JP6189049B2 - Complex - Google Patents

Description

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

  Metal plates and their press-molded products, or so-called “metal shapes” formed by casting, forging, cutting, powder metallurgy, etc., are indispensable members for manufacturing all industrial products including automobiles. is there. The composite in which the metal base material and the molded body of the resin composition are joined is lighter than a component made of only metal, but has a higher strength than a component made only of resin, such as a mobile phone or a personal computer. Used in electronic equipment. 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 method of patent documents 1-3, the adhesiveness of the aluminum alloy and the molded object of a resin composition is improved by roughening the surface of an aluminum alloy.

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

  In the composites described in Patent Documents 1 to 3, the surface of the metal base material is roughened in order to use the anchor effect. As described above, if fine irregularities are formed on the surface of the metal base material for the purpose of anchor effect, a fine gap is likely to be formed between the metal base material and the molded body of the resin composition. For this reason, in the composites described in Patent Documents 1 to 3, the resin composition may not be bonded to the metal base material with sufficient bonding strength.

  This invention is made | formed in view of this point, and an object of this invention is to provide the composite_body | complex with which the molded object of the thermoplastic resin composition is integrated with sufficient high intensity | strength with the metal raw material.

  The inventors of the present invention have joined the metal base material and the thermoplastic resin composition via the organic resin layer, and the degree of expansion and contraction due to heat at the time of molding the metal base material and the thermoplastic resin composition. The present invention has been completed with further consideration.

That is, the present invention relates to the following composites.
[1] Thermoplastic resin composition bonded to a surface of the metal base material and the surface of the paint metal base material by injection molding or thermocompression bonding, and a metal base material and an organic resin layer disposed thereon And the organic resin layer includes a polycarbonate-containing polyurethane having a polycarbonate unit, and the molding shrinkage of the thermoplastic resin composition is 1.1% or less, and the metal shape member A composite having a ratio αp / αm of a linear expansion coefficient αp of the thermoplastic resin composition to a linear expansion coefficient αm of 4 or less.
[2] The ratio of the mass of the polycarbonate unit to the mass of the total resin in the organic resin layer is 15 to 80% by mass, and the thickness of the organic resin layer is 0.2 μm or more. [1] The complex described in 1.

Moreover, this invention relates to the manufacturing method of the following composites.
[3] It has a metal base material and a painted metal base material having an organic resin layer disposed thereon, and a molded body of a thermoplastic resin composition bonded to the surface of the paint metal base material. A method for producing a composite, comprising the step of joining a molded body of the thermoplastic resin composition to the surface of the organic resin layer by injection molding or thermocompression bonding, and the organic resin layer has a polycarbonate unit. The molding shrinkage rate of the thermoplastic resin composition containing a polycarbonate-containing polyurethane is 1.1% or less, and the ratio of the linear expansion coefficient αp of the thermoplastic resin composition to the linear expansion coefficient αm of the metal base material αp / αm is a method for producing a complex, which is 4 or less.
[4] The ratio of the mass of the polycarbonate unit to the mass of the total resin in the organic resin layer is 15 to 80% by mass, and the thickness of the organic resin layer is 0.2 μm or more. [3] A method for producing the composite according to 1.

  ADVANTAGE OF THE INVENTION According to this invention, the composite body with which the metal raw material and the molded object of the thermoplastic resin composition are integrated with sufficient high intensity | strength through an organic resin layer can be provided.

It is a figure which shows roughly an example of the composite_body | complex which concerns on this invention.

1. Composite The composite according to the present invention has a painted metal shape material and a molded body of a thermoplastic resin composition bonded to the surface thereof. Hereafter, each component of the composite_body | complex which concerns on this invention is demonstrated.

(1) Painted metal shape material The painted metal shape material has a metal shape material and an organic resin layer disposed on the surface of the metal shape material. Hereinafter, each component of the painted metal shape material will be described.

(Metal element)
The kind of metal which comprises a metal raw material is not specifically limited. For example, the metal may be iron, a metal other than iron, or an alloy. Examples of the metal base material include cold-rolled steel sheet, galvanized steel sheet, Zn-Al alloy plated steel sheet, Zn-Al-Mg alloy plated steel sheet, aluminum plated steel sheet, stainless steel sheet (austenite, martensite, ferrite, (Including ferrite and martensite two-phase systems), metal plates such as aluminum plates, aluminum alloy plates and copper plates, press-formed products thereof, castings and forgings such as aluminum die-casting and zinc die-casting, cutting, powder metallurgy These include various metal members formed by, for example. The metal shaped material may be subjected to known coating pretreatments such as degreasing and pickling as necessary.

