WO2020218277A1 - 電子機器筐体、その製造方法および金属樹脂複合体 - Google Patents
電子機器筐体、その製造方法および金属樹脂複合体 Download PDFInfo
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- WO2020218277A1 WO2020218277A1 PCT/JP2020/017156 JP2020017156W WO2020218277A1 WO 2020218277 A1 WO2020218277 A1 WO 2020218277A1 JP 2020017156 W JP2020017156 W JP 2020017156W WO 2020218277 A1 WO2020218277 A1 WO 2020218277A1
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- WIPO (PCT)
- Prior art keywords
- electronic device
- device housing
- metal member
- dissimilar material
- antenna cover
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3456—Antennas, e.g. radomes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3481—Housings or casings incorporating or embedding electric or electronic elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
Definitions
- the present invention relates to an electronic device housing, a manufacturing method thereof, and a metal resin composite.
- the shape of the antenna element is not a shape protruding from the notebook PC body but is built in the housing body from the viewpoint of portability and prevention of damage when dropped. ..
- light metals such as magnesium alloys and aluminum alloys, which are frequently used as housing materials, have a property of inhibiting the transmission of radio waves. Therefore, when a metal housing is used as the housing of an electronic device equipped with a built-in antenna, for example, an opening is formed at a position corresponding to the antenna element of the housing, and this opening is used as a plastic antenna cover.
- the structure is such that the plastic portion and the metal member are tightly connected with each other (for such a structure, refer to, for example, Patent Documents 1 and 2).
- a method of binding mechanical engagement by rivets or the like can be considered.
- a gap may be generated in the engaging portion, or the engaging portion may loosen due to long-term use, which may adversely affect the strength of the entire electronic device.
- insert molding As a method different from mechanical engagement, a method of joining and integrating a metal housing and a plastic antenna cover by insert molding can be considered. It is considered that insert molding can solve the above-mentioned problem in mechanical engagement. Further, insert molding is a method having excellent productivity, and further, the strength of the obtained joint portion and the watertightness of the joint interface are excellent.
- the plastic material is deformed or deteriorated in the annealing step for removing the residual stress generated by the high temperature treatment applied to the metal member side during insert molding.
- the joint strength is lowered.
- the use of lightweight magnesium alloys as metal members has been increasing for the purpose of weight reduction.
- the above problem becomes more remarkable because a relatively high temperature is required for sufficient annealing of the magnesium alloy.
- the present invention has been made to solve the above problems.
- One of the objects of the present invention is to provide an electronic device housing in which a metal member and a plastic antenna cover are joined and integrated, which has sufficient heat resistance against annealing after insert molding.
- the present invention is as follows.
- the plastic antenna cover is an electronic device housing which is a molded body of a thermoplastic resin composition containing a thermoplastic polyester resin having a melting point Tm of 250 ° C. or higher.
- the electronic device housing described in An electronic device housing in which the thermoplastic polyester resin contains a structural unit derived from an aromatic dicarboxylic acid-based monomer and a structural unit derived from a diol having an alicyclic skeleton. 4. 3. 3. 3.
- the thermoplastic resin composition is an electronic device housing containing 40 to 80% by mass of the thermoplastic polyester resin (P). 6. 1. 1. ⁇ 5. The electronic device housing according to any one of the above.
- the thermoplastic resin composition is an electronic device housing containing a polymer component (Q) other than the thermoplastic polyester resin (P). 7. 6.
- the electronic device housing described in The thermoplastic resin composition is an electronic device housing containing 1 to 20% by mass of the other polymer component (Q). 8. 6. Or 7.
- the electronic device housing described in The other polymer component (Q) is an electronic device housing containing a copolymer (D) having a structural unit derived from an olefin and a structural unit having a cyclic oxyhydrocarbon structure. 9. 8. The electronic device housing described in The other polymer component (Q) further comprises an ethylene / ⁇ -olefin copolymer (E1), polybutylene terephthalate (E2), polycarbonate (E3) and isophthalic acid-modified polycyclohexylene methylene terephthalate (E4). An electronic device housing containing one or more polymers (E) selected from the group. 10. 9.
- the electronic device housing described in The mass ratio of the copolymer (D) to the polybutylene terephthalate (E2), the polycarbonate (E3) and the isophthalic acid-modified polycyclohexylene methylene terephthalate (E4) is 1: 1 to 1:10.
- An electronic device housing in which the metal member is a kind selected from the group consisting of magnesium or magnesium alloy, aluminum or aluminum alloy, titanium or titanium alloy, and copper or copper alloy. 13. 1. 1. ⁇ 12.
- the electronic device housing according to any one of the above.
- a manufacturing method for manufacturing an electronic device housing in which the following steps 1 to 5 are carried out in this order.
- Step 1) A step of preparing a metal member.
- Step 2) The metal member and a thermoplastic resin composition containing a thermoplastic polyester resin having a melting point Tm of 250 ° C. or higher are joined and integrated by insert molding, and the metal member and the plastic antenna cover are joined together.
- the process of manufacturing a body (Step 3) A step of annealing the dissimilar material joint at 180 to 350 ° C.
- Step 4 The surface of at least the portion of the metal member of the heat-treated dissimilar material joint to which the plastic antenna cover is not bonded is oxidized by at least one method selected from the group consisting of anodization, microarc oxidation and chemical conversion treatment.
- Step 5 A step of forming a coating film layer in a region of the surface-modified dissimilar material joint including at least a joint portion between a metal member and a plastic antenna cover.
- the resin member is a metal resin composite which is a molded product of a thermoplastic resin composition containing a thermoplastic polyester resin having a melting point Tm of 250 ° C. or higher.
- an electronic device housing in which a metal member and a plastic antenna cover are joined and integrated, which has sufficient heat resistance against annealing after insert molding.
- FIG. 5 is a diagram schematically showing a structure that can be seen when viewed from the S direction by enlarging the portion surrounded by the circle ⁇ in FIG. It is a figure for demonstrating "dissimilar material joint A" in an Example. It is a figure for demonstrating "the dissimilar material joint B" in an Example.
- FIG. 1 is an external view of a notebook PC (notebook PC1) which is an example of an electronic device.
- the notebook PC 1 is composed of a main body unit (palm rest portion) 1a and a display unit 1b.
- the main body unit 1a houses main components such as a printed wiring board on which a CPU is mounted and a hard disk drive device in a flat box-shaped housing.
- the display unit 1b is usually connected to the main body unit 1a via a hinge mechanism.
- a liquid crystal display panel and the like are housed in the flat box-shaped housing of the display unit 1b.
- the metal member 4 and the plastic antenna cover 2 are joined and integrated by insert molding at the broken line portion (shown in FIG. 1). That is, it can be said that the display unit 1b is a dissimilar joint body of a metal member and a plastic antenna cover.
- FIG. 2 is a diagram schematically showing a display unit 1b cut along the X-ray line of FIG.
- FIG. 3 is a diagram schematically showing a structure that can be seen when viewed from the S direction by enlarging the portion surrounded by the circle ⁇ in FIG. It can be said that FIG. 3 is an enlarged view of a part of the cross section when the display unit 1b is cut along the X-ray line of FIG.
- the plastic antenna cover 2 is a molded product of a thermoplastic resin composition containing a thermoplastic polyester resin (P) having a melting point Tm of 250 ° C. or higher. As a result, it has sufficient heat resistance against annealing after insert molding. That is, deformation and deterioration of the plastic antenna cover 2 can be suppressed. This is particularly effective when the metal member 4 is a magnesium alloy that requires annealing at a relatively high temperature.
- the plastic antenna cover 2 is a molded body of a thermoplastic resin composition containing a thermoplastic polyester resin (P) having a melting point Tm of 250 ° C. or higher, the metal member 4 and the plastic antenna cover 2 are joined.
- P thermoplastic polyester resin
- Tm melting point
- the coating layer 5 is provided on the surface of the dissimilar material joint, no step is generated or the step is extremely small in the joint 7 and its vicinity (indicated as a point P in FIG. 3).
- the merit of being able to do it removes deformation that occurs mainly on the metal member side, which occurs when a metal member and a plastic antenna cover are joined and integrated to manufacture a dissimilar material joint by insert molding using an appropriate mold.
- the dissimilar material joint is high-temperature annealing (annealed)
- the amount of deformation of the plastic can be reduced, and it is easy to avoid the phenomenon that a gap is generated in the joint portion 7 (the plastic antenna cover is used.
- the plastic antenna cover is used.
- it is a heat-resistant plastic containing a thermoplastic polyester resin having a Tm of 250 ° C. or higher).
- the coating film layer 5 is formed on the surface of the dissimilar material joint, the occurrence of a step can be suppressed, and an electronic device housing having excellent design is provided.
- the dissimilar material joint in which the metal member 4 and the plastic antenna cover 2 are joined is first oxidized with a chemical solution or the like to modify the surface, and then the surface of the dissimilar material joint is coated. Even when the layer 5 is provided, it is possible to suppress a step at the joining interface (joining portion 7) and its vicinity. If the joining at the joining interface (joining portion 7) is insufficient, the chemical solution may invade the joining portion 7 during surface modification and the joining portion 7 may be partially destroyed. Further, when the plastic antenna cover 2 is deformed by the annealing, a gap is formed in the joint portion 7, and the chemical liquid easily invades through the joint portion 7.
- a step (depression) tends to occur in the vicinity of the point P of the coating film layer 5.
- the joining force at the joining portion 7 can be sufficiently strengthened, and the deformation / deterioration of the plastic antenna cover 2 due to annealing is suppressed, so that the intrusion of the chemical solution is suppressed.
- a step (depression) is unlikely to occur near the point P of the coating film layer 5.
- the L-shaped plastic antenna cover 2 and the metal member 4 are connected by a notched structure.
- this structure is not particularly limited. Joint structures such as butt joints, diagonal joints, lost joints, actual joints, and phase joints are arbitrarily adopted.
- the surface modification film can be formed by, for example, an oxidation treatment method such as anodization, microarc oxidation, or chemical conversion treatment, which will be described later.
- the surface modification film is, for example, an oxide film.
- the antenna element 3 is arranged in the plastic antenna cover 2. Although only one antenna element 3 is drawn in FIGS. 1 and 2 for convenience, in an actual notebook PC, a plurality of antenna elements 3 may be arranged on the peripheral edge of the display unit 1b.
- the metal member 4 which is a constituent member of the electronic device housing of the present embodiment, the thermoplastic resin composition constituting the plastic antenna cover 2, the coating film layer 5, and the like will be sequentially described.
- Metal member As the metal member 4, a metal that can be bonded to the thermoplastic resin composition by insert molding and that exhibits desired performance as an electronic device housing can be used without limitation.
- the material of the metal member 4 include aluminum, iron, copper, magnesium, tin, nickel, zinc, and alloys thereof. Of these, magnesium or magnesium alloys, aluminum or aluminum alloys, titanium or titanium alloys, copper or copper alloys are preferable, and magnesium or magnesium alloys are more preferable, from the viewpoint of contributing to weight reduction of the metal member 4 and the electronic device housing. ..
- magnesium-based alloys include alloys of magnesium with elements such as aluminum, manganese, silicon, zinc, zirconium, copper, lithium, thorium, silver and yttrium.
- the shape of the metal member 4 is not particularly limited.
- the shape can be arbitrarily determined according to the type and application of the electronic device housing.
- the shape includes a flat shape, a curved plate shape, a rod shape, a tubular shape, an indefinite shape, and the like.
- the contact portion with the thermoplastic resin composition (hereinafter, also simply referred to as “contact portion”) is preferably flat.
- the metal member 4 having a desired form can be manufactured by a known metal processing method, for example, a thinning process including plastic working by pressing, punching, cutting, polishing, electric discharge machining, and the like.
