JP2016179545A - COATED Al-CONTAINING METAL SHAPED MATERIAL, COMPLEX HAVING COATED Al-CONTAINING METAL SHAPED MATERIAL AND MOLDING OF THERMOPLASTIC RESIN COMPOSITION BONDED TOGETHER, AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated AL-containing metal shaped material having superior bondability and sealability when bonded to a molding of a thermoplastic resin composition.SOLUTION: A coated AL-containing metal shaped material comprises an AL-containing metal shaped material comprising aluminum or aluminum alloy, and a coating formed on the surface of the AL-containing metal shaped material. The coating includes polycarbonate unit-containing polyurethane resin. The ratio of the mass of the polycarbonate unit to the total resin mass in the coating is 15-80 mass%. The thickness of the coating is 0.5 μm or more.SELECTED DRAWING: None

Description

  The present invention relates to a coated Al-containing metal preform, a composite in which a painted Al-containing metal preform and a molded body of a thermoplastic resin composition are joined, and a method for producing the same.

  A metal plate or a press-formed product thereof, or a so-called “metal base material” formed by casting, forging, cutting, powder metallurgy or the like is used in various industrial products such as automobiles. In addition, a composite in which a metal shape member and a molded body of a resin composition are joined is lighter than a component made only of metal and higher in strength than a component made only of a resin. Used in various electronic devices such as computers. Among metals, aluminum (Al) and aluminum alloy (Al alloy) are preferably used because they have a small specific gravity and can be reduced in weight. Conventionally, such a composite has been manufactured by fitting a metal base material and a molded body of a resin composition. However, the method for producing a composite by fitting has a large number of work steps and has low productivity. Therefore, in recent years, it is common to manufacture a composite by joining a metal base material and a molded body of a resin composition by insert molding.

  When producing a composite by insert molding, it is important to improve the adhesion between the metal base material and the molded body of the resin composition. As a method for improving the adhesion between the metal shaped material and the molded body of the resin composition, for example, it is proposed to roughen the surface of the metal shaped material before performing insert molding (patent) References 1-3). In the methods of Patent Documents 1 to 3, the surface of the Al alloy is roughened to improve the bondability between the Al alloy and the molded body of the resin composition.

JP 2006-027018 A JP 2004-050488 A JP 2005-342895 A

  The composites described in Patent Documents 1 to 3 have a problem in that the adhesion between the Al alloy shaped material and the molded body of the resin composition is not sufficient because the composites are joined by the anchor effect. Moreover, in the manufacturing method of the composite_body | complex described in patent documents 1-3, in order to roughen the surface of Al alloy shaped material, it is fine between Al alloy shaped material and the molded object of a resin composition. Gaps are easily formed. For this reason, in the composites described in Patent Documents 1 to 3, the sealability between the Al alloy shaped material and the molded resin composition is low, and the Al alloy shaped material and the molded resin composition There was a risk of gas or liquid leaking from between.

  The present invention has been made in view of the above points, and when coated with a molded body of a thermoplastic resin composition, the coated Al-containing metal element and the coated Al-containing metal element are excellent in adhesion and sealing properties. It aims at providing the composite_body | complex in which the shape material and the molded object of the thermoplastic resin composition were joined, and its manufacturing method.

  The present inventors have found that the above-mentioned problems can be solved by forming a predetermined coating film on the surface of the Al-containing metal shape material, and have further studied and completed the present invention.

That is, the present invention relates to the following painted Al-containing metal shapes.
[1] An Al-containing metal shape member made of aluminum or an aluminum alloy, and a coating film formed on a surface of the Al-containing metal shape material, wherein the coating film includes a polycarbonate unit-containing polyurethane resin. The ratio of the mass of the polycarbonate unit to the total resin mass in the coating film is 15 to 80% by mass, and the film thickness of the coating film is 0.5 μm or more, and the molded body of the thermoplastic resin composition Painted Al-containing metal shape material for joining.
[2] The heat according to [1], wherein the coating film includes an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V, Mo and W, or a combination thereof. Painted Al-containing metal shape material for joining with a molded body of a plastic resin composition.

The present invention also relates to the following composites.
[3] The coated Al-containing metal profile according to [1] or [2], and a molded body of a thermoplastic resin composition bonded to the surface of the painted Al-containing metal profile. Complex.
[4] The thermoplastic resin composition is an acrylonitrile-butadiene-styrene resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, or a combination thereof. The complex according to [3].

