JP2004216609A - Composite comprising metal and thermoplastic resin composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite comprising a metal-shaped article and a thermoplastic resin composition having both of the advantage of a metallic housing and the advantage of a synthetic resin structure in the housing of an electronic device, an on-vehicle structural component or the like, and also to provide its manufacturing method. <P>SOLUTION: The composite comprising the metal and the thermoplastic resin composition is manufactured by forming fine unevenness to the surface of the processed metal shaped article by a chemical etching method or the like, coating the treated metal shaped article with a urethane curable two-pack type ink/coating material, inserting the coated metal shaped article in an injection mold, and injecting a thermoplastic resin composition mainly comprising PBT in the mold. A filler for lowering the coefficient of linear expansion is added to the thermoplastic resin composition. The composite comprising the metal and the thermoplastic resin composition thus injection molded is extremely excellent in tensile shear breaking strength. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a composite of metal and resin used for a housing or a structural member of an electronic device, and a method for manufacturing the same. More specifically, the present invention relates to a composite in which a metal alloy shaped article made by various types of machining and a thermoplastic resin are integrated, and a method for producing the same.
[0002]
The present invention is capable of producing, with high dimensional accuracy, an integrated member in which a thermoplastic resin composition containing polybutylene terephthalate (hereinafter, referred to as “PBT”) as a component is adhered to a metal shape. It is a technology that can be done. It can be used not only in the electronic equipment industry but also in the manufacture of housings and parts for many machines and electric equipment such as structural parts for vehicles and building materials.
[0003]
[Prior art]
Techniques for integrating metal and resin are required from a wide range of fields such as manufacturing parts for automobiles, household appliances, industrial equipment, and the like, and many adhesives have been developed for this purpose. Adhesives that function at room temperature or by heating are used for joining metals and synthetic resins together, and this method is currently a common technique.
[0004]
However, when an adhesive is used in actual production, a great deal of labor is required for adjusting and managing the use conditions of the adhesive due to poor positional displacement of the adhesive and changes in the four seasons. For this reason, research has been conventionally conducted on a more rational joining method that does not use an adhesive.
[0005]
Magnesium, aluminum and its alloys such as light metals and iron alloys such as stainless steel, a method of integrating high-strength engineering resin without the intervention of adhesives, for example, injection molding a resin component on the metal side If a molding method for bonding (hereinafter referred to as "injection bonding") can be used, there is no need to worry about errors such as misalignment of bonding positions, changes in the four seasons, shape errors due to temperature and humidity, and processing errors. Method.
[0006]
Among engineering resins, PBT has high mechanical strength, and is excellent in heat resistance, electric properties, and chemical resistance. In addition, it has a good fluidity and a high crystallization rate, so it is suitable for molding, and is widely used mainly in the fields of automobiles and electric / electronic devices. Therefore, if the PBT can be injection-bonded to the light metals and iron alloys, it can be expected to be used in a wide range of industrial fields and various applications.
[0007]
However, if the thermoplastic resin composition containing PBT is injected by inserting the metal into a mold without any surface treatment, no adhesion occurs. Therefore, the present inventors have proposed a method for treating the surface of a metal-shaped object, a method for curing an ink or paint applied to the surface of the metal-shaped object subjected to the treatment, and a method for injection-molding the thermoplastic resin composition. We thought that the development would enable PBT injection bonding, and made intensive research and development.
[0008]
In addition, as a prior art, it is made of hard thermoplastic resin such as polycarbonate (Poly-Carbonate: hereinafter, referred to as "PC") and acrylonitrile-butadiene-styrene (hereinafter, referred to as "ABS"). After printing and curing a special ink on a molded product and inserting the special ink into a mold, the thermoplastic elastomer (Thermo Plastic Poly-Ester Elastomer: hereinafter, referred to as “TPEE”) as a main component is a thermoplastic elastomer (Thermo Plastic). Elastomer: hereinafter, referred to as “TPE”.) By injecting the composition, the printing layer and the TPE composition portion are bonded to each other, and as a result, the hard thermoplastic resin molded article and the TPE composition portion are bonded. There are things that the body of. This technology is open to the public and commercialized. That is, injection bonding of a TPE composition containing TPEE as a main component by an insert molding method to a hard thermoplastic resin has already been put to practical use.