- At least the joint portion 7 of the surface of the metal member 4 with the plastic antenna cover 2 may be surface-treated by any method. From the viewpoint of further increasing the joint strength between the metal member 4 and the thermoplastic resin composition, it is preferable that the joint portion 7 of the metal member 4 with the plastic antenna cover 2 is roughened. Specifically, the joint portion 7 of the metal member 4 with the plastic antenna cover 2 preferably has a fine concavo-convex structure in which convex portions having a spacing period of 5 nm to 500 ⁇ m are forested.
- the "interval period" is an average value of the distances from the convex portion existing on the fine uneven surface to the adjacent convex portion, and can be obtained from, for example, a photograph taken with an electron microscope or a laser microscope. Specifically, 50 convex portions are arbitrarily selected from the photographs obtained by photographing the contact portion of the metal member 4 with an electron microscope or a laser microscope, and the distances of these convex portions to the adjacent convex portions. Are measured respectively. Then, the value obtained by calculating the added average of the distances to the adjacent convex portions for the 50 convex portions is defined as the interval period.
- the interval period can be said to be a value corresponding to the average length RSm of the roughness curve elements defined in JIS B 0601.
- the interval period is preferably 10 nm to 300 ⁇ m, more preferably 20 nm to 200 ⁇ m.
- the thermoplastic resin composition can sufficiently penetrate into the recesses on the surface of the fine concavo-convex surface, and the bonding strength between the metal member and the thermoplastic resin composition can be further improved.
- the interval period is 300 ⁇ m or less, the generation of a gap at the interface between the metal and the resin of the obtained dissimilar material joint can be suppressed. Therefore, it is possible to efficiently prevent impurities such as water from entering the gap. This leads to suppression of a decrease in strength when, for example, a dissimilar material joint is used under high temperature and high humidity.
- the average hole depth of the recesses in the fine concavo-convex structure is preferably 5 nm to 250 ⁇ m.
- a ten-point average roughness Rz jis measured according to JIS B 0601 can be adopted.
- the chemical roughening method includes (i) immersion in an aqueous solution of an inorganic base such as caustic soda or an aqueous solution of an inorganic acid such as hydrochloric acid or nitrate, (ii) immersion in an aqueous solution of an organic acid such as citric acid or malonic acid, and (iii).
- the roughening method may be appropriately selected or used in combination depending on the type of metal to be roughened, the joining strength required for the dissimilar material joint, and the like.
- the surface of the metal member 4 may be further subjected to chemical conversion treatment for the purpose of preventing corrosion after being roughened by the above method.
- chemical conversion treatment when the metal member 4 is a magnesium or magnesium alloy member, it is preferable to perform a chemical conversion treatment in view of the fact that it is easily naturally oxidized by moisture and oxygen in the air.
- the chemical conversion treatment include chromate treatment using an aqueous solution of chromic acid or potassium dichromate, and chemical conversion treatment using an aqueous solution of a manganese phosphate compound or a weakly acidic aqueous solution of potassium permanganate.
- the metal member 4 may be surface decolorized by further treating it with a water-soluble reducing agent such as hydroxylamine sulfate in addition to the above chemical conversion treatment.
- a water-soluble reducing agent such as hydroxylamine sulfate
- thermoplastic resin composition contains a thermoplastic polyester resin (P) as a resin component.
- the thermoplastic resin composition further contains one or more of other polymer components (Q), additives (R), fillers (F) and the like.
- the melting point Tm of the thermoplastic polyester resin (P) is 250 ° C. or higher.
- the melting point Tm is preferably 270 ° C. or higher, more preferably 280 ° C. or higher.
- the upper limit of the melting point Tm is not particularly limited, but is, for example, 350 ° C., preferably 335 ° C. from the viewpoint of lowering the heating temperature during insert molding to save energy cost.
- the melting point Tm is 250 ° C. or higher, discoloration or deformation of the molded product of the resin composition due to contact with the molten metal member is suppressed.
- the melting point is 350 ° C. or lower, decomposition of the thermoplastic polyester resin (A) is suppressed upon contact with the molten metal member, which is preferable.
- the melting point Tm of the thermoplastic polyester resin (P) is preferably in the range of 250 to 350 ° C., more preferably in the range of 270 to 350 ° C., and in the range of 290 to 335 ° C. Is even more preferable.
- the melting point Tm of the thermoplastic polyester resin (P) can be measured by a differential scanning calorimetry (DSC) according to JIS K 7121. Specifically, about 5 mg of the resin is sealed in a measuring aluminum pan and heated from room temperature to 340 ° C. at 10 ° C./min using DSC7 manufactured by Perkin Elemer. To completely melt the resin, hold at 340 ° C. for 5 minutes and then cool to 30 ° C. at 10 ° C./min. After standing at 30 ° C. for 5 minutes, the second heating is performed at 10 ° C./min to 340 ° C. The peak temperature (° C.) in this second heating is defined as the melting point Tm of the resin.
- DSC differential scanning calorimetry
- the crystallinity determined by the wide-angle X-ray diffraction profile is 50% or less, preferably 47% or less, more preferably 45% or less. There is no particular lower limit (may be 0%), but in reality it is 10% or more, preferably 20% or more.
- the crystallinity is calculated from the ratio of the peak area derived from the crystalline structure to the total diffraction peak area. For example, it can be calculated from the peak area ratio derived from the crystalline structure when measured with a Cu radiation source using a wide-angle X-ray diffractometer (RINT2100: Rigaku). When the melting point Tm is 250 ° C.
- the plastic antenna cover 2 and the metal member 4 are more firmly bonded to each other.
- the dimensional accuracy is further improved, and it is easy to obtain an appearance having excellent design, in which no step is observed near the joint interface between the two even after the top coat is applied.
- thermoplastic polyester resin (P) contains a structural unit (a1) derived from an aromatic dicarboxylic acid and a structural unit (a2) derived from a diol having an alicyclic skeleton. Is preferable.
- the structural unit (a1) preferably contains at least a structural unit derived from a terephthalic acid-based monomer.
- the amount of the structural unit derived from the terephthalic acid-based monomer is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 60 to 100 mol%, based on the total structural unit (a1). is there.
- the structural unit (a1) may include a structural unit derived from an aromatic dicarboxylic acid-based monomer other than terephthalic acid.
- the amount of this structural unit is, for example, 0 to 70 mol%, preferably 0 to 60 mol%, and more preferably 0 to 40 mol% with respect to the entire structural unit (a1).
- terephthalic acid-based monomer examples include terephthalic acid and terephthalic acid ester.
- terephthalic acid esters include dimethyl terephthalate and the like.
- aromatic dicarboxylic acid-based monomer other than the terephthalic acid-based monomer examples include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and esters of these aromatic dicarboxylic acids (preferably having 1 to 4 carbon atoms of the aromatic dicarboxylic acid). Alkyl ester) and the like.
- the total amount of the structural unit derived from the terephthalic acid-based monomer and the structural unit derived from the aromatic dicarboxylic acid-based monomer other than terephthalic acid is 100 in the structural unit derived from the dicarboxylic acid in the thermoplastic polyester resin (P). It is preferably mol%.
- the thermoplastic polyester resin (P) is derived from a small amount of a structural unit derived from an aliphatic dicarboxylic acid or a polyvalent carboxylic acid having 3 or more carboxylic acid groups in the molecule. It may further include structural units. The amount of these structural units is, for example, 10 mol% or less, preferably 5 mol% or less, in the total structural units of the thermoplastic polyester resin (P).
- the number of carbon atoms of the aliphatic dicarboxylic acid is not particularly limited. It is preferably 4 to 20, more preferably 6 to 12.
- Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, decandicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and the like. Of these aliphatic dicarboxylic acids, adipic acid is preferable.
- the polyvalent carboxylic acid include tribasic acids such as trimellitic acid and pyromellitic acid and polybasic acids.
- the structural unit (a2) derived from the diol having an alicyclic skeleton is a structural unit derived from an alicyclic diol having 4 to 20 carbon atoms. It is preferable to have.
- the structural unit (a2) can increase the heat resistance of the thermoplastic resin composition and reduce the water absorption.
- alicyclic diols are dialcohols having an alicyclic hydrocarbon skeleton with 4 to 20 carbon atoms, such as 1,3-cyclopentanediol, 1,3-cyclopentanedimethanol, and 1,4-cyclohexane. Examples thereof include diols, 1,4-cyclohexanedimethanol, 1,4-cycloheptanediol, and 1,4-cycloheptanedimethanol.
- the alicyclic diol is preferably a compound having a cyclohexane skeleton from the viewpoints of further enhancing the heat resistance of the thermoplastic resin composition, further reducing the water absorption, and being easily available. More preferably, it is 1,4-cyclohexanedimethanol.
- Alicyclic diols have isomers such as cis / trans structures.
- the thermoplastic polyester resin (P) preferably contains a larger amount of structural units derived from the alicyclic dialcohol having a transformer structure.
- the cis / trans ratio of the structural unit derived from the alicyclic diol is preferably 50/50 to 0/100, more preferably 40/60 to 0/100.
- the thermoplastic polyester resin (P) may contain a structural unit derived from an aliphatic diol. Thereby, the melt fluidity of the thermoplastic resin composition can be further enhanced.
- the aliphatic diol include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol and the like.
- the thermoplastic polyester resin (P) has only one of a structural unit (a2) derived from a diol having an alicyclic skeleton and a structural unit derived from an aliphatic diol as a structural unit derived from a diol. It may have both.
- the structural unit derived from the diol is a structural unit (a2) derived from a diol having an alicyclic skeleton (preferably a component unit derived from a diol having a cyclohexane skeleton, and more preferably a component unit derived from cyclohexanedimethanol.
- a component unit derived from an aliphatic diol is contained in an amount of 0 to 70 mol%.
- the proportion of the structural unit (a2) derived from the diol having an alicyclic skeleton is more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%.
- the proportion of structural units derived from the aliphatic diol is more preferably 0 to 50 mol%, still more preferably 0 to 40 mol%.
- the total amount of the structural unit (a2) derived from the diol having an alicyclic skeleton and the structural unit derived from the aliphatic diol is 100 mol% of the diol-derived structural unit in the thermoplastic polyester resin (P). Is preferable. However, depending on the desired properties, the thermoplastic polyester resin (P) may further contain a small amount of structural units derived from aromatic diols. Examples of aromatic diols include bisphenol A, hydroquinone, 2,2-bis (4- ⁇ -hydroxyethoxyphenyl) propane, and EO adducts of bisphenol A.
- the proportion of the structural unit derived from the aromatic diol can be, for example, 10 mol% or less, preferably 5 mol% or less, in the total structural unit of the thermoplastic polyester resin (P).
- the intrinsic viscosity [ ⁇ ] of the thermoplastic polyester resin (P) is preferably 0.3 to 1.5 dl / g. When the intrinsic viscosity is in the above range, the fluidity of the thermoplastic resin composition during molding is further increased.
- the intrinsic viscosity [ ⁇ ] of the thermoplastic polyester resin (P) can be adjusted within the above range by adjusting the molecular weight of the thermoplastic polyester resin (P). For details of the method for measuring the intrinsic viscosity [ ⁇ ], refer to the examples below.
- thermoplastic resin composition may contain a polymer component (Q) other than the thermoplastic polyester resin (P).
- the bonding strength between the metal member and the resin composition after the annealing treatment after bonding is particularly unlikely to decrease, and / Alternatively, the bonding strength is higher than that before the annealing treatment.
- the other polymer component (Q) is preferably a copolymer having a structural unit derived from olefin and a structural unit having a cyclic oxyhydrogen structure (hereinafter, also referred to as “copolymer (D)”), and One or more polymers (E) selected from the group consisting of ethylene / ⁇ -olefin copolymer (E1), polybutylene terephthalate (E2), polycarbonate (E3) and isophthalic acid-modified polycyclohexylene methylene terephthalate (E4).
