JP2018034437A - Method for producing composite body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a composite body which has a high bonding force of a coated metallic material to a molded body of a thermoplastic resin composition and suppresses deformation due to heat shrinkage during production.SOLUTION: There is provided a method for producing a composite body which has a coated metallic material containing a metallic material and an organic resin layer which is arranged on the metallic material and has a thickness of 0.2 μm or more, and a molded body of a thermoplastic resin composition joined to the coated metallic material. The organic resin layer has weldability to the thermoplastic resin composition, the production method includes a step of bringing the molded body into contact with the organic resin layer, and a step of generating heat by electromagnetic induction of the metallic material, and heating and welding the organic resin layer constituting at least a part of an adhesion portion where the organic resin layer and the molded body are brought into contact with each other with the molded body to join the molded body and the coated metallic material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a composite in which a molded body of a thermoplastic resin composition is joined to a painted metal base material.

  The metal element is a metal plate, a press-molded product thereof, or a metal member formed by casting, forging, cutting, powder metallurgy, or the like. The metal shape material is indispensable for manufacturing all industrial products including automobiles today. A composite in which a molded body of a thermoplastic resin composition is bonded to a metal base material is lighter than a component made of only metal, but has higher strength than a component made of only resin. For this reason, the complex is used in electronic devices such as mobile phones and personal computers.

  As a method for producing the composite, for example, a method is known in which the molded body is joined by insert molding to a painted metal shaped material having an organic resin layer having a weldability with the shaped material on the surface of the metal shaped material. (For example, refer to Patent Document 1). The manufacturing method can provide a composite having a high bonding strength of the painted metal preform to the molded body.

JP 2013-043402 A

  In general, the thermal expansion coefficient of the thermoplastic resin composition is larger than the thermal expansion coefficient of the metal base material. Moreover, in the said manufacturing method, both the molded object of the said thermoplastic resin composition and a coating metal raw material are heated to the melting temperature vicinity of a thermoplastic resin composition. Therefore, in the case where the metal base material has flexibility, the molded body of the thermoplastic resin composition joined to the painted metal base material contracts more than the metal base material by cooling after insert molding, The metal blank may be bent, resulting in deformation of the composite. Thus, the above manufacturing method still has room for study from the viewpoint of preventing deformation of the composite.

  An object of the present invention is to provide a method for producing a composite having a high bonding strength of a coated metal shaped material to a molded body of a thermoplastic resin composition and in which deformation due to thermal shrinkage during production is suppressed. .

  The present inventors welded the organic resin layer and the molded body of the thermoplastic resin composition with heat generated by heat generated by the electromagnetic induction of the painted metal shape material having the organic resin layer, Thus, it has been found that the deformation due to thermal shrinkage during the production of the composite can be sufficiently suppressed by joining the molded body and the painted metal preform, thereby completing the present invention.

That is, the present invention relates to the following method for producing a composite.
[1] A painted metal shape material including a metal shape material and an organic resin layer having a thickness of 0.2 μm or more disposed on the metal shape material, and a thermoplastic bonded to the painted metal shape material A method of manufacturing a composite body having a molded body of a resin composition, the step of bringing the molded body into close contact with the organic resin layer, and heating the metal base material by electromagnetic induction, so that the organic resin layer And the step of heat-welding the organic resin layer and the molded body constituting at least a part of a close contact portion where the molded body and the molded body are in close contact with each other, and joining the molded body and the painted metal shaped material. The organic resin layer has a weldability to the thermoplastic resin composition.
[2] The method for producing a composite according to [1], wherein the organic resin layer includes a polypropylene-based resin, and the molded body is a molded body of a polypropylene-based resin composition.
[3] The organic resin layer includes a polyurethane-based resin, and the molded body is a molded body of a polybutylene terephthalate-based resin composition, a molded body of a polyamide-based resin composition, or an acrylonitrile-butadiene-styrene-based resin composition. The manufacturing method of the composite_body | complex as described in [1] which is a molded object of.
[4] The method for producing a composite according to any one of [1] to [3], wherein the organic resin layer contains a metal compound rust inhibitor.

  According to the present invention, when the molded body of the thermoplastic resin composition is bonded to the organic resin layer, the heated portion of the molded body can be made sufficiently small, and deformation due to thermal shrinkage of the molded body is substantially reduced. It is possible to prevent. Therefore, according to the present invention, it is possible to provide a composite body in which the bonding strength of the painted metal preform to the molded body is high and deformation due to thermal shrinkage during manufacture is suppressed.

FIG. 1A is a plan view schematically showing a composite according to an embodiment of the present invention and a heat-welded portion by electromagnetic induction in the composite, and FIG. 1B is a diagram of the composite in FIG. 1A. It is sectional drawing along line 1B-1B. FIG. 2A is a plan view schematically showing a composite according to another embodiment of the present invention, and a heat-welded portion by electromagnetic induction in the composite, and FIG. 2B is still another embodiment of the present invention. It is a figure which shows typically the composite_body | complex which concerns on a form, and the heat welding part by the electromagnetic induction in the said composite_body | complex. FIG. 3A is a plan view schematically showing a composite according to still another embodiment of the present invention and a heat-welded part by electromagnetic induction in the composite, and FIG. 3B is a plan view of the composite. It is sectional drawing along line 3B-3B in the inside. FIG. 4A is a plan view schematically showing a sample for a tensile test produced in an example and a heat-welded portion by electromagnetic induction in the sample, and FIG. 4B is a front view of the sample. It is a figure for demonstrating the curvature amount of the composite_body | complex measured in the Example.

1. Manufacturing method of composite body The manufacturing method of the composite body according to the present embodiment is a coated metal body shape including a metal body shape material and an organic resin layer having a thickness of 0.2 μm or more disposed on the metal body shape material. A step of closely adhering a molded body of a thermoplastic resin (hereinafter also simply referred to as a “molded body”) to the organic resin layer of the material, and generating heat by electromagnetic induction to form the organic resin layer A step of heat-welding the organic resin layer and the molded body constituting at least a part of a close contact portion in close contact with the molded body, and joining the molded body and the painted metal shaped material. is there. The method for producing a composite according to the present embodiment may further include steps other than the above steps. For example, the method for manufacturing a composite according to the present embodiment may include a step of producing the painted metal shape material before the step of closely attaching the formed body.

1-1. In the step of closely attaching the molded body to the organic resin layer, in the step of closely contacting the molded body to the organic resin layer, for example, the molded body includes at least a portion to be joined to the molded body and a painted metal shape material. It arrange | positions in contact with the organic resin layer on the surface of a coating metal shape member so that the part which should be joined adheres. In this step, the part to be joined of the molded body only needs to be in contact with the part to be joined of the painted metal base material at least when the metal base material is heated by electromagnetic induction. In the above step, it is preferable from the viewpoint of misalignment and the like that the molded body and the painted metal shape material are urged and adhered to each other by a fixing jig or the like. At this time, when the jig is disposed between an induction coil that generates a magnetic field for generating heat by the electromagnetic induction and the metal raw material, the jig transmits electromagnetic waves. Must be made of material.

