JP2751335B2 - Manufacturing method of copper-plated resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-resistant fiber-reinforced or unreinforced thermoplastic or thermosetting resin molded article having a heat deformation deterioration temperature higher than 165 ° C. The present invention relates to a novel method of forming a copper-plated molded product, in which copper is firmly and uniformly vapor-deposited in grooves, holes, etc. without special pretreatment. Alternatively, it is suitably used for various purposes as a base for plating copper or other metals.

[Conventional technology and its problems]

In general, as a method for forming a copper film on a thermoplastic resin molded product, there are an electroless plating method, a vapor deposition method, a pressure welding method, adhesion with an adhesive, and the like.

The electroless plating method is the most common and is an excellent method because low-temperature plating is possible, but usually requires a special pretreatment. In order to omit or simplify the pretreatment step, there is a method of using a molded article from a composition in which a diene rubber or the like is previously compounded, but the original performance of the resin is often deteriorated. Also, in the case of a resin molded product containing a reinforcing material such as glass fiber, it is difficult to perform good plating in which the surface of the reinforcing material is also firmly adhered to at the same time. However, there was a defect such as easy peeling.

Conventional vapor deposition methods require special equipment for vapor deposition, and depending on the type of article, require a pretreatment to improve adhesiveness. In addition, although it is appropriately used such as a pressure welding method and bonding with an adhesive, it cannot be press-bonded, and the shape of a molded product is limited, and when an adhesive is used, the adhesive layer becomes thicker and the adhesive layer becomes thicker. There are drawbacks such as deterioration of the physical properties of the obtained article.

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, heretofore, there is no example of applying this method to a molded article of a thermoplastic resin or a thermosetting resin, and there is no method suitable for mass production, and the method has not 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 studying a method for providing an economical and high-quality resin molded product having a copper film formed thereon by a simple method.

That is, the present invention is a method of producing a copper-plated resin molded product by heating a resin molded product having a deformation deterioration temperature higher than 165 ° C. and copper formate in a non-oxidizing atmosphere, and producing the molded product. When preparing a container or a placement tool to be placed, and also plating copper on a contact portion of the container or the placement tool that comes into contact with the molded article generated when the container or the placement tool is placed,
Copper formate is interposed in the contact portion, and further, a desired amount of copper formate is placed in the container or the disposing tool, and the molded article is deformed and deteriorated at 165 ° C. or more in a non-oxidizing atmosphere or under reduced pressure. A method for producing a copper-plated resin molded product, characterized in that a temperature between 130 ° C. and the predetermined temperature is raised and maintained at a rate of 1 deg / min or more to a predetermined temperature in a range of not more than the temperature, and Copper formate is placed on the inner surface of the lid of the container or on the placement tool, and the amount of copper formate per total surface area of the plating space in which the resin molded product and copper formate are stored or placed is 0.001 g / cm ^3. And the distance from the plated part of the resin molded product is
This is a method for producing a copper-plated resin molded product, which is within 5 cm.

 Hereinafter, the present invention will be described.

The resin molded product having a deformation deterioration temperature higher than 165 ° C. of the present invention is usually injection molding, compression molding, transfer molding,
Usually, it is a three-dimensional molded product having grooves, holes and the like formed by other means, and is made of a heat-resistant thermoplastic resin or a thermosetting positive resin.