Furthermore, this invention relates to the manufacturing method of the following composites.
[5] A method for producing a composite in which a painted Al-containing metal shape material and a molded body of a thermoplastic resin composition are joined, the step of preparing a painted Al-containing metal shape material, and the painted Al Inserting the metal-containing metal-containing material into an injection mold; injecting the thermoplastic resin composition into the injection-molding mold; and the thermoplastic resin composition on the surface of the painted Al-containing metal raw material The coated Al-containing metal profile is formed of an Al-containing metal profile made of aluminum or an aluminum alloy, and a coating formed on the surface of the Al-containing metal profile. The coating film contains a polycarbonate unit-containing polyurethane resin, the ratio of the mass of the polycarbonate unit to the total resin mass in the coating film is 15 to 80% by mass, and the film thickness of the coating film Is 0 It is 5μm or more, the production method of the composite.

  ADVANTAGE OF THE INVENTION According to this invention, when it joins with the molded object of a thermoplastic resin composition, the coating Al containing metal shape material which is excellent in adhesiveness and sealing performance, and a coating Al containing metal shape material, and a thermoplastic resin composition It is possible to provide a composite in which the molded body is joined.

FIG. 1 is a schematic diagram showing the structure of a composite for evaluating adhesion. FIG. 2 is a schematic diagram showing a configuration of a composite for evaluating gas sealing properties.

1. Painted Al-containing metal profile The coated Al-containing metal profile according to the present embodiment includes an Al-containing metal profile consisting of Al or an Al alloy, and a coating film formed on the surface of the Al-containing metal profile. And have. Moreover, as for the coating Al containing metal raw material, the surface treatment film may be formed between the Al containing metal raw material and the coating film. Hereinafter, each element of the painted Al-containing metal profile will be described.

(1) Al-containing metal shape material The kind of Al-containing metal shape material used as the coating substrate is not particularly limited as long as it is made of an Al-containing metal selected from Al and an Al alloy. Examples of the Al-containing metal shaped material include rolled products such as plate materials and extruded shapes, and die-cast products formed by casting, forging, cutting, powder metallurgy, and the like. The Al-containing metal shape material may be subjected to known coating pretreatments such as degreasing and pickling as necessary.

(2) Surface treatment film In the coated Al-containing metal shape material, a chemical conversion treatment film or an alumite film may be formed between the Al-containing metal shape material and the coating film. The chemical conversion treatment film is formed on the surface of the Al-containing metal profile, and improves the adhesion of the coating film to the Al-containing metal profile and the corrosion resistance of the Al-containing metal profile. In addition, the anodized film can improve the corrosion resistance and wear resistance of the Al-containing metal material, and can also have other functions such as decoration. These films may be formed on the entire surface of the surface of the Al-containing metal shape member, or may be formed on only a part of the surface.

The kind of chemical conversion treatment which forms a chemical conversion treatment film is not specifically limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, phosphate treatment and the like. The adhesion amount of the chemical conversion treatment film formed by chemical conversion treatment is not particularly limited as long as it is within a range effective for improving coating film adhesion and corrosion resistance. For example, in the case of a chromate film, the adhesion amount may be adjusted so that the total Cr conversion adhesion amount is 5 to 100 mg / m ² . Further, in the case of a chromium-free coating, the Ti-Mo composite coating has a range of 10 to 500 mg / m ² , and the fluoroacid-based coating has a fluorine equivalent or total metal element equivalent deposit of 3 to 100 mg / m ^2. The adhesion amount may be adjusted. Moreover, what is necessary is just to adjust the adhesion amount so that it may become 0.1-5 g / m < ² > in the case of a phosphate membrane | film | coat.

Examples of the alumite treatment include a method of performing electrolysis using Al as an anode in a treatment bath containing dilute sulfuric acid, oxalic acid, or the like. Thereby, the surface of Al is electrochemically oxidized, and a porous film of aluminum oxide (Al ₂ O ₃ ) can be formed. Another example of the alumite treatment includes a method of treating Al with an acid having a low dissolving power with respect to Al oxide such as boric acid. As a result, a thin oxide layer having a thickness of several tens to several hundreds of nanometers can be formed on the surface of Al. Further, if necessary, the alumite film may be sealed. Examples of the sealing treatment include pore inactivation by a chemical reaction and pore filling by a polymer. For example, the alumite film may be β-aluminated by hydration with a high-temperature liquid such as boiling water or nickel acetate solution, or pressurized steam, and the pore wall may be hydrated and expanded for sealing. Further, the alumite film may be colored by adsorbing a metal salt, an organic dye or the like to the porous using the porous property of the alumite film.