1-2. The step of bonding the formed body to the metal shaped material In the step of bonding the formed body to the painted metal shaped material, the organic resin layer and the formed body are obtained by heating the metal shaped material by electromagnetic induction. The organic resin layer and the molded body constituting at least a part of the close contact portion in close contact with each other are heated and welded, and thereby the molded body and the painted metal shaped member are joined. In this step, at least the organic resin layer may be heated and welded to the molded body. However, as long as the degree of deformation by heat is within an allowable range, the molded body is also heated at the same time. It may be welded to the organic resin layer.

  Although the part heated in the said process may be the whole surface of the said close_contact | adherence part, it is preferable from a viewpoint of suppressing deformation | transformation, such as curvature of a composite_body | complex, that it is only a part of the said close_contact | adherence part. Examples of a part of the contact portion include a circular or rectangular or other polygonal region (see FIG. 1A) including the center of the contact portion, a single or a plurality of dotted regions (see FIG. 2A), and a plane of the contact portion. A linear region along the center line in the shape, a linear region along the edge in the planar shape of the contact portion (see FIGS. 2B and 3A), a linear region along the diagonal line in the planar shape of the contact portion Regions, and combinations thereof. The organic resin layer heated and welded forms a joint with the molded body.

  At this time, for example, a known induction coil is arranged in the vicinity of the painted metal shape member so that the metal shape material in contact with the portion to be heated of the close contact portion is heated, and an alternating current is supplied to the induction coil. A current or intermittent direct current may be passed. The induction coil generates a magnetic field by the current and heats the metal shape material by electromagnetic induction.

  The target temperature of the contact portion by heating is set higher than the temperature at which the organic resin constituting the organic resin layer is dissolved.

  The frequency of the alternating current is not particularly limited, and for example, it can be used from a low frequency of about 100 Hz to a high frequency of 1 MHz. Since it is only necessary to heat the vicinity of the surface layer of the metal shaped material, heating is possible at any frequency regardless of the thickness of the painted metal shaped material, but 10 kHz to 100 kHz is more preferable.

  The shape of the induction coil is not particularly limited as long as a part or the entire surface of the metal shape member to which the molded body is bonded can generate heat. From the viewpoint of making it difficult for partial bonding failure of the joint due to partial heat generation, the shape of the induction coil preferably has a planar shape parallel to the close contact portion, for example, a flat shape. There is no limitation on the diameter and the number of turns of the induction coil.

  The arrangement of the induction coil is not particularly limited, but when the metal base material includes a non-magnetic material such as copper, aluminum, or nonmagnetic austenitic stainless steel, the painted metal base material and the thermoplastic resin composition A transverse system in which the induction coil is arranged so as to sandwich the molded body is preferable. The distance between the induction coil and the metal shape material may be arbitrarily selected from the output during heating by electromagnetic induction and the target temperature of the painted metal shape material.

  The output of the induction coil may be adjusted according to the type of the metal shape material, and when the metal shape material includes a magnetic material, such as ordinary steel or a ferritic stainless steel plate, a relatively low output, for example, 0. Heat generation is possible at 5 kW or more, and when the metal shape material includes a non-magnetic shape material such as an aluminum alloy, an austenitic stainless steel plate or a copper plate, the output needs to be high, for example, 3 kW or more, Moreover, it is necessary to make it high output, so that the distance of an induction coil and a metal raw material becomes large.

  By the above procedure, the molded body of the thermoplastic resin composition can be bonded to the surface of the painted metal base material.

  In the case of producing the composite by injection molding of the molded body, the entire molded body and the vicinity of the adhesion portion of the coated metal shaped material are heated to near the melting temperature. For this reason, the compact joined to the painted metal shape material undergoes a large thermal contraction in the entire shaped body compared to the painted metal shape material. Therefore, when the metal element can be deformed like a flexible metal plate, the painted metal element is bent by the thermal contraction of the molded body, and the composite is deformed.

  The deformation is more conspicuous in a planar shape in which the compact is smaller than the painted metal profile (see, for example, the composite 100 described in FIGS. 1 and 2). This is because even if the deformation amount of the composite at the end of the formed body in the planar shape is an allowable small amount, the end of the painted metal element in the planar shape becomes larger due to the deformation of the end of the formed body. This is because the amount of deformation of the composite at the end of the painted metal preform may be unacceptably large.

  In addition, the deformation of the composite due to the paint metal shape material being bent by the heat shrinkage of the molded body is a center portion of the planar shape, and even in a structure where the surface area of the formed body is larger than the surface area of the painted metal shape material, More prominent. This is because even in this structure, a slight deformation amount due to thermal contraction at the center portion in the planar shape of the composite increases the deformation amount at the end in the planar shape of the composite.

  However, as described above, in the method for manufacturing a composite according to the present embodiment, only the portion where the molded body and the painted metal shape material are in contact with each other can be heated. For this reason, compared with the case where a molded object is joined to a paint metal plastic material by injection molding, the part to be heated of the molded object becomes very small. Therefore, since the portion where the molded body contracts due to cooling after joining is limited, the amount of deformation at the end of the painted metal shaped member or the end of the composite tends to be large (easily deformed) as in the above structure. ) Even if it is a composite having a structure, it is possible to provide a composite in which deformation due to heat shrinkage during production is suppressed.

1-3. Step of Producing Paint Metal Shaped Material In the step of producing the painted metal shape material, an organic resin layer is formed on the surface of the metal shape material or the surface of a surface treatment film described later.

(Metal element)
The metal shape material means a shape obtained by applying heat or force to a metal. The metal base material used as the coating substrate is a metal plate, a press-molded product thereof, or a metal member formed by casting, forging, cutting, powder metallurgy, or the like.

  There are no particular limitations on the type of metal that constitutes the metal base material as long as it is a metal that can generate heat by electromagnetic induction. 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.

  The shape of the metal base material is not particularly limited as long as the shape of the thermoplastic resin composition to be described later is joined.

(Surface treatment film)
A surface treatment film may be disposed on the surface of the metal base material. The surface treatment film improves the adhesion between the metal base material and the organic resin layer and the corrosion resistance of the painted metal base material. The surface treatment film may be disposed on at least a portion of the surface of the painted metal shape member to be joined with the molded body of the thermoplastic resin composition, or may be disposed on the entire surface of the metal shape material.

  The surface treatment film can be formed by applying a surface treatment liquid containing a component constituting the film to be adhered to the surface of the metal base material and drying the applied surface treatment liquid. The coating method of the surface treatment liquid is not particularly limited, and may be appropriately selected from known coating methods. Examples of the coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. The drying conditions for the surface treatment liquid may be set as appropriate according to the composition of the surface treatment liquid. For example, the metal shape material coated with the surface treatment liquid is put in a drying oven without washing with water, and heated so that the temperature of the metal shape material reaches 80 to 250 ° C. A uniform surface treatment film can be formed on the surface.

The type of surface treatment for forming the surface treatment film is not particularly limited. Examples of the surface treatment include chromate treatment, chromium-free treatment, phosphate treatment and the like. The adhesion amount of the surface treatment film formed by the surface treatment is not particularly limited as long as it is within a range effective for improving the adhesion and corrosion resistance of the coating film. 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 Ti-Mo composite film has a Ti equivalent adhesion amount of 1 to 500 mg / m ² , and the fluoroacid-based film has a fluorine equivalent adhesion amount or a total metal element equivalent adhesion amount of 3 to 100 mg / m ² . The adhesion amount may be adjusted so that Moreover, in the case of a phosphate film, what is necessary is just to adjust the adhesion amount of each surface treatment film so that the phosphorus conversion adhesion amount may be 0.1-5 g / m < ² >.