[0009]
[Problems to be solved by the invention]
The present invention has been made under the above-mentioned technical background, and achieves the following objects.
It is an object of the present invention to provide a method for forming a metal mold and closing a mold and injecting a thermoplastic resin composition containing PBT as a component. It is an object of the present invention to provide a composite of a metal and a thermoplastic resin composition stably fixed thereby and a method for producing the same.
[0010]
Another object of the present invention is to provide a composite of a metal and a thermoplastic resin composition, including a treatment method applied to the surface of the metal shape, in order to enhance the adhesive strength between the metal shape and the thermoplastic resin composition, and its production. It is to provide a method.
Still another object of the present invention is to provide a method for curing an ink or paint applied to a metal shape, and an injection bonding method for the thermoplastic resin composition, in order to increase the adhesive strength between the metal shape and the thermoplastic resin composition. An object of the present invention is to provide a composite of a thermoplastic resin composition including a method and a method for producing the same.
[0011]
[Means for Solving the Problems]
The present invention employs the following means to achieve the above object.
The composite of the metal and the thermoplastic composition containing PBT as main components of the present invention is a processed metal shape, and a coating material containing a thermosetting resin composition coated on the surface of the metal shape. And a shape of a thermoplastic resin composition containing PBT as a component integrally fixed to the upper surface of the coating material by heat and pressure.
[0012]
The metal shaped object may be subjected to chemical etching on its surface. The coating material is preferably thermosetting. The resin composition of the coating material is preferably a paint or an ink containing a hydroxyl group or a carboxylic acid group. It is preferable that the thermoplastic composition contains a filler.
[0013]
Further, the present invention provides a process of processing a metal alloy material into a metal shape, or a process of processing a metal alloy material into a metal shape and chemically etching, and applying a urethane-curable two-part ink or paint to the metal shape. Curing, inserting the coated and cured metal shape into a mold or the like, and injecting, pressing or co-extruding the thermoplastic resin composition containing the PBT, comprising: A method for producing a composite is provided.
[0014]
Hereinafter, each technical means of the present invention will be described in detail.
(Metal shaped object)
The metal constituting the metal shape used in the present invention is preferably aluminum, magnesium, iron, or a metal alloy containing copper as a main component. The metal is processed into a desired shape by machining such as casting, forging, pressing, cutting, and cutting to produce a metal alloy shape. Since these machining methods are not the gist of the present invention, the details will not be described.
[0015]
These metal alloy shapes often have oil attached to them in the process of processing the shape. In addition, there may be rust. It is desirable to remove rust by polishing. Oil adhering to the surface of the metal shaped object can be removed by degrease the surface with an organic solvent or the like. Thereafter, it may be possible to proceed to the application step as it is, but it is desirable to add the chemical etching step described in the following section in order to ensure adhesion between the application layer and the metal.
[0016]
[Chemical etching process]
The chemical etching step of the present invention is a step in which a surface of a metal-shaped object is subjected to a chemical corrosion treatment so as to roughen the surface and form an uneven shape. That is, this is a process for increasing the adhesion to the ink / paint layer described later in detail by forming the irregularities. Therefore, the chemical etching step may be performed before the printing / painting step described in detail later.
[0017]
In some cases, chemical etching is performed on a metal alloy material as a raw material, but it is preferably performed on a processed metal shape. Further, as a result, fine irregularities only need to be formed on the surface of the metal-shaped object. Therefore, not only chemical etching but also polishing by air blasting may be used.
[0018]
A corrosive aqueous solution is prepared for the type of metal alloy used.