(3) Coating film The coating film contains a polycarbonate unit-containing polyurethane resin, and improves the adhesion of the molded article of the thermoplastic resin composition to the Al-containing metal preform. As will be described later, the coating film may further contain a polycarbonate unit-free resin as an optional component. The coating film may be formed on the joint surface of the surface of the Al-containing metal shape material as in the case of the chemical conversion treatment film. Is formed.

  The polycarbonate unit-containing polyurethane resin has a polycarbonate unit in the molecular chain. “Polycarbonate unit” refers to the structure shown below in the molecular chain of a polyurethane resin. The polycarbonate unit-containing polyurethane resin and the thermoplastic resin contained in the molded article of the thermoplastic resin composition described later have similar skeletons (such as benzene rings) and functional groups, respectively. Therefore, when the thermoplastic resin composition is insert-molded with respect to the painted Al-containing metal profile, the polycarbonate unit-containing polyurethane resin is compatible with the thermoplastic resin composition and is firmly bonded. Therefore, the adhesiveness of the molded article of the thermoplastic resin composition to the coating film can be improved by including the polycarbonate unit-containing polyurethane resin in the coating film.

  The polycarbonate unit-containing polyurethane resin can be prepared, for example, by the following steps. An organic polyisocyanate, a polycarbonate polyol, and a polyol having a tertiary amino group or a carboxyl group are reacted to produce a urethane prepolymer. In addition, within the range which does not impair the objective of this invention, it is possible to use together polyols other than a polycarbonate polyol compound, for example, polyester polyol, polyether polyol, etc.

  Moreover, the tertiary amino group of the produced urethane prepolymer is neutralized with an acid or quaternized with a quaternizing agent, and then chain-extended with water to produce a polyurethane resin containing a cationic polycarbonate unit. be able to.

  In addition, by neutralizing the carboxyl group of the produced urethane prepolymer with basic compounds such as triethylamine, trimethylamine, diethanolmonomethylamine, diethylethanolamine, caustic soda and caustic potassium, and converting them to carboxylic acid salts, anionic A polycarbonate unit-containing polyurethane resin can be produced.

  Polycarbonate polyol includes carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, It can be obtained by reacting with a diol compound such as diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, or 1,6-hexanediol. The polycarbonate polyol may be chain-extended with an isocyanate compound.

  The kind of organic polyisocyanate is not specifically limited. Examples of organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydro Naphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexyl Down diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, include 4,4'-dicyclohexylmethane diisocyanate. These organic polyisocyanates may be used alone or in combination of two or more.

  The coating film may further contain a polycarbonate unit-free resin as an optional component. Polycarbonate unit-free resin further improves the adhesion of the coating film to the Al-containing metal profile. The type of the polycarbonate unit-free resin is not particularly limited as long as it does not contain a polycarbonate unit in the molecular chain, but from the viewpoint of improving the coating film adhesion to the Al-containing metal shape material, it contains a polar group. Those are preferred. Examples of the type of polycarbonate unit-free resin include epoxy resins, polyolefin resins, phenolic resins, acrylic resins, polyester resins, and polycarbonate unit-free polyurethane resins. These resins may be used alone or in combination of two or more.

  Examples of the type of epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and the like. Examples of the type of polyolefin resin include polyethylene resin and polypropylene resin. Examples of the type of phenolic resin include novolak type resins and resol type resins. The polycarbonate unit-free polyurethane-based resin can be obtained by copolymerizing a diol and a diisocyanate. Examples of the type of diol include polycarbonate diol, bisphenol A, 1,6-hexanediol, 1,5-pentanediol, and the like. Examples of the type of diisocyanate include aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and the like.

  The ratio of the mass of the polycarbonate unit to the total resin mass is 15 to 80% by mass. When the proportion of the mass of the polycarbonate unit is less than 15% by mass, the adhesiveness of the molded body of the thermoplastic resin composition to the coating film may not be sufficiently obtained, and as a result, the sealing property may not be sufficiently obtained. is there. On the other hand, when the proportion of the mass of the polycarbonate unit is more than 80% by mass, the adhesion of the coating film to the Al-containing metal shaped material cannot be sufficiently obtained, and as a result, the sealing property may not be sufficiently obtained. is there. The ratio of the mass of the polycarbonate unit to the total mass of the resin can be determined by nuclear magnetic resonance spectroscopy (NMR analysis) using a sample in which the coating film is dissolved in chloroform.