(Chemical conversion coating)
A chemical conversion treatment film may be disposed between the metal base material and the organic resin layer. The chemical conversion treatment film is disposed on the surface of the metal base material, and improves the adhesion between the metal base material and the organic resin layer and the corrosion resistance of the painted metal base material. The chemical conversion coating may be disposed at least in a region (joint surface) to be joined to the molded body of the thermoplastic resin composition in the surface of the metal raw material, but usually on the entire surface of the metal raw material. Has been placed.

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 film formed by the 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 . In the case of a chromium-free film, the amount of adhesion is 10 to 500 mg / m ² for a Ti-Mo composite film, and the amount of adhesion in terms of fluorine or the total metal element in terms of adhesion in a fluoroacid-based film is 3 to 100 mg / m ^2. Can be adjusted. Moreover, what is necessary is just to adjust the adhesion amount of each chemical conversion treatment film so that it may become 0.1-5 g / m < ² > in the case of a phosphate membrane | film | coat.

(Organic resin layer)
The organic resin layer is disposed on the surface of the metal base material (or chemical conversion film). The organic resin layer improves the adhesion between the metal base material and the molded body of the thermoplastic resin composition.

  The organic resin layer includes a polycarbonate-containing polyurethane (hereinafter also referred to as “PC-containing polyurethane”). The PC-containing polyurethane has a functional group that hydrogen bonds with a metal base material such as a carboxyl group or an amino group, and has sufficient adhesion to both the metal base material and the molded body of the thermoplastic resin composition. . The PC-containing polyurethane may further have other functional groups other than carboxyl groups and amino groups that hydrogen bond with the metal base material. Moreover, the weight average molecular weight of PC containing polyurethane is not specifically limited in the range with which the effect of this invention is acquired.

  PC-containing polyurethane has polycarbonate units in the molecular chain. “Polycarbonate unit” refers to the structure shown below in the molecular chain of polyurethane. These carbonate groups may be present individually or continuously in the PC-containing polyurethane. The content of the polycarbonate unit in the organic resin layer is 15 to 80% by mass with respect to the mass of the total resin in the organic resin layer, with respect to both the metal raw material and the molded body of the thermoplastic resin composition. It is preferable from the viewpoint of increasing the adhesive strength of the organic resin layer. When the content of the polycarbonate unit is less than 15 mass, the organic resin layer may not adhere to the metal shape material with sufficient strength. When the content is greater than 80 mass%, the organic resin layer may be a thermoplastic resin. It may not adhere to the molded product of the composition with sufficient strength.

  The PC-containing polyurethane 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.

  In addition, neutralizing the tertiary amino group of the produced urethane prepolymer with an acid or quaternizing with a quaternizing agent, followed by chain extension with water to produce a polyurethane containing a cationic polycarbonate unit. Can do.

  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 Polycarbonate unit-containing polyurethanes can be produced. The PC-containing polyurethane may be the above-mentioned cationic polycarbonate unit-containing polyurethane or an anionic polycarbonate unit-containing polyurethane.

  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.

  Alternatively, the PC-containing polyurethane can be obtained as a commercial product.

  The presence of the PC-containing polyurethane in the organic resin layer can be confirmed using ordinary analytical equipment such as NMR (nuclear magnetic resonance), IR (infrared spectroscopy), GC-MS (gas chromatograph mass spectrometry). Is possible.

  The PC-containing polyurethane may be cross-linked. The crosslinking of the PC-containing polyurethane can be performed by, for example, a crosslinking agent having two or more groups that react with the functional group hydrogen-bonding with the metal raw material in the PC-containing polyurethane. Crosslinking the PC-containing polyurethane is preferable from the viewpoint of improving the strength of the organic resin layer. As the crosslinking agent, a known crosslinking agent used for crosslinking of the PC-containing polyurethane can be used. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, a melamine crosslinking agent, or a crosslinking agent having a metal salt. The amount of the crosslinking agent used is appropriately determined within a range in which both the adhesion of the organic resin layer to the metal base material and the effect of crosslinking in the PC-containing polyurethane are obtained.

