JP6051141B2 - Composite and production method thereof - Google Patents

Description

The present invention is a complex molded body is bonded to the thermoplastic resin composition for coating metal formed and fabricated material and relates to its production how.

  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.

  The composite is generally manufactured by joining a molded body of a thermoplastic resin composition to a metal base material by insert molding. In the method for producing the composite, for example, the molded body may be joined by insert molding to a painted metal base material having an organic resin layer having weldability with the molded body on the surface of the metal base material. It is known (see, for example, 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 molded body is larger than the thermal expansion coefficient of the metal base material. In the manufacturing method, both the molded body and the painted metal shaped material are heated to around the melting temperature of the thermoplastic resin composition. For this reason, when the metal shape material has flexibility, the molded body joined to the painted metal shape material contracts more than the metal shape material by cooling after insert molding, and the metal shape material is As a result, the composite may be deformed. Thus, the above manufacturing method still has room for study from the viewpoint of preventing deformation of the composite.

  An object of this invention is to provide the composite_body | complex with which the joining of the coating metal shape material with respect to the molded object of a thermoplastic resin composition was high, and the deformation | transformation by the heat shrink at the time of manufacture was suppressed.

  The inventors of the present invention have made heat shrinkage during production by joining a molded body of a thermoplastic resin composition having a sufficiently large surface area compared to the surface area of a painted metal preform to the painted metal preform by laser welding. The present inventors have found that the deformation due to can be sufficiently suppressed, and further studied to complete the present invention.

That is, the present invention relates to the following composites.
[1] A painted metal shape material comprising 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 molded body of a resin composition, wherein the organic resin layer has weldability to the thermoplastic resin composition, and the molded body is welded to the organic resin layer by laser welding. A composite joined to the painted metal profile.
[2] The 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 composite according to [1], wherein the composite is
[4] The composite according to any one of [1] to [3], wherein the organic resin layer contains a metal oxide.
[5] The composite according to any one of [1] to [4], wherein the molded body contains glass fibers.

Moreover, this invention relates to the manufacturing method of the following composites.
[6] A painted metal shape material comprising 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 molded product of a resin composition, wherein the organic resin layer has a weldability to the thermoplastic resin composition, and the manufacturing method includes forming the composite on the organic resin layer. And forming the organic resin layer by irradiating at least a part of the close contact portion where the organic resin layer and the molded body are in close contact with each other from the molded body side or the metal shaped material side. And a step of welding the formed body to the painted metal base material.
[7] The method for producing a composite according to [6], wherein the organic resin layer includes a polypropylene-based resin, and the molded body is a molded body of a polypropylene-based resin composition.
[8] 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 [6] which is a molded object of.
[9] The organic resin layer according to any one of [6] to [8], in which the organic resin layer includes a metal oxide and irradiates at least a part of the adhesion portion with laser light from the molded body side. A method for producing a composite.
[10] The method for producing a composite according to any one of [6] to [9], wherein the molded body contains glass fibers.

  According to the present invention, the heated portion of the molded body when the molded body of the thermoplastic resin composition is welded to the organic resin layer 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.

1A is a plan view of the composite according to the first embodiment of the present invention, and FIG. 1B is a cross-sectional view of the composite along the line AA in FIG. 1A. FIG. 2A is a diagram schematically showing a second form of the laser welded portion in the composite, and FIG. 2B is a diagram schematically showing a third form of the laser welded portion in the composite, FIG. 2D is a diagram schematically showing a fourth form of the laser welding portion in the composite. FIG. 3A is a plan view of the composite according to the second embodiment of the present invention, and FIG. 3B is a cross-sectional view of the composite along the line AA in FIG. 3A. FIG. 4A is a plan view of a sample for a tensile test produced in the example, and FIG. 4B is a front view of the sample for a tensile test. It is a figure for demonstrating the curvature amount of the composite_body | complex measured in the Example.

1. Complex A complex according to one embodiment of the invention is shown in FIGS. 1A and 1B. 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 thermoplastic resin composition. The length of the molded body 20 is shorter than the length of the painted metal preform 10, and the molded body 20 is disposed 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 laser welding portion 30. The laser welded portion 30 is a portion irradiated with laser light at the interface between the molded body 20 and the organic resin layer 104, and is a portion where the organic resin layer 104 is laser welded to the molded body 20. The laser welded portion 30 is formed in a straight line along the longitudinal direction of the molded body 20 at the center in the width direction of the molded body 20.