  It is preferable that the coating film further includes a metal (valve metal) oxide, hydroxide or fluoride selected from the group consisting of Ti, Zr, V, Mo and W, or a combination thereof. By dispersing these metal compounds in the chemical conversion film, the corrosion resistance of the Al-containing metal shaped material can be further improved. In particular, these metal fluorides are also expected to suppress corrosion at film defects by a self-repairing action.

  The coating film may further contain a soluble metal phosphate or complex phosphate, or a poorly soluble metal phosphate or complex phosphate. Soluble metal phosphates and composite phosphates further improve the corrosion resistance of the Al-containing metal profile by complementing the self-healing action of the metal fluorides. Further, the hardly soluble metal phosphate and the composite phosphate are dispersed in the coating film to improve the film strength. For example, the soluble metal phosphate or complex phosphate, or the poorly soluble metal phosphate or complex phosphate is a salt of Al, Ti, Zr, Hf, Zn or the like.

  The film thickness of a coating film will not be specifically limited if it is 0.5 micrometer or more. When the film thickness of the coating film is less than 0.5 μm, the adhesion and sealing properties cannot be sufficiently improved when bonded to the molded body of the thermoplastic resin composition. Although the upper limit of the film thickness of a coating film is not specifically limited, It is about 20 micrometers. Even if the film thickness of the coating film exceeds 20 μm, no further improvement in adhesion can be expected.

  The coating film may further contain additives such as an etching agent, an inorganic compound, a lubricant, a color pigment, and a dye as necessary.

  An etching agent improves the adhesiveness of the coating film with respect to Al containing metal shape material by activating the surface of Al containing metal shape material. Examples of the type of the etching agent include fluorides such as hydrofluoric acid, ammonium fluoride, zircon hydrogen fluoride, and titanium hydrogen fluoride.

  The inorganic compound densifies the coating film and improves water resistance. Examples of the types of inorganic compounds include inorganic oxide sols such as silica, alumina, and zirconia; phosphates such as sodium phosphate, calcium phosphate, manganese phosphate, and magnesium phosphate.

  The lubricant can suppress galling on the surface of the painted Al-containing metal profile. Examples of the types of lubricants include organic lubricants such as fluorine, polyethylene, and styrene; inorganic lubricants such as molybdenum disulfide and talc.

  The color pigment and the dye impart a predetermined color tone to the coating film. Examples of the types of color pigments include inorganic pigments and organic pigments. Examples of the type of dye include organic dyes.

  The manufacturing method of the coating Al containing metal raw material which concerns on this Embodiment is not specifically limited. For example, a painted Al-containing metal profile can be produced by the following method.

  First, an Al-containing metal shape material to be a coating base material is prepared. When forming a surface treatment film such as a chemical conversion treatment film or an alumite film, the surface treatment is performed before the coating film is formed. When the surface treatment film is not formed, the film is formed as it is.

  When forming a chemical conversion treatment film on the surface of the Al-containing metal raw material, the chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid to the surface of the Al-containing metal raw material and drying it. The method for applying the chemical conversion liquid is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. What is necessary is just to set suitably the drying conditions of a chemical conversion liquid according to the composition of a chemical conversion liquid, etc. For example, an Al-containing metal element coated with a chemical conversion treatment solution is placed in a drying oven without being washed with water, and heated so that the ultimate plate temperature is in the range of 80 to 250 ° C. A uniform chemical conversion coating can be formed on the surface of the profile.

  The coating film can be formed by applying and baking a paint containing a polycarbonate unit-containing polyurethane resin on the surface of the Al-containing metal element (or chemical conversion film). The method for applying the paint is not particularly limited and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. The baking condition of the paint may be set as appropriate according to the composition of the paint. For example, an Al-containing metal shape material coated with a paint is put into a drying oven and dried with a hot air drier so that the ultimate plate temperature is within a range of 110 to 200 ° C. A uniform coating film can be formed on the surface of the (or chemical conversion coating).

  As described above, the painted Al-containing metal shape material according to the present embodiment contains a predetermined amount of the polycarbonate unit-containing polyurethane resin, and has a coating film having a thickness of 0.5 μm or more. It is excellent in the adhesiveness of the molded body of the thermoplastic resin composition, and is excellent in the sealing property in the composite. Moreover, the coated Al-containing metal shape material according to the present embodiment can be easily manufactured by simply applying and baking a paint containing a polycarbonate unit-containing polyurethane resin.

2. Composite A composite can be produced by joining a molded body of a thermoplastic resin composition to the surface of a painted Al-containing metal preform according to the present embodiment.