  The organic resin layer may further contain a resin other than the PC-containing polyurethane described above as long as the effect of the present invention is obtained. As the other resin, for example, a resin having a skeleton (such as a benzene ring) and a functional group similar to PC-containing polyurethane can be selected. When the organic resin layer further contains such other resins, the resin component in the organic resin layer is heated when the molded body of the thermoplastic resin composition is injection-molded or thermocompression bonded to the painted metal shape material. It is more compatible with the plastic resin composition, and the organic resin layer and the thermoplastic resin composition are more strongly bonded. Therefore, it is preferable that the organic resin layer further contains the other resin from the viewpoint of improving the adhesion of the molded body of the thermoplastic resin composition to the organic resin layer. Such other resins are appropriately selected from known resins. Examples of other resins include polypropylene, polyurethane, acrylic resin, acrylic / styrene resin, vinyl acetate, EVA (ethylene-vinyl acetate copolymer resin), fluorine resin, ester resin, and olefins other than polypropylene. Resins, and combinations thereof are included. Content of the said other resin in an organic resin layer should just be a range with which the effect by the mixing | blending of said other resin is acquired, for example, is 0-500 mass parts with respect to 100 mass parts of said PC containing polyurethane.

  Moreover, the organic resin layer may contain a rust preventive agent. The rust preventive agent improves the corrosion resistance of the painted metal preform and the composite according to the present invention. The kind of rust preventive agent is not specifically limited. Examples of the rust preventive agent preferably include an oxide, hydroxide or fluoride of a metal (valve metal) 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 painted metal shaped material can be further improved. In particular, these metal fluorides can also be expected to suppress corrosion at film defects by a self-repairing action.

  The organic resin layer may further contain a soluble or hardly soluble metal phosphate or composite phosphate. The soluble metal phosphate or composite phosphate further improves the corrosion resistance of the metal base material by complementing the self-healing action of the metal fluoride. Further, the hardly soluble metal phosphate or composite phosphate is dispersed in the organic resin layer to improve its strength. For example, the soluble or poorly soluble metal phosphate or complex phosphate is a salt such as Al, Ti, Zr, Hf, Zn.

  The organic resin layer may contain a lubricant. The lubricant can suppress the occurrence of galling on the surface of the painted metal profile. The type of lubricant is not particularly limited. Examples of lubricants include organic waxes such as fluorine, polyethylene, styrene, and polypropylene, and inorganic lubricants such as molybdenum disulfide and talc. It is preferable that the compounding quantity of the lubricant in an organic resin layer is 1-20 mass parts with respect to 100 mass parts of total mass of resin in an organic resin layer. When the lubricant is less than 1 part by mass, the generation of galling may not be sufficiently suppressed. On the other hand, when the amount of the lubricant exceeds 20 parts by mass, no significant improvement is observed in the effect of suppressing the generation of galling, and the lubricity is too high and the handleability may be poor.

  The organic resin layer may contain an antifoaming agent. An antifoamer makes it difficult to generate bubbles when preparing a coating for an organic resin layer, which will be described later. The type of the antifoaming agent is not particularly limited, but an appropriate amount of a known silicone-based antifoaming agent may be added as necessary.

  The melting point of the resin composition constituting the organic resin layer is equal to or less than that of the thermoplastic resin composition molded product from the viewpoint of bonding the molded product of the thermoplastic resin composition to the painted metal preform with sufficient strength. preferable. Although the minimum of melting | fusing point of the said resin composition is not specifically limited, For example, according to a viewpoint which ensures the blocking resistance of a coating metal raw material, it is 60 degreeC.

  The thickness of the organic resin layer is preferably 0.2 μm or more. When the thickness of the organic resin layer is less than 0.2 μm, the surface of the metal base material may not be uniformly covered. Thereby, the composite having an organic resin layer having a thickness of less than 0.2 μm may cause a fine gap between the metal base material and the molded body of the thermoplastic resin composition. If fine voids are generated, the sealing performance of the composite may be reduced. On the other hand, the upper limit of the thickness of the organic resin layer is not particularly limited, but is preferably 10 μm or less, and more preferably 3 μm or less. Even if the thickness of the organic resin layer exceeds 10 μm, no significant performance improvement is observed, and it is disadvantageous from the viewpoint of productivity and cost.

(2) Molded body of thermoplastic resin composition The molded body of the thermoplastic resin composition is bonded to the surface of the coated metal shaped material (the surface of the organic resin layer on the metal shaped material). The shape of the molded body of the thermoplastic resin composition is not particularly limited as long as it is a shape that is in contact with the joint surface described above in the painted metal base material, and may be appropriately selected depending on the application.

  The kind of the thermoplastic resin contained as a main component in the thermoplastic resin composition is not particularly limited. Examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin, polyamide resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polycarbonate resin. These thermoplastic resins may be used alone or in combination of two or more. Moreover, although the melting point of the said thermoplastic resin is not specifically limited, For example, it is 280 degrees C or less.