For example, in the case of an aluminum alloy, a 0.1 to 1.0% aqueous solution of sodium hydroxide is prepared. A1100 alloy, A5052 alloy, A6063 alloy, etc. of Japanese Industrial Standards (JIS) are immersed at room temperature for 0.5 to 3.0 minutes, washed with water and dried, or immersed for 0.5 to 3.0 minutes, It may be washed with water, immersed in 0.01 to 1.00% dilute nitric acid for about 1 minute, washed with water and dried. When these are observed on the surface with an electron microscope, it can be seen that irregularities of 0.2 to 1.0 μ are observed and that they are finely etched.
[0019]
Hydrochloric acid is suitable as an etching agent for stainless steel and high silicon iron which are iron alloys, and dilute nitric acid is suitable for carbon steels. Dilute nitric acid is suitable for all copper alloys, pure copper, brass and white copper alloys. However, the copper alloy can also be etched with concentrated aqueous ammonia. Dilute hydrochloric acid is suitable for magnesium alloys.
There are aqueous solutions that can be etched for other metal species as well. There are many types of metal alloys used for electronic equipment housings, parts used in automobiles and the like, and it is difficult to verify all of them. It is important, however, that the purpose of the chemical etching process of the present invention is to cause fine irregularities and pores to form on the metal surface by etching. Here, what needs attention is the reagent concentration, the liquid temperature and the immersion time.
[0020]
It is also necessary to adjust the etching time by using an aqueous solution having a relatively low concentration. When immersed in a high-concentration corrosive solution for a long time, fine irregularities disappear and large irregularities may appear as if the butter is melted, which in turn lowers the adhesive strength of the coating film. That is, the effect of forming the fine uneven surface and expecting the anchor effect may be reversed.
In order to find the optimum etching conditions, it is necessary to check the unevenness with an electron microscope. As a result of the confirmation, if fine irregularities can be formed on the metal surface, the adhesiveness of inks and paints described in detail below will be significantly improved.
[0021]
As described above, after immersion in a corrosive aqueous solution and chemical etching, the substrate is washed with water and dried. In addition, when there is a possibility that even a slight amount of corrosion will occur over time, it is preferable to carry out a neutralization treatment after washing with water, further washing with water, and drying. That is, when hydrochloric acid or the like is used for etching a metal, the metal is then immersed in aqueous ammonia to neutralize it for neutralization. Further, it is preferable that the metal is thereafter washed with water and dried. When sodium hydroxide or the like is used for etching a metal, it is preferable that after etching, immersion in dilute nitric acid, washing with water, and drying.
[0022]
[Printing and painting]
The printing / coating in the present invention involves interposition of fixation of the thermoplastic resin composition to the metal shape, and maintains fixation to both. This printing / painting is performed by applying a coating material containing a thermosetting resin composition to the surface of the metal shape. As the coating material, many paints and inks that can correspond to each metal material and each metal alloy material have been proposed and known. A coating layer can be formed by applying a paint or ink suitable for each metal material on the surface of the metal shape. The thermoplastic resin composition and the coating layer are bonded and fixed by injection molding or the like.
[0023]
Here, the ink and paint used as the coating material only need to be excellent in adhesion to both the metal shaped article and the thermoplastic resin composition, and are preferably urethane-curable two-pack type. Of these, many systems are composed of a main liquid of an ink or paint having a hydroxyl group or a carboxylic acid group and a secondary liquid (curing agent liquid) composed of an isocyanate compound, and these are preferable. In addition, there is a one-component urethane curable paint in which a curing agent is already mixed in the main liquid, but in practice, a curing accelerator which promotes curing is often used by mixing it. These are also included.
[0024]
These inks and paints are printed or painted on the surface of the metal object to be applied. The curing after printing and coating is preferably performed under the curing conditions instructed by the ink / paint manufacturer or slightly relaxed. For example, if the curing condition is 80 ° C. for 1 hour, it is preferable to set the temperature at 70 to 80 ° C. for 40 to 60 minutes. However, there is no particular limitation on the delay time from the application curing to the next step, ie, the bonding step such as injection molding, and the result is the same even after several days or months.