  The molded body of the thermoplastic resin composition is bonded to the surface (more precisely, the surface of the coating film) of the aforementioned coated Al-containing metal shape material. The shape of the molded article of the thermoplastic resin composition is not particularly limited and can be appropriately selected depending on the application.

  The kind of thermoplastic resin which comprises the molded object of a thermoplastic resin composition is not specifically limited. Examples of thermoplastic resins include acrylonitrile-butadiene-styrene (ABS) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, polyamide (PA) Resin, polyphenylene sulfide (PPS) resin, and combinations thereof. Among these, a thermoplastic resin having a benzene ring contained in a polycarbonate unit is preferable, and a PBT resin or a PPS resin is particularly preferable.

  The PBT resin is obtained, for example, by condensing 1,4-butanediol and terephthalic acid, and has the following structure.

  The PPS resin is obtained, for example, by condensing p-dichlorobenzene and sodium sulfide in an amide solvent, and has the following structure.

  The thermoplastic resin composition may contain an inorganic filler, a thermoplastic polymer, and the like from the viewpoints of molding shrinkage, material strength, mechanical strength, scratch resistance, and the like. In particular, when a thermoplastic resin having no benzene ring is used, it is preferable to blend a thermoplastic polymer having a benzene ring.

  An inorganic filler improves the rigidity of the molded object of a thermoplastic resin composition. The kind of inorganic filler is not particularly limited, and a known substance can be used. Examples of inorganic filler types include fiber fillers such as glass fiber, carbon fiber, and aramid resin; carbon black, calcium carbonate, calcium silicate, magnesium carbonate, silica, talc, glass, clay, lignin, mica, quartz powder And powder fillers such as glass spheres; pulverized products of carbon fibers and aramid fibers. Although the compounding quantity of an inorganic filler is not specifically limited, The inside of the range of 5-50 mass% is preferable. An inorganic filler may be used independently and may be used in combination of 2 or more type.

  The thermoplastic polymer improves the impact resistance of the molded article of the thermoplastic resin composition. The kind of thermoplastic polymer is not particularly limited. Examples of the thermoplastic polymer having a benzene ring include acrylonitrile-butadiene-styrene (ABS) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, polystyrene ( PS) resin and polyphenylene ether (PPE) resin are included. Examples of the thermoplastic polymer having no benzene ring include polyolefin resins. A thermoplastic polymer may be used independently and may be used in combination of 2 or more type.

3. Manufacturing method of composite body The manufacturing method of the composite body according to the present embodiment includes 1) a first step of preparing a coated Al-containing metal shape material, and 2) using the painted Al-containing metal shape material as an injection mold. A second step of inserting, and 3) a third step of joining a molded body of the thermoplastic resin composition to the surface of the coated Al-containing metal element.

  Hereinafter, each process of the manufacturing method of the composite_body | complex which concerns on this Embodiment is demonstrated.

(1) First Step In the first step, a painted Al-containing metal shape material is prepared by the above-described procedure.

(2) Second Step In the second step, the painted Al-containing metal shape material prepared in the first step is inserted into the injection mold. The painted Al-containing metal shape material may be processed into a desired shape by pressing or the like.

(3) Third Step In the third step, a high-temperature thermoplastic resin composition is injected at a high pressure into the injection mold in which the painted Al-containing metal shape material is inserted in the second step. At this time, it is preferable to provide a gas vent in the injection mold so that the thermoplastic resin composition flows smoothly. The high-temperature thermoplastic resin composition comes into contact with the coating film formed on the surface of the painted Al-containing metal profile. The temperature of the injection mold is preferably near the melting point of the thermoplastic resin composition.

  After completion of injection, the mold is opened and released to obtain a composite. The composite obtained by injection molding may be annealed after molding to eliminate internal distortion due to molding shrinkage.

  By the above procedure, the composite body can be manufactured by joining the molded body of the thermoplastic resin composition to the surface of the painted Al-containing metal preform according to the present embodiment. A predetermined coating film having excellent adhesion to both the Al-containing metal preform and the molded body of the thermoplastic resin composition is formed on the coated Al-containing metal preform of the present embodiment. For this reason, the composite according to the present embodiment is also excellent in the adhesion between the Al-containing metal preform and the molded body of the thermoplastic resin composition, and the sealing performance in the composite.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples.

1. Preparation of painted Al-containing metal profile (1) Al-containing metal profile The following 6 types of Al alloys defined in the Japanese Industrial Standard (JIS H 4140) as the coating base for painted Al-containing metal profiles Each board was prepared.

  For A1050 having a plate thickness of 0.5 mm, an anodized Al alloy plate (coated base material 1) and an anodized Al alloy plate (coated base material 2) were prepared.

