-clad films, copper-clad laminates, and other uses, or as it is or by forming an oxidation-resistant coating to improve electrical conductivity and thermal conductivity. It is suitably used as a membrane.

Claims (1)

[Claims] A mixed solution containing a copper compound selected from copper hydroxide or organic acid copper and a polyhydric alcohol as essential components was applied to a desired part of a thermoplastic resin article whose heat distortion temperature under low load was 165°C or higher. A method for producing a copper film-formed article, comprising heating and holding the thermoplastic resin article at a temperature of 165° C. or higher and lower than the thermal deformation temperature under a low load in a non-oxidizing atmosphere.