(Organic resin layer)
The organic resin layer is disposed on the metal base material, that is, on the surface of the metal base material or the surface of the surface treatment film. The organic resin layer enhances the bonding strength of the painted metal shape material to the molded body of the thermoplastic resin composition.

  The organic resin layer is produced by applying an organic resin paint containing the material of the organic resin layer to the surface of the metal shape material and heating the applied organic resin paint.

  The organic resin paint contains an organic resin described later. The organic resin paint may further contain a crosslinking agent and an additive described later. The organic resin paint may further contain a solvent. The solvent is a liquid that can uniformly dissolve or disperse various components in the organic resin paint. The type of the solvent is not particularly limited as long as it is a liquid that evaporates in the process of forming the organic resin layer, and is preferably water.

  The organic resin layer is formed by applying the organic resin coating to the surface of the metal base material (or surface treatment film) and evaporating the solvent (water) by, for example, heat drying. The method for applying the organic resin paint is not particularly limited, and may be appropriately selected from known methods. Examples of the coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. The method for heating the organic resin paint applied to the metal base material is not particularly limited. Although the ultimate temperature of the metal shape material during heating is not particularly limited, for example, the organic resin layer is configured from the viewpoint of forming an organic resin layer that is closely adhered to the surface of the metal shape material (or surface treatment film). The melting point of the composition is preferably 250 ° C. or higher.

  The organic resin may have a functional group (hydrogen-bonding functional group) that forms a hydrogen bond with the metal base material and has a weldability to the thermoplastic resin composition that constitutes the molded body. Examples of the hydrogen bonding functional group include a carboxyl group and an amino group. For example, if the thermoplastic resin composition is a polypropylene resin composition, the organic resin preferably includes a polypropylene resin. In addition, if the thermoplastic resin composition is a polybutylene terephthalate resin composition, a polyamide resin composition, or an acrylonitrile-butadiene-styrene resin composition, the organic resin preferably includes a polyurethane resin. . One or more organic resins may be used.

  The organic resin described above can be obtained as a commercial product. In addition, the presence of the organic resin in the organic resin layer can be confirmed by ordinary analytical equipment such as NMR, IR, and GC-MS.

  Furthermore, the organic resin may be cross-linked. The crosslinking of the organic resin can be performed by, for example, a crosslinking agent having two or more crosslinking functional groups that react with the hydrogen bonding functional group in the organic resin. Crosslinking the organic resin 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 the organic resin 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, and a crosslinking agent having a metal salt. The amount of the crosslinking agent used is appropriately determined within a range in which both the adhesiveness of the organic resin layer to the metal shape material and the effect of crosslinking in the organic resin are obtained.

(Polypropylene resin)
The polypropylene resin is a polymer compound containing a polypropylene skeleton and the hydrogen bonding functional group. Examples of the polypropylene resin include acid-modified polypropylene. The acid-modified polypropylene is a polypropylene in which a carboxyl group or an anhydride group thereof is introduced into a structural unit of polypropylene. The amount of the hydrogen bonding functional group in the polypropylene resin is appropriately determined from a range in which sufficient adhesiveness to the metal base material is obtained. The polypropylene resin may further contain a functional group other than the hydrogen bonding functional group.

  The content of the acid-modified polypropylene is 40% by mass or more based on the total resin in the organic resin layer, from the viewpoint of increasing the bonding strength between the molded body of the thermoplastic resin composition and the painted metal shape material. preferable. When the acid-modified polypropylene content in the organic resin layer is less than 40% by mass, the weldability of the organic resin layer to the molded body of the thermoplastic resin composition may be lowered. Thereby, sufficient joining force may not be acquired between the said molded object and a coating metal shape material. The upper limit of the content of the acid-modified polypropylene can be appropriately determined within the range where the effects of the present invention can be obtained.

  The melt viscosity of the organic resin layer composed of the acid-modified polypropylene is preferably 1000 to 10,000 mPa · s. When the said melt viscosity is less than 1000 mPa * s, the said organic resin layer may flow in the case of welding with the molded object of a thermoplastic resin composition. For this reason, an organic resin layer does not weld to a thermoplastic resin composition, and the joining force between the said molded object and a coating metal shape material may become inadequate. On the other hand, when the melt viscosity is more than 10,000 mPa · s, the weldability of the organic resin layer to the molded body may be lowered and become insufficient. For this reason, the joining force between the said molded object and a coating metal raw material may become inadequate. The melt viscosity is measured with a Brookfield viscometer.

  The acid value of the acid-modified polypropylene is preferably 1 to 500 mgKOH / g. If the acid value of the acid-modified polypropylene is within the above range, the acid-modified polypropylene itself acts as a surfactant by neutralizing the acid-modified polypropylene when preparing the emulsion described later.

  It is preferable that the acid-modified polypropylene has a melting point of 60 to 120 ° C. and the acid-modified polypropylene has a crystallinity of 5 to 20%. The acid-modified polypropylene having the above melting point and crystallinity has high wettability with respect to the surface of the metal base material. For this reason, it is preferable from a viewpoint of forming the organic resin layer closely_contact | adhered also to the fine unevenness | corrugation of the surface of a metal raw material. When the melting point is less than 60 ° C. or the crystallinity is less than 5%, the organic resin layer is softened at a relatively low temperature. For example, the coating metal shape material has insufficient blocking resistance during storage. Sometimes. When the melting point is higher than 120 ° C. or the crystallinity is higher than 20%, the bondability between the molded body and the painted metal shape may be lowered.

  Note that the melting point and crystallinity of the acid-modified polypropylene hardly change between the state contained in the organic resin paint (coating for the organic resin layer) (before baking) and the state of the organic resin layer (after baking). Therefore, the degree of crystallinity of the acid-modified polypropylene in the organic resin layer can be examined by measuring an organic resin paint described later containing the acid-modified polypropylene by X-ray diffraction by the Ruland method.

  The acid-modified polypropylene can be prepared, for example, as an acid-modified polypropylene emulsion having acid-modified polypropylene as a dispersoid. The acid-modified polypropylene emulsion can be prepared by preparing an acid-modified polypropylene and then dispersing the acid-modified polypropylene in water. Various surfactants may be added as an emulsifier to the acid-modified polypropylene emulsion.

  Polypropylene is known for the stereoregularity of isotactic, tactic, syndiotactic, hemi-isotactic and stereotactic. The stereoregularity of the polypropylene in the acid-modified polypropylene is preferably isotactic from the viewpoint of mechanical properties such as rigidity and impact strength or durability.

  The weight average molecular weight of the polypropylene is preferably 1000 to 300,000, and more preferably 5000 to 100,000. When the weight average molecular weight of polypropylene is less than 1000, the strength of the organic resin layer may be lowered. On the other hand, when the weight average molecular weight of polypropylene exceeds 300000, the viscosity increases when the polypropylene is acid-modified, which may make the operation difficult.