  For A2017 with a plate thickness of 0.5 mm, an Al alloy plate (coating substrate 3) that was not anodized was prepared.

  About A5052 whose plate | board thickness is 0.5 mm, the Al alloy board (coating base material 4) which has not been anodized was prepared.

  For A6063 having a plate thickness of 2 mm, an Al alloy plate not subjected to alumite treatment (painted base material 5) and an Al alloy plate not subjected to alumite treatment (painted base material 6) were prepared.

(2) Preparation of paint Add polycarbonate unit-containing resin, polycarbonate unit-free resin and various additives to water so that the ratio of the mass of the polycarbonate (PC) unit to the total mass of the resin is the predetermined ratio shown in Table 1. Thus, a paint having a non-volatile component of 20% was prepared (see Table 1). In addition, when multiple types of polycarbonate unit non-containing resin were used, it mix | blended so that each polycarbonate unit non-containing resin might become equivalent. In addition, 0.5 wt% ammonium fluoride (Morita Chemical Co., Ltd.) as an etching agent, 2 wt% of colloidal silica (Nissan Chemical Industry Co., Ltd.) as an inorganic compound, and phosphoric acid (Kishida Chemical Co., Ltd.) 0.5% by mass of each company).

  For each of the polycarbonate unit-containing resins shown in Table 1, a polyurethane resin containing 90% by mass of a polycarbonate unit was a test product (dry solid content of 30% by mass) prepared by a resin manufacturer. Moreover, the resin composition whose polycarbonate unit is 100 mass% was prepared with the following method. A polycarbonate plate (Takiron Co., Ltd.) having a thickness of 2.0 mm was cut into about 5 mm squares to obtain polycarbonate pieces. 30 g of a polycarbonate piece cut into 200 g of methylene chloride was added, and the mixture was stirred for 3 hours while heating so that the liquid temperature became 40 ° C., thereby dissolving the polycarbonate piece in methylene chloride. By this step, a resin composition having a polycarbonate unit of 100% by mass was prepared.

  About each polycarbonate unit non-containing resin shown by Table 1, the polycarbonate unit non-containing polyurethane resin used HUX-232 (dry solid content 30 mass%; ADEKA Corporation). As the epoxy resin, Adeka Resin EM-0434AN (dry solid content: 30% by mass; ADEKA Corporation) was used. As the polyolefin resin, Hardren NZ-1005 (dry solid content 30% by mass; Toyobo Co., Ltd.) or MGP 1650 (Maruyoshi Chemical Co., Ltd.) was used. As the phenolic resin, Tamanol E-100 (dry solid content: 52% by mass; Arakawa Chemical Industries, Ltd.) was used.

(3) Formation of coating film The coated substrate was immersed in an alkaline degreasing aqueous solution (pH = 12) at a liquid temperature of 60 ° C. for 1 minute to degrease the surface. Next, a paint is applied to the surface of the degreased coating substrate with a roll coater, and dried with a hot air dryer so that the ultimate plate temperature becomes 150 ° C., thereby forming a coating film having a film thickness shown in Table 1. did.

  For each of the painted Al-containing metal shapes, the painted Al-containing metal shape No. Table 1 shows the ratio of the PC unit, the ratio of the PC unit-containing resin, the ratio of the PC unit-free resin, the film thickness of the coating film, and the coating substrate.

・ＰＣユニット含有樹脂
Ａ：ＰＣユニット９０質量％含有ポリウレタン樹脂
Ｂ：ＰＣユニット１００質量％樹脂組成物
・ＰＣユニット非含有樹脂
ａ：ＰＣユニット非含有ポリウレタン樹脂（ＨＵＸ−２３２）
ｂ：エポキシ系樹脂（アデカレジンＥＭ−０４３４ＡＮ）
ｃ：ポリオレフィン系樹脂（ハードレンＮＺ−１００５）
ｄ：フェノール系樹脂（タマノルＥ−１００）
・塗装基材
１：Ａ１０５０（アルマイト処理）
２：Ａ１０５０
３：Ａ２０１７
４：Ａ５０５２
５：Ａ６０６３（アルマイト処理）
６：Ａ６０６３

PC unit-containing resin A: PC unit 90% by mass polyurethane resin B: PC unit 100% by mass resin composition PC unit non-containing resin a: PC unit non-containing polyurethane resin (HUX-232)
b: Epoxy resin (Adeka Resin EM-0434AN)
c: Polyolefin resin (Hardylene NZ-1005)
d: Phenolic resin (Tamanol E-100)
・ Coating substrate 1: A1050 (Alumite treatment)
2: A1050
3: A2017
4: A5052
5: A6063 (Alumite treatment)
6: A6063

2. Preparation of composite (1) Painted Al-containing metal shape material The above-mentioned painted Al-containing metal shape materials No. 1 to 20 were prepared.