  The molding shrinkage rate of the thermoplastic resin composition is 1.1% or less. The molding shrinkage of the thermoplastic resin composition can be adjusted by a known method. For example, the molding shrinkage rate can be adjusted by adding a filler or the like to a thermoplastic resin composition containing a thermoplastic elastomer. Further, the mold shrinkage can be adjusted by changing the mixing ratio of the crystalline resin and the amorphous resin.

The molding shrinkage rate (%) of the thermoplastic resin composition is the volume of the molten thermoplastic resin composition (for example, the volume of the thermoplastic resin composition having the melting point of the thermoplastic resin or the cavity of the injection mold). Va, when the volume of a thermoplastic resin composition (for example, a thermoplastic resin composition at room temperature (20 ° C.)) solidified by cooling from the molten state is represented by Vb, is obtained by the following formula.
{(Va−Vb) / Va} × 100

  When the molding shrinkage rate is larger than 1.1%, the molded body of the thermoplastic resin composition may not be sufficiently firmly bonded to the painted metal shape material. The molding shrinkage rate is preferably 0.9% or less and more preferably 0.7% or less from the viewpoint of further increasing the bonding strength of the molded body of the thermoplastic resin composition to the painted metal base material. preferable. For example, the molding shrinkage decreases when the filler content or the amorphous resin content in the thermoplastic resin composition is large.

  Moreover, when the linear expansion coefficient of the thermoplastic resin composition is αp, the ratio αp / αm of the linear expansion coefficient αp of the thermoplastic resin composition to the linear expansion coefficient αm of the metal base material is 4 or less. When the ratio is larger than 4, the molded body of the thermoplastic resin composition may not be sufficiently firmly bonded to the painted metal shape material. The ratio αp / αm is preferably 3.5 or less from the viewpoint of further increasing the bonding strength of the molded body of the thermoplastic resin composition to the painted metal preform. αm and αp are determined by measuring the amount of dimensional change associated with the temperature change of the material, for example, by TMA (Thermal Mechanical Analysis). For example, αp decreases as the filler content in the thermoplastic resin composition increases.

  The thermoplastic resin composition may further contain components other than the organic resin as long as the effects of the present invention are obtained. Examples of such other components include fillers. It is preferable to add a filler to the thermoplastic resin composition from the viewpoint of adjusting the molding shrinkage of the thermoplastic resin composition and the linear expansion coefficient αp of the thermoplastic resin composition. Moreover, the rigidity of the molded object of a thermoplastic resin composition can be improved by mix | blending a filler with a thermoplastic resin composition.

  The thermoplastic elastomer improves the impact resistance of the molded article of the thermoplastic resin composition. The kind of thermoplastic elastomer is not particularly limited. Examples of thermoplastic elastomers include polyolefin resins, polystyrene resins, and combinations thereof.

  The filler reduces the molding shrinkage of the molded article of the thermoplastic resin composition and improves the rigidity. The kind of filler is not particularly limited, and a known substance can be used. Examples of fillers 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, glass sphere Powder fillers such as: pulverized carbon fiber or aramid fiber. A filler may be used independently and may be used in combination of 2 or more type. The filler content in the thermoplastic resin composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 40% by mass.

  The molding shrinkage rate of the thermoplastic resin composition can also be adjusted by mixing a crystalline resin and an amorphous resin. Generally, the molding shrinkage rate of the crystalline resin is larger than the molding shrinkage rate of the amorphous resin. Therefore, if the mixing ratio of the amorphous resin to the crystalline resin is increased, the molding shrinkage rate of the thermoplastic resin composition can be decreased.

  The manufacturing method of the composite_body | complex which concerns on this invention is not specifically limited. For example, the composite according to the present invention can be produced by the method described below.

2. Method for Producing Composite The composite according to the present invention can be produced, for example, by a method including a step of joining a molded body of a thermoplastic resin composition to the surface of the organic resin layer by injection molding or thermocompression bonding. Such a method includes, for example, (1) a first step of preparing the above-mentioned coated metal preform, and (2) a heated thermoplastic resin composition in contact with the surface of the coated metal preform, And a second step of joining a molded body of the thermoplastic resin composition to the surface of the metal base material. Hereinafter, each step will be described.

(1) 1st process In the 1st process, the above-mentioned paint metal shape material is prepared. Prior to forming the organic resin layer of the painted metal shape material, a chemical conversion treatment film may be formed on the metal shape material. The chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid to the surface of the metal base 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, the metal raw material coated with the chemical conversion treatment solution is put into a drying oven without being washed with water, and heated so that the ultimate temperature of the metal raw material becomes 80 to 250 ° C. A uniform chemical conversion coating can be formed on the surface.

