JP4188071B2 - Composite of metal and thermoplastic composition and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite of a metal and a thermoplastic composition used for a housing or a structural member of an electronic device and a method for producing the same. More specifically, the present invention relates to a technique in which a plurality of members, which have conventionally been formed of a metal member and a rubber O-ring or a rubber filler, are integrated and replaced with a single or a small number of members.
[0002]
The present invention relates to a thermoplastic resin composition mainly composed of a thermoplastic polyester elastomer (Thermo Plastic Polylastomer: hereinafter referred to as TPEE), which is a kind of a thermoplastic elastomer (hereinafter referred to as TPE). This is a technique capable of giving the attached integrated member with high dimensional accuracy. The present invention relates not only to the electronic equipment industry described above but also to the manufacture of housings and parts for many machines and electrical equipment.
[0003]
[Prior art]
  Integrating metal and rubberTrickThe technique has been developed for a long time and is now used in many fields, as seen in the production examples of tires produced by vulcanizing and bonding metal tire cords and rubber. However, a technique for integrating metal and TPE without using an adhesive is not known.
[0004]
If it is possible to strongly bond (fix) the metal part and the TPE part in the molded product obtained by inserting the metal shape into the injection mold and closing the mold and injecting the TPE, the metal and the TPE It becomes a very reasonable integration method. Because, when trying to paste and integrate a metal shape and a shape made of rubber or TPE by using an adhesive, in actual production, for example, in the case of mass production of several tens of thousands per day, This is because the work and management is difficult.
[0005]
It will be crying at a high defect rate, being swayed by misalignment of adhesion and adjustment of adhesive usage conditions due to changes in the seasons. As a method of injection molding the resin to the inserted metal shape and bonding them together (hereinafter referred to as “injection bonding”), if this injection bonding method is successful, there is no need to consider the misalignment of the bonding position. If it is stable, there is no need to worry about errors such as seasonal changes, shape errors due to temperature and humidity, and processing errors.
[0006]
Traditionally, there has been little interest in injection bonding of metal and TPE. The fact is that there was not so much use, and some demand has been dealt with exclusively by the vulcanization bonding method of metal and rubber. However, these days, there is a tendency to use metal frames in electronic devices, especially mobile phones and PDAs, and this uses a design that installs components that are vulnerable to vibration and components that generate vibration, such as liquid crystal display panels and small speakers. I'm out. On the metal frame, a small rubber member is sandwiched between the frame and the component to make a vibration cushioning material. There is a movement to replace the small rubber member with TPE. Therefore, considering that a small TPE member is assembled on a metal frame, it is natural to consider whether the injection bonding method can be used as a reasonable method.
[0007]
However, TPEs are not bonded at all if they are inserted into a mold without any surface treatment. Therefore, the present inventors have conducted extensive research and development on the assumption that injection bonding of TPE may be possible by performing some kind of treatment on the surface of the metal shaped object.
[0008]
In addition, as a conventional technique, a special ink is printed and cured on a molded product made of a rigid thermoplastic resin such as a polycarbonate resin or an ABS resin, and after inserting this into a mold, a TPE composition mainly composed of TPEE is injected. Then, there is one in which the printed layer and the TPE composition part are bonded, and as a result, the rigid thermoplastic resin molded product and the TPE composition part are integrated. This technology is open to the public and commercialized. That is, for a hard thermoplastic resin, injection bonding by the insert molding method of a TPE composition mainly composed of TPEE has already been put into practical use.
[0009]
[Problems to be solved by the invention]
The present invention has been made based on the technical background as described above, and achieves the following object.
When the metal shape is inserted into the mold and the mold is closed and the TPE composition is injected, the inventors have integrated the metal portion and the TPE composition portion with the necessary adhesive force and heat. The method of obtaining a composite of a plastic composition has been intensively developed and studied. Specifically, we thought that this would be possible by performing some kind of treatment on the surface of the metal shaped object, so we decided to develop a surface treatment method.
[0010]
[Means for Solving the Problems]
  In order to achieve the above object, the present invention employs the following means.
