JP2003246009A - Composite of metal and thermoplastic composition and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture an integrated composite which makes the merit of a TPE member and that of a metal shaped matter compatible, enables omission of an assembling process, shows high productivity and also has no problem about dimensional precision, in regard to an electronic appliance, a household electrical appliance, etc. <P>SOLUTION: The metal shaped matter is inserted into an injection mold for molding a push button part 8, a peripheral buffering part 9, a liquid crystal plate buffering part 10 and a speaker buffering part 11. The surface of the metal shaped matter is already subjected to specific coating or printing. A thermoplastic resin composition constituted mainly of a thermoplastic polyester elastomer is filled by injection molding and a TPE member portion is molded. A metal part and the portion of a TPE composition are joined integrally in a molded intermediate frame. This simple process can be realized by general ideas of applying, curing and injection bonding of a prescribed coating material or ink. The manufacturing method is helpful also to reduction of weight and simplification of processes for various machine components and structures other than the electronic and household electrical appliances. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite of a metal and a thermoplastic composition used for a casing or a structural member of electronic equipment and a method for producing the same. More specifically, the present invention relates to a technique in which a plurality of members, which are conventionally composed of a metal member and a rubber O-ring or a rubber filler, are integrated and replaced with one or a small number of composite members.

The present invention relates to a thermoplastic polyester elastomer (Thermo Plastic Elastomer: TPE) which is a kind of a thermoplastic elastomer (Thermo Plastic Elastomer: TPE).
lastic Poly-Ester Elastomer: integrated member to which a thermoplastic resin composition containing TPEE as a main component is attached,
This is a technology that can be applied with high dimensional accuracy. It relates not only to the electronic equipment industry mentioned above, but also to the manufacture of housings and parts for many mechanical and electric devices.

[0003]

2. Description of the Related Art A post-process for integrating metal and rubber has been developed for a long time and is now used in various fields as seen in the production example of tires produced by vulcanizing and adhering metal tire cords and rubber. ing. However, there is no known technique for integrating metal and TPE without using an adhesive.

If a metal product is inserted into an injection molding die, the mold is closed, and TPE is injected, the metal part and the TPE part can be strongly adhered (fixed) to each other in the obtained molded product. It is a very rational method for integrating with TPE. The reason is that if metal shaped objects and rubber or TPE shaped objects are pasted and integrated by using an adhesive, in actual production, for example, in the case of mass production of tens of thousands of pieces per day, Because the work and management are difficult.

[0005] It will be overwhelmed by the misalignment of the adhesive and the adjustment of the usage conditions of the adhesive due to the changes of the four seasons, and the high defect rate will make the person cry. A method of injecting a resin into the inserted metal shape to bond them together (hereinafter,
This is called "injection bonding". ), If this injection bonding method succeeds, it is not necessary to consider the displacement of the bonding position, and if the bonding is stable, then there will be no concern about errors such as seasonal changes, shape errors due to temperature and humidity, and processing errors. .

Heretofore, there has been little interest in injection bonding metal and TPE. The fact is that it did not have that much use, and some demand has been met exclusively by the vulcanization bonding method of metal and rubber. However, in recent years, there is a tendency to use a metal frame in electronic devices, particularly mobile phones and PDAs, and it is designed to install parts sensitive to vibration and parts that generate vibration, such as liquid crystal display boards and small speakers. It has started to break out. A small rubber member is sandwiched between the frame and the parts on the metal frame to serve as a vibration damping material.
There is a movement to replace manufacturing. Therefore, the metal frame has a small T
It is natural to think that the injection bonding method can be used as a rational method on the assumption that the PE member is assembled.

However, if the TPEs are injected by inserting the metal into the mold without any surface treatment, no adhesion occurs. Therefore, the inventors of the present invention have conducted research and development with the idea that injection-bonding of TPE may be possible by performing some treatment on the surface of a metal shape object.

As a conventional technique, a TPE composition containing TPEE as a main component is prepared by printing and curing a special ink on a hard thermoplastic resin molded article such as a polycarbonate resin or an ABS resin, and inserting this into a mold. In some cases, the printed layer and the TPE composition part are adhered by injection, and as a result, the hard thermoplastic resin molded product and the TPE composition part are integrated. This technology is open to the public and commercialized. That is, for hard thermoplastic resins, TPEE
Injection bonding of a TPE composition containing as a main component by an insert molding method has already been put into practical use.