  Alternatively, as shown in FIGS. 2A to 2C, the laser welded portion 30 may be formed in a diagonal shape in the planar shape of the molded body 20, or formed in the form of dots at the four corners of the planar shape of the molded body 20. It may be formed, or may be formed in a rectangle along the edge in the planar shape of the molded body 20.

Moreover, the composite_body | complex which concerns on other embodiment of this invention is shown to FIG. 3A and FIG. 3B. 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 planar shape of the collar portion 404 is the same as the planar shape of the painted metal preform 10. The organic resin layer 104 in the composite 200 is welded to the collar portion 404 of the molded body 40 by the laser welding portion 50. The laser welded portion 50 is formed in a rectangular shape at the center of the width of the collar portion 404 along both the opening edge of the recessed portion 402 and the edge of the painted metal element 10.
Hereinafter, each component of the composite will be described.

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

(Metal element)
The metal element is a metal member. 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. 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 on the surface of the metal base material. The chemical conversion 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. A chemical conversion treatment film may be arrange | positioned at the part joined to the molded object of a thermoplastic resin composition among the surfaces of a coating metal shape material, and may be arrange | positioned at the whole surface of a metal shape material.

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 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 . What is necessary is just to adjust adhesion amount so that it may become. Moreover, in the case of a phosphate film, what is necessary is just to adjust the adhesion amount of each chemical conversion 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 arrange | positioned on the metal raw material, ie, the surface of a metal raw material, or the surface of a chemical conversion 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 a layer made of an organic resin having sufficient adhesion to the metal base material. The organic resin should just have both the adhesiveness with respect to a metal raw material, and the weldability with respect to a thermoplastic resin composition. For example, 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 is preferably a polyurethane resin. . Moreover, if the said thermoplastic resin composition is a polypropylene resin composition, it is preferable that the said organic resin is a polypropylene resin. One or more organic resins may be used.

(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 with the coated metal shaped material to the molded body of the thermoplastic resin composition. 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 article of the thermoplastic resin composition may be lowered. Thereby, sufficient joining force of the coating metal shape material with respect to the said molded object may not be obtained. 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, the organic resin layer is not welded to the thermoplastic resin composition, and the bonding strength of the painted metal preform to the molded body may be insufficient. 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 of the coating metal shape material with respect to the said molded object 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 of the painted metal shape material to the molded body 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 required after molding 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 is more than 300,000, the viscosity may increase in the modification step described later, 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 di-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyethyl hexanoate, Peroxides such as tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and azonitriles such as azobisisobutyronitrile and azobisisopropionitrile are included. 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 α, β-unsaturated carboxylic acids or anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid and aconitic anhydride Contains acid. 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 compounds having one or more double bonds per molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) -2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) Isobornyl acrylate, benzyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 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, -Hexanediol, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, (meth) acrylate-2-ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, acrylamide, etc. (Meth) acrylic acid monomers and styrene monomers such as styrene, α-methylstyrene, paramethylstyrene, chloromethylstyrene, and the like. 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-based resin is a polymer compound including a polyurethane skeleton and a functional group capable of hydrogen bonding with the metal base material. Examples of the polyurethane-based resin include polycarbonate-containing polyurethane (hereinafter also referred to as “PC-containing polyurethane”). Examples of the functional group capable of hydrogen bonding to the metal shape member (hydrogen bonding functional group) include a carboxyl group and an amino group. 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 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, 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 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 polycarbonate polyol includes carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, methylpentanediol, dimethylbutanediol, and butylethylpropanediol. , Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and other diol compounds. 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 the initiator include ammonia; aliphatic primary or secondary monoamines such as methylamine and ethylamine; aliphatic primary or secondary such as ethylenediamine, hexamethylenediamine, and N, N′-dimethylethylenediamine. Secondary polyamines; and aromatic primary or secondary mono- or polyamines such as aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline, and the like. 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 also 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.

  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 (such as a carboxyl 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.

(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 metal oxides, resins other than the above organic resins, rust preventives, phosphorus compounds, lubricants and antifoaming agents.

  One or more metal oxides may be used. A metal oxide improves the weldability of the organic resin layer with respect to the said molded object. This is because the metal oxide absorbs laser light irradiated at the time of laser welding and promotes the welding of the organic resin layer to the molded body, and further increases the bonding force of the painted metal shape material to the molded body, Conceivable. Examples of metal types in the metal oxide include Si, Ti, Zr, V, and Mo. Examples of the metal oxide include a metal compound-based rust inhibitor described later.