  The composite of the metal and the thermoplastic composition of the present invention includes a processed metal shape, a coating material containing a curable resin composition coated on the surface of the metal shape, and an upper surface of the coating material.injection moldingBased on thermoplastic polyester elastomer and / or thermoplastic polyurethane elastomer bonded together bysetIn a composite of a metal and a thermoplastic composition comprising a shaped product,
  The resin composition of the coating material is one or more selected from polyurethane resin, epoxy alkyd resin, and modified alkyd resin.
  The method for producing a composite of a metal and a thermoplastic composition includes a curing step in which the coating material is applied to the surface of the metal shaped article and a curing treatment, and the metal shaped article that has been subjected to the curing treatment. Including an insert step of inserting the product into an injection mold, and an injection step of injecting the thermoplastic composition.
  The coating material may be thermosetting. The resin composition of the coating material is preferably a paint or ink containing active hydrogen. The technical means of the present invention will be described in detail below.
[0011]
[Metal shape]
Basically, any metal material can be used. This is because fixing by injection molding is performed between the coating layer applied to the metal surface and the TPEE composition, so that there is no problem as long as the metal shape and the coating layer are sufficiently bonded. Many paints and inks that can correspond to each metal material and each metal alloy material have been proposed and known. Therefore, paint suitable for each metal alloy material is applied to the base, and the adhesiveness at the time of injection molding with TPE may be applied to the overcoat (heat fusion by softening resin, not heat fusion by molten resin, or adhesion) In the present invention, heat fusion, adhesion, and fixation are used synonymously).
[0012]
However, when two kinds of paints are actually simply applied repeatedly, inconveniences such as a decrease in heat-fusibility during injection molding often occur. According to the test by the present inventors, in such a case, the problem can be solved by finely adjusting the curing conditions such as semi-curing the base coating and then overcoating. Furthermore, a paint suitable for the metal is applied to the base, and a paint that adheres but is less reactive, such as a one-component acrylic resin paint, is cured once, and further, a TPE coating is applied thereon. It is also possible to apply a coating material that has been confirmed to have adhesiveness during injection molding and cure it.
[0013]
FIG. 1 shows an example of the structure of an electronic device such as a mobile phone, which is an integrated product of a metal frame and a TPE component. In many cases, the metal material used in such a case is a plate material made of an aluminum alloy, a magnesium alloy, or stainless steel (hereinafter referred to as SUS) as a processing material. In the present invention, aluminum alloy, magnesium alloy, and thixomold grade magnesium alloy used for die casting can be used. Furthermore, it can also be used for various iron alloys other than SUS, various copper alloys including brass (brass), nickel alloys, tin alloys, and the like. Furthermore, surface-treated metal materials such as tin (zinc iron plate) and various metal-plated metals can also be used.
[0014]
In the case of molding by injection molding, the metal shape has the shape and structure required for inserts for injection molding by machining such as sawing, milling, electrical discharge machining, drilling, pressing, grinding and polishing. To be processed. Metal shapes that have been processed into the required shape and structure must be free of processing oil on the surface to be painted or printed, and can also be left on the surface for a long period of time to leave a coating of hydroxide or oxide. It is necessary that the generally called rust is not made. These need to be removed by cleaning, grinding, polishing, blasting, barreling, or the like. In particular, it is very effective for adhesion of paint and ink that the rust is removed by polishing or blasting to renew the surface.
[0015]
In addition, in the case of chemical etching, for example, an aluminum alloy, it is preferable to immerse the metal shape in an aqueous caustic soda solution for a short time. The surface of the metal shaped object is microscopically dissolved, and the surface becomes a fine textured surface with fine irregularities, which is effective for adhesion of paint and ink. This alkali etching requires additional treatment such as subsequent washing with water and neutralization such as soaking in dilute nitric acid so that the alkali content does not remain, but it is particularly effective because the coating becomes very easy to ride.
[0016]
For other metal materials, it is best to perform chemical etching in addition to machining such as grinding, polishing and blasting. However, these pretreatment processes increase the number of steps and increase the cost. Therefore, these pretreatments can be performed if the necessary heat fusion properties at the time of injection molding can be obtained with good reproducibility without further improvement. There is no need to do work.