[0009]

The present invention has been made based on the above technical background, and achieves the following objects. The present inventors have found that when a metal shape is inserted into a mold and then the mold is closed and the TPE composition is injected, the metal part and the TPE composition part are integrated with a necessary adhesive force and heat. The method for obtaining the composite of the plastic composition was intensively researched and developed. Specifically, we thought that it would be possible to do this by treating the surface of metal objects with some kind of treatment, and decided not to develop a surface treatment method.

[0010]

The present invention adopts the following means in order to achieve the above object. The composite of the metal and the thermoplastic composition of the present invention is 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. It is formed of a thermoplastic compound mainly composed of a thermoplastic polyester elastomer and / or a thermoplastic polyurethane elastomer, which are integrally fixed by heat and pressure. The coating material is preferably thermosetting. The resin composition of the coating material is a paint containing active hydrogen,
Or it is good to use ink. Hereinafter, the technical means of the present invention will be described in detail.

[Metallic Shape] Basically, any material can be used as the metal material. Because the fixing by injection molding is performed between the coating layer applied on the metal surface and the TPEE composition, no problem occurs if the metal shape and the coating layer are sufficiently adhered. Many paints and inks that can be applied to each metal material and each metal alloy material have been proposed and are known. Therefore, a paint suitable for each metal alloy material is applied to the base, and the adhesiveness at the time of injection molding with TPE is applied to the topcoat (heat fusion with a softening resin instead of heat fusion with a molten resin, or adhesion may be performed. In the present invention, heat fusion, adhesion, and fixation are used synonymously.) It is sufficient to apply a coating material which has been confirmed.

However, when two kinds of paints are simply overlaid on top of each other, there are many inconveniences such as deterioration of heat fusion property during injection molding. According to tests by the inventors,
In such a case, it is possible to solve it by finely adjusting the curing conditions such as semi-curing the base coating and then top coating. Furthermore, a paint suitable for the metal is applied to the base, and a paint that adheres but has low reactivity, such as a one-component acrylic resin paint, is applied and cured once, and then T
It is also possible to apply a coating material which has been confirmed to have adhesiveness during PE injection molding, and to cure it.

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 TPE parts. As a metal material used in such a case, a plate material made of aluminum alloy, magnesium alloy, or stainless steel (hereinafter referred to as SUS) is often used as a processing material. In the present invention, an aluminum alloy, a magnesium alloy, or a thixomold grade magnesium alloy used for die casting can be used.
Further, it can be used for metals such as various iron alloys other than SUS, various copper alloys including brass (brass), nickel alloys, tin alloys, and the like. Further, surface-treated metal materials typified by galvanized iron (zinc iron plate) and various metal-plated metals can also be used.

In the case of molding by injection molding, the metal shape is required as an insert for injection molding by mechanical processing such as sawing, milling, electric discharge machining, drilling, pressing, grinding and polishing. Processed into shape and structure. Metallic objects that have been processed into the required shape and structure must have no processing oil, etc. on the surface they are to be painted or printed on, and after being left for a long period of time, a film of hydroxide or oxide must be left on them. It is necessary that rust, which is generally called, is not formed. These must be removed by washing, grinding, polishing, blasting, barreling, etc. In particular, it is very effective to remove paints such as rust and blast to renew the surface, which is very effective for adhesion of paint and ink.

In addition, for chemical etching, for example, in the case of aluminum alloy, it is advisable to immerse the metallic shape in the caustic soda aqueous solution for a short time. The surface of the metal shape is microscopically melted to form a fine grained 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 dipping 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.

With other metal materials, it is best to carry out chemical etching in addition to machining such as grinding, polishing and blasting. However, since these pretreatment processes increase the number of steps and increase the cost, if the necessary heat fusion property during injection molding can be finally obtained with good reproducibility even if it is not so much, these pretreatments can be performed. You don't have to do any work.

[Coating Material] As the coating material, a coating material containing a thermosetting resin composition or another curable resin composition can be used. As the thermosetting resin composition, polyurethane resin-based paint, ink, alkyd resin-based paint, modified alkyd resin-based paint, or epoxy alkyd resin-based paint can be used. Other curable resin compositions include modified alkyd paints containing oils and fats that are also oxidatively hardened by air, and polyurethane-based paints that are hardened by moisture in the air, and these can also be used. These paints and inks are one-part and two-part
It is commercially available as a liquid paint ink, and these can also be suitably used.