[0025]
(Thermoplastic resin composition)
In the present invention, the thermoplastic resin composition to be fixed to the metal contains PBT. PBT is tough and flexible, and has the highest electrical properties among thermoplastics, so it is widely used for electrical equipment housings and structural parts for vehicles, and can be integrated with metal objects. Various uses are born by becoming.
[0026]
As the thermoplastic resin composition used in the present invention, a polymer of PBT alone, a polymer compound of PBT and PC, a polymer compound of PBT and ABS, a polymer compound of PBT and polyethylene terephthalate (Poly-ethylene Terephthalate: hereinafter, referred to as “PET”) ), And a polymer compound of PBT and poly-styrene (hereinafter, referred to as “PS”) are preferred.
[0027]
TPEE is an example of a copolymer containing PBT. TPEE is usually an alternating block having a shape in which a number of hard segments composed of PBT and soft elements composed of terephthalic acid ester of poly-tetramethylene ether glycol (hereinafter referred to as “PTMEG”) are alternately connected. It is a copolymer. Although it is an elastomer, it is included in the subject because it can be injection-bonded to metal.
[0028]
Further, the content of the filler is very important from the viewpoint of making the linear expansion coefficients of the metal alloy shaped article and the thermoplastic resin composition equal. As the filler, glass fiber, carbon fiber, aramid fiber, and other high-strength fibers similar thereto are preferable. It is very preferable that the thermoplastic resin composition contains calcium carbonate, magnesium carbonate, silica, talc, clay, pulverized carbon fiber and aramid fiber, and other kinds of inorganic fillers for resin filling.
[0029]
In addition, even if it is a thermoplastic resin composition containing PBT, if it is the above-mentioned elastomer, there is no necessity of the filler at all. The reason is that the distortion caused by the difference between the linear expansion coefficients of the metal and the resin is eliminated by the elasticity of the elastomer.
Even when no filler is contained, a very strong force is required to remove the thermoplastic resin composition adhered firmly to the metal. However, when a composite molded with a thermoplastic resin composition that is not an elastomer is subjected to a temperature cycle test, in a resin system containing no filler, the adhesive strength is rapidly reduced by repeating the cycle.
This has two causes.
[0030]
One is that there is a large difference in the coefficient of linear expansion between the metal shape and the thermoplastic resin composition. For example, aluminum or magnesium has a larger coefficient of linear expansion among metals, but is still much smaller than PBT. The presence of the filler lowers the linear expansion coefficient of the PBT-containing resin composition, and decreases the linear expansion coefficient of the metal alloy (2.31 × 10 3 in pure aluminum). ^-5 2.48 × 10 in pure magnesium ^-5 1 with brass. 75 × 10 ^-5 1.07 × 10 in carbon steel ^-5 , 25 ° C). If the type and content of the filler are selected, the coefficient of linear expansion can be set to a value very close to that of the metal alloy.
[0031]
The other is the relationship between the cooling shrinkage of the metal shaped article after insert molding and the molding shrinkage of the thermoplastic resin composition. The molding shrinkage of the PBT-containing resin composition containing no filler is 0.6 to 1.4%. On the other hand, the cooling shrinkage of the metal alloy is 0.2 to 0.3% for the aluminum alloy, for example, assuming that the metal alloy is cooled by 100 to 150 ° C. from the time of injection to room temperature. This is smaller than the molding shrinkage of the resin, and varies considerably. If the resin shrinks after a certain period of time from the release of the mold, distortion occurs near the interface, and the interface is destroyed by a slight impact and peeled off.
[0032]
As a specific example, in the case of an aluminum alloy, the linear expansion coefficient (specifically, the linear expansion coefficient with respect to a temperature change) is 2.0 to 2.5 × 10 ^-5 ° C ^-1 It is. On the other hand, the linear expansion coefficient of the PBT-containing resin is 7 to 8 × 10 ^-5 ° C ^-1 It is. In order to reduce the coefficient of linear expansion of the resin, the content of the filler is preferably large, and the content is more preferably 20% or more and 30% or more. In fact, when PBT or a polymer compound containing PBT contains a high-strength fiber or an inorganic filler at a content of 30 to 50%, the linear expansion coefficient becomes 2 to 3 × 10 ^-5 ° C ^-1 It approaches the metal alloy considerably.