  Content of the said metal oxide in an organic resin layer can be suitably determined in the range by which the function of the said metal oxide is expressed. For example, the content of the metal oxide in the organic resin layer is such that, from the viewpoint of the bonding strength, the Si equivalent content is 0.5 mass% or more, the Ti equivalent content is 0.005 mass% or more, and the Zr equivalent content It is preferable that the amount is 0.05% by mass or more, the Mo equivalent content is 0.005% by mass or more, or the V equivalent content is 0.02% by mass or more. In addition, the content of the metal oxide in the organic resin layer is such that the content in terms of Si is less than 23.5 mass%, the content in terms of Ti is less than 0.6 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% by mass, the content in terms of Mo is less than 3.0% by mass, or the content in terms of V is less than 3.0% by mass.

  Said other resin can improve the weldability of the organic resin layer with respect to the said molded object, and can join the said molded object firmly with a coating metal shape material. It is preferable that the organic resin layer further contains the other resin from the viewpoint of improving the adhesion of the organic resin layer to the molded body. The other resin is appropriately selected from known resins, and may be one kind or more. 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 the effect by the mixing | blending of said other resin, for example, is 0-150 mass parts with respect to 100 mass parts of above-mentioned organic resins.

  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 are 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.

  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 antifoaming agent may be added to the antifoaming agent.

(Properties of organic resin layer)
The organic resin layer has a thickness of 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 said organic resin layer is comprised by the composition containing the organic resin mentioned above and the said additive mix | blended arbitrarily. 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.

(2) Molded body of thermoplastic resin composition The molded body of the thermoplastic resin composition is bonded to the organic resin layer of the painted metal preform by laser welding. The shape of the molded body is not particularly limited as long as it is a shape that is in close contact with the surface of the painted metal base material, and can be appropriately determined according to the application 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 type of the thermoplastic resin composition can be determined according to the weldability of 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, glass sphere Powder fillers such as carbon fiber and pulverized carbon fiber or aramid fiber. 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.

2. Manufacturing method of composite body The composite body according to the present invention includes a step of bringing the molded body into close contact with the organic resin layer, and at least part of a close contact portion where the organic resin layer and the molded body are in close contact with each other. And irradiating a laser beam from the metal shape member side to weld the organic resin layer to the shaped body and joining the shaped body to the metal shaped material. In addition to the above steps, the method may further include other steps such as a step of preparing the painted metal preform.

  For example, in the step of preparing the painted metal shape material, the chemical conversion treatment film may be formed on the metal shape material before forming the organic resin layer of the painted 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 coating method of the chemical conversion 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. 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 shape material is produced by forming an organic resin layer on the surface of the metal shape material or the surface of the chemical conversion film. 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 base material and heating the applied organic resin paint.

  The organic resin paint contains the organic resin described above. The organic resin paint may further contain the above-described crosslinking agent and additive. Furthermore, the organic resin paint may further contain a solvent. The solvent is a liquid that can uniformly dissolve or disperse the 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, preferably water. is there. For example, the organic resin paint contains an acid-modified polypropylene-based aqueous emulsion, a non-acid-modified water-based resin emulsion, a crosslinking agent, a rust inhibitor, a lubricant, a stabilizer, and an antifoaming agent. Content of the solid content in the said organic resin coating material can be suitably determined according to the applicability | paintability of the said organic resin coating material, or the thickness of the coating film formed, for example, is 5-30 mass%.

  The organic resin layer is formed by applying the organic resin coating to the surface of the metal base material (or chemical conversion 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. The ultimate temperature of the metal base material during heating is not particularly limited. For example, the organic resin layer is formed from the viewpoint of forming an organic resin layer in close contact with the surface of the metal base material (or chemical conversion film). The melting point of the composition is preferably 250 ° C. or higher.

  In the step of bringing the molded body into close contact with the organic resin layer, for example, the molded body has at least a portion to be bonded to the molded body and a portion to be bonded to the painted metal base material. And placed on the surface of the painted metal profile. 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 shape material at least during irradiation with the laser beam. 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.

