JP2011104789A - Method of manufacturing metallic composite laminated component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a metallic composite laminated component which can obtain the metallic composite laminated component having excellent adhesiveness between a metal plate and thermoplastic resin and reducing warping, does not necessarily require surface treatment of a specific die and the metal plate, facilitates work processes and is used for injection molding of the thermoplastic resin made of polyphenylene sulfide resin and/or liquid crystalline polymer on the metal plate. <P>SOLUTION: When the metallic composite laminated component is manufactured by injection molding of the thermoplastic resin made of polyphenylene sulfide resin and/or liquid crystalline polymer on the metal plate, a mold having a heat insulating layer formed on the entire surface of at least a portion of a mold interior surface where the metal plate comes into contact with the mold interior surface is used. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a metal composite laminated component in which a thermoplastic resin layer is laminated on a metal plate by injection molding.

  Conventionally, electrical and electronic parts manufactured by combining thermoplastic resin and metal parts by injection molding of thermoplastic resin by molding methods such as insert molding, outsert molding, hoop molding, etc. Widely used in communication equipment, automotive parts, etc.

  In addition, among metal composite parts that are a composite of thermoplastic resin and metal parts, metal composite laminate parts in which a thermoplastic resin is laminated on part or all of the surface of a metal plate are functional and lightweight. From the viewpoints of performance, design, etc., it has been attracting attention as a housing for small information / communication equipment such as mobile phones and notebook personal computers.

  The thermoplastic resin used in such a metal composite laminated part is desired to have strength that can withstand external impacts and to be injection-moldable from the viewpoint of manufacturing efficiency. For this reason, use of polyphenylene sulfide resin and liquid crystalline polymer having excellent moldability in addition to mechanical properties, heat resistance, and the like for metal composite laminated parts is being studied.

  However, when metal composite laminate parts are manufactured by injection molding using polyphenylene sulfide resin or liquid crystalline polymer as the thermoplastic resin, the linear expansion coefficient of these thermoplastic resins is small compared to other resins. Since the shrinkage after molding is greatly different between the metal plate at low temperature and the thermoplastic resin at a very high processing temperature, the metal plate and resin are different in the mold. A molded product that has been in close contact also has a problem in that the adhesion between the metal plate and the resin decreases after molding. In addition, since these thermoplastic resins have a very high processing temperature, the thermoplastic resin on the surface of the metal plate rapidly solidifies due to the contact between the molten thermoplastic resin and the low-temperature metal plate in the mold. In other words, in the normal manufacturing method, there is a problem that it is difficult to manufacture a metal composite laminated part having excellent adhesion between the metal plate and the thermoplastic resin. Furthermore, when a polyphenylene sulfide resin or a liquid crystalline polymer is laminated on a metal plate by injection molding, it is a problem that the obtained metal composite laminated part is likely to be warped.

  For this reason, when metal composite laminate parts are manufactured using polyphenylene sulfide resin or liquid crystalline polymer, the injection molding method cannot be applied due to the problem of adhesion between the metal plate and the thermoplastic resin, and the metal plate and the heat The complicated operation | work which laminates | stacks the molded article of a plastic resin using an adhesive tape or an adhesive agent is required.

  For this reason, when polyphenylene sulfide resin or liquid crystalline polymer is injection-molded on a metal plate, the adhesion between the metal plate and the thermoplastic resin is improved, and the occurrence of warpage of the resulting metal composite laminate part is reduced. Development of a method to do this is desired.

  Examples of a method for improving the adhesion between a thermoplastic resin and a metal in a metal composite molded article comprising a thermoplastic resin and a metal part include, for example, a styrene polymer, an ABS resin, or a copolymer thereof, polyethylene, polypropylene, and the like. In blow molding methods using resins such as olefin polymer, modified polyphenylene ether resin, vinyl chloride polymer or copolymer, polycarbonate, polyamide, polyester, polyacetal, etc., specify part of the part that contacts the metal parts of the mold A method of coating with a heat-resistant polymer having a thermal conductivity of (Patent Document 1) has been proposed.