[0033]
At this time, the molding shrinkage also decreases. Regarding the molding shrinkage, since the high crystallinity of PBT increases the shrinkage, a compound obtained by mixing a resin with low crystallinity, PET, PC, ABS, PS, and the like can be expected. However, since the PBT concentration also decreases, the optimum content can only be determined by trial and error.
[0034]
〔injection molding〕
The injection molding of the present invention is a molding method for forming a desired structure by attaching a thermoplastic resin composition to a surface of a coating material printed and painted on a metal shape.
[0035]
The bonding (fixing) between the metal shape and the thermoplastic resin composition is performed by the injection molding method described below.
[0036]
Injection molding method is to prepare a mold for injection molding, open the mold, insert a metal alloy shape into one of them, close the mold, inject the thermoplastic resin composition, and mold Is a method of releasing the mold. Injection molding is the most excellent molding method in terms of shape flexibility and productivity. Although it cannot be said unconditionally because it differs depending on the metal shape and size, it is possible to use a man-made vertical molding machine or a horizontal molding machine for a small amount of molding. In the case of a horizontal molding machine, a depressurizing hole is formed at an insert portion of a mold, and the pressure is reduced at the time of insertion. In order to efficiently perform a large number of moldings, it is preferable to insert a metal object using a robot using a horizontal molding machine.
[0037]
The injection conditions will be described in detail. The mold effect and the injection temperature are almost the same as those in the usual injection molding, or the bonding effect can be obtained under slightly higher conditions. The gate structure of the mold preferably uses a pin gate if possible. This is because, in a pin gate, the resin temperature instantaneously rises due to shear friction generated when the resin passes, and this often produces a good effect on the adhesive strength. In short, it is better to devise so that the high-temperature resin melt contacts the bonding surface as far as possible without hindering smooth molding.
[0038]
[Methods other than injection molding]
The bonding (fixing) between the metal shape and the thermoplastic resin composition containing PBT described above may be a method other than the injection molding method.
A molding method in which both a metal alloy shape and a shape made of a thermoplastic resin composition are inserted into a mold, closed with the other mold and pressed while heating, that is, an integrated product can be obtained by hot press molding. . Although not a method suitable for mass production, it can be used depending on the shape. The principle of bonding is the same as the injection bonding described above.
In addition, when an integrated product such as a pipe-like material or a plate-like material is required, a method called extrusion molding is used. This extrusion molding can also be used. It is only important that the above-mentioned thermoplastic resin composition comes into contact with the surface of the treated metal alloy when it is in a heated and molten state, and a molding method is not theoretically selected. However, the pressure applied between the molten resin and the metal surface in the extrusion molding is significantly lower than that in the injection molding or the like. In this respect, it is not expected to exhibit the strongest adhesive strength, but the design may be sufficiently usable for practical use.
[0039]
[Action]
According to the present invention, for example, a two-component urethane-curable ink is applied and cured on the surface of a metal-shaped object, and a thermoplastic resin composition containing PBT is injection-molded on the applied surface, thereby forming a metal-shaped object. A thermoplastic resin composition containing PBT as a component can be firmly adhered and fixed.
[0040]
It is preferable that the surface of the metal-shaped object is subjected to chemical etching. Fine irregularities are formed by the chemical etching, and the adhesion to the ink coating layer is enhanced.
In addition, by adding a high concentration of filler to the thermoplastic resin composition, the coefficient of linear expansion is reduced. By reducing the difference from the linear expansion coefficient of the metal-shaped object, it is possible to prevent interfacial destruction due to strain.
[0041]
By using the present invention, it is possible to reduce the weight of mobile electronic devices and home appliances, reduce the weight of in-vehicle devices and components, reduce the weight of arms and legs of robots, and supply components and housings in many other fields. Become.
[0042]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, examples of the present invention will be described in detail.