- E1 ethylene / ⁇ -olefin copolymer
- E2 polybutylene terephthalate
- E3 polycarbonate
- isophthalic acid-modified polycyclohexylene methylene terephthalate (E4) is also one or more selected from the group consisting of "polymer (E)”).
- the crystallinity When the crystallinity is low, the solidification rate of the resin is slow, so that it is considered that the molten resin easily penetrates deep into the metal due to the uneven structure of the metal, and the bonding strength becomes higher. As a result, it is considered that the invasion of the chemical solution at the time of surface modification is suppressed and the decrease in the bonding strength is suppressed.
- the copolymer (D) has a structural unit derived from an olefin and a structural unit having a cyclic oxyhydrocarbon structure.
- the copolymer (D) may further have a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester.
- Examples of structural units derived from olefins constituting the copolymer (D) include structural units derived from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene and the like. Of these, structural units derived from ethylene are preferred.
- Examples of the structural unit having a cyclic oxyhydrocarbon structure constituting the copolymer (D) include a structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester.
- Examples of ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.
- methacrylic acid glycidyl ester is preferable.
- structural units derived from ⁇ , ⁇ -unsaturated carboxylic acid ester constituting the copolymer (D) include methyl acrylate, acrylate ester containing ethyl acrylate, butyl acrylate and the like, and methyl methacrylate.
- the structural unit derived from the ⁇ , ⁇ -unsaturated carboxylic chain ester may have a cyclic oxyhydrocarbon structure such as a glycidyl ester group.
- the copolymer (D) may be a copolymer containing a structural unit derived from an olefin and a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid glycidyl ester.
- the copolymer (D) is a copolymer containing an ethylene unit, a methyl acrylate unit and a structural unit derived from glycidyl methacrylate, and is, for example, ethylene / methyl acrylate / glycidyl methacrylate represented by the following structural formula. Copolymers can be mentioned.
- n, m and l each independently represent a positive integer.
- the copolymer (D) represented by the above structural formula contains 30 to 99 masses of ethylene-derived constituent units with respect to the total amount (100% by mass) of ethylene units, methyl acrylate units, and glycidyl methacrylate-derived constituent units. It is preferably contained in a proportion of%, more preferably 50 to 95% by mass.
- the copolymer (E1) is preferably an ethylene-based copolymer of ethylene and at least one type of ⁇ -olefin having 3 to 20 carbon atoms.
- “Mainly ethylene” means, for example, that the structural unit derived from ethylene is 50 mol% or more, preferably 60 mol% or more, among all the structural units.
- the copolymer (E1) has a function of suppressing variation in bonding strength between the metal member and the resin composition when the thermoplastic resin composition is bonded to the metal member.
- ⁇ -olefins having 3 to 20 carbon atoms examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and the like. Be done. Of these, propylene, 1-butene, 1-hexene and 1-octene are preferable. These ⁇ -olefins may be used alone or in combination of two or more.
- the ratio of the structural unit derived from the ⁇ -olefin having 3 to 20 carbon atoms is preferably 5 to 30 mol%, more preferably 8 to 30 mol%, still more preferably 10 to 25 mol%. %.
- the copolymer (E1) may be a random copolymer of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, or a block copolymer. A random copolymer is preferable.
- the density of the copolymer (E1) is preferably 0.85 to 0.95 g / cm 3 , and more preferably 0.87 to 0.93 g / cm 3 .
- the melt flow rate (MFR) of the copolymer (E1) measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K 7210: 1999 shall be 0.5 to 100 g / 10 minutes. Is preferable, and 1 to 80 g / 10 minutes is more preferable. When the melt flow rate of the copolymer (E1) is in this range, the fluidity of the thermoplastic resin composition during molding tends to increase.
- the polybutylene terephthalate (E2) that can be used is not particularly limited.
- a polymer containing a structural unit derived from dimethyl terephthalate or high-purity terephthalic acid and a structural unit derived from 1,4-butanediol can be used without particular limitation.
- Examples of commercially available products include NOVADURAN manufactured by Mitsubishi Engineering Plastics Co., Ltd., TPS-PBT manufactured by Toray Plastics Precision Co., Ltd., and Juranex 500FP manufactured by Polyplastics Co., Ltd.
- the polycarbonate (E3) that can be used is not particularly limited. Commercially available products include Teijin's Panlite L-1225Y, Idemitsu Kosan's Tafflon, Sumika Polycarbonate's SD Polyca, Chimei's Wonder Light, Teijin's Panlite, Mitsubishi Engineering Plastics' Novarex, and Iupiron. Can be mentioned.
- Isophthalic acid-modified polycyclohexylene methylene terephthalate is a polycyclohexylene methylene terephthalate produced by condensation polymerization of terephthalic acid or a derivative thereof and cyclohexylene methylene diol, and is a raw material monomer terephthalic acid or its derivative. A part (but not all) of the derivative is replaced with isophthalic acid or a derivative thereof.
- the ratio of isophthalic acid or its derivative to the total amount of the raw material dicarboxylic acid or its derivative (the total amount of terephthalic acid or its derivative and isophthalic acid or its derivative) is usually less than 50 mol%.
- Examples of commercially available products of isophthalic acid-modified polycyclohexylene methylene terephthalate (E4) include those manufactured by Eastman Chemical Company, product name: Durastar, and brand: DS2000.
- the mass ratio ((D) :( E)) of the copolymer (D) and the polymer (E) is It is about 1: 0.1 to 1: 0.5.
- the other component (Q) one or more selected from the group consisting of the copolymer (D) and the group consisting of polybutylene terephthalate (E2), polycarbonate (E3) and isophthalic acid-modified polycyclohexylene methylene terephthalate (E4).
- the mass ratio ((D): ⁇ (E2) + (E3) + (E4) ⁇ ) is, for example, 1: 1 to 1. It is 1:10, preferably 1: 2 to 1:10, and more preferably 1: 3 to 1: 8.
- the thermoplastic resin composition may contain the additive (R).
- the additive (R) include antioxidants (phenols, amines, sulfurs, phosphoric acids, etc.) and heat stabilizers (lactone compounds, vitamin Es, hydroquinones, copper halides, iodine compounds, etc.).
- Light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines, ogizanilides, etc.), flame retardants (bromine-based, chlorine-based, phosphorus-based, antimony-based, inorganic-based, etc.), lubricants, fluorescent increase
- Known additives such as whitening agents, plasticizing agents, thickeners, antistatic agents, mold release agents, pigments, crystal nucleating agents, foaming agents, and foaming aids can be mentioned.
- the thermoplastic resin composition may further contain a filler (F) from the viewpoint of adjusting the difference in linear expansion coefficient between the metal member 4 and the plastic antenna cover 2 and improving the mechanical strength of the antenna cover 2 itself.
- a filler (F) for example, one or more kinds can be selected from the group consisting of glass fiber, carbon fiber, carbon particle, clay, talc, silica, mineral and cellulose fiber. Of these, one or more selected from glass fiber, carbon fiber, talc, and minerals are preferable.
- the amount of each component can be set as follows with respect to the whole (100% by mass) of the thermoplastic resin composition.
- Thermoplastic polyester resin (P) 40 to 80% by mass, preferably 50 to 70% by mass, more preferably 55 to 65% by mass.
- -Other polymer components (Q) 1 to 20% by mass, preferably 2 to 15% by mass, more preferably 5 to 15% by mass.
- -Additive (R) 0.1 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass.
- Filler (F) 5 to 50% by mass, preferably 10 to 50% by mass, more preferably 20 to 40% by mass.
- the dimensional accuracy can be further improved. Further, it is possible to sufficiently suppress the generation of a gap at the joint interface between the plastic antenna cover 2 and the metal member 4, and when the coating layer 5 is provided on the gap, the coating layer 5 is substantially near the joint portion 7. It is easy to obtain a dissimilar material joint with no upper step and excellent design.
- thermoplastic resin composition may be a mixture of particles of each of the above components, a pre-kneaded one, or the like. Further, each component may be mixed and put into the hopper of the apparatus at the time of insert molding (injection molding).
- the thermoplastic resin composition may contain, for example, a thermoplastic polyester resin having a melting point Tm of 50 ° C. or higher and lower than 250 ° C., an amorphous resin, or the like.
- a typical example of the former is polybutylene terephthalate, and a typical example of the latter is polycarbonate.
- the amount thereof is usually about half or less than that of the thermoplastic polyester resin (P).
- the coating film layer 5 is continuously formed on a part or all of the surface including the joint portion between the metal member 4 and the plastic antenna cover 2. More preferably, the coating film layer 5 is continuously formed on the entire outer surface side including the joint portion.
- the coating film layer 5 usually has a function of protecting and decorating (improving the design) of the electronic device housing. As described above, there is no engagement step (trace) on the outer surface (near the point P in FIG. 3) of the joint portion 7 between the metal member 4 and the plastic antenna cover 2 and its vicinity, or it. Can be made extremely small. Therefore, the step is suppressed even on the surface of the coating film layer 5.
- the coating film layer 5 formed at the joint portion 7 between the metal member 4 and the plastic antenna cover 2 no step is observed in the coating film layer 5 formed at the joint portion 7 between the metal member 4 and the plastic antenna cover 2, and therefore the design is excellent.
- the average thickness of the coating film layer 5 is, for example, 10 to 500 ⁇ m, preferably 20 to 300 ⁇ m.
- the main components constituting the coating film layer 5 are, for example, a film-forming substance, a pigment, an additive and the like.
- the film-forming substance include known resins.
- the film-forming substance include known resins.
- the pigment include carbon black and titanium white.
- the additive include a plasticizer, a flame retardant, a lubricant, a stabilizer, and a foaming agent.
- metal fine particles such as aluminum powder and silver powder.
- the electronic device housing of the present embodiment is preferably manufactured by carrying out the following steps 1 to 5 in this order.
- Step 1 A step of preparing the metal member 4.
- Step 2 The metal member 4 and the thermoplastic resin composition containing the thermoplastic polyester resin having a melting point Tm of 250 ° C. or higher are joined and integrated by insert molding, and the metal member and the plastic antenna cover are joined together. The process of manufacturing a body.
- Step 3 A step of annealing the dissimilar material joint at 180 to 350 ° C. for 1 to 30 minutes to convert it into a heat-treated dissimilar material joint.
- Step 4 The surface of at least the portion of the metal member of the heat-treated dissimilar material joint to which the plastic antenna cover is not bonded is oxidized by at least one method selected from the group consisting of anodization, microarc oxidation and chemical conversion treatment.
- Step 5 A step of forming a coating film layer 5 in a region of the surface-modified dissimilar material joint including at least a joint portion between a metal member and a plastic antenna cover.
- Step 1 is a step of preparing the metal member 4.
- at least the joint portion 7 of the surface of the metal member 4 with the plastic antenna cover 2 may be surface-treated. From the viewpoint of further increasing the bonding strength between the metal member 4 and the thermoplastic resin composition, it is preferable that at least the bonding portion 7 of the metal member 4 is roughened.
- step 2 the metal member 4 and the thermoplastic resin composition containing the thermoplastic polyester resin (P) having a Tm of 250 ° C. or higher are joined and integrated by insert molding to form a dissimilar material joint between the metal member and the plastic.
- "Insert molding” is a type of injection molding. Specifically, a metal member is inserted into a mold in advance, and a molten resin is injection-molded into the mold to integrate the metal member and the resin. It is a molding technology that is transformed into.
- the metal member 4 is installed in a mold for injection molding.