  However, the method described in the example of Patent Document 1 is a blow molding method using an ABS resin, in which a part of the contact portion of the mold and the metal part (bolt or nut) is subjected to a specific heat. This is a method of eliminating the filling failure of the ABS resin by coating with a heat-resistant polymer of conductivity and making it difficult to remove the metal part from the ABS resin, and has excellent moldability of polyphenylene sulfide resin, liquid crystalline polymer, etc. In the method of injection molding using a resin, the problem of poor filling is unlikely to occur in the first place. Therefore, the effect of improving the adhesion by eliminating the defective filling cannot be expected. Moreover, since the metal part used in the Example of patent document 1 is a thing by which the groove | channel was cut in the contact part with thermoplastic resins, such as a volt | bolt and a nut, a metal part and Adhesion with thermoplastic resin can be improved, but in metal composite laminated parts in which a thermoplastic resin is laminated on a metal plate, the contact portion between the metal plate and the thermoplastic resin is a smooth surface, so poor filling Even if this is resolved, improvement in adhesion cannot be expected. Furthermore, Patent Document 1 does not disclose any problem of warpage.

  Examples of a method for improving the adhesion between a metal part and a polyphenylene sulfide resin or a liquid crystalline polymer include, for example, a metal part that has been subjected to a surface treatment such as etching to have a specific surface roughness and a thermoplastic resin such as a polyphenylene sulfide resin. Are combined by a method such as injection molding (Patent Document 2) or a holding piece having a heating device and a cooling device for holding a metal part, and the temperature of the holding piece is lowered by a temperature-decreasing crystallization of a thermoplastic resin. After the metal part is heated to a temperature equal to or higher than the conversion temperature (Tc), injection molding is performed, the holding piece is rapidly cooled to 150 ° C. or less, and then a molded product in which the metal part and the thermoplastic resin are combined is taken out from the mold. A method (Patent Document 3) and the like have been proposed.

  However, the method described in Patent Document 2 has a problem in that a metal part needs to be surface-treated in advance by a method such as etching, and the surface treatment cannot always be applied to all metals. Further, in the method described in Patent Document 3, it is necessary to use a special metal part holding piece provided with a heating device and a cooling device, and it is costly to remodel the metal part holding piece, and the complicated temperature of the holding piece. Control is necessary and the manufacturing process of a molded product that is a composite of metal parts and thermoplastic resin becomes complicated, and the mold and holding piece are repeatedly subjected to rapid temperature changes, and the mold life is shortened. There are problems such as.

  Furthermore, Patent Documents 2 and 3 do not disclose any improvement in warpage occurring in a molded product in which a metal part and a thermoplastic resin are combined.

Japanese Patent Application Laid-Open No. 07-178765 International Publication No. 2004/041533 Pamphlet JP 2008-132756 A

  The present invention has been made in order to solve the above-described problems, and a metal composite laminate component having excellent adhesion between a metal plate and a thermoplastic resin and having little warpage can be obtained. Provided is a method for producing a metal composite laminate part, in which a thermoplastic resin comprising a polyphenylene sulfide resin and / or a liquid crystalline polymer is injection-molded on a metal plate, which does not necessarily require a surface treatment of the metal plate and has a simple work process. There is to do.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, when producing a metal composite laminated part by injection molding a thermoplastic resin comprising a polyphenylene sulfide resin and / or a liquid crystalline polymer onto a metal plate, at least the metal plate and the mold inner surface The present inventors have found that the above-mentioned problems can be solved by using a mold in which a heat insulating layer is formed on the entire surface in contact with the metal, and have completed the present invention. Specifically, the present invention provides the following.

  (1) Heat composed of polyphenylene sulfide resin and / or liquid crystalline polymer by injection molding using a mold in which a heat insulating layer is formed on the entire surface of the mold inner surface where at least the metal plate contacts the mold inner surface. A method for producing a metal composite laminate component, wherein a plastic resin is laminated on the metal plate.

  (2) The method for producing a metal composite laminated part according to (1), wherein the thermoplastic resin is a polyphenylene sulfide resin.

  (3) The said heat insulation layer is a manufacturing method of the metal composite laminated component of (1) or (2) description whose heat conductivity is 5 W / m * K or less.

  (4) The said heat insulation layer is a manufacturing method of the metal composite laminated component in any one of (1) to (3) containing a polyimide resin.

  (5) The method for producing a metal composite laminate part according to any one of (1) to (4), wherein the metal composite laminate part is a casing of an electric / electronic product.