  The acid modification of polypropylene is carried out by dissolving polypropylene in toluene or xylene, and in the presence of a radical generator, an α, β-unsaturated carboxylic acid and / or an acid anhydride of α, β-unsaturated carboxylic acid and / or 1 This can be done using compounds having one or more double bonds per molecule. Alternatively, using an apparatus capable of raising the temperature to the softening temperature or melting point of polypropylene, the α, β-unsaturated carboxylic acid and / or α, β-unsaturated in the presence or absence of a radical generator. Carboxylic acid anhydrides and / or compounds having one or more double bonds per molecule can be used. When the polypropylene modification reaction is carried out as a solution in an organic solvent such as toluene and / or xylene, or in a heterogeneous dispersion system carried out in a non-solvent such as an aqueous system, nitrogen substitution is sufficiently performed. There is a need. In this way, acid-modified polypropylene can be prepared.

  Examples of the radical generator include peroxide and azonitrile. Examples of the azonitrile include di-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyethyl hexanoate, tert- Examples include butyl peroxypivalate, methyl ethyl ketone peroxide, and di-tert-butyl peroxide. Examples of the azonitrile include azobisisobutyronitrile and azobisisopropionitrile. It is preferable that the compounding quantity of a radical generator is 0.1-50 mass parts with respect to 100 mass parts of polypropylene. Moreover, 0.5-30 mass parts is especially preferable.

  Examples of the α, β-unsaturated carboxylic acid or anhydride thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid and anhydrous Aconitic acid is included. The α, β-unsaturated carboxylic acid or acid anhydride thereof may be one kind or more. When two or more of the above α, β-unsaturated carboxylic acids or acid anhydrides thereof are used in combination, the physical properties of the organic resin layer are often improved.

  Examples of the compound having one or more double bonds per molecule include (meth) acrylic acid monomers and styrene monomers. Examples of the (meth) acrylic acid monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-hydroxy Ethyl, (meth) acrylate-2-hydroxypropyl, (meth) acrylate-4-hydroxybutyl, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, (meth) Benzyl acrylate, (meth) acrylate-2-hydroxybutyl, benzyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, di (meth) acrylic acid (di) ethylene glycol, di (meth) ) Acrylic acid-1,4-butanediol, di (meth) acrylic acid-1,6-hexanedioe , Tri (meth) acrylate of trimethylolpropane, di (meth) glycerol acrylate, (meth) acrylic acid 2-ethylhexyl, lauryl (meth) acrylic acid, (meth) acrylate, stearyl and acrylamide. Examples of the styrenic monomer include styrene, α-methylstyrene, paramethylstyrene, and chloromethylstyrene. Furthermore, vinyl monomers such as divinylbenzene, vinyl acetate, and vinyl esters of versatic acid can be used in combination with the above compounds.

  One or more compounds having one or more double bonds per molecule may be used. It is preferable that the compounding quantity of the said compound is 0.1-50 mass parts with respect to 100 mass parts of polypropylene. Especially preferably, it is 0.5-30 mass parts.

(Polyurethane resin)
The polyurethane resin is a polymer compound including a polyurethane skeleton and the hydrogen bonding functional group. Examples of the polyurethane-based resin include polycarbonate-containing polyurethane (hereinafter also referred to as “PC-containing polyurethane”). The amount of the hydrogen-bonding functional group in the polyurethane resin is appropriately determined from a range in which sufficient adhesion to the metal base material can be obtained. The polyurethane resin may further contain a functional group other than the hydrogen bonding functional group. The weight average molecular weight of the polyurethane resin is not particularly limited as long as the effect of the present invention is obtained.

  PC-containing polyurethane has polycarbonate units in the molecular chain. “Polycarbonate unit” refers to the structure shown below in the molecular chain of polyurethane. The said polycarbonate unit may exist individually in the said PC containing polyurethane, and may exist continuously. 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, and adhesion to the metal shape material and weldability to the thermoplastic resin composition It is preferable from the viewpoint of improving both. 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. The composition may not be welded with sufficient strength. The ratio of the mass of the polycarbonate unit to the mass of the total resin can be determined by nuclear magnetic resonance spectroscopy (NMR analysis) using a sample in which the organic resin layer is dissolved in chloroform.

  The PC-containing polyurethane can be prepared, for example, by the following steps. First, a urethane prepolymer is produced by reacting an organic polyisocyanate, a polycarbonate polyol, and a polyol having a tertiary amino group or a carboxyl group. In addition, it is possible to use together polyols other than polycarbonate polyol, for example, polyester polyol, polyether polyol, etc. within the range in which the effect of this invention is acquired.

  Next, 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. Thus, a cationic polycarbonate unit-containing polyurethane can be produced. Alternatively, the carboxyl group of the urethane prepolymer is neutralized with a basic compound such as triethylamine, trimethylamine, diethanolmonomethylamine, diethylethanolamine, caustic soda, or caustic potassium, and converted to a carboxylic acid salt. Thus, an anionic polycarbonate unit-containing polyurethane can be produced. The PC-containing polyurethane may be a cationic polycarbonate unit-containing polyurethane or an anionic polycarbonate unit-containing polyurethane.

  The kind of the organic polyisocyanate is not particularly 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 and, include 4,4'-dicyclohexylmethane diisocyanate. The organic polyisocyanate may be one kind or more.

  The said polycarbonate polyol is obtained by making a carbonate compound and a diol compound react. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Examples of the diol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 4 -Butanediol, 1,4-cyclohexanediol, 1,6-hexanediol and the like are included. The polycarbonate polyol may be a compound chain-extended with an isocyanate compound. The polycarbonate polyol may be one kind or more.

  A polyol having a tertiary amino group or a carboxyl group can be obtained, for example, by acid-base reaction or dehydration condensation of an alkanolamine and a dicarboxylic acid in the presence of an initiator. Examples of such initiators include ammonia, primary or secondary monoamines, primary or secondary aliphatic polyamines, and primary or secondary aromatic mono- or aromatic polyamines. Etc. are included. Examples of the primary or secondary monoamines include methylamine and ethylamine. Examples of the primary or secondary aliphatic polyamines include ethylenediamine, hexamethylenediamine, N, N′-dimethylethylenediamine, and the like. Examples of the primary or secondary aromatic mono- or aromatic polyamines include aniline, diphenylamine, toluenediamine, diphenylmethanediamine, and N-methylaniline. Examples of the alkanolamines include monoethanolamine and diethanolamine. Examples of the dicarboxylic acid include adipic acid and phthalic acid. The polyol having a tertiary amino group or carboxyl group may be a compound chain-extended with an isocyanate compound. The polyol having the tertiary amino group or carboxyl group may be one kind or more.

  The organic resin described above can be obtained as a commercial product. In addition, the presence of the organic resin in the organic resin layer can be confirmed by ordinary analytical equipment such as NMR, IR, and GC-MS.

(Additive)
The organic resin layer may further contain an additive as long as the effects of the present invention are obtained. Examples of the additive include a rust inhibitor, a phosphorus compound, a lubricant, an antifoaming agent, an etching agent, an inorganic compound, and a coloring material.

  The said rust preventive improves the corrosion resistance of a coating metal shape material, As a result, improves the corrosion resistance of a composite_body | complex. One or more rust inhibitors may be used. Examples of the rust inhibitor include a metal compound rust inhibitor, a non-metal compound rust inhibitor, and an organic compound rust inhibitor. The content of the rust preventive agent in the organic resin layer can be appropriately determined from the range in which the rust preventive effect of the rust preventive agent and the effect of the present invention can be obtained according to the type of the rust preventive agent.