Here, as the thermoplastic resin, nylon-6, nylon-66, nylon-6 / 66, nylon-11, nylon-
3, MXD6 derived from meta-xylylenediamine and aliphatic dicarboxylic acids, general-purpose engineering plastics such as polyamide resins such as MXD6 / 10, crystalline polyester resins such as polybutylene terephthalate and polyethylene terephthalate; P-hydroxybenzoic acid; Phthalic acid, a wholly aromatic polyester having a main monomer such as bisphenol, or an aromatic polyester liquid crystal polymer obtained by grafting polyethylene terephthalate or the like onto these,
Polyetherimide, polysulfone, polysulfone, polyethersulfone, polyetheretherketone, polyphenyleneether, engineering plastics such as polyphenylenesulfide and the fibers of these polymers, minerals, and other filler reinforced materials and the like, among them, It is preferable that the above-mentioned deformation deterioration temperature is 190 ° C. or more, and it is also suitably applied to a fiber-reinforced one. Further, as the thermosetting resin, phenol resin, diallyl phthalate resin, epoxy resin, polyamine-bismaleimide resin, polymaleimide-epoxy resin, polymaleimide-isocyanate resin, cyanate resin, cyanate-epoxy resin, cyanate-polymaleimide resin And ordinary thermosetting resins such as cyanate-epoxy-polymaleimide resin; the above-mentioned thermosetting resins and polyamide (nylon), aromatic polyester, polyetherimide, polyetheretherketone, polysulfone, polyphenyleneether, etc. Thermosetting so-called "IPN" obtained by blending with engineering plastics and further adding catalysts as appropriate; polyolefin such as polyethylene, organic peroxide as a crosslinking agent for resins such as 1,2-polybutadiene, and more appropriately Cross-linking curable resins mixed with dical polymerizable polyfunctional compounds, thermosetting resins, etc., as well as glass, carbon, alumina, other fibers, fiber woven fabrics, powders, etc. And the like.

The copper formate of the present invention is a cupric formate compound such as anhydrous copper formate, copper formate tetrahydrate or a mixture thereof.

The resin molded product of the present invention is placed in a container or a placement tool, and copper formate is interposed at a contact portion between the container and the placement tool that comes into contact with the resin molded product at that time. The method of interposition is a method of simply arranging fine powder of copper formate or a method of dissolving copper formate in a solvent having a relatively low boiling point which does not substantially react with copper formate or uniformly dispersing the powder by brushing, dipping, spraying. Coat with a coat, bar coat, roll coat, or other means.
Examples of the method include heating at a temperature of 0 ° C. or lower, particularly 110 ° C. or lower, or drying under reduced pressure. Suitable solvents for preparing the solution here include water, alcohols, aliphatic hydrocarbons,
Aromatic hydrocarbons, and others preferably having a boiling point of 200 ° C. or lower are exemplified.In particular, in the case of anhydrous copper formate, water-free organic solvents such as heptane, hexane, cyclohexane, octane, propanol, and butanol It is preferable to use a dispersion solution obtained by kneading, for example, heptanol, benzene, toluene, xylene and the like and copper formate fine powder. The coating can be used in the same manner as the printing ink composition, and in this case, a method of selecting a solvent having a higher boiling point and drying it under reduced pressure can also be used.

In addition, the method of disposing a desired amount of copper formate in the container or the disposing tool simply involves placing copper formate powder on the disposing portion provided on the bottom, the inner surface of the lid, or the upper part of the container or disposing device, as described above. A solution in which copper is dissolved or a solution in which copper formate powder is dispersed is applied to the bottom of the placement tool, the inner surface of the lid, and the placement portion provided on the top,
It depends on the method of drying.

Here, the total arrangement amount of copper formate is the sum of the total surface area of the resin molded product to be plated, the inner surface of the container and the total surface area of the arrangement tool, and the surface area of equipment for plating these (such as the area of the heating equipment container). summed by is intended to be primarily determined 0.001 g / cm ² or more, preferably 0.003~0.3g / cm ^2. Also, adjust the distance between the resin molded product to be plated and copper formate.
It is preferable to set the thickness within 5 cm, particularly within 1 cm, for more uniform plating.

When copper plating is applied to part of the resin molded product,
A method is used in which a portion other than a desired portion is covered with a peelable resist or the like, plated, and then the resist is peeled.

As described above, the resin molded product is stored or arranged together with the copper formate, and these are placed in a non-oxidizing atmosphere or under reduced pressure.
The range of 5 ° C. or higher and lower than the deformation deterioration temperature of the molded product is kept at a predetermined temperature, and the temperature between 130 ° C. and the predetermined temperature is raised and maintained at a rate of 1 deg / min or more, whereby the copper-plated resin molded product is produced. obtain.