[Example 1]
A commercially available A5052 aluminum alloy plate having a thickness of 1 mm was purchased. From this, 20 rectangular pieces of 100 mm × 25 mm were obtained. This aluminum piece was attached to a rubber sheet with a double-sided tape and put into a blast device.
[0043]
The air pulse time was set so that the polishing was at a level of about 5 μm, and air blasting was performed. It was taken out of the apparatus, immersed in 4.0 liters of tap water and stirred, opened in a plastic colander, and washed with running tap water. Next, a plastic container containing 3.0 liters of a 0.2% aqueous sodium hydroxide solution was prepared, and the aluminum piece was immersed for 2.0 minutes while maintaining the liquid temperature at 50 ° C. Next, the plate was washed with running tap water, immersed in 1.0 liter of dilute nitric acid having a concentration of 0.01% for 1.0 minute, washed again with running water, placed in a blast dryer at 70 ° C. for 20 minutes, and dried.
[0044]
The next day, the aluminum piece was transferred to a jig and solid-printed with a screen printer. The ink used was a urethane-curable two-pack ink "VIC White (manufactured by Seiko Advance)". The mixing ratio of the main liquid, the designated curing agent, and the solvent was 100: 10: 30 by weight, and the solvent used was 1% hydrocyclohexanone. After printing, it was placed in a warm air dryer and cured at 100 ° C. for 1 hour.
[0045]
The printed aluminum piece was inserted into an injection mold. Close the mold and inject with PBT / PC resin (PBT about 70% and PC about 30%, original resin is Mitsubishi Rayon Co.) compound pellet containing 15% carbon fiber, 10% glass fiber and 15% fine powder talc. As shown in No. 1, an integrated composite was obtained.
[0046]
FIG. 1 shows the aluminum metal piece 1 described above. Usually, it is a metal piece having a size of 25 mm in width, 100 mm in length and 1 mm in thickness. The thermoplastic resin composition is injected from the pin gate 3 to form a plate 2 having a width of 23 mm, a length of 100 mm, and a thickness of 2 mm. The plate-shaped object 2 is bonded to the metal piece 1 on an adhesive surface having a width of 23 mm and a length of 12.5 mm.
[0047]
The mold temperature during molding was 100 ° C., and the final temperature of the heating tube and the nozzle temperature of the injection molding machine were 260 ° C. After the molded article was molded and left in a room for 3 days, both ends of the composite were pulled to examine the shear breaking force. When the test was performed on ten molded products using a tensile tester, the average tensile shear fracture strength was 3.4 MPa (35 kg / cm). ² )Met. That is, a strong adhesive force was exhibited.
[0048]
[Example 2]
A commercially available A1100 aluminum alloy plate having a thickness of 1 mm was purchased. From this, 10 rectangular pieces of 100 mm × 25 mm were obtained. This aluminum piece was attached to a rubber sheet with a double-sided tape and put into a blast device. The air pulse time was set so that the polishing was at a level of about 5 μm, and air blasting was performed. It was taken out of the apparatus, immersed in 4 liters of tap water, stirred, opened in a plastic colander, and washed with running tap water.
[0049]
Next, a plastic container containing 1 liter of a 3% aqueous solution of hydrazine monohydrate was prepared, and the aluminum piece was immersed for 2 minutes while maintaining the liquid temperature at 50 ° C. Then, the plate was washed with running tap water and dried in a blast dryer at 70 ° C. for 20 minutes.
Thereafter, printing and injection molding were performed in exactly the same manner as in Example 1. After the molded article was left in the room for 3 days, both ends of the composite were pulled to examine the shear breaking force. When the test was carried out on ten molded products using a tensile tester, the average tensile shear fracture strength was 3.7 MPa (38 kg / cm). ² )Met. That is, a strong adhesive force was exhibited.
[0050]
[Example 3]
A commercially available pure copper plate having a thickness of 1 mm was purchased. From this, 10 rectangular pieces of 100 mm × 25 mm were obtained. This copper piece was stuck on a rubber sheet with a double-sided tape and placed in a blasting device. The air pulse time was set so that the polishing was at a level of about 5 μm, and air blasting was performed. It was taken out of the blasting device, immersed in 4 liters of tap water and stirred, then poured into a plastic colander and washed with running tap water.