  Examples of the metal compound rust preventive include oxides, hydroxides of metals selected from the group consisting of Si, Ti, Zr, V, Mo, Cr, Hf, Nb, Ta, W, Mg, and Ca. Or fluoride.

  The content of the rust inhibitor in the organic resin layer can be appropriately determined within a range in which the function of the metal compound rust inhibitor is expressed. For example, the content of the rust inhibitor in the organic resin layer is 0.5 mass% or more in terms of Si, 0.005 mass% or more in terms of Ti, and Zr content in terms of corrosion resistance. Is 0.05% by mass or more, the Mo equivalent content is 0.005% by mass or more, and the V equivalent content is preferably 0.02% by mass or more. In addition, the content of the rust inhibitor in the organic resin layer is such that the content in terms of Si is less than 23.5% by mass, the content in terms of Ti is less than 0.6% by mass, from the viewpoint of storage stability of the organic resin paint. It is preferable that the content in terms of Zr is less than 12.0 mass%, the content in terms of V is less than 3.0 mass%, and the content in terms of Mo is less than 3.0 mass%.

  Examples of the non-metallic compound rust inhibitor include a phosphoric acid compound such as diammonium hydrogen phosphate and a thiol compound such as thiourea.

  Examples of the organic compound rust inhibitor include inhibitors and chelating agents. Examples of such inhibitors include carboxylic acids such as oleic acid, dimer acid, naphthenic acid, metal carboxylate soaps (lanolin Ca, Zn naphthenate, oxidized wax Ca, Ba salts, etc.), sulfonates (Na, Ca, Ba). Sulfonates), amine salts, and esters (such as glycerin esters of higher fatty acids, sorbitan monoisostearate, sorbitan monooleate). Examples of the chelating agent include EDTA (ethylenediaminetetraacetic acid), gluconic acid, NTA (nitrilotriacetic acid), HEDTA (hydroxyethyl, ethylenediaminetriacetic acid), DTPA (diethylenetriaminepentaacetic acid), and Na citrate. included.

  The lubricant can suppress galling on the surface of the painted metal profile. One or more lubricants may be used, and the type of lubricant is not particularly limited. Examples of the lubricant include organic waxes such as fluorine, polyethylene, styrene, and polypropylene, and inorganic lubricants such as molybdenum disulfide and talc. The content of the lubricant in the organic resin layer is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the organic resin and the other resin in the organic resin layer. When the lubricant is less than 1 part by mass, generation of galling may not be sufficiently suppressed. On the other hand, when the amount of the lubricant exceeds 20 parts by mass, the effect of suppressing the generation of galling reaches a peak, and the lubricity is too high and the handleability may be inferior.

  The antifoaming agent suppresses the generation of bubbles during the preparation of the organic resin paint described later. One or more antifoaming agents may be used. The type of antifoaming agent is not particularly limited. An appropriate amount of a known antifoaming agent such as a silicone-based antifoaming agent may be added to the antifoaming agent.

  The said etching agent improves the adhesiveness of the organic resin layer with respect to a metal raw material by activating the surface of a metal raw material. Examples of the etching agent include fluorides such as hydrofluoric acid, ammonium fluoride, zircon hydrogen fluoride, and titanium hydrogen fluoride.

  The inorganic compound improves the water resistance by densifying the organic resin layer. Examples of the inorganic compound include inorganic oxide sols such as silica, alumina and zirconia, and phosphates such as sodium phosphate, calcium phosphate, manganese phosphate and magnesium phosphate.

  The color material imparts a predetermined color tone to the organic resin layer. Examples of the color material include inorganic pigments, organic pigments, and organic dyes.

(Properties of organic resin layer)
The thickness of the organic resin layer is 0.2 μm or more. If the thickness of the organic resin layer is less than 0.2 μm, the bonding strength of the painted metal preform to the molded body may be insufficient. Moreover, when the thickness of the organic resin layer is less than 0.2 μm, the function of the additive contained in the organic resin layer (for example, the rust preventive action of the rust preventive agent) may be insufficient. The upper limit value of the thickness of the organic resin layer is not particularly limited, but can be determined from the viewpoint that the above effect reaches its peak, the viewpoint of productivity, the viewpoint of cost, and the like. For example, the thickness of the organic resin layer is preferably 10 μm or less, and more preferably 3 μm or less.

  The formed organic resin layer is composed of a composition including the organic resin described above and the additive that is optionally blended. The melting point of the composition is preferably equal to or less than that of the molded body of the thermoplastic resin composition, and is preferably 60 to 160 ° C., for example. When the melting point of the composition is less than 60 ° C., the organic resin layer is softened at a relatively low temperature, so that the blocking resistance of the coated metal base material may be insufficient. When the melting point of the composition is higher than 160 ° C., the bondability of the coated metal shaped material to the molded body may be insufficient. The melting point of the resin composition can be adjusted by the type of organic resin and the use of additives.

  The organic resin layer may uniformly cover a region where the adhesion portion (welded portion) is formed on the surface of the metal raw material, or may be dispersed in the region to cover the surface of the metal raw material. May be.

1-4. About the molded body of a thermoplastic resin composition The molded body of a thermoplastic resin composition should just be a molded object which has a shape closely_contact | adhered to the surface of a coating metal raw material. The shape of the thermoplastic resin composition is not particularly limited as long as the above conditions are satisfied, and can be appropriately determined according to the use of the composite.

  Examples of the thermoplastic resin composition constituting the molded body include polypropylene (PP) resin composition, polybutylene terephthalate (PBT) resin composition, polyamide (PA) resin composition, acrylonitrile-butadiene-styrene. (ABS) resin composition, polyvinyl chloride (PVC) resin composition, methacrylic acid (PMMA) resin composition, polyethylene (PE) resin composition, polyacetal (POM) resin composition, and these Combination. The kind of the thermoplastic resin composition can be determined according to the weldability with the organic resin layer.

  The molding shrinkage rate of the thermoplastic resin composition is preferably 1.1% or less from the viewpoint of suppressing deformation due to temperature change during production of the composite. The molding shrinkage of the thermoplastic resin composition can be adjusted by a known method. For example, the molding shrinkage can be adjusted by adding a filler to the thermoplastic resin composition, the mixing ratio of the crystalline resin and the amorphous resin in the thermoplastic resin composition, or the like. The amorphous resin is, for example, PVC or PMMA. Examples of the crystalline resin include PE, PP, and POM. The molding shrinkage can be lowered, for example, by increasing the filler content or increasing the mixing ratio of the amorphous resin to the crystalline resin.

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

  When the molding shrinkage rate is larger than 1.1%, the coated metal shaped material may not be sufficiently firmly bonded to the molded body. The molding shrinkage ratio is preferably 0.9% or less, and more preferably 0.7% or less, from the viewpoint of further increasing the bonding strength of the painted metal preform to the molded body.

  Further, αp / αm is preferably 6 or less from the viewpoint of suppressing deformation due to a temperature change during the production of the composite. αp is a linear expansion coefficient of the thermoplastic resin composition, and αm is a linear expansion coefficient of the metal base material. When αp / αm is larger than 6, the coated metal shaped material may not be sufficiently firmly bonded to the molded body. αp / αm is preferably 4.5 or less from the viewpoint of further increasing the bonding strength of the painted metal preform to the molded body. 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 and thermoplastic elastomers.