As the heating device, radiation heating such as infrared rays, electron beams, and microwaves, an electric furnace, an oven, oil heating, pressurized steam heating, and other means are appropriately selected. It may be any of a batch type or a continuous type heating machine having an introduction section, a heating section, and a cooling take-out section for articles to be heated. In addition, depending on the deformation deterioration temperature of the resin molded product, the heat treatment temperature and the deformation deterioration temperature may be close to each other.

The heating method is performed under a substantially non-oxidizing atmosphere or under reduced pressure.
There is no particular limitation, except that the temperature is raised and maintained at a predetermined temperature in the range of 165 ° C. or more and the deformation deterioration temperature of the molded article at a rate of 1 deg / min or more between 130 ° C. and the predetermined temperature. 165 ℃
As described above, the method of putting the molded product into a heating device having a hot plate as a heating unit set at a predetermined temperature in a range equal to or lower than the deformation deterioration temperature of the molded product can increase the heating rate. Heating rate 1-50 ° C /
It is preferable to heat to a predetermined temperature at a rate of 2 to 35 ° C./minute, and to keep the temperature at the same temperature. The heating time is 3 hours or less, preferably 1 to 60 minutes. If the rate of temperature rise is less than 1 ° C./min, the resulting plated film becomes non-uniform, the adhesive strength becomes poor, and the amount of generated copper powder tends to increase. Although there is no particular problem from the generation of the plating film at the highest, it is not preferable because the tendency of the plating film to become non-uniform increases.

Non-oxidizing atmosphere can be obtained by a known method such as N ₂ , Ar, CO ₂ , CO, H
Examples of the method of introducing a gas such as _2, a method of reducing the volume inside the heating device containing the molded product and substantially setting the gas atmosphere to a decomposition gas atmosphere of copper formate, particularly when using a continuous heating device By reducing the opening area of the inlet and the outlet to the heating section, it is possible to easily maintain the decomposition gas atmosphere without using an inert gas. In addition, the method of reducing the pressure is a method particularly effective for attaching a copper plating film having excellent gloss and good adhesion, a method using a heater capable of reducing the pressure, a container capable of reducing the pressure of the molded article to be plated. A method of arranging a decompression chamber only in a container or a method of decompressing only the inside of a container, or a method of arranging a decompression chamber at an introduction portion and an extraction portion of a molded article to be plated, particularly using a continuous heating device, is used. Preferably, the pressure is 200 Torr or less, particularly 30 Torr or less.

The copper-plated molded product of the present invention is manufactured by the above method. In the present invention, copper formate is interposed between the resin molded product, and a container or an arrangement tool for heat treatment in which a desired amount of copper formate is further coexisted, for plating on a heating device. It is preferable because the efficiency of loading and unloading of the resin molded product can be increased and the unevenness of the plating conditions can be reduced, and it is particularly suitable when mass production is performed commercially.

Here, as the container and the disposing tool, there are no particular limitations on the metal, resin, and other materials as long as they are made of a material that can withstand the processing temperature, but are usually made of aluminum, iron, copper, and other metals. It is. For the container or the placement tool, a plurality of molded products are arranged more densely, and an optimal shape is appropriately selected or designed according to the shape of the molded product, the heating equipment to be used, etc. so as to facilitate the loading and unloading operations. .

After the heat treatment by the above method, the resultant is cooled to room temperature to obtain a resin molded product having a desired portion plated with copper. In addition, the copper powder generated from copper formate, which did not participate in the formation of the plating film on the resin molded product, adheres to the bottom of the container or the arrangement tool, and has a form in which copper plating adheres to the container or the arrangement tool surface. The copper powder is easily removed by light wiping, air blowing, or other means. Further, the surface of the container and the arrangement tool is plated with copper, but can be reused as it is. The removed copper-plated resin molded product is subjected to a known rust preventive treatment as necessary, and is easily subjected to known electroless plating or electrolytic plating of copper, nickel, gold or other metals. These processes are appropriately performed as needed.