(2) Thermoplastic resin composition Examples of the thermoplastic resin composition include acrylonitrile-butadiene-styrene (ABS) resin compositions, polyethylene terephthalate (PET) resin compositions, and polybutylene terephthalate (PBT) shown in Table 2. Six types of resin compositions were used: a resin-based resin composition, a polycarbonate (PC) -based resin composition, a polyamide (PA) -based resin composition, and a polyphenylene sulfide (PPS) -based resin composition. Various thermoplastic polymers and various fillers shown in Table 2 are added to each thermoplastic resin composition. The mold shrinkage is a measured value in the flow direction.

  As the ABS resin composition, Excelloy CK10G20 (no clear melting point is observed; Techno Polymer Co., Ltd.) was used.

  As a PET resin composition, a sample (melting point: 230 ° C.) from a resin manufacturer was used.

  As the PBT resin composition, Novaduran 5710F40 (melting point 230 ° C .; Mitsubishi Engineer Plastics Co., Ltd.) was used.

  Europin GS-2030MR2 (melting point 250 ° C .; Mitsubishi Engineer Plastics Co., Ltd.) was used as the PC resin composition.

  As the PA-based resin composition, Amilan CM3511G50 (melting point 216 ° C .; Toray Industries, Inc.) was used.

  As the PPS resin composition, 1130MF1 (melting point 280 ° C .; Polyplastics Co., Ltd.) was used.

  About the thermoplastic resin composition used for preparation of the composite, the thermoplastic resin composition No. Table 2 shows the type of thermoplastic resin composition, the type of thermoplastic polymer, the proportion of filler, the molding shrinkage, and the resin temperature during injection molding.

(3) Production of Complex for Adhesion Evaluation FIG. 1 is a schematic diagram showing the configuration of a complex for adhesion evaluation. The coated Al-containing metal profile was inserted into the injection mold, and the molten thermoplastic resin composition was injected into the injection mold. The volume of the portion into which the thermoplastic resin composition flows in the injection mold is 30 mm wide × 100 mm long × 4 mm thick, and the region of 30 mm wide × 30 mm long is coated with an Al-containing metal element and heat. The plastic resin composition is in contact. After injecting the thermoplastic resin composition into the injection mold, the thermoplastic resin composition was cooled and solidified to obtain a composite of the coated Al-containing metal preform and the molded article of the thermoplastic resin composition. .

(4) Production of Composite for Gas Sealing Evaluation FIG. 2 is a schematic diagram showing a configuration of a composite for gas sealing evaluation. A coated Al-containing metal shaped material having a through-hole having a diameter of 10 mm in the center was inserted into an injection mold, and a molten thermoplastic resin composition was injected into the injection mold. The volume of the portion into which the thermoplastic resin composition flows in the injection mold is 20 mm in diameter × 3 mm in thickness, and the coated Al-containing metal element and the thermoplastic resin composition are in the region of 5 mm around the through hole. Things are in contact. After injecting the thermoplastic resin composition into the injection mold, the thermoplastic resin composition was cooled and solidified to obtain a composite of the coated Al-containing metal preform and the molded article of the thermoplastic resin composition. .

3. Evaluation of composite (1) Evaluation of adhesion In a composite for adhesion evaluation, the coated Al-containing metal raw material and the molded body of the thermoplastic resin composition were pulled at a speed of 100 mm / min in the same plane direction. The strength when peeled (peel strength) was measured. At this time, the fractured portion is observed and peeled between the Al-containing metal shape member and the coating film, or peeled between the coating film and the molded body of the thermoplastic resin composition. I observed it. “X” when the peel strength is less than 1.0 kN, “△” when it is 1.0 kN or more and less than 1.5 kN, “◯” when it is 1.5 kN or more and less than 2.0 kN, or 2.0 kN or more The case was evaluated as “「 ”. As a material that can withstand practical use, a composite having a peel strength of 1.5 kN or more (◯ or ◎) was judged to be acceptable.