  The filler reduces the molding shrinkage of the molded body and improves the rigidity of the molded body. The kind of filler is not particularly limited, and a known substance can be used. One or more fillers may 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 and glass spheres Powder fillers such as carbon fibers and aramid fibers. Among these, glass fibers are more preferable from the viewpoint of maintaining the light transmittance of the molded body. From the above viewpoint, the content of the filler in the thermoplastic resin composition is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass.

  The thermoplastic elastomer improves the impact resistance of the molded body. The kind of thermoplastic elastomer is not particularly limited, and one or more thermoplastic elastomers may be used. Examples of thermoplastic elastomers include polyolefin resins, polystyrene resins, and combinations thereof.

1-5. Effect According to the present embodiment, there is provided a method for manufacturing a composite body in which the bonding strength of the painted metal preform to the molded body is high and deformation due to thermal shrinkage during manufacturing is suppressed.

2. Composite The composite according to the present embodiment includes a painted metal shape material including a metal shape material and an organic resin layer having a thickness of 0.2 μm or more disposed on the metal shape material, and the coating material. A molded body of a thermoplastic resin composition bonded to a metal base material, wherein the organic resin layer has weldability to the thermoplastic resin composition, and the molded body is made of the metal It is a composite body in which the organic resin layer is welded to the molded body by heat heated by electromagnetic induction of the raw material, thereby joining the painted metal raw material. The composite according to the present embodiment can be manufactured by the method for manufacturing the composite according to the above-described embodiment.

  An example of a composite manufactured by the method described above is shown in FIG. 1A, which is a plan view, and FIG. 1B, which is a cross-sectional view taken along line 1B-1B in FIG. 1A. As shown in FIGS. 1A and 1B, the composite 100 has a painted metal preform 10 and a molded body 20. The painted metal base material 10 includes a metal base material 102 and an organic resin layer 104. The organic resin layer 104 is disposed on the entire surface of the metal base material 102. The molded body 20 is composed of a thermoplastic resin composition, and the organic resin layer 104 has weldability to the molded body 20. The length in the longitudinal direction of the molded body 20 is shorter than the length in the longitudinal direction of the painted metal preform 10, and the molded body 20 is arranged at the center in the longitudinal direction of the painted metal preform 10.

  The organic resin layer 104 is welded to the molded body 20 by the heating unit 30 using electromagnetic induction. The heating unit 30 is a part heated by heat generated by electromagnetic induction of the metal shape member 102 in contact with the organic resin layer 104 in which the molded body 20 is disposed, and the heat due to the heat generation conducted the metal shape material. As a result, the organic resin layer 104 is heated and welded. The heating unit 30 is formed in a circular shape in the center of the molded body 20.

  Or the heating part 30 by electromagnetic induction may be formed in the shape of a dot at the four corners in the planar shape of the molded body 20 as shown in FIGS. 2A to 2B, or at the edge in the planar shape of the molded body 20. You may form in a rectangle along. In addition, the heating part 30 which has the rectangular shape along the edge in planar shape can be formed by moving the induction coil along the edge in planar shape, outputting it.

  Another example of the composite manufactured by the above procedure is shown in FIG. 3B, which is a cross-sectional view taken along line 3B-3B in FIGS. 3A and 3A. As shown in FIGS. 3A and 3B, the composite 200 has a painted metal preform 10 and a molded body 40. The molded body 40 includes a concave portion 402 having a rectangular planar shape and a flange portion 404 surrounding the opening of the concave portion 402. The organic resin layer 104 in the composite 200 is welded to the collar portion 404 of the molded body 40 by the heating unit 50 by electromagnetic induction. The electromagnetic induction heating unit 50 is formed in a rectangular shape along the opening edge of the recess 402.

  According to this Embodiment, the composite_body | complex in which the joining force of the coating metal preform with respect to the said molded object is high, and the deformation | transformation by the heat shrink at the time of manufacture is suppressed is provided.

  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. Preparation of painted metal plate (1) Metal plate As hot-dip Zn-Al-Mg alloy plated steel sheet hot-dip Zn-Al-Mg alloy plated steel sheet, coating weight per one side was used molten Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet of 45 g / ^{m 2} . The base steel plate was a cold rolled steel plate (SPCC) having a thickness of 0.8 mm.

B. Stainless steel plate As a stainless steel plate, SUS304, 2B finishing material having a thickness of 0.8 mm was tried.

C. Aluminum alloy plate As the aluminum alloy plate, A5052 having a thickness of 0.5 mm and not anodized was used.

(2) Preparation of Organic Resin Paint An organic resin emulsion, polyethylene wax and a crosslinking agent were added to water to prepare an organic resin paint having a nonvolatile component of 20% by mass.

  As the organic resin emulsion, an urethane resin emulsion and a polypropylene resin emulsion were used. A commercially available polyurethane resin emulsion (Adekabon titer HUX-386, manufactured by ADEKA Corporation, simply referred to as “UE”) was used as the urethane resin emulsion. A commercially available acid-modified polypropylene resin emulsion (Hardren NZ-1005, manufactured by Toyobo Co., Ltd., also simply referred to as “PPE”) was used as the polypropylene resin emulsion.

  A commercially available polyethylene wax (E-9015, manufactured by Toho Chemical Industry Co., Ltd.) was used as the polyethylene wax. The addition amount of the polyethylene wax is 3.0 parts by mass with respect to 100 parts by mass of the total mass of the organic resin.

  As the crosslinking agent, a commercially available epoxy crosslinking agent (HUX-XW3, manufactured by ADEKA Corporation) was used. The addition amount of a crosslinking agent is 3.0 mass parts with respect to 100 mass parts of total mass of the said organic resin.

  A rust inhibitor and an antifoaming agent were further added to the obtained organic resin paint.

  As the rust preventive agent, a metal compound (B1), a nonmetal compound (B2), and an organic compound (B3) were used.

Si, Ti, Zr, V, and Mo oxides were used for the metal compound (B1). SiO ₂ (manufactured by Nissan Chemical Industries, colloidal silica ST-N, also referred to as “B11”) was used as the Si oxide. As the Ti oxide, TiO ₂ (IV) (manufactured by Kishida Chemical, also referred to as “B12”) was used. As the Zr oxide, (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ (first rare element chemical industry, also referred to as “B13”) was used. V ₂ O ₅ (Taiyo Kogyo Co., Ltd., also referred to as “B14”) was used as the V oxide. As the Mo oxide, (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O (Kishida Chemical Co., Ltd., also referred to as “B15”) was used. The above metal compounds were added alone or in combination.

Phosphorus oxide and thiol compound were used for the nonmetallic compound (B2). As the phosphorus oxide, (NH ₄ ) ₂ HPO ₄ (Kishida Chemical Co., Ltd., also referred to as “B21”) was used. NH ₂ CSNH ₂ (Kishida Chemical Co., Ltd., also referred to as “B22”) was used as the thiol compound. The non-metallic compounds were added alone or in combination.

A chelate compound was used as the organic compound (B3). As the chelate compound, Na ₃ (C ₃ H ₅ O (COO) ₃ ) (Kishida Chemical Co., Ltd., also referred to as “B31”) was used.

  As the antifoaming agent, a commercially available silicone-based antifoaming agent resin (KM-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The addition amount of the antifoaming agent is 0.05% by mass with respect to the total mass of the organic resin.