  The painted metal element is produced by forming an organic resin layer on the surface of the metal element. The organic resin layer is produced by applying a coating for the organic resin layer containing the material for the organic resin layer to the surface of the metal base material and heating the applied coating.

  The said coating material for organic resin layers contains PC containing polyurethane mentioned above, for example. The coating material for organic resin may further contain the above-described crosslinking agent and other resin, if necessary. Furthermore, the coating material for organic resin may contain a solvent as necessary. The type of the solvent is not particularly limited as long as it is a liquid that can uniformly dissolve or disperse various components in the coating for the organic resin, and is a liquid that evaporates in the process of forming the organic resin layer, preferably water. . For example, the coating for the organic resin layer contains a PC-containing polyurethane aqueous emulsion, an aqueous resin emulsion of the other resin, a crosslinking agent, a rust preventive agent, a lubricant, a stabilizer and an antifoaming agent. The solid content in the coating for the organic resin layer can be appropriately determined according to the coating property of the coating and the thickness of the coating film to be formed, and is, for example, 5 to 30% by mass. The content of the PC-containing polyurethane in the paint for the organic resin layer can be prepared, for example, by blending a PC-containing polyurethane emulsion and an aqueous resin emulsion of another resin.

  The organic resin layer is formed by applying a paint containing the PC-containing polyurethane to the surface of a metal base material (or chemical conversion film) and evaporating the solvent (water) by, for example, heat drying. The method for applying the coating material for the organic resin layer 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 heating method of the coating material for the organic resin layer applied to the metal base material is not particularly limited. Although the ultimate temperature of the metal base material during heating is not particularly limited, from the viewpoint of forming an organic resin layer closely adhered to the surface of the metal base material (or chemical conversion film), for example, a resin in the organic resin layer The melting point of the composition is preferably 280 ° C. or lower.

(2) Second Step In the second step, the molded body of the heated thermoplastic resin composition is brought into contact with the surface of the painted metal preform, and the thermoplastic resin composition is molded on the surface of the painted metal preform. Join the body. The painted metal shape material may be processed in advance into a desired shape by pressing or the like.

  For example, after the painted metal material prepared in the first step is inserted into the injection mold, the molten thermoplastic resin composition is injected into the injection mold at high pressure (ie, injection molding). That's fine. At this time, it is preferable to provide a gas vent in the injection mold so that the thermoplastic resin composition flows smoothly. The molten thermoplastic resin composition is molded inside the injection mold to form a molded body, and is compatible with the organic resin layer formed on the surface of the metal base material. For this reason, a compatible layer having a nano-order thickness is formed between the thermoplastic resin composition and the organic resin layer. At this time, the temperature of the injection mold is preferably near the melting point of the thermoplastic resin in the thermoplastic resin composition. In addition, the composite obtained by injection molding may be annealed after molding to eliminate internal distortion due to molding shrinkage.

  Alternatively, after setting the painted metal preform prepared in the first step and the molded body of the thermoplastic resin composition in a thermocompression press machine, heat and heat are applied to these painted metal preform and the thermoplastic resin composition. What is necessary is just to apply pressure (that is, heat-pressing). At this time, heating and pressurization may be performed on all or a part of the molded body of the painted metal preform and the thermoplastic resin composition. It is necessary to heat and press at least one or both of the joint surfaces of the molded body of the thermoplastic resin composition and the painted metal base material. Part of the heated and pressurized organic resin layer and part of the thermoplastic resin composition are melted and compatible. For this reason, a compatible layer having a nano-order thickness is formed between the thermoplastic resin molded body and the organic resin layer. The method of heating and the method of pressurizing the molded body of the painted metal base and the thermoplastic resin composition are not particularly limited. Examples of the heating method include heater heating, electromagnetic induction heating, and ultrasonic heating. Examples of the pressurizing method include pressurization by human power, pressurization using a vise and the like.

  Furthermore, the manufacturing method described above may include other steps than the first step and the second step described above as long as the effects of the present invention are obtained.

  By the above procedure, the composite body according to the present invention can be manufactured by joining the molded body of the thermoplastic resin composition to the surface of the painted metal base material.

  As described above, in the present invention, the molding shrinkage of the thermoplastic resin composition is sufficiently small, 1.1% or less. Further, the ratio αp / αm between the linear expansion coefficient αm of the metal base material and the linear expansion coefficient αp of the thermoplastic resin composition is also sufficiently small as 4 or less. Therefore, when the thermoplastic resin composition is joined to the painted metal shape member by heat, the difference between the shrinkage amount of the thermoplastic resin composition and the shrinkage amount of the metal shape material during cooling can be reduced. For this reason, even if the molded body of the thermoplastic resin composition and the metal shape member deviate on the joining surface during cooling, it is considered that this deviation does not affect the joining state of both.