- the melt of the thermoplastic resin composition containing the thermoplastic polyester resin (P) is injection-molded into a mold through an injection molding machine. By cooling the melt of the thermoplastic resin composition bonded to the metal member 4, the metal member 4 and the plastic antenna cover 2 are integrated into a dissimilar material joint.
- thermoplastic resin composition is injection-molded so as to be in contact with the fine concavo-convex structure.
- the inner surface temperature of the mold during injection and holding pressure is preferably equal to or higher than the glass transition temperature of the thermoplastic resin composition, and more preferably 5 to 100 ° C. higher than the glass transition temperature.
- the melt of the thermoplastic resin composition is injected into a mold in which the roughened metal member 4 is arranged at a cylinder temperature of 280 to 350 ° C. and an injection speed of 10 to 30 mm / sec.
- the holding pressure can be 70 to 120 MPa, and the holding time can be 10 to 30 seconds. After that, by opening the mold and releasing the mold, a dissimilar material joint can be obtained.
- known injection foam molding or high-speed heat cycle molding that rapidly heats and cools the mold may be used in combination with insert molding (injection molding).
- Step 3 is a step of annealing the dissimilar material joint obtained in step 2 at 180 to 350 ° C. for 1 to 30 minutes to convert it into a heat-treated dissimilar material joint.
- Annealing is also known as aging hardening treatment, stress relief annealing treatment, and the like. Annealing is usually performed to remove residual stress caused by heating operations such as forging, casting, cold working, welding, machining, injection molding, etc., and to correct deformation caused by dimensional change.
- the annealing temperature varies depending on the metal type constituting the metal member 4, the resin type constituting the plastic antenna cover 2, and the like, but is usually 180 to 350 ° C., preferably 190 to 330 ° C., more preferably 200 to 300 ° C. Particularly preferably, it is 200 to 280 ° C.
- the annealing time is usually 1 to 30 minutes, preferably 5 to 20 minutes.
- Annealing is performed, for example, by heating a dissimilar material joint on a temperature-controlled hot plate under normal pressure or pressure. After that, if necessary, heating is stopped in a pressurized state, and in some cases, the shape of the dissimilar material joint is physically restrained, and a slow cooling operation is performed.
- step 4 the surface of the metal member of the heat-treated dissimilar material joint obtained in step 3 to which at least the plastic is not bonded is subjected to a group consisting of anodizing, micro-arc oxidation (MAO oxidation) and chemical conversion treatment. It is a step of obtaining a surface-modified dissimilar material joint by oxidation treatment by at least one selected method. By performing this step, the stability of the surface of the metal member 4 in air can be improved, which is preferable. Further, in this treatment, fine uneven holes on the order of nm are formed on the surface of the metal member, which also contributes to improving the adhesion to the coating film layer formed in the subsequent step 5.
- a known method can be used without limitation for the anodizing treatment.
- MAO oxidation is usually carried out by applying a high voltage in an alkaline electrolytic solution in which an alkali metal salt of phosphoric acid or pyrophosphoric acid is dissolved.
- the chemical conversion treatment is a chromate treatment in which the entire surface is covered with a thin layer of acid-valent chromium by immersing in chromium or potassium permanganate, or a thin layer of a manganese phosphate-based compound by immersing in an aqueous solution of a manganese salt containing phosphoric acid. Examples of the treatment method of covering the entire surface with a thin layer of manganese dioxide by immersing in an aqueous solution of potassium permanganate as weakly acidic can be exemplified.
- These oxidation treatments may be a selective treatment of only the metal portion to which the plastic is not bonded, or may be a treatment of the entire dissimilar material bonded body. From the viewpoint of increasing the treatment speed, it is usually carried out in a state where the entire dissimilar material joint is immersed in the treatment solution.
- Step 5 is a step of forming the coating film layer 5 in the region of the surface-modified dissimilar material joint including at least the joint portion 7 between the metal member 4 and the plastic antenna cover 2.
- the components constituting the coating film layer 5 are as described above.
- a coating material in which the components constituting the coating film layer 5 are dissolved or dispersed in a general-purpose solvent (organic solvent) such as ethanol, acetone, an aliphatic hydrocarbon, or an aromatic hydrocarbon is applied to the surface of the surface-modified dissimilar material bond. Paint on.
- the coating film layer 5 is formed by distilling off volatile components such as a solvent by heating (or by natural drying) as necessary.
- known methods such as brush coating, roller coating, dip coating, and spray coating can be applied without limitation.
- a primer layer as a base layer may be provided.
- the crystallinity of the plastic antenna cover determined by the wide-angle X-ray diffraction profile is preferably 50% or less, preferably 47% or less, more preferably. It is 45% or less. There is no particular lower limit (may be 0%), but in reality it is 10% or more, preferably 20% or more.
- the method for determining the crystallinity is as described above. Therefore, a new description will be omitted.
- the low crystallinity of the plastic antenna cover in the final electronic device housing means that the molten resin easily penetrated to the back due to the uneven structure of the metal at the manufacturing stage of the electronic device housing. It is thought to mean.
- the bonding strength between the metal member and the plastic antenna cover of the electronic device housing having a low crystallinity of the plastic antenna cover is good, and the bonding strength tends to be difficult to decrease.
- the crystallinity of the plastic antenna cover can be adjusted by adjusting the crystallinity of the raw material thermoplastic polyester resin (P) or adjusting the temperature conditions of steps 2 and 3 above. ..
- the electronic device housing of the present embodiment can be used in various fields.
- the field of notebook PCs such as the main body unit and display unit of notebook PCs
- the field of mobile devices such as housings and frame bodies for mobile phones and smartphones
- the field of cameras such as covers and mirror boxes for digital single-lens reflex cameras. Can be done.
- a metal-resin composite in which a magnesium alloy member and a resin member are joined and integrated (the resin member here is a molded product of a thermoplastic resin composition containing a thermoplastic polyester resin having a melting point Tm of 250 ° C. or higher). Is preferably applicable to various fields not limited to electronic device housings.
- the magnesium alloy in the above-mentioned "metal-resin composite in which the magnesium alloy member and the resin member are joined and integrated” is as described in the section ⁇ Electronic device housing>.
- Specific matters concerning the resin member in the above-mentioned "metal-resin composite in which the magnesium alloy member and the resin member are joined and integrated" are as described in (Thermoplastic resin composition) of ⁇ Electronic equipment housing>. Is. Regarding the method of joining and integrating in the above-mentioned "metal resin composite in which a magnesium alloy member and a resin member are joined and integrated", for example, insert molding and annealing described in ⁇ Manufacturing method of electronic device housing>. Etc. can be appropriately applied.
- thermoplastic polyester resin p
- copolymer (D) As the copolymer (D), an epoxy group-containing ethylene methacrylate copolymer (LOTADER GMA AX8900 manufactured by Arkema Co., Ltd. (LOTADER is a registered trademark of the same company) was prepared. Hereinafter, this copolymer may be referred to as a copolymer (d).
- a copolymer (d) As the copolymer (D), an epoxy group-containing ethylene methacrylate copolymer (LOTADER GMA AX8900 manufactured by Arkema Co., Ltd. (LOTADER is a registered trademark of the same company) was prepared.
- this copolymer may be referred to as a copolymer (d).
- the total pressure was maintained at 8.0 kg / cm 2- G by continuously supplying ethylene, and polymerization was carried out at 80 ° C. for 30 minutes. After introducing a small amount of ethanol into the system to terminate the polymerization, unreacted ethylene was purged. A white solid was precipitated by pouring the resulting solution into a large excess of methanol.
- This white solid was recovered by filtration and dried under reduced pressure overnight to obtain a white solid ethylene / 1-butene copolymer.
- the 1-butene content of this ethylene / 1-butene copolymer was 14 mol%, the density was 870 kg / m 3 , and the MFR (JIS K 7210: 1999, 190 ° C., 2160 g load) was 3.6 g / 10 minutes.
- this ethylene / 1-butene copolymer may be referred to as a copolymer (e).
- the intrinsic viscosity [ ⁇ ] and the melting point Tm of each resin were measured by the following methods, respectively.
- the melting point Tm was measured according to the regulations of JIS K 7121. Specifically, about 5 mg of the resin was sealed in an aluminum pan for measurement and heated from room temperature to 340 ° C. at 10 ° C./min using DSC7 manufactured by Perkin Elemer. To completely melt each resin, it was held at 340 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min. After standing at 30 ° C. for 5 minutes, the second heating was performed at 10 ° C./min to 340 ° C. The peak temperature (° C.) in this second heating was defined as the melting point Tm of the resin.
- a magnesium plate (thickness 2 mm) of alloy number AZ31B was cut into a length of 45 mm and a width of 18 mm, or a length of 50 mm and a width of 10 mm (the former is for producing the following dissimilar material joint A). The latter is for producing the following dissimilar material joint B).
- the surface of the cut magnesium plate was roughened by the method described in Experimental Example 1 of International Publication No. 2008/133096.
- the surface roughness of the magnesium plate after roughening was measured using a surface roughness measuring device "Surfcom 1400D" manufactured by Tokyo Seimitsu Co., Ltd. As a result, it was confirmed that the ten-point average roughness Rz was in the range of 2 to 3 ⁇ m, and the average length RSm of the roughness curve elements was in the range of 90 to 110 ⁇ m.
- the joint strength of dissimilar material joints is evaluated by the tensile shear strength. Specifically, a special jig is attached to the tensile tester model 1323 manufactured by Aiko Engineering Co., Ltd., and then the dissimilar material joint A (details will be described later) schematically shown in FIG. 4 is installed. At room temperature (23 ° C.), the metal member and the resin member of the dissimilar material joint A are pulled in opposite directions under the conditions of a distance between chucks of 60 mm and a tensile speed of 10 mm / min. At this time, the load when the metal member 103 and the resin member 105 are broken and separated is obtained.
- the tensile shear strength is measured for five dissimilar material joints A to which the same thermoplastic resin composition is bonded, and the average value thereof is adopted as the joint strength.
- the standard deviation is also calculated in order to grasp the variation of the measured values.
- the "dissimilar material joint A" has a form as schematically shown in FIG. More specifically, the dissimilar material joint A is described in the above 2.
- a resin member 105 is bonded to one end (hatched portion in FIG. 4: the size of the shaded portion is 5 mm ⁇ 10 mm) of the magnesium alloy member (indicated by reference numeral 103 in FIG. 4) prepared in.
- FIG. 5 schematically shows the suitability for topcoating of the coating film layer, that is, as a dissimilar material bonding body for visually evaluating whether or not a step is observed at the bonding site when the coating film layer is formed on the surface of the dissimilar material bonding body.
- the dissimilar material joint B is formed by joining the metal member 103 (made of magnesium alloy) and the resin member 105 so as to be butted against each other (the joint portion is 2 mm ⁇ 10 mm).
- the surface modification (oxidation treatment) of the metal member 103 and the formation of the coating film are carried out as described in (1) and (2) below.
- Kurimoto Technical Report No. 1 was applied to the entire surface of the dissimilar material joint B.
- Micro-arc oxidation (MAO) is applied in accordance with the description on pages 64, 38-43.
- MAO Micro-arc oxidation
- a commercially available acrylic-modified epoxy resin, Unitect 20 manufactured by Kansai Paint Co., Ltd.
- is brush-coated and then dried at 80 ° C. for 10 minutes to provide a coating film layer.
- Whether or not a step is observed in the coating film layer is confirmed as follows.
- the boundary region between the resin member 105 and the metal member 103 of the dissimilar material joint B is irradiated with an LED light from an oblique angle of 45 °, and it is visually confirmed whether or not there is a step on the painted surface.