[0017]
[Coating material]
As the coating material, a thermosetting resin composition or a coating material containing another curable resin composition can be used. As the thermosetting resin composition, polyurethane resin paint, ink, alkyd resin paint, modified alkyd resin paint, and epoxy alkyd resin paint can be used. Other curable resin compositions include oil- and fat-added modified alkyd paints that are oxidatively cured by air, polyurethane-based paints that are cured by moisture in the air, and the like. These paints and inks are commercially available as one-part or two-part paint inks, and these can also be suitably used.
[0018]
There is another point in utilizing these coating materials in the practice of the present invention, which is curing conditions. The present inventors consider that it is important that active hydrogen groups exist in the coating material layer after curing based on the experience cultivated in the past. For example, in the case of polyurethane resin-based paints and inks, it is effective to satisfy the curing conditions provided by the paint ink manufacturer or to make them slightly sweeter, for example, to lower the curing temperature by about 20 ° C.
[0019]
In other words, if the curing conditions are significantly stricter than the curing conditions suggested by the manufacturer, the adhesive strength will be reduced when the thermoplastic resin composition containing TPEE is injected onto these coating films, which will be substantially useless. There are many. In two-part polyurethane resin paints and inks, it is common to use isocyanate (R-N = C = O) compounds as curing agents, but many active hydrogen groups remain in situations where they do not reach full cure. It is presumed that this active hydrogen group may react with molten TPEE.
[0020]
Similar judgments can be made for coating materials containing other curable resins. If the coating material is not a curable coating material, it melts and flows when a thermoplastic resin such as TPEE is injected, which is useless. On the other hand, the adhesiveness at the time of injection molding of TPEE seemed to be weak to the surface where they were completely cured and almost no active hydrogen groups remained.
[0021]
Epoxy alkyd resin-based paints include a high-temperature curing type and a low-temperature curing type, but both can be used in the present invention. In the high temperature curing type, curing is usually performed at 120 ° C. or more, but it is preferable to lower the baking temperature instructed by the manufacturer by about 20 ° C. The low temperature curing type may be under the curing conditions specified by the manufacturer, but it was seen that the period until the insert molding after the curing was limited. It seems to last for a week even in the summer, but I don't know if the storage area is unusually hot.
[0022]
As the modified alkyd resin-based paint, a one-component one can be preferably used. Also in this case, the baking temperature is preferably 10 to 20 ° C. lower than the temperature specified by the manufacturer. It seemed that the time period until insert molding after curing was also limited. This also has no effect on quality for about a week in summer. According to the experiments by the present inventors, it was a two-component polyurethane-based resin paint or ink that could be used without any problem for various metals.
[0023]
However, these polyurethane resin-based paints and the like are generally weak in adhesion to metal. Most of the paints and inks marketed in this system are not for metal coating but for resin coating. As described above, when the metal surface is carefully pretreated by the above-described chemical etching or the like, it is found that these paints and inks are strongly bonded, and these also have no problem as a coating material.
[0024]
However, depending on the use of the product, it may not be possible to pre-treat the metal shaped object for careful painting. In such a case, a metal paint, preferably an epoxy paint, an alkyd resin paint or the like is first applied to the metal shape, and a polyurethane resin paint is first applied on the upper surface thereof. However, this application does not necessarily result in a strong coating by simply performing overcoating.
[0025]
If the base coating is simply dried and then repeatedly applied, the coatings often interfere with each other and the necessary properties of the polyurethane resin coating are lost, or the adhesive force due to heat-sealing during injection molding often decreases rapidly. On the other hand, when the base coating is sufficiently cured and then repeatedly applied, the integrally molded product obtained therefrom has a low adhesive strength. In this case, when the fracture surface is viewed, it is often peeled off between the base and the top coating layer. In short, the adhesion by thermal fusion between the paint and the thermoplastic resin composition at the time of injection molding has a strength that is not a problem in practical use, but the adhesion between the coating films is poor.
[0026]
In conclusion, one method is to harden the base coating while loosening the base coating, and then apply the top coating on the base coating to cure. However, trial and error tests that determine the curing conditions for both paints are necessary, and the supply of paints and inks with stable physical properties that answer these requirements is a condition. The other method is a method in which a coating layer that adheres to both sides and does not cause a problem is sandwiched between two kinds of coating films, and a one-component coating can be used as an intermediate layer as described above. In implementation, since the cost is considered in addition to the stability of the process, it cannot be determined which is better.