  In the step of joining the molded body to the painted metal shaped member, at least a part of the planar shape of the contact portion is irradiated with laser light from the molded body side or the painted metal shaped member side to thereby form the organic resin layer. Is welded to the molded body. The portion irradiated with the laser beam in the step may be the entire surface of the close contact portion, but it is preferable that only a part of the close contact portion is from the viewpoint of suppressing deformation such as warpage of the composite. Examples of a part of the contact portion include one or more points, a center line in the planar shape of the contact portion, a line along an edge in the planar shape of the contact portion, a diagonal line in the planar shape of the contact portion, and these Combination.

Various lasers can be used as the laser light source. Examples of such lasers include ruby lasers, YAG lasers, Nd: YAG lasers, solid state lasers such as diode-pumped solid state lasers; liquid lasers such as dye lasers; gas lasers such as CO ₂ lasers; and semiconductor lasers. included. The laser oscillation method may be, for example, either a pulse laser or a CW laser. The laser light irradiation conditions can be appropriately determined within a range where the effects of the present invention can be obtained. For example, the laser beam may be irradiated with a laser output of 30 to 200 W, a spot area of 0.1 to 10 mm ² and a spot moving speed of 1 to 10 mm / second.

  Further, laser beam irradiation may be performed intermittently. Intermittent irradiation with laser light is preferable from the viewpoint of reducing laser energy. Moreover, it is possible to adjust the joining force of the coating metal shaped material with respect to the said molded object (it weakens the said joining force) by intermittent irradiation of a laser beam.

  The portion welded by laser light irradiation (laser welded portion) generally has a shape scanned by laser light because laser welding is performed almost simultaneously with laser light irradiation. More specifically, the laser welded portion is constituted by points or lines, or a set of these when viewed in plan. From such a planar shape of the welded portion, it is possible to confirm that the weld between the metal base material and the molded body in the composite is laser welding.

  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 composite according to the present embodiment, the laser welded portion is usually formed by a linear shape, a dotted shape, or a combination thereof. For this reason, compared with the case where a molded object is joined to a paint metal plastic material by injection molding, the part heated to the melting temperature vicinity by laser welding of a composite_body | complex becomes very small. Therefore, even if the compact is to be shrunk to a greater extent than the metal base material due to the heat shrinkage at the part, the part where the heat shrinkage of the composite does not occur is much larger, so the composite does not deform.

  Although it is preferable to irradiate the close contact portion with the laser beam from the molded body side, the molded body has a sufficient thickness even if the molded body has light transmittance, or a sufficient amount of filler that scatters laser light. In the case where it is contained, the laser beam is not sufficiently irradiated to the contact portion, and a sufficient bonding force of the coated metal shaped material to the formed body may not be obtained. In this case, the organic resin layer can be welded to the molded body by irradiating laser light from the metal raw material side toward the contact portion.

  However, for example, when the metal base material has a sufficient thickness or a complicated back surface shape, laser welding may not be performed by laser light irradiation from the metal base material side. In this case, by including the above-described metal oxide in the organic resin layer, laser welding by irradiation of laser light from the molded body side becomes possible. This is considered because the metal oxide in the organic resin layer easily absorbs laser light and improves the weldability of the organic resin layer to the molded body. In addition, by including the metal oxide in the organic resin layer, the laser from the molded body side can be used even when the laser beam is irradiated with lower energy by changing the type of laser or reducing the output of the laser. It is expected that the molded body can be laser-welded to a painted metal plate by light irradiation.

  By the way, in the case of producing the composite 100 by injection molding of a 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 base material can be deformed like a flexible metal plate, the coated metal material is bent by the thermal contraction of the molded body, and the composite is deformed.

  The deformation is more remarkable in the structure in which the formed body is smaller than the painted metal shape material in the planar shape as in the composite body 100. 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 shaped material 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.

  Moreover, even in a structure in which the surface area of the formed body is larger than the surface area of the painted metal shaped material at the center portion of the planar shape as in the composite body 200, it is more remarkable. 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, since the present embodiment can prevent deformation due to thermal shrinkage during the molding of the composite by laser welding as described above, the amount of deformation of the end portion becomes large as in the above structure ( It is possible to provide a composite in which deformation due to heat shrinkage during manufacture is suppressed even if the composite has a structure that is easily deformed.