  In addition, the organic resin layer disposed between the molded body of the thermoplastic resin composition and the metal base material is strongly bonded to the metal base material by hydrogen bonding or the like on the one hand, and the thermoplastic resin composition on the other hand. A compatible layer is formed between the molded body and the molded body of the thermoplastic resin composition through the compatible layer. Furthermore, the organic resin layer is considered to have a lower molecular density than the metal base material and the molded body of the thermoplastic resin composition, and thus has a more flexible structure. It is done. For this reason, while the composite is cooled from the temperature at the time of bonding to the room temperature, the organic resin layer is in close contact with both the metal raw material and the molded body of the thermoplastic resin composition, and the above-described strong against both of them. It is believed that the bond is maintained from the time of molding until after molding.

  As described above, in the composite according to the present invention, the organic resin layer and the metal base material, and the organic resin layer and the molded body of the thermoplastic resin composition are firmly bonded, so that the painted metal base Excellent adhesion between the material and the molded body of the thermoplastic resin composition.

  Hereinafter, although this invention is demonstrated in detail with reference to the Example at the time of using a metal plate as a metal raw material, this invention is not limited by these Examples.

1. Fabrication of composite (1) Paint substrate (metal shape material)
A. Paint substrate 1
The surface of SUS430 with a plate thickness of 0.8 mm is No. The finished coating substrate 1 was prepared by finishing four. When the thermal expansion coefficient (αm) of the coated substrate 1 was determined as an average linear expansion coefficient from 20 to 100 ° C. using TMA, the linear expansion coefficient (αm) of the coated substrate 1 was 10 × 10 ⁻⁶ / K. Met.

B. Paint base 2
A cold rolled steel sheet (SPCC) with a plate thickness of 0.8 mm is prepared as a coated base material 2 with a molten Zn-6 mass% Al-3 mass% Mg alloy-plated steel sheet with a coating amount of 45 g / m ² per side. did. The linear expansion coefficient (αm) of the coated substrate 2 was 12 × 10 ⁻⁶ / K.

C. Paint base 3
A cold-rolled steel plate (SPCC) having a plate thickness of 0.8 mm was prepared as a coated base material 3 with a molten Al-9 mass% Si alloy-plated steel plate having a plating adhesion amount of 45 g / m ^{2 on} one side. The linear expansion coefficient (αm) of the coated substrate 3 was 12 × 10 ⁻⁶ / K.

D. Paint base 4
An aluminum alloy plate (A1050) having a plate thickness of 0.8 mm was prepared as the coating substrate 4. The linear expansion coefficient (αm) of the coated substrate 4 was 23 × 10 ⁻⁶ / K.

(2) Preparation of paint PC-containing polyurethane resin (A), polyurethane resin not containing PC (B), and polyethylene wax (C) so that the ratio of the mass of the PC unit to the total mass of the resin is 80% by mass ) Was added to water to prepare a prepaint 1 having a non-volatile component of 20% by mass. In this prepaint 1, ammonium molybdate (Kishida Chemical Co., Ltd.): 0.5% by mass, zirconium carbonate (Zircosol AC-7; Daiichi Rare Element Chemical Co., Ltd.): 0.5% by mass as a rust preventive agent , And silicone-based antifoaming agent (KM-73; Shin-Etsu Chemical Co., Ltd.): 0.05% by mass, respectively, to prepare paint 1. “Zircozole” is a registered trademark of Daiichi Rare Element Chemical Co., Ltd.

  Similarly, the paint 2 having a PC unit content of 40 parts by mass, the paint 3 having a PC unit content of 15 parts by mass, the paint 4 having a PC unit content of 85 parts by mass, and The coating material 5 whose said content of a PC unit is 10 mass parts was prepared, respectively. Moreover, the coating material 6 was prepared like the coating material 1 except having used the polyurethane-type resin (B) which does not contain PC instead of PC containing polyurethane resin (A).

A. PC-containing polyurethane resin Adekabon titer HUX-386 (ADEKA Corporation) was used as the PC-containing polyurethane resin (A). For the PC-containing polyurethane resin (A) containing 80% by mass or more of PC units, a mixture of a polyurethane resin composition containing 90% by mass of PC units and HUX-386 was used. “Adekabon titer” is a registered trademark of ADEKA Corporation.

B. Polyurethane resin not containing PC A polyurethane resin emulsion (Adekabon titer HUX-232; ADEKA Co., Ltd.) was used as the polyurethane resin (B) for adjusting the ratio of the PC unit content to the total resin mass.