[0027]
Even without using a polyurethane resin paint or ink, it can be relatively strongly bonded by injection molding with a simple application. For example, when the metal material is SUS, in addition to polishing and cleaning of the metal surface, one layer of epoxy alkyd resin-based paint or modified alkyd resin paint can be bonded by injecting the TPE composition by curing after application. However, it should be noted that even in this case, there are precautions as described above regarding the curing conditions and the subsequent storage period. In addition to the above, the coating on the metal surface may be a UV curable ink or a UV curable paint that is cured by irradiation with ultraviolet (UV) light.
[0028]
[TPE composition]
The TPE composition used in the present invention is a thermoplastic resin composition containing TPEE as a main component. The content of a preferable composition for this composition will be described. As TPEE, a block polymer in which a hard segment made of polyalkylene terephthalate and a soft segment made of terephthalic acid ester of poly (polymethylene ether) glycol can be used.
[0029]
Furthermore, a multi-block polymer in which a number of hard segments composed of polybutylene terephthalate and a number of soft segments composed of terephthalic acid ester of polytetramethylene ether glycol are alternately connected can be preferably used. This is commercially available from many resin manufacturers as TPEEs.
[0030]
In addition to TPEE, ethylene propylene rubber (hereinafter referred to as EPR), nitrile rubber (hereinafter referred to as NBR), styrene / ethylene / butylene / styrene block polymer (hereinafter referred to as SEBS), raw rubber such as soft vinyl chloride, or a compound obtained by compounding TPE is also preferably used. it can. Further, it may contain a plasticizer, a crystallization nucleating agent, a pigment, a dye, a filler, an antioxidant, a release accelerator, and other performance improving additives.
[0031]
In general, commercially available TPEE has a higher hardness than silicone rubber or the like, and therefore, it is usual to add SEBS or a plasticizer to lower the hardness. In addition, a plasticizer may be added to improve moldability, and a crystallization nucleating agent may be added to improve translucency. Mold accelerator may be added. TPEE-based compositions in which these are compounded are also commercially available. These can also be used suitably.
If attention is paid to the adhesive force in the adhesion by injection molding, the TPEE content in the thermoplastic resin composition containing TPEE as a main component is preferably 50% or more.
[0032]
[Insert and injection molding]
Adhesion (adhesion) between the metal shaped article and the thermoplastic resin composition is performed by an injection molding method described below. The machined metal shape is coated on the surface with the coating material described above. The coated metal shape is inserted into an injection mold. Since it differs depending on the metal shape and size, it cannot be generally stated, but for a small amount of molding, a man-made vertical molding machine can be used, or a horizontal molding machine may be used. In the case of a horizontal molding machine, manned molding work can be performed by opening a decompression hole in the insert part of the mold and reducing the pressure at the time of insertion so that the metal shaped object is not sucked and dropped. In order to efficiently perform a large number of moldings, it is better to use a robot to insert metal objects using a horizontal molding machine.
[0033]
The mold is opened, a metal shaped object is inserted, the mold is closed, and then the thermoplastic resin composition containing TPEE as a main component is injected. After cooling, the mold is opened and the molded product is released. In order to advance the adhesion by injection molding in a preferable state, the molten resin composition is preferably brought into contact with the coated surface at as high a temperature as possible. Therefore, it is better that the mold temperature is high at a level that does not hinder molding. Specifically, the injection into the molding cavity (the space portion in which the shape to be formed by the thermoplastic resin composition) is preferably a pinpoint gate.
[0034]
When the thermoplastic resin composition containing TPEE as a main component passes through this gate, frictional heat is generated, and the temperature of the thermoplastic resin composition instantaneously increases by several tens of degrees centigrade. Further, in the molding of the TPE composition, since the mold release is generally difficult, the mold temperature is often set as low as 20 to 30 ° C. Produce an effect. However, depending on the shape of the cavity, if the mold temperature is raised, it may become difficult to release the mold and the molding itself may be impossible. In these cases, there is no choice but to reexamine such as changing the molding shape or increasing the hardness of the resin material.