〔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 1 100 parts of anhydrous copper formate powder and 50 parts of butyl alcohol were kneaded to obtain a dispersion solution in which the anhydrous copper formate powder was uniformly dispersed (hereinafter referred to as treatment liquid 1).

Thickness 3mm, width 140 obtained by injection molding nylon MXD6 from carbon fiber reinforced meta-xylylenediamine and adipic acid
A slightly curved spectacle frame molded product with a height of 55 mm and a height of 55 mm was prepared.

It is made of aluminum 200 mm long, 300 mm wide and 60 mm high.A nozzle with a cock for gas injection and discharge is provided on the horizontal part, and an aluminum sheet with a width of 40 mm and a thickness of 0.3 mm is bent as an auxiliary tool for placement on this inner surface, A box having a protruding portion having a height of 10 mm and having a cross section viewed from a direction perpendicular to the bending surface at intervals of 13 mm and having a height of 10 mm was fixed, and a box having a wire mesh-covered lid was prepared.

Apply treatment liquid 1 to the entire inner surface including the lid of this box,
And dried with anhydrous copper formate. The disposition amount of anhydrous copper formate on the inner surface of the container including the disposing tool surface and the inner surface of the container lid was 140 g and 60 g, respectively.

Place and store 30 glasses frames in the above box, N ₂
After closing the lid while blowing the gas into the box from the nozzle and removing the N ₂ blowing pipe, put it between the heating plates of a heater preheated to 230 ° C with upper and lower heating plates that can be decompressed. The pressure was reduced to several Torr, and the pressure was maintained for 30 minutes. The rate of temperature rise in the box was 7 ° C./min, and the amount of anhydrous copper formate per total surface area in the box was 0.06 g / cm ² .

The decompression was stopped, the box was taken out, and allowed to cool to room temperature to obtain a copper-plated eyeglass frame.

The resulting spectacle frame has a glossy copper film evenly in close contact with the placement tool and the contact area with the container inner wall.There is no adhesion due to the continuation of the copper plating layer at the contact section, Also, no excessive copper film was formed.

The thickness of this copper film is 0.2 to 0.5 μm, and the surface resistance is 0.05
0.50.5Ω / □, the result of a cross cut test using cellophane tape was 100/100.

As a result of performing electrolytic copper plating using this frame, a uniform glossy copper-plated eyeglass frame was obtained.

Example 2 In Example 1, a box with the same lid as in Example 1 was placed in the heater, and the lid was closed while blowing N ₂ from the nozzle into the box. Example 1
An eyeglass frame uniformly plated with copper was obtained.

Example 3 An eyeglass frame plated with copper was obtained in the same manner as in Example 1, except that an aqueous solution saturated with copper formate was used instead of the treatment liquid 1. The copper plating thickness was 0.2 to 0.7 μm, and the appearance was slightly uneven.

Example 4 In Example 1, instead of the glasses frame, the diameter was about
Using a gear of 35mm and height of about 10mm, about 40mm as a placement tool
The procedure was performed in accordance with Example 1 except that a corner wire mesh was fixed to the bottom of the box.

The copper plating thickness of the obtained copper plating gear is 0.2-0.5μm
Met.

Example 5 As a model molded product, a square groove having a width of 2 mm and 1 mm on one side, V
A grooved part and drill holes having diameters of 3 mm, 1 mm, and 0.6 mm were formed, and the other surface was smooth, and a molded article made of the resin described below having a thickness of 3 mm, a width of 40 mm, and a length of 145 mm was prepared.