There is another point in utilizing these coating materials in the practice of the present invention, which is the curing condition. From the experience cultivated in the past, the present inventors
The presence of active hydrogen groups in the coating material layer after curing is considered important. For example, in the case of polyurethane resin-based paints and inks, the curing conditions provided by the coating ink manufacturer may be used, or the coating may be made slightly sweeter.
It is effective to lower the temperature by about 0 ° C.

In other words, if the curing conditions are markedly stricter than the curing conditions offered by the manufacturer, TPEE
In many cases, when a thermoplastic resin composition containing is injected into these coating films, the adhesive strength is reduced and it is practically useless. Two
Isocyanate (RN = C = O) compounds are usually used as curing agents in liquid polyurethane resin-based paints and inks, but many active hydrogen groups remain in situations where complete curing cannot be achieved. It is presumed that this active hydrogen group may react with molten TPEE.

The same viewpoint can be applied to other coating materials containing a curable resin. Unless the coating material is a curable coating material, a thermoplastic resin such as TPEE melts and flows when injected, and is useless. On the other hand, the adhesion of TPEE during injection molding seemed to be weak on the surface where they were completely cured and almost no active hydrogen groups remained.

Epoxy alkyd resin type coatings include high temperature curing type and low temperature curing type, but both can be used in the present invention. The high-temperature curing type usually cures at 120 ° C or higher, but the baking temperature specified by the manufacturer is 20
It is preferable to lower the temperature by about 0 ° C. The low temperature curing type may have the curing conditions specified by the manufacturer, but it seems that the period until the insert molding after the curing is limited. It seems that it will last for a week even in the summer, but I do not know well if the place is unusually hot.

As the modified alkyd resin-based paint, one-component type 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 also appears that the period of time after curing until insert molding is limited. This also does not affect the quality in the summer for about a week. According to the experiments conducted by the present inventors, it was possible to use two-component polyurethane resin paints and inks that could be used for various kinds of metals without much trouble.

However, these polyurethane resin type paints and the like generally have weak adhesion to metal. Most of the paints and inks marketed in this family of paints are not for metal coating but for resin coating. As described above, when the surface of the metal is carefully pretreated by the above-described chemical etching, it has been found that these paints and inks also adhere strongly, and there is no problem as a coating material.

However, depending on the use of the product, there are cases where pretreatment for careful painting cannot be performed on the metal shape. In such a case, it is first attempted to apply a metallic paint, preferably an epoxy-based paint, an alkyd resin-based paint or the like to the metal shape, and then apply a polyurethane resin-based paint on the upper surface thereof. However, this coating does not necessarily result in a strong coating by simply performing overcoating.

If the base paints are over-dried only by simple drying, the paints may interfere with each other and the necessary properties of the polyurethane resin-based paint may be lost, or the adhesive strength due to the heat-sealing property during injection molding often decreases sharply. . On the other hand, when the base paint is sufficiently cured and then overcoated, the integrally molded article obtained therefrom has a weak adhesive strength. In this case, looking at the fractured surface, it is often peeled off between the base and the top coating layer. In short, the adhesion of the coating material and the thermoplastic resin composition at the time of injection molding by heat fusion has a strength to the extent that there is no problem in practical use, but the adhesion between the coating films is poor.

In conclusion, one method is to cure the undercoat paint while loosening it and then apply the top paint there and cure. However, a trial-and-error test is required to determine the curing conditions for both paints, and the supply of paints and inks with stable physical properties that meet these requirements is a condition. Another way is 2
As described above, the one-component paint can be used as an intermediate layer by sandwiching a paint layer that adheres to both sides and does not cause a problem between the two kinds of paint films. In implementation, cost is taken into consideration in addition to process stability, so it cannot be determined which is better.

Even if a polyurethane resin-based paint or ink is not used, it can be bonded by relatively strong injection molding with a simple application. For example, when the metal material is SUS, in addition to polishing and cleaning of the metal surface, it is possible to inject and bond the TPE composition by curing after coating one layer of the epoxy alkyd resin-based paint or the modified alkyd resin paint. However, it should be noted that even in this case, there are the above-mentioned precautions regarding the curing conditions and the storage period thereafter. In addition to the above, the coating on the metal surface is not
It may be a UV curable ink or a UV curable coating which is cured by being irradiated with V).