[0035]
[Methods other than molding / injection molding]
The above-described adhesion (fixation) between the metal shape and the thermoplastic resin composition may be a method other than the injection molding method. Insert a metal shape that has been applied and cured and a thin resin shape that is made of a thermoplastic resin composition containing TPEE as a main component into the mold, and close and press the pair of molds while heating. An integrated product of both can also be obtained by a molding method, that is, hot press molding. Although it does not seem to be a suitable method for mass production, it may be usable depending on the product shape. The principle of bonding (fixing) between the two is the same as the bonding by the injection molding described above.
[0036]
In addition, a method called extrusion molding is used for pipes, plates, and the like, but the present invention can also be used in this extrusion molding. It is only important that the above-described thermoplastic resin composition is in contact with the metal surface that has been applied and cured when it is in a heated and melted state, and any molding method may be used theoretically. However, in extrusion molding, the pressure applied between the molten resin and the metal surface is significantly lower than in injection molding or the like. Although it cannot be expected to show the strongest adhesive strength in this respect, for example, if it does not require adhesive strength, such as a material that adheres a heat insulating material or coating material to the outer periphery of a pipe, it is an extrusion molding. Also good.
[0037]
[Action]
According to the present invention, a metal shaped product and a thermoplastic resin composition containing TPEE as a main component can be firmly bonded by injection molding using insert means or other methods. This is made possible by applying and curing a paint or ink containing a thermosetting, UV, or other curing agent synthetic resin on a metal shape, and melting the surface at a high temperature and high pressure. It is because a coating film and a thermoplastic resin composition can adhere | attach by contacting the thermoplastic resin composition containing as a main component.
[0038]
The adhesive force between the metal shape and the coating film is also important, and physical etching and chemical etching of the metal shape are also effective. By using the present invention, weight reduction and process rationalization of mobile electronic devices and home appliances can be realized. These contribute to the electronic equipment industry.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described with reference to examples.
[Example 1]
FIG. 1 shows an example of the structure of a mobile phone, and is an exploded parts diagram. Here, the structure is composed of five large parts, and includes an upper case 1 from the top, a hard key 3 in which a plurality of parts are connected, a middle frame 4, a printed board portion 13, a lower case 14, and the like. As shown in FIG. 2, the middle frame 4 is composed of a metal shaped object 5 that is a press-processed product of a 1 mm thick sheet made of aluminum alloy (JIS A5052) and a printed circuit board portion 13. FIG. 3 shows a shape after injection molding of a TPE composition using this as a material. The hook and boss 6 are not installed in the middle frame of FIG. 3, but this is installed in a separate process after the product shown in FIG. 3 is completed.
[0040]
In this example, the manufacturing process of the metal / TPE composition integrated product shown in FIG. 3 from the metal shaped product 5 shown in FIG. 2 will be described. As shown in FIG. 3, the aluminum alloy metal shaped object 5 has a push button part 8, a peripheral buffer part 9 disposed on the outer periphery of the metal shaped object 5 for protection from vibrations, and also protects the liquid crystal. For this purpose, a liquid crystal plate buffer 10 and a speaker buffer 11 for protecting the speaker are installed.
[0041]
The aluminum alloy plate shape made of A5052 manufactured by pressing shows the metal shape 5 of FIG. 2, but is immersed in acetone (CH3COCH3) for several seconds in order to remove processing oil or the like that appears to adhere to the pressing. Further, this was immersed in a 1% strength aqueous sodium hydroxide solution for 0.5 minutes and alkali etched, then washed with water, neutralized by immersion in a 1% strength aqueous nitric acid solution for 1 minute, sufficiently washed with water and dried.
[0042]
“B8655 paint (manufactured by Musashi Paint Co., Ltd., Toshima-ku, Tokyo)” which is a one-component modified alkyd resin paint of a metal paint was diluted with a special solvent and applied to the required surface of the aluminum alloy shaped product. The indicated curing condition of this paint was 120 ° C. × 1 hour, but it was treated for 1 hour at 100 ° C., which was 20 ° C. lower. Next, a commercially available one-component acrylic resin ink was diluted with cyclohexanone to obtain a coating viscosity, and was applied by overcoating and dried at 80 ° C. for 1 hour. Next, the designated curing agent and cyclohexanone were mixed with a commercially available two-component polyurethane resin-based ink to form a coating viscosity, and the resultant was overcoated, and baked at 90 ° C., which was 10 ° C. higher than the designated curing conditions.