. Molded article 1: Nylon MXD6 from carbon fiber reinforced meta-xylylenediamine and adipic acid (trade name: Reny 1022, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded article 2: Nylon MXD6 from glass fiber reinforced meta-xylylenediamine and adipic acid (trade name: Reny E-40, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded article 3: Carbon fiber reinforced nylon 6/66 copolymer. Molded article 4: polyarylate. (Product name: U-Polymer, manufactured by Unitika Ltd.) Molded article 5: polysulfone. (Product name: Udel Polysulfone, manufactured by Amoco Chemicals Co., Ltd.). Molded product 6: 20% by weight glass fiber reinforced polyether sulfone (Mitsui Toatsu Co., Ltd.). Molded product 7: polyetherimide (trade name; Ultem, manufactured by GE) Molded product 8: Polyetheretherketone (trade name: Victrex, manufactured by ICI, UK). Molded product 9: Glass fiber reinforced polyethylene terephthalate resin. Molded product 10: Glass fiber reinforced polycarbonate resin. (Product name: Iupilon, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Molded article 11: glass fiber reinforced polyphenylene sulfide resin. An aluminum sheet having a width of 40 mm and a thickness of 0.3 mm was bent as a placement tool to prepare a comb having a height of 20 mm at intervals of 13 mm as viewed in a direction perpendicular to the bent surface, and this was used in Example 1. It was fixed in the box instead of the placement tool.

Using this container, copper anhydrous formate was placed in the same manner as in Example 1. The arrangement amounts of anhydrous copper formate on the inner surface of the container including the arrangement tool surface and the inner surface of the container lid were 165 g and 60 g, respectively.

The above molded product was placed and stored in a box, and plated under the processing conditions shown in Table 1. The results are shown in Table 1.

The appearance of the copper film was determined by visual observation. ○ indicates the formation of a glossy uniform adhesion copper film, and △ indicates the deformation of the molded product.

Example 6 A copper-plated thermosetting resin molded product was produced in the same manner as in Example 5 except that the following thermosetting resin molded product was used instead of molded products 1 to 10. The results are shown in Table 2.

. Molded product 12: Glass fiber reinforced epoxy resin (Mitsubishi Gas Chemical Co., Ltd.). Molded article 13: Glass fiber reinforced product using tetrafunctional epoxy resin (trade name: Tetrad X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) synthesized from xylylenediamine and epichlorohydrin. Molded article 14: Carbon fiber reinforced cyanate-maleimide-epoxy resin (Mitsubishi Gas Chemical Co., Ltd.) [Functions and Effects of the Invention] According to the manufacturing method of the present invention as described above, a copper film with excellent adhesion is formed by electroless plating or the like unless conventionally subjected to a special pretreatment. A molded article having a glossy vapor-deposited copper film having excellent adhesion can be easily produced on a resin molded article which has been difficult to perform by extremely simple means.

In addition, since a large amount can be batch-processed and copper plating can be performed on the entire surface, mass production is easy.

The copper plating layer of this copper plating resin molded product is electroplated,
It can be easily and uniformly plated with copper, nickel, chromium, silver, gold, and other materials by electroless plating or other means. Therefore, it is suitably used as it is or as an inexpensive undercoating for these plated products. Things.

Claims (3)

(57) [Claims] 1. A method for producing a copper-plated resin molded product by heating a resin molded product having a deformation deterioration temperature higher than 165 ° C. and copper formate in a non-oxidizing atmosphere, wherein the molded product is disposed. When preparing a container or an arrangement tool to be plated, and also plating copper on a contact portion of the container or the arrangement tool that comes into contact with the molded product generated when the container or the arrangement tool is arranged, copper formate is interposed in the contact portion. Then, a desired amount of copper formate is further placed in the container or in the placement tool, and in a non-oxidizing atmosphere or under reduced pressure,
Copper, characterized in that the molded article is heated to a predetermined temperature in a range of not more than 165 ° C. and not more than the deformation deterioration temperature of the molded article, from 130 ° C. to the predetermined temperature at a rate of 1 deg / min or more, and maintained. Manufacturing method of plated resin molded products. 2. A method for producing a copper-plated resin molded product according to claim 1, wherein said desired amount of copper formate is disposed on an inner surface of a lid of said container or on an upper portion of a disposition tool. 3. The amount of copper formate per total surface area of a plating space in which said resin molded product and copper formate are stored or arranged is 0.000.
2. The method for producing a copper-plated resin molded product according to claim 1, wherein the resin molded product is at least 1 g / cm ³ and the distance from the plated portion of the resin molded product is within 5 cm.