  According to the production method of the present invention, a metal composite laminate part having excellent adhesion between a thermoplastic resin and a metal plate can be obtained by injection molding of a polyphenylene sulfide resin and / or a liquid crystalline polymer. For this reason, the complicated operation | work which laminates | stacks a metal plate and a thermoplastic resin component with an adhesive agent, an adhesive tape, etc. becomes unnecessary, and a metal composite laminated component can be provided inexpensively with high production efficiency.

  Moreover, according to the manufacturing method of this invention, the curvature which arises in the metal composite laminated component obtained can be suppressed. For this reason, the metal composite laminated part of a desired shape can be manufactured stably.

  Furthermore, according to the manufacturing method of the present invention, it is not always necessary to use a mold including a holding piece or the like including a heating device and a cooling device. This eliminates the need for mold remodeling and complicated temperature control of the holding piece, and enables a metal composite laminated part to be manufactured at a low cost by a simple process.

It is a schematic diagram of the test piece for adhesive strength measurement manufactured in the Example. It is a schematic diagram of the metal plate used for manufacture of the test piece for curvature amount measurement in an Example. It is a schematic diagram of the test piece for curvature amount measurement manufactured in the Example.

  Hereinafter, an embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiment, and can be implemented with appropriate modifications within the scope of the object of the present invention. .

  The present invention relates to a method for producing a metal composite laminated part by laminating a thermoplastic resin comprising a polyphenylene sulfide resin and / or a liquid crystalline polymer on a metal plate by injection molding, and at least the metal plate and the die on the inner surface of the die A mold having a heat insulating layer formed on the entire surface in contact with the inner surface is used. Hereinafter, the present invention will be described in the order of a thermoplastic resin, a metal plate, a heat insulating layer, a forming method, and a metal composite laminated part.

[Thermoplastic resin]
In the specification and claims of this application, “thermoplastic resin” is not only a material of a thermoplastic resin alone, but also various types of fillers and / or various additives added to the thermoplastic resin. It also means a thermoplastic resin composition.

  The thermoplastic resin used in the present invention preferably has a deflection temperature under load of 250 ° C. or higher, more preferably 280 ° C. or higher, from the viewpoint of heat resistance when used as a casing. For this reason, the thermoplastic resin used in the present invention comprises a liquid crystalline polymer and / or a polyphenylene sulfide resin. Further, by using a liquid crystalline polymer and / or a polyphenylene sulfide resin, it becomes possible to produce a surface mount electrical / electronic component excellent in mechanical properties, electrical properties, and dimensional accuracy with good moldability.

  Among polyphenylene sulfide resins and liquid crystalline polymers, it is more preferable to use a polyphenylene sulfide resin because it is easy to obtain a metal composite laminate part having excellent adhesion between a metal plate and a thermoplastic resin.

  In the present invention, the polyphenylene sulfide resin and / or the liquid crystalline polymer can be used in combination with one or more other thermoplastic resins as long as the object of the present invention is not impaired. Specific examples of the thermoplastic resin that can be combined with the polyphenylene sulfide resin and / or the liquid crystal polymer include polyethylene, polypropylene, polyamide, polyacetal, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide resin, Examples include polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, fluorine resin, and thermoplastic elastomer. These thermoplastic resins can be used in combination of two or more.

[Polyphenylene sulfide resin]
Examples of the polyphenylene sulfide resin (polyphenylene thioether resin) that can be used as the thermoplastic resin in the present invention include a homopolymer having a polyphenylene sulfide skeleton- (Ar-S-)-[wherein Ar represents a phenylene group] and a copolymer. A polymer is included.

  Examples of the phenylene group (—Ar—) include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group (for example, an alkylphenylene group having a substituent such as a C1-5 alkyl group, phenyl Arylphenyl group having a substituent such as a group), p, p′-diphenylenesulfone group, p, p′-biphenylene group, p, p′-diphenylene ether group, p, p′-diphenylenecarbonyl group, etc. Can be illustrated. The polyphenylene sulfide resin may be a homopolymer using the same repeating unit among the phenylene sulfide groups composed of such phenylene groups, and includes different repeating units from the viewpoint of processability of the composition. It may be a copolymer.