  As described above, the composite according to the present embodiment includes a metal base material and a painted metal base material having an organic resin layer having a thickness of 0.2 μm or more disposed on the metal base material. A molded article of a joined thermoplastic resin composition, the organic resin layer has weldability to the thermoplastic resin composition, and the molded article is welded to the organic resin layer by laser welding. Bonded to the painted metal profile. And the manufacturing method of the said composite_body | complex is the above-mentioned molded object side or the said metal element in the process which makes the said molded object contact | adhere to the said organic resin layer, and at least one part of the contact | adherence part which the said organic resin layer and the said molded object contact | adhered. Irradiating a laser beam from the shape material side to weld the organic resin layer to the shaped body and joining the shaped body to the painted metal shape material. Therefore, according to the present embodiment, 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.

  In the present embodiment, the organic resin layer includes a polyurethane-based resin, and the molded body is a molded body of a PBT-based resin composition, a molded body of a PA-based resin composition, or a molded body of an ABS-based resin composition. Or the organic resin layer contains a polypropylene resin, and the molded body is a molded body of a polypropylene resin composition, from the viewpoint of improving the bondability of the coated metal shaped material to the molded body Is even more effective.

  Moreover, in this Embodiment, it is much more effective that the said organic resin layer contains a metal oxide from a viewpoint of improving the bondability of the coating metal preform with respect to the said molded object. In addition, the organic resin layer contains a metal oxide, even if the molded body contains glass fibers (which easily scatters laser light), and the organic layer is irradiated with laser light from the molded body side. This is even more effective from the viewpoint of enabling laser welding of the resin layer to the molded body.

  Moreover, in this Embodiment, it is much more effective from the viewpoint of providing the composite_body | complex with which the said molded object contains glass fiber in which the deformation | transformation by the heat shrink at the time of manufacture was suppressed.

  In the present embodiment, the molding shrinkage rate of the thermoplastic resin composition is sufficiently small as 1.1% or less, and the linear expansion coefficient αm of the metal base material and the linear expansion coefficient αp of the thermoplastic resin composition It is more effective that the ratio αp / αm is as small as 6 or less from the viewpoint of improving the adhesion between the molded body and the painted metal shape material. This is because the difference between the heat shrinkage of the molded body and the metal shape material at the time of manufacture is reduced, and the deviation between the formed body and the metal shape material at the contact portion affects the bonding state of both. This is thought to be because it can be suppressed to a level that does not affect

  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 coated metal plate (1) Metal plate Molten Zn-6 mass% Al-3 mass% obtained by plating a molten Zn-6 mass% Al-3 mass% Mg alloy on both surfaces of a base steel sheet as a coating original sheet An Mg alloy plated steel sheet (hereinafter also referred to as “Zn—Al—Mg alloy plated steel sheet”) was prepared. The plating adhesion amount per side in the Zn—Al—Mg alloy plated steel sheet is 45 g / m ² . The base steel plate is a cold rolled steel plate (SPCC) having a thickness of 0.6 mm.

(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; ADEKA Corporation, also simply referred to as “UE”) was used as the urethane resin emulsion. A commercially available acid-modified polypropylene resin emulsion (Hardren NZ-1005; Toyobo Co., Ltd., also simply referred to as “PPE”) was used for the polypropylene resin emulsion.

  As the polyethylene wax, a commercially available polyethylene wax (E-9015; Toho Chemical Co., Ltd.) was used. The addition amount of polyethylene wax is 3.0 mass% with respect to the total mass of the said organic resin.

  As the crosslinking agent, a commercially available epoxy crosslinking agent (HUX-XW3; ADEKA Corporation) was used. The addition amount of a crosslinking agent is 3.0 mass% with respect to the 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; 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.

(3) Evaluation of stability of organic resin coating The storage stability of the 12 prepared organic resin coatings was evaluated. Each organic resin paint placed in a sealed container was stored in a constant temperature bath at 40 ° C., and the state of the organic resin paint was observed. About each organic resin coating material, what was stable for 30 days or more was evaluated as "(circle)", and what thickened or solidified in less than 30 days was evaluated as "*". The results are shown in Tables 1 and 2.

  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 phosphorus element, “SH” is (thiol component), “Zr” is zirconium, “V” is vanadium, “Si” is silicon, “Ti” is titanium, “Mo” is Molybdenum is shown respectively. Moreover, the rust preventive agent without the said elements etc. is added with the following content.