C. Polyethylene wax Polyethylene wax (HYTEC E-9015; Toho Chemical Industry Co., Ltd.) was added in an amount of 5.0% by mass relative to the total mass of the resin. “HYTEC” is a registered trademark of Toho Chemical Co., Ltd.

(3) Formation of organic resin layer The coated substrate 1 was immersed in an alkaline degreasing aqueous solution (Surf Cleaner SD-270; Nippon Paint Co., Ltd., pH = 12) at a liquid temperature of 40 ° C. for 1 minute to degrease the surface. Next, the coating material 1 is applied to the surface of the degreased coating substrate 1 with a roll coater so that the dry film thickness is 2.0 μm, and the coating plate 1 is applied at a temperature at which the ultimate plate temperature becomes 150 ° C. The paint 1 was dried with a hot air dryer to form an organic resin layer. The base material I is a painted metal shape member having this organic resin layer. Moreover, except having changed the coating base material and the coating material as shown in Table 1, the organic resin layer was formed on the surface of the coating base material similarly to the base material I, and the base materials II-IX were produced. Furthermore, the coating base material 2 which does not apply a coating material was prepared as the base material X. Table 1 shows the materials of the substrate I to the substrate X and their physical properties. “Surf Cleaner” is a registered trademark of Nippon Paint Co., Ltd.

(4) Thermoplastic Resin Composition As an acrylonitrile-butadiene-styrene copolymer (ABS) resin composition, Exelloy CK-10G20 (injection temperature 260 ° C .; Technopolymer Corporation) was prepared. This resin composition contains 20% by mass of glass fiber as a filler. This resin composition is referred to as “resin composition i”. “Excelloy” is a registered trademark of Techno Polymer Co., Ltd.

  Moreover, Novaduran 5010R3-2 (injection temperature 260 ° C .; Mitsubishi Engineering Plastics) and Novaduran 5710F40 (injection temperature 260 ° C .; Mitsubishi Engineering Plastics) were prepared as polybutylene terephthalate (PBT) resin compositions. . The former does not contain glass fiber, and the latter contains 40% by mass of glass fiber as a filler. The former resin composition is referred to as a resin composition ii, and the latter resin composition is referred to as a resin composition iii. “Novaduran” is a registered trademark of Mitsubishi Engineering Plastics Corporation.

  Moreover, as a polyamide (PA66) type-resin composition, Amilan CM-3001-N (injection temperature 260 degreeC; Toray Industries, Inc.) and Amilan CM-3511-G50 (injection temperature 260 degrees C; Toray Industries, Inc.) were prepared. The former does not contain glass fiber, and the latter contains 50% by mass of glass fiber as a filler. The former resin composition is referred to as a resin composition iv, and the latter resin composition is referred to as a resin composition v. “Amilan” is a registered trademark of Toray Industries, Inc.

  Moreover, as a polyphenylene sulfide (PPS) resin composition, Torelina A900 (injection temperature 320 ° C .; Toray Industries, Inc.) and Fortron 1140A7 (injection temperature 320 ° C .; Polyplastics Co., Ltd.) were prepared. The former does not contain glass fiber, and the latter contains 40% by mass of glass fiber as a filler. The former resin composition is referred to as a resin composition vi, and the latter resin composition is referred to as a resin composition vii. “Torelina” is a registered trademark of Toray Industries, Inc.

  Each resin composition i at a mold temperature of 60 ° C. and a holding pressure of 80 MPa at a mold temperature having a width of 100 mm × length of 100 mm × thickness of 3 mm at the injection temperature of each resin composition i to vii. -Vii was injection-molded, and the molding shrinkage of each resin composition i-vii when cooled to 20 ° C was determined. Moreover, the linear expansion coefficient ((alpha) p) of each resin composition i-vii was calculated | required as an average linear expansion coefficient from 20 to 100 degreeC using TMA. Table 2 shows the compositions and physical properties of the resin compositions i to vii.

(5) Joining of painted metal shape material and molded body of thermoplastic resin composition Joining of coated metal mold and thermoplastic resin composition for measuring bonding strength by injection molding Inserting base material I into an injection mold and injecting molten resin composition i into the cavity of the injection mold Then, as shown in FIG. 1, a composite 1 (reference numeral 13) in which the resin composition i (reference numeral 12) was joined to the surface of the substrate I (reference numeral 11) by injection molding was produced. The shape of the cavity is width (W1) 30 mm × length (L1) 100 mm × thickness (T1) 4 mm. The shape of the base material I is width (W2) 30 mm × length (L2) 100 mm × thickness (T2) 0.8 mm. The base material I and the resin composition i are joined at a portion having a length of 30 cm from each other. The composite I was produced by injecting the resin composition i into the cavity at an injection temperature of 260 ° C. and then cooling and solidifying it. The composites 1 to 8 and 14 to 14 were changed in the same manner as the composite 1 except that the base material and the resin composition were changed as shown in Table 3 and the injection temperature was changed to the above-described injection temperature of each resin composition. 19 was produced. Table 3 shows combinations of the base material and the resin composition in each composite.