  As the homopolymer, a linear polymer having a p-phenylene sulfide group as a repeating unit is preferably used. As the copolymer, a combination containing a p-phenylene sulfide group as a main repeating unit and an m-phenylene sulfide group is preferable. Among copolymers containing a p-phenylene sulfide group as a main repeating unit and containing an m-phenylene sulfide group, the p-phenylene sulfide group is contained in an amount of 60 mol% or more from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. The copolymer on the line containing is more preferable, and the copolymer on the line containing 70 mol% or more of p-phenylene sulfide groups is particularly preferable.

  The polyphenylene sulfide resin may be a polymer having a relatively low molecular weight linear polymer whose melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve molding processability, and is reduced from a monomer mainly composed of a bifunctional monomer. It may be a high molecular weight polymer having a substantially linear structure obtained by polymerization. From the viewpoint of physical properties of the obtained molded product, a substantially linear structure polymer obtained by condensation polymerization is preferred. As the polyphenylene sulfide resin, a branched or cross-linked polyphenylene sulfide resin obtained by polymerizing a combination of monomers having three or more functional groups, or a resin composition obtained by blending this resin with the linear polymer can also be used.

  As the polyphenylene sulfide resin, polyphenylene sulfide, polybiphenylene sulfide (PBPS), polyphenylene sulfide ketone (PPSK), polybiphenylene sulfide sulfone (PPSS), and the like can be used. Polyphenylene sulfide resins can be used alone or in combination of two or more.

[Liquid crystal polymer]
The liquid crystalline polymer used as the thermoplastic resin in the present invention is a melt processable polymer having a property capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in the molten stationary state, and optically anisotropic.

  The liquid crystalline polymer is not particularly limited, and is preferably an aromatic polyester or an aromatic polyester amide, and includes an aromatic polyester or a polyester partially containing an aromatic polyester amide in the same molecular chain. They preferably have a logarithmic viscosity (IV) of at least about 2.0 dl / g, more preferably 2.0 to 1.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. .) Are used.

  The aromatic polyester or aromatic polyester amide as the liquid crystalline polymer applicable to the present invention is derived from at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. Aromatic polyesters or aromatic polyester amides having repeating units are particularly preferred.

More specifically,
(1) A polyester mainly composed of repeating units derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly (a) one or more of aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and ( c) Polyester comprising a repeating unit derived from at least one or more of aromatic diol, alicyclic diol, aliphatic diol and derivatives thereof;
(3) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, and (c) Polyester amides comprising repeating units derived from one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof;
(4) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, (c) aromatic Derived from one or more of dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and (d) at least one or more of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof And polyesteramides composed of repeating units. Furthermore, you may use a molecular weight modifier together with said structural component as needed.

  Specific examples of the specific compound that gives the repeating unit constituting the liquid crystalline polymer applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; hydroquinone, resorcinol , 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, aromatic diols such as compounds represented by the following general formula (A) and the following general formula (B); terephthalic acid, Examples include aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, compounds represented by the following general formula (C); and aromatic amines such as p-aminophenol and p-phenylenediamine.

（Ｘ：アルキレン（Ｃ１−Ｃ４）、アルキリデン、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、−ＣＯ−より選ばれる基である。）

（Ｙ：−（ＣＨ_２）_ｎ−（ｎ＝１〜４）、−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）より選ばれる基である。）

(X: alkylene (C1-C4), _{alkylidene, -O -, - SO -,} - SO 2 -, - S -, - a group selected from CO-.)

(Y is a group selected from — (CH ₂ ) _n — (n = 1 to 4) and —O (CH ₂ ) _n O— (n = 1 to 4).

[Filler]
Preferred examples of the filler to be added to the thermoplastic resin include glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber. , Fibrous fillers such as metal fibers, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, Granular packing of wollastonite, iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, ferrite, silicon carbide, silicon nitride, boron nitride, various metal powders, etc. Materials and plate shapes such as mica, glass flakes and various metal foils Hama material, and the like. These fillers may be used in combination of two or more.

  The blending amount of the filler into the thermoplastic resin is not particularly limited as long as the object of the present invention is not impaired. Typically, the filler is blended so as to be 200 parts by mass or less, more preferably 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.

〔Additive〕
Examples of additives to be added to the thermoplastic resin include nucleating agents, carbon black, pigments such as inorganic fired pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants. Two or more of these additives may be used in combination.