  As shown in Tables 1 and 2, the organic resin paints 2 to 7 and 9 to 11 showed good storage stability. The organic resin coatings 3 to 7 and 9 to 11 contained a metal compound rust preventive agent, but exhibited good storage stability. This is because the content of the metal compound rust inhibitor is Ti: less than 0.6 mass%, Zr: less than 12.0 mass%, Mo: less than 3.0 mass%, and V: less than 3.0 mass%. It is thought that there was.

  In addition, since the organic resin coating 1 does not contain any of the organic resin and the rust preventive agent, it is obvious that the organic resin paint 1 exhibits good storage stability under the above storage conditions, and thus the storage stability was not evaluated. . Moreover, since the organic resin paint 8 does not contain a rust preventive agent, it showed good storage stability. Furthermore, the storage stability of the organic resin paint 12 was insufficient. This is presumably because the content of the rust inhibitor of the metal compound was Ti: 0.6% by mass or more and Zr: 12.0% by mass or more.

(4) Formation of organic resin layer The Zn-Al-Mg alloy-plated steel sheet was immersed in an alkaline degreasing aqueous solution (SD-270; Nippon Paint Co., Ltd.) having a liquid temperature of 40 ° C and a pH of 12 for degreasing the surface. Next, the organic resin paint 1 prepared in (2) above was applied to the surface of the degreased Zn—Al—Mg alloy plated steel sheet with a roll coater, and a hot plate dryer was used so that the ultimate plate temperature was 150 ° C. The organic resin layer was formed by drying. Thus, a coated metal plate 1 was obtained. Moreover, it replaced with the organic resin coating material 1, and obtained the coated metal plates 2-12 similarly except having used each of the organic resin coating materials 2-12.

In Table 3, the kind of coating original 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.

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, the coated metal plates 2 to 7 and 9 to 12 each exhibited corrosion resistance with no practical problem. Among them, the coated metal plates 3 to 6, 9, 11 and 12 showed good corrosion resistance. This is because the organic resin layer has a film thickness of 0.2 μm or more, and the content of the metal compound rust inhibitor is Ti: 0.005 mass% or more, Zr: 0.05 mass% or more, Mo: 0.005. This is considered to be because it was not less than mass% and V: not less than 0.02 mass%.

  On the other hand, although the coated metal plates 2, 7, and 10 have no practical problem, they exhibited corrosion resistance lower than the corrosion resistance of the coated metal plates 3-6, 9, 11, and 12. The reason is considered to be that the coated metal plate 2 does not contain a rust inhibitor. About the coated metal plate 7, the content of the rust inhibitor was insufficient (the content of the rust inhibitor of the metal compound was Ti: less than 0.005 mass%, Zr: less than 0.05 mass%, Mo: This is considered to be because it was less than 0.005 mass% and V: less than 0.02 mass%. Regarding the coated metal plate 10, it is considered that the thickness of the organic resin layer was less than 0.2 μm.

  Furthermore, the corrosion resistance of the coated metal plates 1 and 8 was insufficient. The reason is considered that the coated metal plate 1 is not formed with an organic resin layer. This is probably because the coated metal plate 8 does not contain a rust inhibitor.

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.

  The PP resin composition contains 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”) and glass fiber. Novatec BC06C (molding shrinkage ratio: 1.3, Nippon Polypro Co., Ltd.) was used.

  The PBT resin composition includes Novaduran 5710F40 (molding shrinkage ratio: 0.3, Mitsubishi Engineering Plastics Co., Ltd.) containing 40% by mass of glass fiber, and Novaduran 5010R3 (molding shrinkage ratio: 1) containing no glass fiber. .5, Mitsubishi Engineering Plastics Co., Ltd.).

  Exelloy CK-10G20 (molding shrinkage ratio: 0.1, Technopolymer Co., Ltd.) containing 20% by mass of 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 center in the longitudinal direction (X direction) of the overlapped part (adhesion part) is irradiated with laser light from the thermoplastic resin composition side over a length of 28 mm in the width direction, and the coated metal plate 2 and the molded body are formed. Laser welding was performed to form a laser welded portion (reference numeral 70 in FIGS. 4A and 4B). The planar shape of the laser welded portion is a straight line. In this way, a sample for tensile test (reference numeral 300 in FIGS. 4A and 4B) as a composite of the coated metal plate 2 and the molded body of the PBT resin composition was produced.

  The laser used was a fiber output type semiconductor laser module (L10060, 150 W, wavelength 940 nm, manufactured by Hamamatsu Photonics). The fiber tip of the laser module was connected to a condenser lens. The laser spot diameter on the surface of the organic resin layer was 3 mm, the laser output was 100 W, and the stage moving speed was 3 mm / second.