  Organic resin paints 1 to 12 were prepared using the above materials in the types and amounts shown in Table 1 and Table 2 below.

  In Tables 1 and 2, the content of the rust inhibitor is a ratio of a specific element or component in the rust inhibitor to the total mass of the organic resin layer. The said element or component is written together with the numerical value of content of a rust preventive agent. “P” is a phosphorus element, “SH” is a thiol component, “Zr” is zirconium, “V” is vanadium, “Si” is silicon, “Ti” is titanium, “Mo” is molybdenum. , Respectively. Moreover, the rust preventive agent without the said elements etc. is added with the following content.

(3) Formation of organic resin layer The surface of the metal plate A was degreased by immersing it in an alkaline degreasing aqueous solution (SD-270, manufactured by Nippon Paint Co., Ltd.) having a liquid temperature of 40 ° C. and a pH of 12 for 1 minute. Next, the organic resin paint 1 prepared in (2) above is applied to the surface of the degreased metal plate with a roll coater and dried with a hot air dryer so that the ultimate plate temperature is 150 ° C. A layer was formed. Thus, a coated metal plate 1 was obtained. Further, the type of the metal plate is appropriately selected from any one of A to C, and the coated metal plates 2 to 12 are obtained in the same manner except that each of the organic resin paints 2 to 12 is used instead of the organic resin paint 1. It was.

In Table 3, the kind of metal plate, the kind of organic resin coating material, and the film thickness of the organic resin layer of the coated metal plates 1 to 12 are shown. Note that (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ is considered to be present in the state of ZrO in the organic resin layer. V ₂ O ₅ is considered to be present in the form of _V 2 _{O 5} in the organic resin layer. (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O is considered to be present in the state of Mo ₇ O _{24 in} the organic resin layer.

(4) Evaluation of corrosion resistance The coated metal plate 1 was cut into a width of 70 mm and a length of 150 mm, and the end face was sealed on the entire circumference to prepare a sample 1. Next, Sample 1 was put into a salt spray tester, and the white rust generation area ratio after 72 hours was obtained, and the corrosion resistance of the coated metal plate 1 was evaluated from the white rust generation area ratio. The case where the white rust occurrence area ratio after 72 hours of salt spray was less than 10% was evaluated as “◯”, 10% or more but less than 30% as “Δ”, and 30% or more as “x”. Moreover, it replaced with the coating metal plate 1 and evaluated the corrosion resistance of the coating metal plates 2-12 similarly except having used each of the coating metal plates 2-12. The results are shown in Table 3.

  As shown in Table 3, each of the coated metal plates 2 to 9, 11 and 12 exhibited corrosion resistance having no practical problem, possibly due to the action of the metal compound rust preventive agent. In addition, it is considered that the coated metal plates 2, 3, 6-9, 11 and 12 also obtained good corrosion resistance by using a stainless steel plate or an aluminum alloy for the metal plate.

  On the other hand, although the coated metal plate 10 has no practical problem, the coated metal plate 10 exhibited corrosion resistance lower than the corrosion resistance of the coated metal plates 2 to 9, 11 and 12. The reason for this is considered to be that the thickness of the organic resin layer of the coated metal plate 10 was less than 0.2 μm.

  The corrosion resistance of the coated metal plate 1 was insufficient. The reason is considered that the coated metal plate 1 is not formed with an organic resin layer.

2. Preparation and Evaluation of Composite (1) Painted metal plate Each of the coated metal plates 1 to 12 was cut to prepare painted metal plates 1 to 12 having a width (W ₁₁ ) 30 mm × length (L ₁₂ ) 80 mm. (See FIGS. 1A and 1B). In addition, each thickness of the coating metal plates 1-12 is 0.6 mm.

(2) Thermoplastic Resin Composition As the thermoplastic resin composition, polypropylene (hereinafter also referred to as “PP”) resin composition, polybutylene terephthalate (hereinafter also referred to as “PBT”) resin composition, acrylonitrile-butadiene. -A styrene (hereinafter also referred to as "ABS") resin composition was prepared.

  In the PP resin composition, Prime Polypro R-350G (molding shrinkage: 0.2, Prime Polymer Co., Ltd.) containing 30% by mass of glass fiber (hereinafter also referred to as “G”) as an inorganic filler, Novatec BC06C (molding shrinkage ratio: 1.3, Nippon Polypro Co., Ltd.) containing no glass fiber was used.

  The PBT resin composition includes Novaduran 5710F40 (molding shrinkage: 0.3, Mitsubishi Engineering Plastics Co., Ltd.) containing 40% by mass of the above glass fiber, and Novaduran 5010R3 (molding shrinkage: no glass fiber). 1.5, Mitsubishi Engineering Plastics Co., Ltd.) was used.

  Exelloy CK-10G20 (molding shrinkage ratio: 0.1, Technopolymer Co., Ltd.) containing 20% by mass of the glass fiber was used for the ABS resin composition.

(3) Molded body of thermoplastic resin composition Each of the thermoplastic resin compositions is formed into a strip shape having a width (W ₁₁ ) 30 mm × length (L ₁₁ ) 60 mm × thickness (T ₁₁ ) 3 mm by injection molding. The molded body 10 of the thermoplastic resin composition was prepared (see FIGS. 4A and 4B).

[Example 1]
The painted metal plate 2 and the molded body of the PBT resin composition are placed on the stage, and as shown in FIGS. 4A and 4B, one end of the painted metal plate 2 (reference numeral 10 in FIGS. 4A and 4B). When the one end of the shaped body (reference numeral 20 in FIGS. 4A and 4B), was adhered longitudinal length in (X direction) _(L 13) superimposed over 10 mm.

  The overlapped part (contact part) is pressed by a 5mm thick glass plate with a load of 5kgf from the coated metal plate side, an induction coil is placed 10mm away from the contact part in the vertical direction, and the induction coil is energized for 5 seconds. After flowing, the glass plate was allowed to cool for 10 seconds while a load was applied. Then, the glass plate was removed and the composite_body | complex of the coating metal plate 2 and the molded object of the PBT-type resin composition was formed. Thus, a sample for tensile test (reference numeral 300 in FIGS. 4A and 4B), which is a composite of the coated metal plate 2 and a molded body of the PBT resin composition, was produced.

  The induction coil used for electromagnetic induction was a copper tube having a diameter of 5 mm wound in a circular shape three times, including a 1 mm gap and a diameter of 34 mmφ. The distance between the induction coil and the painted metal shape member was 10 mm at a frequency of 80 kHz. The output from the induction coil is changed in the range of 3.0 to 7.8 kW depending on the type of the coated metal plate so that a magnetic field that can generate heat is generated in a range 70 with an area of 35 mm, 10 mm away from the induction coil. It was.

[Examples 2 to 12 and Comparative Examples 1 and 2]
A sample for a tensile test was produced in the same manner as in Example 1 except that the coated metal plate, the type of thermoplastic resin composition, and the output from the induction coil were changed as shown in Table 4 below.

(4) Evaluation of Composite Bonding Strength By pulling the coated metal plate and the molded body of the thermoplastic resin composition in the samples for tensile test obtained in Examples 1 to 12 and Comparative Examples 1 and 2, by the electromagnetic induction described above The strength (peeling strength) of the tensile force when the welded welded portion was broken was measured and used as the joining force of the sample for the tensile test. The direction of pulling the painted metal plate and the thermoplastic resin composition was a direction parallel to the bonding surface and opposite to each other (X direction in FIG. 4A), and the tensile speed was 100 mm / min.