(2) Evaluation of gas sealability After the composite for gas sealability evaluation was immersed in 35 ° C water for 24 hours, it was fixed to a stainless steel sealing jig. Helium gas was sealed from the gas inlet into the sealing jig at a pressure of 0.3 MPa, and the amount of helium leak in the vicinity of the joint between the coated Al-containing metal profile and the molded body of the thermoplastic resin composition was measured. . The helium leak test was conducted using a leak detector (HELIOT 714; ULVAC, Inc.) according to JIS Z 2331: 2006 (Helium leak test method) Annex 3 ((normative) suction method (sniffer method)). When the amount of helium leak is 1.0 × 10 ⁻³ Pa · m ³ / s or more, “×” is 1.0 × 10 ⁻⁵ Pa · m ³ / s or more and 1.0 × 10 ⁻³ Pa · m ^3. “△” when less than / s and 1.0 × 10 ⁻⁷ Pa · m ³ / s or more and less than 1.0 × 10 ⁻⁵ Pa · m ³ / s “○”, 1.0 × The case of less than 10 ⁻⁷ Pa · m ³ / s was evaluated as “◎”. As a material that can withstand practical use, a composite having a helium leak amount of less than 1.0 × 10 ⁻⁵ Pa · m ³ / s (◯ or ◎) was judged to be acceptable.

(3) Evaluation results Tables 3 and 4 show the evaluation results of adhesion and gas sealing properties for each composite.

  In the composite of Comparative Example 1, since the coating film thickness was less than 0.5 μm, the adhesion and gas sealing properties between the coated Al-containing metal shape material and the molded body of the thermoplastic resin composition were insufficient. Met. In the composites of Comparative Examples 2 to 5, the proportion of the mass of the polycarbonate unit relative to the total resin mass in the coating film was less than 15% by mass, so that the molded Al-containing metal preform and the molded product of the thermoplastic resin composition As a result, the gas sealing property was also insufficient. Furthermore, in the composites of Comparative Examples 6 and 7, since the ratio of the mass of the polycarbonate unit to the total resin mass in the coating film was more than 80% by mass, the adhesion between the Al-containing metal shape material and the coating film was poor. It was enough. Further, in the evaluation of gas sealing properties, it was considered that the gas sealing properties were insufficient because the coating was swollen by immersing the composite in water and the molded body of the thermoplastic resin composition was lifted. It is done.

  On the other hand, in the composite of Examples 1-12, the film thickness of a coating film is 0.5 micrometer or more, and the ratio of the mass of the polycarbonate unit with respect to the resin total mass in a coating film exists in the range of 15-80 mass%. For this reason, the adhesion between the coated Al-containing metal element and the molded body of the thermoplastic resin composition and the gas sealing property were excellent.

  The composite containing the painted Al-containing metal shape material of the present invention has excellent adhesion between the painted Al-containing metal shape material and the molded body of the thermoplastic resin composition, and is excellent in gas and liquid sealing properties. Therefore, it is preferably used for an inverter case of an automobile, a case of an ECU (Engine Control Unit), a case of a precision electronic component of an electrical product, and the like.

Claims (5)

An Al-containing metal profile made of aluminum or an aluminum alloy;
A coating formed on the surface of the Al-containing metal profile,
The coating film includes a polycarbonate unit-containing polyurethane resin,
The ratio of the mass of the polycarbonate unit to the total resin mass in the coating film is 15 to 80% by mass,
The film thickness of the coating film is 0.5 μm or more.
Painted Al-containing metal shape material for joining with a molded body of a thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, wherein the coating film includes an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V, Mo, and W, or a combination thereof. Painted Al-containing metal profile for joining with molded objects. The coated Al-containing metal profile according to claim 1 or 2,
A molded body of a thermoplastic resin composition bonded to the surface of the painted Al-containing metal profile,
Having a complex.   The thermoplastic resin composition is an acrylonitrile-butadiene-styrene resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, or a combination thereof. The complex described in 1. A method for producing a composite in which a painted Al-containing metal shape material and a molded body of a thermoplastic resin composition are joined,
Preparing a painted Al-containing metal profile;
Inserting the coated Al-containing metal profile into an injection mold;
Injecting the thermoplastic resin composition into the injection mold, and joining the molded body of the thermoplastic resin composition to the surface of the painted Al-containing metal profile;
Including
The painted Al-containing metal shape material has an Al-containing metal shape material made of aluminum or an aluminum alloy, and a coating film formed on the surface of the Al-containing metal shape material,
The coating film includes a polycarbonate unit-containing polyurethane resin,
The ratio of the mass of the polycarbonate unit to the total resin mass in the coating film is 15 to 80% by mass,
The film thickness of the coating film is 0.5 μm or more.
A method for producing a composite.

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