[0043]
An injection mold corresponding to the aluminum alloy shape portion and the push button portion 8, the peripheral buffer portion 9, the liquid crystal plate buffer portion 10, and the speaker buffer portion 11 installed thereon is prepared. The TPE composition used is a TPEE composition "Primalloy A1500 (manufactured by Mitsubishi Chemical Corporation)" in which a small amount of SEBS is compounded, and a TPEE composition "Dynaflex E5842" in which a plasticizer and a release accelerator are compounded. JSR Co., Ltd.) "2: 1 pellet mixture. The hardness of the pellet is about 70 degrees in terms of JIS A hardness.
[0044]
Molding was carried out at a mold temperature of 60 ° C. and a nozzle of a horizontal 50-ton injection molding machine at 210 ° C. Each TPE composition was all fed by a pinpoint gate. However, the liquid crystal plate buffer 10 and the speaker buffer 11 were provided with two gates each. The aluminum alloy shape was inserted into the movable side of the mold. There are four holes of 3 mm diameter in the mold to be inserted, and the holes are connected to the outside of the mold so that the aluminum alloy shape set by reducing the pressure with a decompressor is sucked and fixed.
[0045]
The mold was closed and the TPE composition was injected, and the mold was opened and released about 20 seconds after injection. The molded product is shown in FIG. Here, each member made of TPE composition was firmly attached to the aluminum alloy shape. 4 is a cross-sectional view of an injection mold when molding each buffer portion on the metal shaped article 5, and is a cross-sectional view showing a state cut along the line AA of FIG. In FIG. 4, it has the coating surface layer 12 painted on the surface of the metal shaped object 5.
[0046]
The push button portion 8 is formed so as to close a large through hole opened in the metal shaped object 5. The peripheral buffer portion 9 also has a shape in which the through-hole opened in the metal shaped object 5 is bonded. As a result, in addition to the heat-fusibility at the time of injection molding, both can be securely fixed, so that reliability as a part can be ensured. The fixed side mold plate 20 shown in FIG. 4 is a fixed part of the injection mold, and the movable side mold plate 21 is a movable part that is in close contact therewith. When the metal shaped object 5 is inserted and placed on the movable side mold plate 21, and the movable side mold plate 21 is moved to the fixed side mold plate 20 and closed, this space is the peripheral buffer portion 9, the liquid crystal plate buffer portion. 10 and molten resin is injected from the pinpoint gate 22 into the cavity forming the speaker buffer 11.
[0047]
[Example 2]
The experiment was performed in the same manner as in Example 1 except that an A6063 aluminum alloy plate (JIS H standard) was used as the metal material of the metal shape. Each TPE composition member adhered firmly to the aluminum alloy shape.
[0048]
[Example 3]
The metal material of the metal shape was a SUS304 plate (JIS H standard) having a thickness of 1 mm, and was pressed and shaped in the same manner as in Example 1. This was cleaned by applying a high pressure steam pulse. After drying, a mixture of a modified alkyd resin paint “B8655 (manufactured by Musashi Paint Co., Ltd.)” and a special solvent was applied and baked at 100 ° C. for 1 hour. Thereafter, in the same manner as in Example 1, it was inserted into a mold, and the same TPE composition as in Example 1 was injection-bonded under the same molding conditions. Each TPE composition member adhered firmly to the shape of the molded SUS304 plate.
[0049]
[Example 4]
The metal material of the metal shape was formed into a SUS304 plate having a thickness of 1 mm, and was pressed and shaped in the same manner as in Example 1. This was immersed in a 10% hydrochloric acid aqueous solution at 25 ° C. for 15 minutes, washed with water, neutralized by immersion in a 1% aqueous sodium hydroxide solution for 5 minutes, washed with water, and dried in hot air at 80 ° C. To this, urethane curable two-component ink “VIC (manufactured by Seiko Advance Co., Ltd.)” is mixed up to the paint viscosity, solvent “PG7394C (manufactured by Fujikura Kasei Co., Ltd.)” and 1% hydrous cyclohexanone is mixed 1: 1. It applied using the paint obtained by diluting with a solvent. Subsequently, it was cured by heating at 70 ° C. for 1 hour.