[0051]
Next, a plastic container containing 1 liter of 10% ammonia water was prepared, and the copper piece was immersed for 10 minutes while maintaining the liquid temperature at 10 ° C. Next, the plate was washed with running tap water and placed in a blow dryer at 70 ° C. for 20 minutes to dry.
[0052]
The next day, the copper pieces were transferred to a jig and solid-printed with a screen printer. The ink used was exactly the same as in Example 1, and the curing conditions were also the same. The printed copper piece was inserted into an injection mold and injection-molded in exactly the same manner as in Example 1 to obtain the shape shown in FIG.
[0053]
After being left in the room for 3 days, the composite material was pulled at both ends to check the shear breaking strength. The tensile shear breaking strength was 2.9 MPa on average (30 kg / cm). ² )Met. That is, a strong adhesive force was exhibited.
[0054]
[Example 4]
A commercially available 1 mm thick SUS304 plate of Japanese Industrial Standard (JIS) was purchased. From this, 10 rectangular pieces of 100 mm × 25 mm were obtained. This stainless steel piece was stuck on a rubber sheet with a double-sided tape and placed in a blasting device. The air pulse time was set so that the polishing was at a level of about 5 μm, and air blasting was performed. It was taken out of the blasting device, immersed in 4 liters of tap water and stirred, then poured into a plastic colander and washed with running tap water.
[0055]
Next, a plastic container containing 1 liter of hydrochloric acid having a concentration of 10% was prepared, and the stainless steel piece was immersed for 30 minutes while maintaining the liquid temperature at 40 ° C. Next, the plate was washed with running tap water and placed in a blow dryer at 70 ° C. for 20 minutes to dry.
[0056]
The next day, the stainless steel pieces were transferred to a jig and solid-printed with a screen printer. The ink used was exactly the same as in Example 1, and the curing conditions were also the same. The printed stainless steel piece was inserted into an injection molding die, and injection molded in exactly the same manner as in Example 1 to obtain the shape shown in FIG.
[0057]
After being left in the room for 3 days, the composite material was pulled at both ends to examine the shear fracture strength. Ten tensile shear fracture strength averaged 3.1 MPa (32 kg / cm) on average. ² )Met. That is, a strong adhesive force was exhibited.
[0058]
[Example 5]
A commercially available 1 mm thick brass plate was purchased. From this, 10 rectangular pieces of 100 mm × 25 mm were obtained. This brass piece was stuck on a rubber sheet with double-sided tape and put into a blasting device. The air pulse time was set so that the polishing was at a level of about 5 μm, and air blasting was performed. It was taken out of the blasting device, immersed in 4 liters of tap water and stirred, then poured into a plastic colander and washed with running tap water.
[0059]
Next, a plastic container containing 1 liter of 10% ammonia water was prepared, and the brass piece was immersed for 30 minutes while maintaining the liquid temperature at 10 ° C. Next, the plate was washed with running tap water and placed in a blow dryer at 70 ° C. for 20 minutes to dry.
[0060]
The next day, the brass pieces were transferred to a jig and solid-printed with a screen printer. The ink used was exactly the same as in Example 1, and the curing conditions were also the same. The printed brass piece was inserted into an injection mold and injection-molded in exactly the same manner as in Example 1 to obtain the shape shown in FIG.
[0061]
After being left in a room for 3 days, the composite material was pulled at both ends to examine the shear breaking strength. Ten tensile shear strengths were 2.7 MPa (28 Kg / cm) on average. ² )Met. That is, a strong adhesive force was exhibited.
[0062]
[Example 6]
A high-temperature and high-humidity test was performed on five of the ten composite articles obtained in Example 1.
Specifically, it was left for 24 hours under the conditions of 90 ° C. and 60% humidity, returned to room temperature over 1 hour, and then subjected to a destructive test using the above tensile tester. The results were the same as the above test results without the high temperature and high humidity test.