- thermoplastic resin composition 63.8 parts by mass of thermoplastic polyester resin (p) -2.0 parts by mass copolymer (d) 0.16 parts by mass of phenolic antioxidant (manufactured by BASF, MPX, hereinafter also referred to as "antioxidant 1”) -0.34 parts by mass of phosphoric acid-based antioxidant (manufactured by ADEKA Corporation, ADEKA STAB (registered trademark) PEP-36, hereinafter also referred to as "antioxidant 2”) -3.0 parts by mass of styrene-modified ethylene polymer as a crystal nucleating agent (intrinsic viscosity [ ⁇ ]: 0.03 dl / g, melt viscosity at 140 ° C.: 40 mPa ⁇ s, weight average molecular weight Mw: 930, molecular weight Distribution Mw / Mn: 1.8, melting point:
- the above-mentioned molten thermoplastic resin composition was subjected to the above-mentioned 2.
- the metal member roughened in 1 was injected into a mold, and injection molding (insert molding) was performed under the conditions of a holding pressure of 100 MPa and a holding time of 15 seconds to obtain 15 dissimilar material joints A.
- Arbitrary 5 pieces were selected from these dissimilar material joint bodies A, and the joint strength (the average value of the 5 values) was determined according to the above method.
- the joint strength was 1560 N.
- the standard deviation was 66N.
- the remaining 10 dissimilar material joints were annealed at 240 ° C. for 1 hour, and then slowly cooled to room temperature. After slow cooling, the joint strength (average value of the five values) was similarly determined for any of the five dissimilar material joints A (heat-treated). The joint strength was 1276N. The standard deviation was 78N. The retention rate of the joint strength before and after the annealing treatment was 82%.
- any one of the dissimilar material joints A was selected, and the crystallinity of the resin member portion obtained by the wide-angle X-ray diffraction profile was determined (the measuring device and the like are thermoplastic polyesters). Similar to the measurement of the crystallinity of the resin (P)). The required crystallinity was 36%.
- dissimilar material joints B were obtained in the same manner as above in terms of the composition of the thermoplastic resin composition and the conditions of injection molding (insert molding).
- the obtained dissimilar material bonded body B was annealed at 240 ° C. for 1 hour, and then slowly cooled to room temperature.
- the entire dissimilar material bonded body B is micro-arc-oxidized (MAO), and then the coating film layer was provided. Then, the state of step generation of the coating film layer was confirmed. As a result of confirmation, no step was confirmed in all five.
- thermoplastic resin composition a dissimilar material bonded body A was prepared and evaluated in the same manner as in Example 1 except that the following was put into an injection molding machine and melt-kneaded. 58.8 parts by mass of thermoplastic polyester resin (p) -5.0 parts by mass copolymer (d) -2.0 parts by mass copolymer (e) 0.16 parts by mass of antioxidant 1 -0.34 parts by mass of antioxidant 2 -3.0 parts by mass of styrene-modified ethylene-based polymer as a crystal nucleating agent (same as in Example 1) ⁇ 0.7 parts by mass of talc ⁇ 30.0 parts by mass of glass fiber (10 ⁇ m diameter)
- the average value of the joint strength of the dissimilar material joint A before the annealing treatment was 1340 N (standard deviation: 10 N), and the average value of the joint strength of the dissimilar material joint A after the annealing treatment was 1340 N (standard deviation: 22 N).
- the retention rate of the joint strength before and after the annealing treatment was 100%.
- any one of the dissimilar material joints A after the annealing treatment was selected, and the crystallinity of the resin member portion obtained by the wide-angle X-ray diffraction profile was determined (the measuring device or the like is a thermoplastic polyester resin). (Same as the measurement of crystallinity in (P)). The required crystallinity was 35%.
- dissimilar material joints B were obtained in the same manner as above in terms of the composition of the thermoplastic resin composition and the conditions of injection molding (insert molding).
- the obtained dissimilar material bonded body B was annealed at 240 ° C. for 1 hour, and then slowly cooled to room temperature.
- the entire dissimilar material bonded body B is micro-arc-oxidized (MAO), and then the coating film layer was provided.
- MAO micro-arc-oxidized
- thermoplastic resin composition As the thermoplastic resin composition, the dissimilar material joint A was produced and evaluated, and the dissimilar material joint B was produced in the same manner as in Example 1 except that the following was put into an injection molding machine and melt-kneaded. And evaluation (including micro-arc oxidation (MAO), formation of coating layer, etc.).
- MAO micro-arc oxidation
- Example 3 53.8 parts by mass of thermoplastic polyester resin (p) -2.0 parts by mass copolymer (d) ⁇ 10 parts by mass of polybutylene terephthalate (above) 0.16 parts by mass of antioxidant 1 -0.34 parts by mass of antioxidant 2 -3.0 parts by mass of styrene-modified ethylene-based polymer as a crystal nucleating agent (same as in Example 1) ⁇ 0.7 parts by mass of talc ⁇ 30.0 parts by mass of glass fiber (10 ⁇ m diameter)
- Example 4 53.8 parts by mass of thermoplastic polyester resin (p) -2.0 parts by mass copolymer (d) ⁇ 10 parts by mass of polycarbonate (above) 0.16 parts by mass of antioxidant 1 -0.34 parts by mass of antioxidant 2 -3.0 parts by mass of styrene-modified ethylene-based polymer as a crystal nucleating agent (same as in Example 1) ⁇ 0.7 parts by mass of talc ⁇ 30.0 parts by mass of glass fiber (10 ⁇ m diameter)
- Example 5 53.8 parts by mass of thermoplastic polyester resin (p) -2.0 parts by mass copolymer (d) 10 parts by mass of isophthalic acid-modified polycyclohexylene methylene terephthalate (above) 0.16 parts by mass of antioxidant 1 -0.34 parts by mass of antioxidant 2 -3.0 parts by mass of styrene-modified ethylene-based polymer as a crystal nucleating agent (same as in Example 1) ⁇ 0.7 parts by mass of talc ⁇ 30.0 parts by mass of glass fiber (10 ⁇ m diameter)
- the retention rate of the joint strength before and after the annealing treatment was 100%. Further, in all of Examples 3 to 5, the crystallinity obtained by the wide-angle X-ray diffraction profile of the resin member portion of the dissimilar material bonded body A after the annealing treatment was determined in the same manner as in Examples 1 and 2. In all of Examples 3 to 5, the required crystallinity was 50% or less (about 30 to 40%). Further, in all of Examples 3 to 5, the suitability for top coating of the coating film layer using the dissimilar material joint B was good, and steps were confirmed in all of the five dissimilar material joints B produced in each example. There wasn't.
- the top coating suitability of the coating film layer was also good. That is, when the coating film layer was formed on the surface of the dissimilar material joint between the metal member 103 and the resin member 105, it was suppressed that a step was generated in the coating film layer. This is because the joint does not break during annealing, and cracks (dents, gaps and depressions) that induce steps even when the entire heat-treated dissimilar joint is immersed in a chemical solution during the surface oxidation treatment of the next stage. It is considered that this is because the occurrence or spread of the disease was suppressed. It is considered that the excellent heat resistance and chemical resistance of the plastic antenna portion of the dissimilar material joint, the high joint strength between the joint portions with the metal member, and the high airtightness / watertightness are the distant causes of this result.
- Comparative Example 1 using a thermoplastic resin composition containing a thermoplastic polyester resin having a Tm lower than 250 ° C., deformation occurred due to annealing after insert molding.
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Abstract
Description
しかし、筐体材料として頻用されるマグネシウム合金やアルミニウム合金等の軽金属は無線電波の伝達を阻害する特性を有する。よって、内蔵型アンテナを備えた電子機器の筐体として金属製の筐体を用いる場合は、例えば、筐体のアンテナ素子に対応する箇所に開口部を形成し、この開口部をプラスチック製アンテナカバーで覆い、プラスチック部と金属部材を緊結する構造とする(このような構造については、例えば、特許文献1、2などを参照)。ここでの緊結する方法として、リベット等による機械的係合などが考えられる。
しかしながら、機械的係合の場合、係合部に隙間が発生する、あるいは、長期間の使用によって係合部が緩むなどして、電子機器全体の強度にも悪影響を及ぼす場合がありうる。
特に最近、軽量化を目的に、金属部材として軽量なマグネシウム合金を用いることが増加している。しかし、本発明者らの知見などによれば、マグネシウム合金の十分なアニーリングには比較的高温が必要であるため、上記問題はより顕著となる。
金属部材と、プラスチック製アンテナカバーとがインサート成形によって接合一体化された電子機器筐体であって、
前記プラスチック製アンテナカバーは、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物の成形体である電子機器筐体。
2.
1.に記載の電子機器筐体であって、
前記プラスチック製アンテナカバーの、広角X線回折プロファイルにより求められた結晶化度が50%以下である電子機器筐体。
3.
1.または2.に記載の電子機器筐体であって、
前記熱可塑性ポリエステル樹脂が、芳香族ジカルボン酸系モノマー由来の構造単位と、脂環骨格を有するジオール由来の構造単位とを含む電子機器筐体。
4.
3.に記載の電子機器筐体であって、
前記芳香族ジカルボン酸系モノマーが、テレフタル酸である電子機器筐体。
5.
1.~4.のいずれか1つに記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、前記熱可塑性ポリエステル樹脂(P)を40~80質量%含む電子機器筐体。
6.
1.~5.のいずれか1つに記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、熱可塑性ポリエステル樹脂(P)以外のその他のポリマー成分(Q)を含む電子機器筐体。
7.
6.に記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、前記その他のポリマー成分(Q)を1~20質量%含む電子機器筐体。
8.
6.または7.に記載の電子機器筐体であって、
前記その他のポリマー成分(Q)は、オレフィン由来の構造単位および環状オキシ炭化水素構造を有する構造単位を有する共重合体(D)を含む電子機器筐体。
9.
8.に記載の電子機器筐体であって、
前記その他のポリマー成分(Q)は、さらに、エチレン・α-オレフィン共重合体(E1)、ポリブチレンテレフタレート(E2)、ポリカーボネート(E3)およびイソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(E4)からなる群より選ばれる1以上のポリマー(E)を含む電子機器筐体。
10.
9.に記載の電子機器筐体であって、
前記共重合体(D)と、前記ポリマー(E)との質量比は、1:0.1~1:0.5である電子機器筐体。
11.
9.または10.に記載の電子機器筐体であって、
前記共重合体(D)と、前記ポリブチレンテレフタレート(E2)、前記ポリカーボネート(E3)および前記イソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(E4)との質量比は、1:1~1:10である電子機器筐体。
12.
1.~11.のいずれか1つに記載の電子機器筐体であって、
前記金属部材が、マグネシウムまたはマグネシウム合金、アルミニウムまたはアルミニウム合金、チタンまたはチタン合金、および、銅または銅合金からなる群より選ばれる一種である電子機器筐体。
13.
1.~12.のいずれか1つに記載の電子機器筐体であって、
前記金属部材の表面の、少なくともプラスチック製アンテナカバーが接合していない部分には耐蝕性の表面改質膜が形成されている電子機器筐体。
14.
電子機器筐体の製造方法であって、以下の工程1~工程5をこの順に実施する製造方法。
(工程1)金属部材を準備する工程。
(工程2)前記金属部材と、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物とを、インサート成形によって接合一体化して、金属部材とプラスチック製アンテナカバーとの異材接合体を製造する工程。
(工程3)前記異材接合体を、180~350℃下で1~30分間アニーリングして、熱処理異材接合体に変換する工程。
(工程4)前記熱処理異材接合体の金属部材における、少なくともプラスチック製アンテナカバーが接合していない部分の表面を、陽極酸化、マイクロアーク酸化および化成処理からなる群より選ばれる少なくとも一つの方法で酸化処理することで表面改質異材接合体を得る工程。
(工程5)前記表面改質異材接合体の、少なくとも金属部材とプラスチック製アンテナカバーの接合部分を含む領域に塗膜層を形成する工程。
15.