[Metal plate]
The material of the metal plate used in the present invention is not particularly limited, and examples thereof include metals such as copper, aluminum and iron, alloys such as phosphor bronze and stainless steel, bonded bodies of different metals, and plated products thereof. It is done. Specific examples of the case where the material is stainless steel include martensitic and austenitic stainless steels.

  The shape of the metal plate is not particularly limited as long as the thermoplastic resin can be laminated by injection molding. In addition to the plate-like portion, the metal plate used in the present invention is a final product such as an electric / electronic product such as a boss for screwing, a rib for reinforcement, an insertion hole for attaching a component such as a gear, etc. It may have various components necessary for assembly. The shape of the portion where the metal plate and the thermoplastic resin contact is not particularly limited, and an arbitrary shape such as a quadrangle, a circle, or the like may be selected as desired. Further, the shape of the surface where the metal plate and the thermoplastic resin are in contact is not particularly limited, and may be a flat surface or a curved surface. The surface where the metal plate and the thermoplastic resin contact is not limited to a single plane or curved surface, and may have a convex portion or a concave portion inside the plane or curved surface of the metal plate.

Although the area of the part which a metal plate and a thermoplastic resin contact in particular is not restrict | limited, 0.1-20 cm < ² > is preferable and 0.5-10 cm < ² > is more preferable. By making the contact area between the metal plate and the thermoplastic resin to be such an area, the effect of improving the adhesion between the metal plate and the thermoplastic resin and the effect of suppressing the warp of the resulting metal composite laminate part appear significantly. It is.

  The thickness of the metal plate is not particularly limited, and the thickness of the metal plate may or may not be uniform. The thickness of the metal plate is typically from 0.1 mm to 5 mm, more preferably from 0.1 mm to 3 mm.

  A metal plate may roughen the surface of the location which contacts a thermoplastic resin beforehand, and may improve adhesion | attachment with a thermoplastic resin. The degree of the roughening treatment is 8 μm or more, preferably 8 to 15 μm, particularly 10 μm or more, expressed as ten-point average roughness (Rz). The roughening treatment can be performed by a method such as polishing, plating, or etching.

[Insulation layer]
In the method for producing a metal composite laminate part of the present invention, a mold is used in which a heat insulating layer is formed on the entire surface of at least the metal inner surface of the mold where the metal plate contacts the inner surface of the mold. By forming a heat-insulating layer over the entire surface where the metal plate and the inner surface of the mold are in contact with each other, the temperature of the metal plate is instantaneously increased by injecting high-temperature molten resin into the mold during injection molding. The temperature of the metal plate and the thermoplastic resin that comes into contact with the metal plate is unlikely to decrease. As a result, the solidification of the thermoplastic resin proceeds slowly while the thermoplastic resin and the surface of the metal plate are sufficiently familiar, and the temperature drop of the metal plate is small, and there is a difference in the amount of shrinkage between the metal and the resin. By becoming smaller, a metal composite laminated part in which the metal plate and the thermoplastic resin are sufficiently adhered can be obtained. If there is a portion on the inner surface of the mold that does not have a heat insulating layer even though it is in contact with the metal plate, the metal plate is rapidly cooled by the mold in that portion, and the effects of the present invention cannot be sufficiently obtained.

  In the present invention, “the heat insulating layer is formed on the entire surface where the metal plate and the inner surface of the mold contact” means that the portion where the metal plate and the inner surface of the mold are in contact is completely covered with the heat insulating layer. In addition to the case where the metal plate is placed in the mold, a slight thermal shift is inevitably formed in the portion where the metal plate and the inner surface of the mold are in contact with each other due to a slight positional shift. This includes cases where there are no parts. The specific area of the heat insulating layer is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more of the area of the portion where the inner surface of the mold contacts the metal plate.

  A material etc. will not be specifically limited if a heat insulation layer can suppress the temperature fall at the interface of the metal plate in a metal mold | die and a thermoplastic resin layer. Further, in the present invention, the metal mold only needs to have a heat insulating layer formed on the entire surface of the inner surface of the mold where the metal plate and the inner surface of the mold are in contact, but the metal plate and the thermoplastic resin are in close contact. It is preferable to form a heat insulation layer on the entire inner surface of the mold from the viewpoint of improving the properties.