[TPE composition] TPE used in the present invention
The composition is a thermoplastic resin composition containing TPEE as a main component. The content of the preferable composition of 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 are bonded can be used.

Further, a multiblock polymer in which a hard segment made of polybutylene terephthalate and a large number of soft segments made of terephthalic acid ester of polytetramethylene ether glycol are alternately bonded can be preferably used. It is commercially available as TPEEs from many resin manufacturers.

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 It can be preferably used. Also, plasticizers, crystallization nucleating agents, pigments, dyes, fillers, antioxidants,
A mold release accelerator and other performance improving additives may be contained.

In general, commercially available TPEE has a higher hardness than silicone rubber and the like, so that SEBS, a plasticizer or the like is usually added to reduce the hardness. Also, a plasticizer may be added to improve moldability, and a crystallization nucleating agent may be added to improve translucency.Since release of silicone oil or the like may be facilitated after mold release. Mold promoters may be added. TPEE-based compositions per se compounded with these are also commercially available. These can also be used suitably. If attention is paid to the adhesive strength in the adhesion by injection molding, the TPEE content in the thermoplastic resin composition containing TPEE as a main component is 50.
% Or more is preferable.

[Insert and Injection Molding] The metal shape and the thermoplastic resin composition are bonded (fixed) by the injection molding method described below. The surface of the machined metal shape is coated with the coating material described above. The coated metal shape is inserted into an injection molding die. Since it differs depending on the metal shape and size, it cannot be generally stated, but for molding a small amount, a vertical molding machine can be used by a man or a horizontal molding machine. In the case of a horizontal molding machine, a depressurization hole is opened at the insert portion of the die, and depressurization is performed at the time of insertion so that a metal shape can be sucked and prevented from falling, and manned molding work can be performed. To efficiently perform a large number of moldings,
It is recommended to use a robot to insert metal shaped objects using a horizontal molding machine.

The mold is opened, the metal shape is inserted, the mold is closed, and then the thermoplastic resin composition containing TPEE as the main component is injected. After cooling, the mold is opened and the molded product is released. In order to promote the adhesion by injection molding in a preferable state, it is preferable that the molten resin composition comes into contact with the coated surface at a temperature as high as possible. Therefore, it is preferable that the mold temperature is high as long as it does not hinder the molding. Specifically, it is preferable that the injection into the molding cavity (the space where the shape to be formed by the thermoplastic resin composition is dug) is injected by a pinpoint gate.

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 instantly rises by several tens of degrees. Further, in the molding of the TPE composition, the mold temperature is often set as low as 20 to 30 ° C. because it is generally difficult to release the mold, but in terms of adhesion, it is good to set the mold temperature as high as 40 to 70 ° C. Produce an effect. However, depending on the shape of the cavity, if the mold temperature is raised, it becomes difficult to release the mold, and molding itself may become impossible. With these, there is no choice but to reexamine by changing the molding shape or increasing the hardness of the resin material.

[Methods Other than Molding / Injection Molding] The metal shape and the thermoplastic resin composition may be bonded (fixed) to each other by a method other than the injection molding method. Into the mold, insert both the coating-cured metal shape and the thin resin shape made of the thermoplastic resin composition containing TPEE as the main component, and close and press the pair of dies while heating. An integrated product of the both can be obtained by a molding method, that is, a hot press molding. I don't think it is a suitable method for mass production, but it may be used depending on the product shape. The principle of adhesion (fixing) between the two is the same as the adhesion by injection molding described above.

In addition, a method called extrusion molding is used for a pipe-shaped material, a plate-shaped material, etc. The present invention can be applied to this extrusion molding. It is only important that the above-mentioned thermoplastic resin composition comes into contact with the metal surface subjected to the coating and curing treatment when it is in a heat-melted state, and theoretically any molding method may be used. However, in extrusion molding, the pressure applied between the molten resin and the metal surface is significantly lower than in injection molding. In this respect, it cannot be expected to exhibit the strongest adhesive force, but if it does not require adhesive strength, such as one that adheres a heat insulating material or a covering material to the outer periphery of the pipe, it is extruded. Is also good.