マグネシウム合金部材と樹脂部材とが接合一体化された金属樹脂複合体であって、
前記樹脂部材は、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物の成形体である金属樹脂複合体。
すべての図面において、同様な構成要素には共通の符号を付し、適宜説明を省略する。
図はあくまで概略図である。図中の寸法比率と実際の物品の寸法比率とは必ずしも一致しない。
図1は、電子機器の一例であるノートPC(ノートPC1)の外観図である。
ノートPC1は、本体ユニット(パームレスト部)1aと、ディスプレイユニット1bから構成されている。
本体ユニット1aは、扁平な箱状筐体内に、例えばCPUを実装したプリント配線板やハードディスク駆動装置のような主要な構成要素を収納したものである。
ディスプレイユニット1bは、通常、ヒンジ機構を介して本体ユニット1aに連結されている。ディスプレイユニット1bの扁平な箱状筐体内には、液晶表示パネルなどが収容されている。
また、図3は、図2における円αで囲われた部分を拡大し、S方向から眺めたときに見える構造を模式的に表した図である。図3は、図1のX―X線に沿ってディスプレイユニット1bを切断したときの断面の一部を拡大して示した図とも言える。
具体的には、適切な金型を用いたインサート成形により金属部材とプラスチック製アンテナカバーとを接合一体化して異材接合体を製造する際に発生する、主に金属部材側に発生する変形を除去するために該異材接合体を高温アニーリング(焼きなまし)した場合であっても、プラスチックの変形量を小さくすることができ、接合部7に隙間が発生する現象を回避しやすい(プラスチック製アンテナカバーが、Tmが250℃以上である熱可塑性ポリエステル樹脂を含む耐熱性プラスチックであるため)。その結果、異材接合体の表面に塗膜層5を形成した場合であっても段差の発生を抑制でき、意匠性に優れた電子機器筐体が提供される。
接合界面(接合部7)での接合が不十分であると、表面改質時に薬液が接合部7に侵入して接合部7が部分破壊しうる。また、アニーリングによってプラスチック製アンテナカバー2が変形すると、接合部7に隙間が生じて薬液が接合部7により侵入しやすくなってしまう。そして、塗膜層5の点P付近に段差(陥没)が生じがちである。しかし、本実施形態では、接合部7での接合力を十分に強くすることができ、かつ、アニーリングによるプラスチック製アンテナカバー2の変形・変質が抑えられるため、薬液の侵入が抑えられる。その結果、塗膜層5の点P付近に段差(陥没)が生じにくい。
また、内表面と外表面のうち、少なくとも外表面側の一部または全部に、意匠性向上を目的とした塗膜層5が塗装されていることが好ましい。前述のように、点P付近に段差は生じないか、または段差が生じるとしてもその段差を極めて小さくすることができるため、塗膜層5の表面にも段差が生じづらい。このことは意匠性向上の点で好ましい。
金属部材4としては、インサート成形によって熱可塑性樹脂組成物と接合することができ、電子機器筐体として所望の性能を奏する金属を制限なく使用できる。
金属部材4の素材として具体的には、アルミニウム、鉄、銅、マグネシウム、錫、ニッケル、亜鉛、これらの合金などが挙げられる。
これらのうち、金属部材4ひいては電子機器筐体の軽量化に資する視点から、マグネシウムまたはマグネシウム合金、アルミニウムまたはアルミニウム合金、チタンまたはチタン合金、銅または銅合金が好ましく、マグネシウムまたはマグネシウム系合金がより好ましい。
マグネシウム系合金の例としては、アルミニウム、マンガン、シリコン、亜鉛、ジルコニウム、銅、リチウム、トリウム、銀およびイットリウムなどの元素とマグネシウムとの合金などを挙げることができる。
冒頭で説明したように、マグネシウム合金を十分にアニーリングするには比較的高温が必要である。しかし、本実施形態では、プラスチック製アンテナカバー2が十分な耐熱性を有するため、比較的高温のアニーリングによっても接合強度低下や接合部7にクラックが発生する現象が抑えられる。
所望の形態の金属部材4は、公知の金属加工法、例えば、プレスなどによる塑性加工、打ち抜き加工、切削、研磨、および、放電加工などを含む除肉加工によって作製可能である。
ちなみに、間隔周期は、JIS B 0601で規定されている粗さ曲線要素の平均長さRSmに対応する値ということができる。
化成処理としては、クロム酸や重クロム酸カリ水溶液を用いたクロメート処理、リン酸マンガン系化合物水溶液や弱酸性とした過マンガン酸カリ水溶液を用いた化成処理などが挙げられる。
熱可塑性樹脂組成物は、樹脂成分として熱可塑性ポリエステル樹脂(P)を含む。
好ましくは、熱可塑性樹脂組成物は、さらに、その他のポリマー成分(Q)、添加剤(R)、充填剤(F)などのうち1種または2種以上を含む。
具体的には、約5mgの樹脂を測定用アルミニウムパン中に密封し、PerkinElemer社製DSC7を用いて、室温から10℃/minで340℃まで加熱する。樹脂を完全融解させるために、340℃で5分間保持し、次いで、10℃/minで30℃まで冷却する。30℃で5分間置いた後、10℃/minで340℃まで2度目の加熱を行う。この2度目の加熱でのピーク温度(℃)を樹脂の融点Tmとする。
結晶化度は、全回折ピーク面積に占める結晶性構造に由来するピーク面積の比率より算出される。例えば、広角X線回折装置(RINT2100:リガク)を用い、Cu線源にて測定したときの結晶性構造に由来するピーク面積比より算出することができる。
融点Tmが250℃以上であり、さらに結晶化度が上記数値であることによって、プラスチック製アンテナカバー2と金属部材4とが一層強固に接合される。また、寸法精度が一層高まり、上塗り塗装を施した後であっても両者の接合界面付近には段差が認められない意匠性に優れた外観を得やすい。
また、構造単位(a1)は、テレフタル酸ではない芳香族ジカルボン酸系モノマーに由来する構造単位を含んでもよい。この構造単位の量は、構造単位(a1)の全体に対して、例えば0~70モル%、好ましくは0~60モル%、より好ましくは0~40モル%である。
テレフタル酸系モノマー以外の芳香族ジカルボン酸系モノマーとしては、イソフタル酸、2-メチルテレフタル酸、ナフタレンジカルボン酸、これらの芳香族ジカルボン酸のエステル(好ましくは芳香族ジカルボン酸の炭素数1~4のアルキルエステル)などが挙げられる。
多価カルボン酸の例としては、トリメリット酸やピロメリット酸などの三塩基酸や多塩基酸を挙げることができる。
具体的には、脂環族ジオールに由来する構造単位のシス/トランス比は、好ましくは50/50~0/100、より好ましくは40/60~0/100である。
脂肪族ジオールの例としては、エチレングリコール、トリメチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール、ヘキサメチレングリコール、ドデカメチレングリコールなどを挙げることができる。
好ましくは、ジオールに由来する構造単位は、脂環骨格を有するジオールに由来する構造単位(a2)(好ましくはシクロヘキサン骨格を有するジオールに由来する成分単位、より好ましくはシクロヘキサンジメタノールに由来する成分単位)を30~100モル%含み、脂肪族ジオールに由来する成分単位を0~70モル%含む。
脂環骨格を有するジオールに由来する構造単位(a2)の割合は、より好ましくは50~100モル%、さらに好ましくは60~100モル%である。
脂肪族ジオールに由来する構造単位の割合は、より好ましくは0~50モル%、さらに好ましくは0~40モル%である。
芳香族ジオールの例としては、ビスフェノールA、ハイドロキノン、2,2-ビス(4-β-ヒドロキシエトキシフェニル)プロパン、ビスフェノールAのEO付加体などを挙げることができる。
芳香族ジオールに由来する構造単位の割合は、熱可塑性ポリエステル樹脂(P)の全構造単位中、例えば10モル%以下、好ましくは5モル%以下であることができる。
熱可塑性ポリエステル樹脂(P)の固有粘度[η]は、熱可塑性ポリエステル樹脂(P)の分子量を調整するなどして上記範囲に調整されうる。
固有粘度[η]の測定方法の詳細は、後掲の実施例を参照されたい。
特に、共重合体(D)とポリマー(E)の両方を用いることで、接合後にアニーリング処理した後の、金属部材と樹脂組成物との接合強度の低下を抑えやすくなる。
また、本発明者らの知見によれば、特に、ポリマー(E)としてポリブチレンテレフタレート(E2)および/またはポリカーボネート(E3)を用いることで、マイクロアーク酸化などの表面改質の際、薬液に浸漬した場合であっても、接合強度が低下しにくい。これは、ポリブチレンテレフタレート(E2)および/またはポリカーボネート(E3)を熱可塑性樹脂組成物に含めることで、熱可塑性樹脂組成物の結晶化度が低くなるためと考えられる。結晶化度が低いと、樹脂の固化速度が遅いので、溶融した樹脂が金属の凹凸構造により奥まで侵入し易くなり、接合強度がより高くなると考えられる。その結果、表面改質時の薬液の侵入を抑えられ、接合強度の低下が抑制されると考えられる。
共重合体(D)を構成する環状オキシ炭化水素構造を有する構造単位の例としては、α,β-不飽和カルボン酸グリシジルエステル由来の構造単位などが挙げられる。α,β-不飽和カルボン酸グリシジルエステルの例としては、アクリル酸グリシジルエステル、メタクリル酸グリシジルエステルなどが挙げられる。これらのうち、メタクリル酸グリシジルエステルが好ましい。
共重合体(D)を構成するα,β-不飽和カルボン酸エステル由来の構造単位の例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチルなどを含むアクリル酸エステル、および、メタクリル酸メチル、メタクリル酸エチルなどを含むメタクリル酸エステルなどに由来する構造単位を挙げることができる。これらのうち、アクリル酸メチルに由来する構造単位が好ましい。
また、共重合体(E1)の、JIS K 7210:1999に準拠し、190℃、2.16kg荷重下で測定されるメルトフローレート(MFR)は、0.5~100g/10分であることが好ましく、1~80g/10分であることがより好ましい。共重合体(E1)のメルトフローレートがこの範囲であると、熱可塑性樹脂組成物の成形時の流動性が高まりやすくなる。
イソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(E4)の市販品としては、イーストマンケミカル社製、製品名:デュラスター、銘柄:DS2000などが挙げられる。
添加剤(R)としては、例えば、酸化防止剤(フェノール類、アミン類、イオウ類、リン酸類など)、耐熱安定剤(ラクトン化合物、ビタミンE類、ハイドロキノン類、ハロゲン化銅、ヨウ素化合物など)、光安定剤(ベンゾトリアゾール類、トリアジン類、ベンゾフェノン類、ベンゾエート類、ヒンダードアミン類、オギザニリド類など)、難燃剤(臭素系、塩素系、リン系、アンチモン系、無機系など)、滑剤、蛍光増白剤、可塑剤、増粘剤、帯電防止剤、離型剤、顔料、結晶核剤、発泡剤、発泡助剤などの公知の添加剤を挙げることができる。
充填材(F)としては、例えば、ガラス繊維、炭素繊維、炭素粒子、粘土、タルク、シリカ、ミネラル、セルロース繊維からなる群から一種または二種以上を選ぶことができる。これらのうち、好ましくは、ガラス繊維、炭素繊維、タルク、ミネラルから選択される一種または二種以上である。
・熱可塑性ポリエステル樹脂(P):40~80質量%、好ましくは50~70質量%、より好ましくは55~65質量%
・その他のポリマー成分(Q):1~20質量%、好ましくは2~15質量%、より好ましくは5~15質量%
・添加剤(R):0.1~10質量%、好ましくは0.1~5質量%、より好ましくは0.2~3質量%
・充填剤(F):5~50質量%、好ましくは10~50質量%、より好ましくは20~40質量%。