  In the present invention, the thermal conductivity of the heat insulating layer formed on the inner surface of the mold is particularly preferably 5 W / m · K or less. By adjusting the thermal conductivity of the heat insulating layer to the above range, the metal plate and the temperature of the thermoplastic resin contacting the metal plate can be sufficiently suppressed, and the adhesion between the metal plate and the thermoplastic resin. Can be further enhanced. The thermal conductivity of the material of the heat insulating layer can be calculated by measuring the thermal diffusivity by a laser flash method, the specific gravity by an Archimedes method, and the specific heat by a differential scanning calorimeter (DSC).

  In addition, since a high-temperature thermoplastic resin flows into the mold during injection molding, the heat insulating layer needs to have heat resistance that can withstand the high temperature during molding.

  As a material of the heat insulation layer used in the manufacturing method of the metal composite laminated component of this invention, the thing containing a polyimide resin is more preferable. This is because the polyimide resin has a thermal conductivity of 5 W / m · K or less and has heat resistance enough to withstand high temperatures during injection molding.

  Specific examples of polyimide resins that can be suitably used in the present invention include pyromellitic acid (PMDA) polyimide, biphenyltetracarboxylic acid polyimide, polyamideimide using trimellitic acid, and bismaleimide resin (bismaleimide / triazine). Benzophenone tetracarboxylic acid-based polyimide, acetylene-terminated polyimide, thermoplastic polyimide, and the like. These polyimide resins can be used in combination of two or more.

  In addition to the polyimide resin, examples of a material that can be suitably used as the heat insulating layer include tetrafluoroethylene resin and polybenzimidazole resin.

  The method for forming the heat insulating layer on the inner surface of the mold is not particularly limited. For example, a solution of a polymer precursor such as a polyimide precursor capable of forming a polymer heat insulating layer is applied to the mold surface and heated to form a solvent. A method of forming a heat insulation layer such as a polyimide film by evaporating and further polymerizing by heating, or vapor-deposition polymerization of a heat-resistant polymer monomer such as pyromellitic acid anhydride and 4,4-diaminodiphenyl ether Methods and the like. For planar molds, a method of adhering by a suitable adhesion method using a polymer heat insulating film, or a method of forming a heat insulating layer by sticking a polymer heat insulating film in the form of an adhesive tape to a desired part of the mold, etc. A heat insulation layer can also be formed. Further, after the heat insulation layer is formed, a chrome (Cr) film or a titanium nitride (TiN) film can be further formed on the surface thereof.

[Molding method]
In the present invention, the molding method for producing the metal composite laminated part is not particularly limited as long as it can laminate a thermoplastic resin on a metal plate by injection molding, and various methods can be used.

  When the metal composite laminated part is formed in the method of the present invention, a preheated metal plate may be used. When the metal plate is preheated, the temperature of the metal plate is preferably 100 to 300 ° C, and more preferably 140 to 250 ° C. By preheating the metal plate, the adhesion between the metal plate and the thermoplastic resin can be further enhanced.

  In the present invention, the injection molding conditions at the time of producing the metal composite laminated part are not limited within the range not impairing the object of the present invention, considering the type of thermoplastic resin to be used, the shape of the metal composite laminated part, etc. It can be suitably selected from general injection molding conditions.

  In the present invention, the shape of the thermoplastic resin layer laminated on the metal plate is not particularly limited. The thickness of the thermoplastic resin layer may be uniform or non-uniform. The thermoplastic resin layer has various bosses for screwing, ribs for reinforcement, insertion holes for attaching parts such as gears, etc., necessary for assembling final products such as electrical and electronic products. You may have a component.

  In the present invention, the mold temperature at the time of producing the metal composite laminated part is not particularly limited as long as the object of the present invention is not impaired, but is preferably 50 to 160 ° C, and preferably 110 to 150 ° C. More preferably, it is 130-150 degreeC. By setting the mold temperature within the above range, the adhesion between the metal plate and the thermoplastic resin can be further enhanced.