[Operation] According to the present invention, a metal shaped article,
A thermoplastic resin composition containing TPEE as a main component,
Strong adhesion can be achieved by injection molding using insert means or other methods. This is made possible by the fact that a metallic shape is coated with a paint or an ink containing a synthetic resin by a thermosetting, UV, or other curing agent and cured, and the surface is melted at high temperature and high pressure with TPEE. By contacting the thermoplastic resin composition containing as a main component,
This is because the coating film and the thermoplastic resin composition can adhere to each other.

The adhesive force between the metal shape and the coating film is also important, and physical etching or chemical etching of the metal shape is also effective. By using the present invention, weight reduction and process rationalization of mobile electronic devices and home electric appliances can be realized. These contribute to the electronic device industry.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be shown below with reference to examples. [Embodiment 1] FIG. 1 is an exploded view of an example of the structure of a mobile phone. Here, the structure is made up of 5 large parts, and from the top as shown in the figure, an upper case 1, a plurality of hard keys 3, a middle frame 4, and a printed circuit board section 1 are connected.
3, lower case 14, etc. The middle frame 4 has an aluminum alloy (JIS A505
2) It consists of a metal-shaped product 5 which is a pressed product of a 1 mm thick sheet and a printed circuit board portion 13. FIG. 3 shows the shape of a TPE composition using this as a material after injection molding. 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 one shown in FIG. 3 is completed.

In this embodiment, the metal shape 5 shown in FIG.
The manufacturing process of the metal / TPE composition integrated product shown in FIG. 3 will be described. As shown in FIG. 3, the aluminum alloy metal shape 5 has a push button portion 8, a peripheral buffer portion 9 arranged on the outer periphery of the metal shape 5 to protect it from vibration, and also protects the liquid crystal. Liquid crystal plate buffer section 1 for
0, a speaker buffer 11 is also installed to protect the speaker.

The aluminum alloy plate shape made of A5052 manufactured by pressing shows the metal shape 5 of FIG. 2, but it is put in acetone (CH3COCH3) for several seconds in order to remove the processing oil and the like that is thought to adhere by pressing. Soak. Further, this was immersed in a 1% strength caustic soda aqueous solution for 0.5 minutes for alkali etching, washed with water, immersed in a 1% strength nitric acid aqueous solution for 1 minute for neutralization, sufficiently washed with water and dried.

"B8655 paint (Musashi Paint Co., Ltd., Toshima-ku, Tokyo)" which is a one-pack modified alkyd resin paint for metal coating is diluted with a special solvent and applied to the necessary surface of the aluminum alloy shaped article. did. The indicator curing condition of this paint was 120 ° C x 1 hour,
Time processed. Next, a commercially available one-component acrylic resin ink was diluted with cyclohexanone to obtain a coating viscosity, which was applied as an overcoat and dried at 80 ° C. for 1 hour. Next, a commercially available two-component polyurethane resin-based ink was mixed with a specified curing agent and cyclohexanone to obtain a paint viscosity, and top-coated and then baked at 90 ° C., which is 10 ° C. higher than the specified curing condition, for 1 hour.

Aluminum alloy shaped part, push button part 8 installed on it, peripheral buffer part 9, liquid crystal plate buffer part 1
0, an injection mold corresponding to the speaker buffer 11 is prepared. The TPE composition used is a TPEE composition "Primalloy A1500" containing a small amount of SEBS compounded.
This was a 2: 1 pellet mixture of Mitsubishi Chemical (manufactured by KK) and TPEE composition "Dynaflex E5842 (manufactured by JSR Corporation)" in which a plasticizer and a mold release accelerator were compounded. The hardness of the pellet is around 70 degrees in JIS A hardness.

Molding was carried out at a mold temperature of 60 ° C. and a horizontal mold of 5
The nozzle temperature of the 0 ton injection molding machine was 210 ° C. All TPE compositions were supplied with pinpoint gates. However, the liquid crystal plate buffer section 10 and the speaker buffer section 1
For No. 1, two gates each were installed. The aluminum alloy shaped article was inserted into the movable side of the die. There are 4 holes with a diameter of 3 mm in the mold at the places to be inserted, and the holes are connected to the outside of the mold so that the aluminum alloy shaped object set by decompressing with a decompressor is fixed by suction.