B. Bonding of Painted Metal Shaped Material for Measuring Bonding Force by Thermocompression Bonding and Thermoplastic Resin Composition A molded body of resin composition iii having a width of 30 mm × length of 100 mm × thickness of 4 mm produced by an injection molding method is obtained at 160 ° C. As shown in FIG. 1, the base material II having a width of 30 mm, a length of 100 mm, and a thickness of 0.8 mm is overlaid in a region of a width of 30 mm × a length of 30 mm at each end, and is heated to 60 MPa at 0.3 MPa. After pressurizing for 2 seconds, the composite 9 was obtained by cooling and solidifying. Except for changing the base material and the resin composition as shown in Table 3, composites 10-13 and 20-23 were produced in the same manner as the composite 9. Table 3 shows combinations of the base material and the resin composition in each composite.

(6) Measurement and evaluation of bonding strength of composites The compact and base material of each composite body obtained in (5) above were parallel to the surface of the base material and in directions opposite to each other at a speed of 100 mm / min. The strength (peel strength) when pulled and broken was measured. The case where the peel strength is less than 1.0 kN is evaluated as “×”, the case where the peel strength is 1.0 kN or more and less than 1.5 kN is evaluated as “Δ”, and the peel strength is 1.5 kN or more. The case of less than 2.0 kN was evaluated as “◯”, and the case where the peel strength was 2.0 kN or more was evaluated as “◎”. The results are shown in Table 3. As for the bonding strength of the composite, “Δ”, “◯” or “「 ”is acceptable.

  As is apparent from Table 3, in the injection molding or thermocompression bonding, the molding shrinkage of the thermoplastic resin composition bonded to the metal shape member having the organic resin layer containing the polycarbonate-containing polyurethane having the polycarbonate unit is 1.1%. In the composites 1 to 13 in which the ratio (αp / αm) of the linear expansion coefficient αp of the thermoplastic resin composition to the linear expansion coefficient αm of the metal base material is 4 or less, the thermoplastic resin composition The molded body was sufficiently firmly bonded to the painted metal profile.

  On the other hand, in both the injection molding and the thermocompression bonding, the composite 17 having a linear expansion coefficient ratio αp / αm of 4 or less and a molding shrinkage ratio larger than 1.1% in the thermoplastic resin composition is a thermoplastic resin. The bonding strength between the molded body of the composition and the painted metal shape material was inferior, and the molded body of the thermoplastic resin composition did not substantially bond to the painted metal shape material. Further, the thermoplastic resin composition has a molding shrinkage ratio larger than 1.1% and a linear expansion coefficient ratio αp / αm larger than 4, and the organic resin layer includes a polycarbonate unit. As for the composites 18 and 22, and the composites 19 and 23 in which the organic resin layer itself is not formed, in the composites 18, 20 and 22, the molded body of the thermoplastic resin composition is used as the painted metal shape material. It was not substantially joined. Moreover, in the composite bodies 14-16, 19, 21, and 23, the molded object of the thermoplastic resin composition did not join to a coating metal shape material.

  The composite containing the painted metal preform according to the present invention has excellent adhesion between the painted metal preform and the molded body of the thermoplastic resin composition. For example, various electronic devices, household appliances, medical devices It is suitably used for automobile bodies, on-vehicle accessories, building materials, and the like.

11 Base Material 12 Resin Composition 13 Composite

Claims (2)

A molded body of a thermoplastic resin composition, which is bonded to the surface of the metal base material and a coated metal base material having an organic resin layer disposed thereon by injection molding or thermocompression bonding. And having
The organic resin layer includes a polycarbonate-containing polyurethane having a polycarbonate unit,
The thickness of the organic resin layer is 0.2 μm or more and 10 μm or less,
The ratio αp / αm of the linear expansion coefficient αp of the thermoplastic resin composition to the linear expansion coefficient αm of the metal base material is 4 or less.
Complex. The ratio of the mass of the polycarbonate unit to the mass of the total resin in the organic resin layer is 15 to 80% by mass.
The composite according to claim 1.

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