[Metal composite laminated parts]
The metal composite laminated part produced by the method of the present invention is not particularly limited as long as a thermoplastic resin is laminated on a metal plate by injection molding. The metal composite laminated part produced by the method of the present invention is excellent in adhesion between the metal plate and the thermoplastic resin layer, and is less likely to be warped after molding. Therefore, it is suitable as a casing for various electric and electronic products. used. Examples of suitable electrical / electronic products using the metal composite laminated part obtained by the method of the present invention as a casing include a mobile phone, a notebook personal computer, a digital camera, a personal digital assistant (PDA), a portable game terminal, etc. Is mentioned.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

<Material>
Polyphenylene sulfide resin 1 (PPS1): manufactured by Polyplastics Co., Ltd. Fortron 1150T7
Polyphenylene sulfide resin 2 (PPS2): Fortron 1140A6 manufactured by Polyplastics Co., Ltd.
Liquid crystalline polymer 1 (LCP1): Polyplastics Co., Ltd., Vectra A460
Metal plate: SUS304 metal plate

<Example 1>
(Insulation layer formation)
As the mold, one having a holding piece for holding a metal insert was used. After uniformly applying the polyimide resin varnish to the entire cavity of the mold, the mold was treated at 250 ° C. for 60 minutes to form a heat insulating layer. The dimension of the holding piece before the heat insulation layer formation and after the heat insulation layer formation was measured, and the dimensional difference caused by forming the heat insulation layer was defined as the film thickness of the heat insulation layer.

(Molding of metal composite laminate products)
Under the injection molding conditions shown in Table 1, the test piece 1 for measuring the adhesion strength shown in FIG. 1 was injection molded at an mold temperature of 120 ° C. using an injection molding machine (TR-40VR manufactured by Sodick Co., Ltd.). .

[Test specimen for measuring adhesion strength]
The test piece for measuring the adhesion strength will be described with reference to FIG. FIG. 1A is a top view of the test piece 1 for measuring adhesion strength, and FIG. 1B is a side view of the test piece for measuring adhesive strength.

  As shown in FIG. 1, a test piece 1 for measuring adhesion strength is a thermoplastic resin layer 12 using a predetermined thermoplastic resin on a metal plate 11 (length 50 mm × width 50 mm × thickness 1 mm) made of SUS304. Is formed. The thermoplastic resin layer 12 has a thickness of 2 mm and has a square portion 13 (length 18 mm × width 18 mm). At the center of the square portion 13, a load applying unit 14 (5 mm long × 9 mm wide × 13 mm high) for applying a load when measuring the adhesion strength is provided.

[Adhesion strength measurement method]
Using Tensilon RTC-1325A (manufactured by Orientec Co., Ltd.), after fixing both ends of the test piece 1 for adhesion strength measurement where the thermoplastic resin layer 12 is not laminated, the load application part of the test piece 1 for adhesion strength measurement A load was applied at a pressing speed of 1 mm / min to a place 4 mm from the joint between the thermoplastic resin layer 12 and the load application unit 14 on a surface having a width of 9 mm, and the peel strength was measured.

<Examples 2 to 4>
Other than changing the thermoplastic resin to the resin shown in Table 2, respectively, blowing hot air on the metal plate mounted on the mold for 30 seconds, and heating the metal insert to about 250 ° C., followed by injection molding In the same manner as in Example 1, a test piece 1 for measuring adhesion strength was molded, and the adhesion strength was measured. The adhesion strength of the metal composite laminate parts obtained in Examples 2 to 4 is shown in Table 2.

<Comparative Example 1>
Except not forming a heat insulation layer in the cavity of a metal mold | die, the test piece 1 for adhesive strength measurement was shape | molded similarly to Example 1, and adhesive strength was measured. The adhesion strength of the metal composite laminated part obtained in Comparative Example 1 is shown in Table 2.

<Comparative Examples 2 and 3>
The thermoplastic resin described in Table 2 was used, a heat insulating layer was not formed in the mold cavity, and hot air was blown on the metal plate mounted on the mold for 30 seconds, and the metal insert was heated to about 250 ° C. A test piece 1 for measuring adhesion strength was molded in the same manner as in Example 1 except that injection molding was performed later, and the adhesion strength was measured. Table 2 shows the adhesion strength of the metal composite laminated parts obtained in Comparative Examples 2 and 3.

<Example 5>
Under the same conditions as in Example 1, a test piece 2 for warping amount measurement shown in FIG. 3 was manufactured by injection molding. Using the obtained test piece 2 for measuring the amount of warpage, the amount of warpage of the obtained metal composite laminate molded article was measured according to the following method for measuring the amount of warpage. Table 2 shows the measurement results of the amount of warpage.