The mold was closed and the TPE composition was injected, and about 20 seconds after the injection, the mold was opened and released. The molded product is shown in FIG. Here, the member made of each TPE composition was firmly attached to the aluminum alloy shaped article. Figure 4
FIG. 4 is a cross-sectional view of an injection molding die when molding each buffer portion in the metal shape object 5, and is a cross-sectional view showing a state cut along the line AA in FIG. 3. In FIG. 4, it has a coating layer 12 coated on the surface of the metal shape object 5.

The push button portion 8 is formed so as to close a large through hole opened in the metal-shaped object 5. The peripheral cushioning portion 9 also has a shape that penetrates the through hole opened in the metal-shaped object 5 and is bonded thereto. As a result, in addition to the heat-sealing property at the time of injection molding, both can be reliably fixed, so that reliability as a component can be ensured. The fixed-side mold plate 20 shown in FIG. 4 is a fixed part of the injection molding die, and the movable-side mold plate 21 is a movable part that comes into close contact with it. The metal shape object 5 is the movable side mold plate 21.
The movable side mold plate 21 is inserted and placed in the fixed side mold plate 2
When it is moved to 0 and closed, the molten resin is injected from the pinpoint gate 22 into the cavity forming the peripheral buffer section 9, the liquid crystal plate buffer section 10, and the speaker buffer section 11 in this space.

[Embodiment 2] A6 is used as the metal material of the metal shape object.
An experiment was performed in exactly the same manner as in Example 1 except that a 063 aluminum alloy plate (JIS H standard) was used. Each TPE composition member was firmly attached to the aluminum alloy shape.

[Embodiment 3] A metal material having a metal shape of SUS304 plate (JIS H standard) having a thickness of 1 mm was used.
It was pressed and shaped in the same manner as in. It was washed 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 dedicated solvent was applied and baked at 100 ° C for 1 hour. After that, it was inserted into the mold exactly as in Example 1, and the same TPE composition as in Example 1 was injection-bonded under the same molding conditions. Each TPE composition member was firmly attached to the shape of the molded SUS304 plate.

[Example 4] A metal material having a metal shape was made into a SUS304 plate having a thickness of 1 mm, and pressed in the same manner as in Example 1 to be shaped. Add this to 10% aqueous hydrochloric acid at 25 ° C.
Then, it was immersed for 15 minutes, washed with water, immersed in a 1% aqueous solution of sodium hydroxide for 5 minutes for neutralization, washed with water, and dried with hot air at 80 ° C. In addition to this, urethane curable two-component ink "V
Using a paint obtained by diluting “IC (manufactured by Seiko Advance Co., Ltd.)” with a solvent of “PG7394C (manufactured by Fujikura Kasei Co., Ltd.)” and a 1: 1 mixed solvent of 1% hydrocyclohexanone until the viscosity of the paint. Applied. Then, it was heat-cured at 70 ° C. for 1 hour.

After that, the same TPE composition as in Example 1 was injected under the same conditions as in Example 1, after inserting into a mold. Each TPE composition member is molded into SUS
It was firmly attached to the 304 plate-shaped object. Urethane-curable inks and paints for stainless steel materials are generally weak in adhesiveness and are not used. However, in this embodiment, a metal plate is chemically etched using hydrochloric acid to form a fine uneven surface on the surface of the SUS plate. By doing so, it was shown that the adhesive strength of urethane-curing ink and paint can be improved.

[Example 5] A metal plate having a thickness of 1 mm was used as the metal material of the metal shape object, and pressed in the same manner as in Example 1 to form a shape. This was immersed in 10% ammonia water at 25 ° C for 3 minutes, washed with water, and dried at 80 ° C with hot air. After this, 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 firmly adhered to the copper plate shape. Urethane-curable inks and paints for metal parts are generally not used because of their weak adhesion. However, by chemically etching the copper surface with ammonia water to make the surface finer, urethane-cured It can be seen that the adhesive strength of the product can be improved.

[0052]

As described above in detail, in the composite of the present invention, the thermoplastic resin composition and the metal shape product, which are mainly composed of the thermoplastic polyester elastomer and / or the thermoplastic polyurethane elastomer to be integrated. And can be easily integrated without peeling. Since the injection bonding method can be used as the manufacturing method, it is possible to manufacture the casings, parts, structures, etc. of various devices that have no problem in dimensional accuracy. The housing, parts, and structures manufactured according to the present invention are useful for reducing the weight and simplifying the device manufacturing process.