[0063]
Next, a temperature shock test was performed on five of the ten samples obtained in Example 1. Specifically, it is a test that puts the sample in the hot air dryer at 85 ° C for 2 hours and in the freezer at −40 ° C for 2 hours. After 5 cycles, the temperature was returned to room temperature over 1 hour. This was subjected to the tensile tester described above to measure the shear fracture strength. The average of the five pieces was 3.0 MPa (31 kg / cm ² ), Which was not much different from those not subjected to the thermal shock cycle test.
[0064]
【The invention's effect】
As described in detail above, according to the present invention, the thermoplastic resin composition containing PBT as a component and the metal alloy shaped article are fixed and integrated without being easily peeled off. Therefore, it is possible to provide a composite of a resin composition and a metal-shaped object utilizing the heat resistance, electrical characteristics, and chemical resistance of PBT. Further, by providing the composite, it is possible to reduce the weight of various housings, components, and structures, including housings for electronic devices and structural components for vehicles.
Further, by using an injection molding method suitable for production, it is useful for simplifying the equipment manufacturing process.
[Brief description of the drawings]
FIG. 1 shows a composite of a metal shaped article and a thermoplastic resin composition containing PBT in an example of the present invention.
FIG. 2 is a side view of FIG. 1;
[Explanation of symbols]
1. Metal pieces
2. Resin part
3 ... Pin gate
4 ... Printing ink layer

Claims (9)

Processed metal shapes,
A coating material containing a thermosetting resin composition coated on the surface of the metal shape,
A composite of a metal and a thermoplastic resin composition comprising a thermoplastic resin composition containing polybutylene terephthalate as a component, which is integrally fixed to the upper surface of the coating material by heat and pressure. In the composite of the metal and the thermoplastic resin composition according to claim 1,
The composite of a metal and a thermoplastic resin composition, wherein the coating material is a two-component urethane-curable material. A composite of the metal and the thermoplastic resin composition according to claim 1 or 2,
A composite of a metal and a thermoplastic resin composition, wherein a surface of the metal shape is chemically etched with an aqueous solution having a corrosive property to a metal species which is a main component of the metal shape. A composite of the metal and the thermoplastic resin composition according to claim 1 selected from claims 1 to 3,
The composite of a metal and a thermoplastic resin composition, wherein a surface of the metal-shaped object is polished by air blasting. A composite of the metal and the thermoplastic resin composition according to claim 1 selected from claims 1 to 4,
A composite of a metal and a thermoplastic resin composition, wherein a filler for resin filling is added to the thermoplastic resin composition. A method for producing a composite of the metal and the thermoplastic resin composition according to claim 1 selected from claim 1, wherein
A step of processing a metal alloy material, which is a raw material of the metal shape, into a metal shape,
A step of applying and curing a urethane-curable two-component coating material on the metal shape,
Inserting the metal-shaped object on which the coating material has been applied and cured into a mold, and injection-molding the thermoplastic resin composition into the mold. How to make the body. A method for producing a composite of the metal and the thermoplastic resin composition according to claim 1 selected from claim 1, wherein
A step of processing a metal alloy material, which is a raw material of the metal shape, into a metal shape,
A step of applying and curing a urethane-curable two-component coating material on the metal shape,
Inserting the metal shape object where the coating material is applied and cured into a mold,
A method of producing a composite of a metal and a thermoplastic resin composition, comprising a step of bringing the thermoplastic resin composition into contact with the surface of the metal-shaped object when the thermoplastic resin composition is in a heat-melted state and bonding. A method for producing a composite of the metal and the thermoplastic resin composition according to claim 6 or 7,
A step of forming fine irregularities on the surface of the metal shape or the metal alloy material. A method for producing a composite of a metal and a thermoplastic resin composition according to claim 1 selected from claims 6 to 8,
A step of including a filler in the thermoplastic resin composition. A method for producing a composite of a metal and a thermoplastic resin composition.

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