[Test specimen for measuring warpage]
The test piece for measuring the amount of warpage will be described with reference to FIGS. 2A is a top view of the metal plate 21 used for manufacturing the test piece 2 for measuring the warpage, and FIG. 2B is a side view of the metal plate 21 used for manufacturing the test piece 2 for measuring the warpage. is there. FIG. 3A is a top view of the test piece 2 for measuring the amount of warpage, and FIG. 3B is an entire cross-sectional view of the test piece 2 for measuring the amount of warpage along the line AA ′ shown in FIG. It is.

  The test piece 2 for measuring the amount of warpage is formed using a metal plate 21 (thickness 1.0 mm) having a thin portion 22 (thickness 0.5 mm) at the center and having four corners cut off as shown in FIG. did. As shown in FIG. 3, in the thermoplastic resin layer 23, the thickness of the thermoplastic resin layer 23 on the thin portion 22 is 0.5 mm, and the thickness of the thermoplastic resin layer outside the metal plate 21 is 1. It laminated | stacked by injection molding on the thin part 22 upper part so that it might be set to 0 mm.

[Warpage measurement method]
The test piece 2 for measuring the amount of warpage is placed on a horizontal table, and the height of the upper surface of the test piece from the table is measured with an image measuring device (9 points (3 points × 3 rows)). Measurement was performed using Quick Vision 404PRO • CNC, manufactured by Mitutoyo Corporation. Of the nine measurement results, the difference between the maximum height and the minimum height was taken as the amount of warpage.

<Example 6>
Except that the thickness of the heat-insulating layer was 10 μm, the test piece 2 for measuring the amount of warpage was molded in the same manner as in Example 5, and the amount of warpage was measured. Table 2 shows the measurement results of the amount of warpage.

<Example 7>
Except for using the thermoplastic resin described in Table 2, the test piece 2 for measuring the amount of warpage was molded in the same manner as in Example 5, and the amount of warpage was measured. Table 2 shows the measurement results of the amount of warpage.

<Comparative Examples 4 and 5>
A test piece 2 for measuring the amount of warpage was produced by injection molding under the same conditions as in Comparative Example 1 except that the thermoplastic resin described in Table 2 was used. Table 2 shows the measurement results of the amount of warpage.

  By comparing Examples 1 to 4 and Comparative Examples 1 to 3, a metal film and a thermoplastic resin are formed by forming a polyimide film as a heat insulating layer in a portion where the metal plate in the mold and the inner surface of the mold are in contact with each other. It can be seen that the adhesion strength with the layer is significantly improved. Moreover, the metal composite obtained by forming a polyimide film as a heat insulation layer in the part which the metal plate in a metal mold | die and a metal mold | die inner surface contact by comparison with Examples 5-7 and Comparative Examples 4 and 5. It can be seen that the amount of warpage occurring in the laminated part can be greatly reduced.

  Moreover, it can be seen from the comparison between Example 1 and Example 2 that the adhesion strength between the metal plate and the thermoplastic resin of the metal composite laminated part can be further improved by preheating the metal plate.

DESCRIPTION OF SYMBOLS 1 Test piece for adhesion strength measurement 11 Metal plate 12 Thermoplastic resin layer 13 Square part 14 Load application part 2 Test piece for warpage amount measurement 21 Metal plate 22 Thin part 23 Thermoplastic resin layer

Claims (5)

  A thermoplastic resin composed of a polyphenylene sulfide resin and / or a liquid crystalline polymer is formed by injection molding using a mold in which a heat insulating layer is formed on the entire surface of the mold inner surface where at least the metal plate contacts the mold inner surface. The manufacturing method of the metal composite laminated component laminated | stacked on the said metal plate.   The method for producing a metal composite laminate part according to claim 1, wherein the thermoplastic resin is made of polyphenylene sulfide resin.   The method for producing a metal composite laminate part according to claim 1 or 2, wherein the heat insulating layer has a thermal conductivity of 5 W / m · K or less.   The said heat insulation layer is a manufacturing method of the metal composite laminated component in any one of Claim 1 to 3 containing a polyimide resin.   The method for manufacturing a metal composite laminate part according to any one of claims 1 to 4, wherein the metal composite laminate part is a casing of an electric / electronic product.

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