各成分の量を適切に調整することによって、プラスチック製アンテナカバー2と金属部材4とがより強固に接合される。また、寸法精度を一層高めることができる。さらに、プラスチック製アンテナカバー2と金属部材4との接合界面に隙間が発生することを十二分に抑えることができ、この上に塗膜層5を設けた場合に、接合部7付近に実質上段差が無い意匠性に優れた異材接合体を得やすい。
本実施形態において、好ましくは、金属部材4とプラスチック製アンテナカバー2との接合部位を含む表面の一部または全部には、連続的に塗膜層5が形成されている。より好ましくは、接合部位を含む外表面側全体に連続的に塗膜層5が形成されている。塗膜層5は、通常、電子機器筐体の保護や装飾(意匠性向上)の機能を有する。
既に述べたように、金属部材4とプラスチック製アンテナカバー2との接合部7およびその近傍の外表面(図3の点P近辺)においては、係合段差(痕跡)が生じないか、またはそれを極めて小さくすることができる。このため、塗膜層5の表面においても段差が抑えられる。好ましい態様として、金属部材4とプラスチック製アンテナカバー2との接合部7に形成された塗膜層5には、段差は認められず、よって意匠性に優れる。
塗膜層5の平均厚みは、例えば10~500μm、好ましくは20~300μmである。
成膜物質としては、公知の樹脂を挙げることができる。例えば、ポリエチレン、プリプロピレン、塩化ビニル樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、ポリウレタン樹脂、フェノール樹脂、エポキシ樹脂などを挙げることができる。
顔料としては、カーボンブラック、チタンホワイトなどを挙げることができる。その他、所望の意匠性などに応じて公知の顔料を1種または2種以上用いることができる。
添加剤としては、可塑剤、難燃剤、潤滑剤、安定剤、発泡剤などを例示できる。
また、塗膜層5に光沢感を付与するために、アルミ粉、銀粉などの金属微粒子を含ませることも可能である。
本実施形態の電子機器筐体は、好ましくは、下記工程1~工程5をこの順に実施することにより製造される。
(工程1)金属部材4を準備する工程。
(工程2)金属部材4と、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物とを、インサート成形によって接合一体化して、金属部材とプラスチック製アンテナカバーとの異材接合体を製造する工程。
(工程3)上記異材接合体を、180~350℃下で1~30分間アニーリングして、熱処理異材接合体に変換する工程。
(工程4)上記熱処理異材接合体の金属部材における、少なくともプラスチック製アンテナカバーが接合していない部分の表面を、陽極酸化、マイクロアーク酸化および化成処理からなる群より選ばれる少なくとも一つの方法で酸化処理することで表面改質異材接合体を得る工程。
(工程5)上記表面改質異材接合体の、少なくとも金属部材とプラスチック製アンテナカバーの接合部分を含む領域に塗膜層5を形成する工程。
「インサート成形」とは、射出成形の一種であり、具体的には予め金型内に金属部材を挿入しておき、そしてその金型内に溶融樹脂を射出成形して金属部材と樹脂を一体化する成形技術である。
工程2の具体的手順としては、まず、金属部材4を射出成形用の金型内に設置する。次いで、熱可塑性ポリエステル樹脂(P)を含む熱可塑性樹脂組成物の溶融物を、射出成形機を通して金型内に射出成形する。金属部材4に接合した熱可塑性樹脂組成物の溶融物を冷却することによって、金属部材4とプラスチック製アンテナカバー2とが一体化した異材接合体となる。
一例として、シリンダー温度280~350℃、射出速度10~30mm/secで、粗面化した金属部材4が配置された金型に熱可塑性樹脂組成物の溶融物を射出する。このとき、保圧は70~120MPa、保圧時間は10~30秒とすることができる。
その後、金型を開き、離型することにより、異材接合体を得ることができる。
アニーリングは別名、時効硬化処理、応力除去焼きなまし処理などとも呼ばれる。アニーリングは、鍛造、鋳造、冷間加工、溶接、機械加工、射出成形などの加熱操作等で生じる残留応力の除去や、寸法変化によって生じた変形の是正のために通常行われる。アニーリング温度は、金属部材4を構成する金属種、プラスチック製アンテナカバー2を構成する樹脂種などによっても異なるが、通常180~350℃、好ましくは190~330℃、より好ましくは200~300℃、特に好ましくは200~280℃である。アニーリング時間は通常1~30分間、好ましくは5~20分間である。
この工程を行うことにより、金属部材4表面の、空気中での安定性を向上できるので好ましい。また、この処理では金属部材表面にnmオーダーの微細凹凸孔が形成されるので、後続の工程5で形成される塗膜層との密着性向上にも資する。
陽極酸化処理については公知の方法が制限なく使用できる。
MAO酸化は、通常、リン酸やピロリン酸のアルカリ金属塩を溶解したアルカリ性電解溶液中で高電圧をかける方法によって行われる。
化成処理は、クロムや重クロム酸カリ等に浸漬して酸価クロムの薄層で全面を覆うクロメート処理や、またはリン酸を含むマンガン塩の水溶液に浸漬してリン酸マンガン系化合物の薄層で全面を覆う処理、弱酸性として過マンガン酸カリの水溶液に浸漬して二酸化マンガンの薄層で全面を覆う処理法などを例示できる。
これらの酸化処理については、プラスチックが接合されていない金属部分のみの選択的処理であってもよいし、異材接合体全体の処理であってもよい。処理スピードを高める観点からは、通常は異材接合体全体を処理溶液中に浸漬させた状態で実施される。
その塗膜層5を構成する成分を、例えば、エタノール、アセトン、脂肪族炭化水素、芳香族炭化水素などの汎用溶媒(有機溶媒)に溶解または分散した塗料を、表面改質異材接合体の表面に塗装する。その後、必要に応じて加熱して(または自然乾燥により)、溶媒等の揮発成分を留去することによって塗膜層5が形成される。
塗装方法としては、はけ塗り、ローラ塗り、浸漬塗り、またはスプレー塗装など公知の方法を制限なく適用できる。塗膜層5を形成する際には、下地層としてのプライマー層を設けてもよい。
結晶化度の求め方は、前述のとおりである。よって、改めての説明は省略する。
最終的な電子機器筐体におけるプラスチック製アンテナカバーの結晶化度が低いということは、電子機器筐体の製造段階において、溶融した樹脂が金属の凹凸構造により奥まで侵入しやすくなっていたことを意味すると考えられる。よって、プラスチック製アンテナカバーの結晶化度が低い電子機器筐体の、金属部材-プラスチック製アンテナカバー間の接合強度は良好であり、接合強度は低下しにくい傾向があると考えられる。
プラスチック製アンテナカバーの結晶化度は、原料の熱可塑性ポリエステル樹脂(P)の結晶化度を調整したり、上記工程2や工程3の温度条件などを調整したりすることで調整することができる。
これまで、金属部材と、プラスチック製アンテナカバーとがインサート成形によって接合一体化された「電子機器筐体」について説明してきた。しかし、アニーリング処理の前後での接合強度の良好な保持率などを考慮すると、本明細書に記載した金属-樹脂接合技術は、電子機器筐体に限定されない種々の用途に好ましく適用される。「種々の分野」の具体例としては、家電機器、車両、建材、日用品などが挙げられるが、もちろんこれら分野のみに限定されない。電子機器筐体以外の好ましい用途としては、バスバーや、端子などの絶縁パーツなどが挙げられる。
上記「マグネシウム合金部材と、樹脂部材とが接合一体化された金属樹脂複合体」における樹脂部材に関する具体的な事項は、<電子機器筐体>の(熱可塑性樹脂組成物)などで説明したとおりである。
上記「マグネシウム合金部材と、樹脂部材とが接合一体化された金属樹脂複合体」における、接合一体化の方法については、例えば、<電子機器筐体の製造方法>で説明した、インサート成形、アニーリング等の方法を適宜適用することができる。
(熱可塑性ポリエステル樹脂(P)の合成)
106.2質量部のジメチルテレフタレートと、94.6質量部の1,4-シクロヘキサンジメタノール(シス/トランス比:30/70)との混合物に、0.0037質量部のテトラブチルチタネートを加え、150℃から260℃まで3時間30分かけて昇温して、エステル交換反応をさせた。
エステル交換反応終了時に、1,4-シクロヘキサンジメタノールに溶解させた0.0165質量部の酢酸マンガン・四水塩を加えて、引き続き0.0299質量部のテトラブチルチタネートを導入して重縮合反応を行った。
得られた重合体の固有粘度[η]は0.6dl/g、融点Tmは290℃であった。
また、得られた重合体について、広角X線回折装置(RINT2100:リガク)を用い、Cu線源にて測定したときの結晶性構造に由来するピーク面積比より算出した結晶化度は、47%であった。
以下、この重合体を、熱可塑性ポリエステル樹脂(p)と記載する場合がある。
共重合体(D)として、エポキシ基含有エチレンメタクリレート共重合体(アルケマ社製 LOTADER GMA AX8900(LOTADERは同社の登録商標)を準備した。
以下、この共重合体を、共重合体(d)と記載する場合がある。
十分に窒素置換したガラス製フラスコに、0.63mgのビス(1,3-ジメチルシクロペンタジエニル)ジルコニウムジクロリドを投入し、1.57mlのメチルアミノキサンのトルエン溶液(Al:0.13ミリモル/リットル)および2.43mlのトルエンをさらに添加して、触媒溶液を得た。
以下、このエチレン・1-ブテン共重合体を、共重合体(e)と記載する場合がある。
DuPont社製、製品名:Crastin、銘柄:S600F10 NC010を準備した。
三菱エンジニアリングプラスチックス社製、製品名:ユーピロン、銘柄:H-3000を準備した。
イーストマンケミカル社製、製品名:デュラスター、銘柄:DS2000を準備した。
0.5gの各樹脂を50mlの96.5質量%硫酸水溶液に溶解させた。得られた溶液の、25℃±0.05℃の条件下での流下秒数を、ウベローデ粘度計を使用して測定し、次式に基づき固有粘度[η]を算出した。
[η]=ηSP/(C(1+0.205ηSP))」
[η]:固有粘度(dl/g)
ηSP:比粘度〔ηSP=(t-t0)/t0〕
C:試料濃度(g/dl)
t:試料溶液の流下秒数(秒)
t0:ブランク硫酸の流下秒数(秒)
融点Tmは、JIS K 7121の規定に準じて測定した。
具体的には、約5mgの樹脂を測定用アルミニウムパン中に密封し、PerkinElemer社製DSC7を用いて、室温から10℃/minで340℃まで加熱した。それぞれの樹脂を完全融解させるために、340℃で5分間保持し、次いで、10℃/minで30℃まで冷却した。30℃で5分間置いた後、10℃/minで340℃まで2度目の加熱を行なった。この2度目の加熱でのピーク温度(℃)を樹脂の融点Tmとした。
合金番号AZ31Bのマグネシウム板(厚み2mm)を、長さ45mm、幅18mm、または、長さ50mm、幅10mmに切断した(前者は下記の異材接合体Aを作製するためのもの、後者は下記の異材接合体Bを作製するためのものである)。
切断されたマグネシウム板の表面を、国際公開第2008/133096号の実験例1に記載の方法によって粗面化した。
粗面化後のマグネシウム板の表面粗さを、東京精密社製の表面粗さ測定装置「サーフコム1400D」を用いて測定した。その結果、十点平均粗さRzが2~3μmの範囲に、粗さ曲線要素の平均長さRSmは90~110μmの範囲にあることを確認した。
まず、評価方法について説明する。