[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 kind of the thermoplastic resin composition, and the laser output were changed as shown in Table 4 below.

(4) Evaluation of bonding strength of composites The above-mentioned laser welded part was pulled by pulling a molded body of a coated metal plate and a thermoplastic resin composition in the samples for tensile tests obtained in Examples 1 to 12 and Comparative Examples 1 and 2. The strength (peeling strength) of the tensile force when ruptured 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. Among them, in the composites according to Examples 5 and 9 to 12, the bonding force was 2.0 kN or more, which was even better. This is considered because the organic resin layer contains a sufficient amount of the metal oxide (B1). In other words, the metal oxide has a property of absorbing laser light. Therefore, even when the laser beam is irradiated from the side of the molded body containing glass fibers that prevent laser transmission, This is probably because sufficient laser weldability was exhibited at the interface with the molded body.

  On the other hand, the composite according to Example 6 had a higher bonding force than the bonded bodies according to Examples 1 to 3, 7 and 8 that did not contain a metal oxide, but the bonding force was 2.0 kN. Did not come. This is presumably because the organic resin layer contained a metal oxide, but its content was small.

  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 placed on a stage, and as shown in FIGS. 1A and 1B, the painted metal plate 2 (reference numeral 10) is centered in the longitudinal direction. The molded body (reference numeral 20) was stacked.

  The center in the width direction of the molded body is irradiated with laser light from the thermoplastic resin composition side over the length of 58 mm in the longitudinal direction to laser weld the coated metal plate 2 and the molded body, and a laser welded portion. (Reference numeral 30 in FIGS. 1A and 1B) was formed. The planar shape of the laser welded portion is a straight line. In this way, a sample for warpage measurement (reference numeral 100 in FIGS. 1A and 1B) was produced as a composite of the coated metal plate 2 and a molded body of the PBT resin composition. Conditions used for the laser and laser light used are the same as those in Example 1.

[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 coated metal plate, the composition of the thermoplastic resin composition, and the laser output were changed as shown in Table 5 below.

[Comparative Example 5]
After the painted metal plate 2 was heated to a predetermined temperature, the PBT resin composition molded body was placed on the center of the painted metal plate 2 in the longitudinal direction, and pressurized with 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 considered because the thickness of the organic resin layer is 0.2 μm or more, and the welded metal plate and the molded body can be welded by laser welding in which the area of the welded portion is sufficiently smaller than that of thermocompression bonding. . In particular, in the composites according to Examples 13 to 22, the maximum warpage amount is even better, less than 0.1 mm, and a molded body having a large molding shrinkage rate that does not contain glass fibers is bonded to a painted metal plate. Even in the composites according to Examples 23 and 24, the maximum warpage amount was good at less than 0.5 mm.

  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 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 Paint metal shape material 20, 40 Molded body 30, 50, 70 Laser welding part 100, 200, 300 Composite 102 Metal shape material 104 Organic resin layer 402 Concave part 404 Brim part

Claims (10)

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 bonded to the painted metal material A composite body comprising:
The organic resin layer has weldability to the thermoplastic resin composition,
The molded body is welded to the organic resin layer by laser welding and bonded to the painted metal shape material.
Complex. The organic resin layer includes a polypropylene resin,
The molded body is a molded body of a polypropylene resin composition.
The composite according to 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 composite according to claim 1.   The said organic resin layer is a composite_body | complex as described in any one of Claims 1-3 containing a metal oxide.   The said molded object is a composite_body | complex as described in any one of Claims 1-4 containing glass fiber. 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 bonded to the painted metal material A method for producing a composite body comprising:
The organic resin layer has weldability to the thermoplastic resin composition,
The manufacturing method includes:
Adhering the molded body to the organic resin layer;
At least a part of the contact portion where the organic resin layer and the molded body are in close contact with each other is irradiated with a laser beam from the molded body side or the metal shape member side to weld the organic resin layer to the molded body and perform the molding. Joining the body to the painted metal profile;
including,
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 6. 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 6. The organic resin layer contains a metal oxide,
Irradiating at least a part of the contact portion with laser light from the molded body side,
The manufacturing method of the composite_body | complex as described in any one of Claims 6-8.   The said molded object is a manufacturing method of the composite_body | complex as described in any one of Claims 6-9 containing a glass fiber.

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