  “X” when the bonding force is less than 1.0 kN, “Δ” when the bonding force is 1.0 kN or more and less than 1.5 kN, and the bonding force is 1.5 kN or more and less than 2.0 kN. In the case of (circle), it evaluated as "(circle)" and the case where the joining force was 2.0 kN or more was evaluated as ((circle)). Table 4 shows the measurement results and evaluation results of the bonding strength (peel strength) of each sample (composite).

  In the composites according to Examples 1 to 12, all had good bonding strength of 1.0 kN or more. This is considered because the thickness of the organic resin layer was 0.2 μm or more.

  On the other hand, in the composite according to Comparative Example 1, the composite was not bonded to the painted metal plate. This is considered because it does not have an organic resin layer. Moreover, in the composite_body | complex which concerns on the comparative example 2, the said joining force was inadequate. This is considered because the film thickness of the organic resin layer was less than 0.2 μm.

[Example 13]
The painted metal plate 2 and the molded body of the PBT resin composition are arranged on a stage, and as shown in FIGS. 1A and 1B, one end of the painted metal plate 2 (reference numeral 10 in FIGS. 1A and 1B). And one end of the molded body (reference numeral 20 in FIGS. 1A and 1B) were stacked and adhered over a length (L ₁₁ ) of 60 mm in the longitudinal direction (X direction).

  The overlapped part (contact part) is pressed with a 5mm thickness glass plate from the coated metal plate side with a load of 5kgf, an induction coil is placed 10mm away from the center of the contact part in the vertical direction, and the induction coil is placed for 5 seconds. After passing an electric current, it was cooled for 10 seconds while applying a load with a glass plate. Then, the glass plate was removed and the composite_body | complex of the coating metal plate 2 and the molded object of the PBT-type resin composition was formed. In this way, a sample for warpage measurement (reference numeral 100 in FIGS. 1A and 1B), which is a composite of the coated metal plate 2 and a molded body of the PBT resin composition, was produced. The conditions regarding the induction coil used and heating by electromagnetic induction are the same as those in the first embodiment.

[Examples 14 to 24 and Comparative Examples 3 and 4]
A sample for warpage measurement as a composite was produced in the same manner as in Example 13 except that the composition of the coated metal plate and the thermoplastic resin composition and the welding method were changed as shown in Table 5 below.

[Comparative Example 5]
After heating the entire surface of the coated metal plate 2 to 240 ° C., the PBT resin composition formed body was placed on the center in the longitudinal direction of the coated metal plate 2 and pressed at a pressure of 2 MPa for 30 seconds. In this way, a comparative sample for warpage measurement was prepared as a composite by thermocompression bonding of the coated metal plate 2 and the molded body of the PBT resin composition. The comparative sample has the same configuration as the above-described warpage measurement sample except that the entire surface of one surface of the formed body is welded to the painted metal plate.

[Comparative Examples 6 and 7]
A comparative sample for warpage measurement was produced in the same manner as in Comparative Example 5 except that the composition of the coated metal plate and the thermoplastic resin composition was changed as shown in Table 5 below.

(5) Evaluation of warpage amount of composite For each of the samples for warpage measurement obtained in Examples 13 to 24 and Comparative Examples 3 to 7, the warpage amounts at both ends in the longitudinal direction of the sample (H in FIG. 5) The largest amount of warpage among _a , H _b ) was measured. “X” when the maximum warpage amount is 0.5 mm or more, “△” when the maximum warpage amount is 0.1 mm or more and less than 0.5 mm, and “○” when the maximum warpage amount is less than 0.1 mm. It was evaluated. Table 5 shows the measurement results and evaluation results of the maximum warpage amount of each sample (composite).

  In the composites according to Examples 13 to 24, the maximum warpage amount was good at less than 0.5 mm. This is because the thickness of the organic resin layer is 0.2 μm or more, and the area of the welded portion is sufficiently smaller than that of thermocompression bonding, so that the coated metal plate and the molded body can be welded by heat welding by electromagnetic induction. it is conceivable that. In particular, in the composites according to Examples 13 to 22 in which a molded body containing glass fibers and having a small molding shrinkage rate is bonded to a painted metal plate, the maximum warpage amount is less than 0.1 mm, and is even better. Even in the composites according to Examples 23 and 24 in which a molded body having no molding fiber and having a large molding shrinkage rate was bonded to a coated metal plate, the maximum warpage amount was less than 0.5 mm, which was favorable.

  On the other hand, in the composite according to Comparative Example 3 in which the coated metal plate does not have the organic resin layer and the composite according to Comparative Example 4 in which the thickness of the organic resin layer is less than 0.2 μm, the maximum warpage amount is measured. In doing so, the coated metal plate and the thermoplastic resin composition were easily peeled off, and the maximum amount of warpage of the composite could not be measured.

  Moreover, in the composite_body | complex which concerns on Comparative Examples 5-7, the largest curvature amount was 0.5 mm or more. This is thought to be because the film thickness of the organic resin layer was 0.2 μm or more, but it was a thermocompression bonding method in which the entire surface of the coated metal plate was heated. That is, even when using a molded body containing glass fiber and having a small molding shrinkage rate, the molded body is heated at the time of pressure bonding and cooled by being allowed to cool after pressure bonding, so that it contracts to a greater extent than the metal plate. This is considered to be because the amount of deformation at the end of the long coated metal plate increases and the maximum warpage amount increases.

  The composite including the painted metal base material of the present invention is bonded to the metal base material and the molded body of the thermoplastic resin composition with a high joining force, and the expected shape is substantially also due to heat shrinkage during production. Maintained. For this reason, the said composite_body | complex is used suitably for various electronic devices, household appliances, a medical device, a motor vehicle body, vehicle mounting goods, a building material etc., for example.

DESCRIPTION OF SYMBOLS 10 Painted metal shape material 20,40 Molded object 30,50 Heating part 70 Range which a magnetic field generate | occur | produces 100,200,300 Composite 102 Metal shape material 104 Organic resin layer 402 Concave part 404 Brim part

Claims (4)

Painted metal material comprising a metal material and an organic resin layer having a thickness of 0.2 μm or more disposed on the metal material, and a thermoplastic resin composition joined to the painted metal material A method for producing a composite body comprising:
Adhering the molded body to the organic resin layer;
The metal base material is heated by electromagnetic induction, and the organic resin layer and the molded body constituting at least a part of a contact portion where the organic resin layer and the molded body are in close contact with each other are heated and welded, and the molding is performed. Joining the body and the painted metal profile,
The organic resin layer has weldability to the thermoplastic resin composition.
A method for producing a composite. The organic resin layer includes a polypropylene resin,
The molded body is a molded body of a polypropylene resin composition.
The manufacturing method of the composite_body | complex of Claim 1. The organic resin layer includes a polyurethane resin,
The molded body is a molded body of a polybutylene terephthalate resin composition, a molded body of a polyamide resin composition, or a molded body of an acrylonitrile-butadiene-styrene resin composition.
The manufacturing method of the composite_body | complex of Claim 1.   The said organic resin layer is a manufacturing method of the composite_body | complex as described in any one of Claims 1-3 containing a metal compound type antirust agent.

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