[0050]
Thereafter, in the same manner as in Example 1, it was inserted into a mold, and the same TPE composition as in Example 1 was injected under the same conditions. Each TPE composition member was molded and adhered firmly to the SUS304 plate shape. In general, urethane curable inks and paints are not used because they have weak adhesion to stainless steel, but in this example, the metal plate is chemically etched using hydrochloric acid, and the surface of the SUS plate is changed to a fine uneven surface. It was shown that the adhesive strength of urethane-curing ink and paint can be improved.
[0051]
[Example 5]
The metal material of the metal shape was made into a copper plate having a thickness of 1 mm, and was pressed and shaped in the same manner as in Example 1. This was immersed in 10% aqueous ammonia at 25 ° C. for 3 minutes, washed with water, and dried with hot air at 80 ° C. Thereafter, the coating material was applied and cured in exactly the same manner as in Example 4, and TPE was injection bonded onto the mold on the insert. Each TPE composition member was molded and adhered firmly onto the copper plate shape. In general, urethane curable inks and paints for metal parts are not used because of their weak adhesive strength, but the urethane surface is made by chemically etching the copper surface with ammonia water to make the surface fine and uneven. It can be seen that the adhesive strength of the product can be improved.
[0052]
【The invention's effect】
As described above in detail, in the composite of the present invention, the thermoplastic resin composition mainly composed of the thermoplastic polyester elastomer and / or thermoplastic polyurethane elastomer and the metal shaped product are easily peeled off. Integrate without. Since the injection bonding method can be used as the manufacturing method, it is possible to make housings, parts, structures and the like of various devices that have no problem in dimensional accuracy. The housing, parts, and structures manufactured by the present invention are useful for reducing the weight and simplifying the device manufacturing process.
[Brief description of the drawings]
FIG. 1 is an exploded parts diagram showing an example of the structure of a mobile phone.
FIG. 2 is a press-processed product of a thick sheet made of an aluminum alloy.
FIG. 3 is a shape after injection molding of a TPE composition using this as a material.
4 is a cross-sectional view of an injection mold when molding each buffer portion on the metal shaped article 5, and is a cross-sectional view showing a state cut along line AA in FIG. 3;
[Explanation of symbols]
1 ... Upper cover
3. Hard key
4 ... Middle frame
13 ... Printed circuit board
5 ... Metal shape
8 ... Push button
9. Peripheral buffer
10. Liquid crystal plate buffer
11 ... Speaker buffer
13 ... Printed circuit board
14 ... Lower case

Claims (6)

Processed metal shapes,
A coating material comprising a curable resin composition coated on the surface of the metal shape,
Complex of the top metal and the thermoplastic composition comprising a shaped article of thermoplastic pairs Narubutsu composed mainly of thermoplastic polyester elastomer and / or thermoplastic polyurethane elastomer secured integrally by injection molding of the coating material In
The composite of a metal and a thermoplastic composition, wherein the resin composition of the coating material is at least one selected from polyurethane resin, epoxy alkyd resin, and modified alkyd resin. The composite of a metal and a thermoplastic composition according to claim 1,
The coating material is thermosetting. A composite of a metal and a thermoplastic composition. In the composite of the metal and the thermoplastic composition according to claim 1 or 2,
The composite of a metal and a thermoplastic composition, wherein the coating material is a paint or ink containing active hydrogen. A composite of a metal and a thermoplastic composition according to claim 1 selected from claims 1 to 3 ,
The coating material is a lower layer made of an electrophilic paint or ink,
A composite of a metal and a thermoplastic composition comprising a plurality of upper layers made of a paint or ink containing a thermosetting or other curable resin composition. A composite of a metal and a thermoplastic composition according to claim 1 selected from claims 1 to 4 ,
The metal shaped object includes a through hole that is a hole penetrating the metal shaped object,
The through hole is filled with the thermoplastic composition. A composite of a metal and a thermoplastic composition. A method for producing a composite of a metal and a thermoplastic composition comprising the metal shaped article according to claim 1 ,
On the surface of the shaped metal, curing process cured by applying the coating material,
Insertion step of inserting a coating processed products of the shaped metal that the curing process, the injection mold and,
Method for producing a composite of an injection process the metal and the thermoplastic composition characterized by comprising injecting the said thermoplastic composition.

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