異材接合体の接合強度は、引っ張りせん断強度で評価する。具体的には、アイコーエンジニアリング社製の引っ張り試験機モデル1323に専用の治具を取り付け、次いで、図4に模式的に示される異材接合体A(詳細は後述)を設置する。室温(23℃)にて、チャック間距離60mm、引張速度10mm/minの条件にて、異材接合体Aの金属部材と樹脂部材とを反対方向に引っ張る。このとき、金属部材103と樹脂部材105とが破断して引き離されたときの荷重を求める。
測定値のバラツキによる影響を小さくするため、同一の熱可塑性樹脂組成物を接合させた5つの異材接合体Aについて引っ張りせん断強度を測定し、それらの平均値を接合強度として採用する。また測定値のバラツキを把握するため標準偏差も求める。
塗膜層の上塗り適性、すなわち、異材接合体の表面に塗膜層を形成した際に、接合部位に段差が認められるかどうかを目視評価するための異材接合体として、図5に模式的に示される突き合わせ試験片(以下、「異材接合体B」とも表記する)を準備する。異材接合体Bは、金属部材103(マグネシウム合金製)と樹脂部材105が突き合わせられたようにして接合しているものである(接合部分は2mm×10mm)。
金属部材103の表面改質(酸化処理)および塗膜の形成については、以下(1)および(2)のようにして行う。
(1)まず、異材接合体Bの全表面に対して、クリモト技報No.64、38~43頁の記載に準拠して、マイクロアーク酸化(MAO)を施す。
(2)次いで、市販のアクリル変性エポキシ樹脂であるユニテクト20(関西ペイント社製)を刷毛塗りし、その後、80℃で10分間乾燥させることにより、塗膜層を設ける。
異材接合体Bの、樹脂部材105と金属部材103の境界領域に、斜め45°からLEDライトを照射し、塗装面に段差があるか否かを目視で確認する。
射出成型機に以下を投入して溶融混練し、熱可塑性樹脂組成物とした。
・63.8質量部の熱可塑性ポリエステル樹脂(p)
・2.0質量部の共重合体(d)
・0.16質量部のフェノール系酸化防止剤(BASF社製、MP-X、以下、「酸化防止剤1」とも記載)
・0.34質量部のリン酸系酸化防止剤(株式会社ADEKA製、アデカスタブ(登録商標)PEP-36、以下、「酸化防止剤2」とも記載)
・結晶核剤としての3.0質量部のスチレン変性エチレン系重合体(固有粘度[η]:0.03dl/g、140℃での溶融粘度:40mPa・s、重量平均分子量Mw:930、分子量分布Mw/Mn:1.8、融点:107℃)
・0.7質量部のタルク
・30.0質量部のガラス繊維(10μm径)
これら異材接合体Aの中から任意の5個を選び、上記方法に従って接合強度(5つの値の平均値)を求めた。接合強度は1560Nであった。また、標準偏差は66Nであった。
アニーリング処理の前後での接合強度の保持率は82%であった。
次いで、上記[塗膜層の上塗り適性(塗膜層に段差があるか否か)]の項で説明したようにして、異材接合体B全体をマイクロアーク酸化(MAO)し、次いで塗膜層を設けた。そして塗膜層の段差発生状況を確認した。
確認の結果、5個全てにおいて段差は確認されなかった。
熱可塑性樹脂組成物として、射出成型機に以下を投入して溶融混練したものを用いた以外は、実施例1と同様にして異材接合体Aの作製や評価を行った。
・58.8質量部の熱可塑性ポリエステル樹脂(p)
・5.0質量部の共重合体(d)
・2.0質量部の共重合体(e)
・0.16質量部の酸化防止剤1
・0.34質量部の酸化防止剤2
・結晶核剤としての3.0質量部のスチレン変性エチレン系重合体(実施例1と同じもの)
・0.7質量部のタルク
・30.0質量部のガラス繊維(10μm径)
次いで、上記[塗膜層の上塗り適性(塗膜層に段差があるか否か)]の項で説明したようにして、異材接合体B全体をマイクロアーク酸化(MAO)し、次いで塗膜層を設けた。そして塗膜層の段差発生状況を確認した。
確認の結果、4個については全く段差が認められず、1個のみについて僅かな段差が認められた。
熱可塑性樹脂組成物として、射出成型機に以下を投入して溶融混練したものを用いた以外は、実施例1と同様にして異材接合体Aの作製や評価、および、異材接合体Bの作製や評価(マイクロアーク酸化(MAO)、塗膜層の形成なども含む)を行った。
・53.8質量部の熱可塑性ポリエステル樹脂(p)
・2.0質量部の共重合体(d)
・10質量部のポリブチレンテレフタレート(上記のもの)
・0.16質量部の酸化防止剤1
・0.34質量部の酸化防止剤2
・結晶核剤としての3.0質量部のスチレン変性エチレン系重合体(実施例1と同じもの)
・0.7質量部のタルク
・30.0質量部のガラス繊維(10μm径)
・53.8質量部の熱可塑性ポリエステル樹脂(p)
・2.0質量部の共重合体(d)
・10質量部のポリカーボネート(上記のもの)
・0.16質量部の酸化防止剤1
・0.34質量部の酸化防止剤2
・結晶核剤としての3.0質量部のスチレン変性エチレン系重合体(実施例1と同じもの)
・0.7質量部のタルク
・30.0質量部のガラス繊維(10μm径)
・53.8質量部の熱可塑性ポリエステル樹脂(p)
・2.0質量部の共重合体(d)
・10質量部のイソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(上記のもの)
・0.16質量部の酸化防止剤1
・0.34質量部の酸化防止剤2
・結晶核剤としての3.0質量部のスチレン変性エチレン系重合体(実施例1と同じもの)
・0.7質量部のタルク
・30.0質量部のガラス繊維(10μm径)
また、実施例3~5の全てにおいて、実施例1および2と同様にして、アニーリング処理後の異材接合体Aの樹脂部材部分の、広角X線回折プロファイルにより求められる結晶化度を求めた。実施例3~5のすべてにおいて、求められた結晶化度は50%以下(30~40%程度)であった。
また、実施例3~5の全てにおいて、異材接合体Bを用いた塗膜層の上塗り適性は良好で、各実施例で作製した5個ずつの異材接合体Bの全てにおいて、段差は確認されなかった。
63.8質量部の熱可塑性ポリエステル樹脂(p)の代わりに、65.8質量部のポリブチレンテレフタレート樹脂(東レ社製、トレコン1401X06、融点Tm:224℃)を用い、かつ、共重合体(d)を用いなかった以外は、実施例1と同様にして、異材接合体Aの作製、アニーリング処理および接合強度の評価を行った。
アニーリング処理前の異材接合体Aの接合強度(5つの値の平均値)は1250Nであった。一方、アニーリング処理後の異材接合体Aにおいては、樹脂部材105の形状が大きく変形してしまい、接合強度の測定は不能であった。
比較例1においては、段差確認用の異材接合体Bの製造は行わなかった。
実施例1~5においては、金属部材103と樹脂部材105とが強く接合し、かつ、その接合力はアニーリング処理(240℃で1時間)でも維持された。
特に、実施例2~5では、アニーリング処理の前後で接合力は100%維持された。これは、恐らくはポリマー(E)に相当する成分による効果と考えられる。
実施例1~5でマイクロアーク酸化(MAO)を施された異材接合体Bの接合強度を評価した。評価の結果、特に、実施例3(ポリブチレンテレフタレート使用)および実施例4(ポリカーボネート使用)で、良好な結果が得られた(マイクロアーク酸化後の接合強度の低下が小さかった)。
1a 本体ユニット
1b ディスプレイユニット
2 プラスチック製アンテナカバー
3 アンテナ素子
4 金属部材
5 塗膜層
7 接合部
103 金属部材
105 樹脂部材
Claims (15)
- 金属部材と、プラスチック製アンテナカバーとがインサート成形によって接合一体化された電子機器筐体であって、
前記プラスチック製アンテナカバーは、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物の成形体である電子機器筐体。 - 請求項1に記載の電子機器筐体であって、
前記プラスチック製アンテナカバーの、広角X線回折プロファイルにより求められる結晶化度は50%以下である電子機器筐体。 - 請求項1または2に記載の電子機器筐体であって、
前記熱可塑性ポリエステル樹脂は、芳香族ジカルボン酸系モノマー由来の構造単位と、脂環骨格を有するジオール由来の構造単位とを含む電子機器筐体。 - 請求項3に記載の電子機器筐体であって、
前記芳香族ジカルボン酸系モノマーは、テレフタル酸である電子機器筐体。 - 請求項1~4のいずれか1項に記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、前記熱可塑性ポリエステル樹脂(P)を40~80質量%含む電子機器筐体。 - 請求項1~5のいずれか1項に記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、熱可塑性ポリエステル樹脂(P)以外のその他のポリマー成分(Q)を含む電子機器筐体。 - 請求項6に記載の電子機器筐体であって、
前記熱可塑性樹脂組成物は、前記その他のポリマー成分(Q)を1~20質量%含む電子機器筐体。 - 請求項6または7に記載の電子機器筐体であって、
前記その他のポリマー成分(Q)は、オレフィン由来の構造単位および環状オキシ炭化水素構造を有する構造単位を有する共重合体(D)を含む電子機器筐体。 - 請求項8に記載の電子機器筐体であって、
前記その他のポリマー成分(Q)は、さらに、エチレン・α-オレフィン共重合体(E1)、ポリブチレンテレフタレート(E2)、ポリカーボネート(E3)およびイソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(E4)からなる群より選ばれる1以上のポリマー(E)を含む電子機器筐体。 - 請求項9に記載の電子機器筐体であって、
前記共重合体(D)と、前記ポリマー(E)との質量比は、1:0.1~1:0.5である電子機器筐体。 - 請求項9または10に記載の電子機器筐体であって、
前記共重合体(D)と、前記ポリブチレンテレフタレート(E2)、前記ポリカーボネート(E3)および前記イソフタル酸変性ポリシクロへキシレンジメチレンテレフタレート(E4)との質量比は、1:1~1:10である電子機器筐体。 - 請求項1~11のいずれか1項に記載の電子機器筐体であって、
前記金属部材が、マグネシウムまたはマグネシウム合金、アルミニウムまたはアルミニウム合金、チタンまたはチタン合金、および、銅または銅合金からなる群より選ばれる一種である電子機器筐体 - 請求項1~12のいずれか1項に記載の電子機器筐体であって、
前記金属部材の表面の、少なくともプラスチック製アンテナカバーが接合していない部分には耐蝕性の表面改質膜が形成されている電子機器筐体。 - 電子機器筐体の製造方法であって、以下の工程1~工程5をこの順に実施する製造方法。
(工程1)金属部材を準備する工程。
(工程2)前記金属部材と、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物とを、インサート成形によって接合一体化して、金属部材とプラスチック製アンテナカバーとの異材接合体を製造する工程。
(工程3)前記異材接合体を、180~350℃下で1~30分間アニーリングして、熱処理異材接合体に変換する工程。
(工程4)前記熱処理異材接合体の金属部材における、少なくともプラスチック製アンテナカバーが接合していない部分の表面を、陽極酸化、マイクロアーク酸化および化成処理からなる群より選ばれる少なくとも一つの方法で酸化処理することで表面改質異材接合体を得る工程。
(工程5)前記表面改質異材接合体の、少なくとも金属部材とプラスチック製アンテナカバーの接合部分を含む領域に塗膜層を形成する工程。 - マグネシウム合金部材と樹脂部材とが接合一体化された金属樹脂複合体であって、
前記樹脂部材は、融点Tmが250℃以上である熱可塑性ポリエステル樹脂を含む熱可塑性樹脂組成物の成形体である金属樹脂複合体。
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