[Brief description of drawings]

FIG. 1 is an exploded view of an example of the structure of a mobile phone.

FIG. 2 is a pressed product of a thick sheet made of an aluminum alloy.

FIG. 3 is a shape of a TPE composition using this as a material after injection molding.

FIG. 4 is a cross-sectional view of an injection molding die when molding each buffer portion in the metal shape object 5, and is a cross-sectional view showing a state cut along the line AA in FIG. 3.

[Explanation of symbols]

1 ... Top cover 3 ... hard key 4 ... Middle frame 13 ... Printed circuit board section 5 ... Metal shape 8 ... Push button part 9 ... Peripheral buffer 10 ... Liquid crystal plate buffer section 11 ... Speaker buffer section 13 ... Printed circuit board section 14 ... Lower case

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29K 105: 22 B29K 105: 22 (72) Inventor Takashi Goto 1-10-5 Nihonbashihonmachi, Chuo-ku, Tokyo Taisei Plus Co., Ltd. (72) Inventor Masao Takahashi 1-10-5 Nihonbashi Honcho, Chuo-ku, Tokyo Taisei Plus Co., Ltd. F-term (reference) 4F100 AB01A AB10 AB31 AK01B AK01D AK41B AK41C AK51B AK51C AK53B AL05B AL05D AL09C BA03 BA04 BA05 BA07 BA10A BA10C CC00B CC00D DC11A EH362 EH462 EJ65B GB41 JB13B JB13D JB16C JL02 JL03 4F206 AA45 AD03 AD20 AD24 AH42 JA07 JB12 JF05 JL02

Claims (9)

[Claims] 1. A processed metal shape, a coating material containing a curable resin composition coated on the surface of the metal shape, and integrally fixed to the upper surface of the coating material by heat and pressure. A composite of a metal and a thermoplastic composition, which comprises a thermoplastic polyester elastomer and / or a thermoplastic compound having a thermoplastic polyurethane elastomer as a main component. 2. The composite of a metal and a thermoplastic composition according to claim 1, wherein the coating material is thermosetting. 3. The composite of a metal and a thermoplastic composition according to claim 1 or 2, wherein the coating material is a coating material containing active hydrogen,
Or a composite of a metal and a thermoplastic composition, which is an ink. 4. The composite of a metal and a thermoplastic composition according to claim 1, wherein the resin composition of the coating material is a polyurethane resin type, an epoxy alkyd resin type, or a modified type. A composite of a metal and a thermoplastic composition, which is one or more selected from alkyd resin systems. 5. A composite of a metal and a thermoplastic composition according to claim 1, wherein the coating material is a lower layer composed of a metal-philic paint or ink, and thermosetting. A composite of a metal and a thermoplastic composition, characterized in that it comprises a coating material containing a curable or other curable resin composition, or a plurality of upper layers composed of ink. 6. A composite of a metal and a thermoplastic composition according to claim 1, wherein the composite of the metal and the thermoplastic composition is coated with the coating material. Metal and thermoplastic composition characterized by being formed by inserting a metal shape into an injection mold and injecting the thermoplastic resin composition containing the thermoplastic polyester elastomer as a main component. Complex. 7. A composite of a metal and a thermoplastic composition according to claim 1, which is selected from any one of claims 1 to 5, wherein the metal shape includes a through hole which is a hole penetrating the metal shape. A composite of a metal and a thermoplastic composition, wherein the through hole is filled with a thermoplastic resin composition containing the thermoplastic polyester elastomer as a main component. 8. A method for producing a composite of a metal and a thermoplastic composition containing a metal shape, wherein the surface of the metal shape is coated with a thermosetting or other curable resin composition. A curing step of applying and curing a material, an insertion step of inserting the coating-treated product of the cured metal shape into an injection molding die,
And an injection step of injecting a thermoplastic resin composition containing a thermoplastic polyester elastomer as a main component, and a method for producing a composite of a metal and a thermoplastic composition. 9. A method for producing a composite of a metal and a thermoplastic composition containing a metal shape, wherein the surface of the metal container includes a thermosetting or other curable resin composition. A curing step of applying and curing a coating material, and fixing the coating-treated product of the cured metal shape and a thermoplastic resin composition containing a thermoplastic polyester elastomer as a main component under high temperature and pressure. A method for producing a composite of a metal and a thermoplastic composition, comprising the steps of: