JP6651324B2 - Composite and method for producing the same - Google Patents

Description

  The present invention relates to a composite and a method for producing the same.

  BACKGROUND ART A metal plate or a press-formed product thereof, or a so-called “metal shaped material” formed by casting, forging, cutting, powder metallurgy, or the like, is used for various industrial products such as automobiles. In addition, a composite body in which a metal base material and a molded body of a resin composition are joined together is lighter than a component made of only metal and has higher strength than a component made of only resin, so Used in various electronic devices such as computers. Conventionally, such a composite has been manufactured by fitting a molded metal body and a molded body of a resin composition. However, the method of manufacturing a composite by fitting has a large number of working steps and low productivity. Therefore, in recent years, it has been general to manufacture a composite body by joining a metal base material and a molded body of a resin composition by insert molding.

  When producing a composite by insert molding, it is important to improve the adhesion between the metal base material and the molded product of the resin composition. As a method for improving the adhesion between the metal base material and the molded product of the resin composition, for example, a method has been proposed in which the surface of the metal base material is roughened before insert molding is performed. References 1 to 3). In the methods of Patent Literatures 1 to 3, the surface of the aluminum alloy is subjected to a roughening treatment to improve the bonding property between the aluminum alloy and a molded body of the resin composition.

  Further, in Patent Document 4, a metal member, an organic coating layer such as a triazine thiol derivative, and a laminated body obtained by laminating a hot melt film, after disposing a material containing a thermoplastic resin so as to be in contact with the hot melt film, A method is described in which a hot melt film is melted, and the laminate and a molded article of a thermoplastic resin are joined to produce a composite.

JP 2006-027018 A JP-A-2004-050488 JP 2005-342895 A JP 2013-244725 A

  In the composites manufactured by the methods described in Patent Literatures 1 to 3, since they are joined by the anchor effect, there is a problem that the adhesion between the metal base material and the molded body of the resin composition is not sufficient. Further, in the method of manufacturing a composite described in Patent Documents 1 to 3, since the surface of the metal base material is subjected to a roughening treatment, there is also a problem that a manufacturing process is complicated and a manufacturing cost is increased.

  Further, in the composite produced by the method described in Patent Document 4, the adhesion between the molded article of the thermoplastic resin and the metal base material cannot be said to be sufficiently high, and a composite having higher adhesion is desired. I was

  Further, the methods described in Patent Documents 1 to 4 are for joining a molded article of a resin composition to a metal base material. In order to expand the use of the composite, when attempting to produce a composite in which a material other than the resin composition is bonded to the metal base material, the methods described in Patent Documents 1 to 4 use a method other than the resin composition. It was unknown whether sufficient adhesion would occur between the material and the metal base material.

  The present invention has been made in view of such a point, and even when various materials are joined, it is excellent in the adhesiveness thereof and can be easily manufactured. It is an object of the present invention to provide a composite containing the same and a method for producing the same.

The present invention relates to the following complex and a method for producing the complex.
[1] A composite having a metal base material and a coated metal base material including an organic resin layer formed on the surface of the metal base material, a hot melt film, and an object to be bonded, The composite, wherein the hot melt film is welded to the organic resin layer and the object.
[2] The composite according to [1], wherein the organic resin layer contains a polypropylene resin.
[3] The composite according to [1], wherein the organic resin layer contains a polyurethane resin.
[4] The composite according to any one of [1] to [3], wherein the amount of the organic resin layer attached is 0.2 g / m ² or more.
[5] The composite according to any one of [1] to [4], wherein the melting point of the hot melt film is 50 to 200 ° C.
[6] The object according to any one of [1] to [5], wherein the joined body includes a molded body of one or more materials selected from the group consisting of a ferrous metal, a non-ferrous metal, an organic resin, and glass. The conjugate of claim 1.
[7] The composite according to any one of [1] to [6], wherein the organic resin layer contains a rust inhibitor.
[8] A coated metal base material including a metal base material and an organic resin layer formed on the surface of the metal base material, and a hot melt film disposed so as to be in contact with the organic resin layer For the laminate, a step of arranging the joined body so as to be in contact with the hot melt film, and heating at least a part of the hot melt film that is in contact with the joined body, thereby heating the hot melt film. Welding the organic resin layer and the article to be joined.
[9] The method for producing a composite according to [8], further comprising a step of forming the laminate by disposing the hot melt film on the metal base material so as to be in contact with the organic resin layer. .
[10] The method for producing a composite according to [8] or [9], wherein the organic resin layer contains a polypropylene-based resin.
[11] The method for producing a composite according to [8] or [9], wherein the organic resin layer contains a polyurethane resin.
[12] The method for producing a composite according to any one of [8] to [11], wherein the amount of the organic resin layer attached is 0.2 g / m ² or more.
[13] The method for producing a composite according to any one of [8] to [12], wherein the melting point of the hot melt film is 50 to 200 ° C.
[14] The method according to any one of [8] to [13], wherein the object includes a molded body of one or more materials selected from the group consisting of a ferrous metal, a non-ferrous metal, an organic resin, and glass. A method for producing the composite according to the above.
[15] The method for producing a composite according to any one of [8] to [14], wherein the organic resin layer contains a rust inhibitor.

  ADVANTAGE OF THE INVENTION According to this invention, even if various materials are joined, it is excellent in the adhesiveness and can be easily manufactured. Is done.

FIG. 1A is a plan view according to an example of the composite of the present invention, and FIG. 1B is a cross-sectional view of the composite along the line 1B-1B in FIG. 1A. FIG. 2A is a plan view according to another example of the composite of the present invention, and FIG. 2B is a cross-sectional view of the composite along line 2B-2B in FIG. 2A. FIG. 3A is a plan view of a sample for a tensile test manufactured in the example, and FIG. 3B is a front view of the sample for a tensile test.

1. Composite The composite of the present invention has a coated metal base material, a hot melt film, and an object to be joined. The hot melt film is welded to the organic resin layer of the painted metal base material and the article to be joined, and joins the painted metal base material and the article to be joined.

  FIG. 1A is a plan view of an example of the composite of the present invention, and FIG. 1B is a cross-sectional view of the composite taken along line 1B-1B in FIG. 1A. 1A and 1B, the composite 100 includes a coated metal base material 10, a hot-melt film 30, and a joined body 20. The painted metal base material 10 has a metal base material 102 and an organic resin layer 104. In the composite 100, the coated metal base material 10 and the joined body 20 are joined by welding the hot melt film 30 to both the organic resin layer 104 and the joined body 20.

  A composite according to another embodiment of the present invention is shown in FIGS. 2A and 2B. 2A and 2B, the composite 200 includes the painted metal base material 10, the hot melt film 30, and the article 40 to be joined. The article 40 has a recess 402 having a rectangular planar shape and a flange 404 surrounding the opening of the recess 402. The hot melt film 30 in the composite 200 has the same shape as the flange portion 404 of the joined body 40, and the hot melt film 30 is welded to both the flange portion 404 of the joined body 40 and the organic resin layer 104. Thus, the coated metal base material 10 and the article to be joined 40 are joined.

1-1. Painted metal base material The coated metal base material according to the present invention includes a metal base material and an organic resin layer. The organic resin layer is formed on the surface of the metal base material. The coated metal base material may be formed with a chemical conversion coating between the metal base material and the organic resin layer, but the coated metal base material according to the present invention includes an organic resin layer and a hot melt film. Has a high adhesion, so that it is not necessary to have a chemical conversion coating. Hereinafter, each element of the painted metal base material will be described.

(1) Metal Shaped Material A metal shape shaped material is a metal that is given a shape by applying heat, force, or the like to the metal. The metal base material to be a coating substrate is a metal plate, a press-formed product thereof, or a metal member formed by casting, forging, cutting, powder metallurgy, or the like. The type of the metal base material is not particularly limited. Examples of the metal base material include a metal plate, a pressed product of the metal plate, a metal member, and the like. Examples of the metal plate include a galvanized steel plate, a Zn-Al alloy-plated steel plate, a Zn-Al-Mg alloy-plated steel plate, a Zn-Al-Mg-Si alloy-plated steel plate, an aluminum-plated steel plate, and a stainless steel plate (austenitic, Site-based, ferrite-based, and ferrite-martensite two-phase systems), aluminum plates, aluminum alloy plates, and copper plates. The metal plate may be a rolled steel plate such as a cold rolled steel plate. Examples of the metal member include various metal members formed by casting, forging, cutting, powder metallurgy, and the like, including aluminum die casting and zinc die casting. The metal preform may have been subjected to a known coating pretreatment such as degreasing or pickling, if necessary.

(2) Chemical conversion coating As described above, the coated metal element may have a chemical conversion coating formed between the metal element and the organic resin layer. The chemical conversion coating is formed on the surface of the metal base material, and improves the adhesion between the metal base material and the organic resin layer and the corrosion resistance of the metal base material. The chemical conversion coating may be formed on at least a region (joining surface) of the surface of the metal base material that is to be bonded to a body to be bonded, which will be described later. Preferably, it is formed on the entire surface of the material.

The type of chemical conversion treatment for forming the chemical conversion coating is not particularly limited. Examples of the chemical conversion treatment include a chromate treatment, a chromium-free treatment, a phosphate treatment, and the like. The amount of the chemical conversion coating formed by the chemical conversion treatment is not particularly limited as long as it is within a range effective for improving the adhesion between the metal base material and the organic resin layer and the corrosion resistance of the metal base material. For example, in the case of a chromate film, the adhesion amount may be adjusted so that the total adhesion amount in terms of Cr is 5 to 100 mg / m ² . Also, when the chromium-free coating, Ti-Mo adhesion amount of complex in the film-coating 10 to 500 mg / ^{m 2,} the fluoro acid based coating fluorine equivalent coating weight or total metal element equivalent coating weight of 3 to 100 mg / ^{m 2} The amount of adhesion may be adjusted so as to fall within the range. In the case of a phosphate film, the amount may be adjusted so that the amount of the coating is 0.1 to 5 g / m ² .

(3) Organic resin layer The organic resin layer is a layer containing an organic resin, and improves the adhesion between the metal base material and the hot melt film. The organic resin layer is formed on the metal base material, that is, on the surface of the metal base material or the surface of the chemical conversion coating. By welding the organic resin layer to the hot melt film, in the composite of the present invention, the metal base material and the object to be bonded are more firmly adhered to each other via the organic resin layer and the hot melt film.

  The type of the organic resin contained in the organic resin layer is not particularly limited as long as it has a functional group (hydrogen bonding functional group) capable of hydrogen bonding with the metal base material and has a welding property to a hot melt film. Not done. Examples of the hydrogen bonding functional group include a carboxyl group and an amino group. Examples of the resin having a hydrogen bonding functional group and having an adhesive property to a hot melt film include an epoxy resin, a polyolefin resin, a phenol resin, an acrylic resin, a polyester resin, and a polyurethane containing no polycarbonate unit. System resin. These resins may be used alone or in combination of two or more.

  Examples of the epoxy resin include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AD epoxy resin, and the like. Examples of the olefin-based resin include a polyethylene resin, a polypropylene resin, and the like. Phenolic resins include novolak resins, resole resins, and the like. A polyurethane resin is obtained by copolymerizing a diol and a diisocyanate. Examples of the diol include bisphenol A, 1,6-hexanediol, 1,5-pentanediol, etc. other than the polycarbonate diol. Examples of isocyanates include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like.

  The above-mentioned organic resin 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 instruments such as NMR, IR, and GC-MS.

  Further, the organic resin may be crosslinked. The cross-linking of the organic resin can be performed, for example, by a cross-linking agent having two or more cross-linkable 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-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, a melamine-based crosslinking agent, and a crosslinking agent having a metal salt. The amount of the cross-linking agent used is appropriately determined within a range in which both the adhesiveness of the organic resin layer to the metal base material and the effect of the cross-linking in the organic resin are obtained.

  From the viewpoint of further improving the adhesiveness with a hot melt film described later, the organic resin as the material of the organic resin layer is preferably a polypropylene resin or a polyurethane resin. The polyurethane-based resin preferably contains a polycarbonate resin containing a polycarbonate unit. The organic resin layer may be formed on at least a part of the surface of the metal base material, similar to the chemical conversion coating, on the bonding surface with the body to be bonded, but from the viewpoint of further improving the adhesion, It is preferable that the organic resin layer is formed on the entire bonding surface.

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

  The content of the acid-modified polypropylene is preferably 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 coated metal base material and the hot melt film. As a result, a sufficient joining force of the painted metal element to the article to be joined may not be obtained. The upper limit of the content of the acid-modified polypropylene can be appropriately determined as long as 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 from 1,000 to 10,000 mPa · s. If the melt viscosity is less than 1000 mPa · s, the organic resin layer may flow during welding with the article to be joined. For this reason, the organic resin layer is not welded to the article to be joined, and the joining strength of the painted metal base material to the article to be joined may be insufficient. On the other hand, when the melt viscosity is more than 10,000 mPa · s, the adhesiveness of the organic resin layer to the hot melt film may decrease and become insufficient. For this reason, the joining strength of the painted metal base material to the article to be joined may be insufficient. The melt viscosity is measured with a Brookfield viscometer.

  The acid value of the acid-modified polypropylene is preferably from 1 to 500 mgKOH / g. When 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 an emulsion described below.

  The acid-modified polypropylene preferably has a melting point of 60 to 120 ° C, and the acid-modified polypropylene has a crystallinity of 5 to 20%. Acid-modified polypropylene having the above melting point and crystallinity has high wettability to the surface of the metal base material. For this reason, it is preferable from the viewpoint of forming an organic resin layer in close contact with fine irregularities on the surface of the metal base 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, so that, for example, the blocking resistance of the coated metal material during storage becomes insufficient. Sometimes. When the melting point is higher than 120 ° C. or the crystallinity is higher than 20%, the bondability of the coated metal material to the object to be bonded may be reduced.

  The melting point and crystallinity of the acid-modified polypropylene hardly change between the state contained in the organic resin paint (paint for the organic resin layer) (before baking) and the state of the organic resin layer (after baking). Therefore, the crystallinity of the acid-modified polypropylene in the organic resin layer can be determined by measuring the below-described organic resin paint containing the acid-modified polypropylene by X-ray diffraction using the Ruland method.

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

  The stereoregularity of isotactic, atactic, syndiotactic, hemiisotactic and stereotactic is known for polypropylene. The stereoregularity of 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 from 1,000 to 300,000, and more preferably from 5,000 to 100,000. When the weight average molecular weight of the polypropylene is less than 1000, the strength of the organic resin layer may be reduced. On the other hand, when the weight average molecular weight of the polypropylene is more than 300,000, the viscosity may be increased when the polypropylene is acid-modified, so that the work may be difficult.

  The acid modification of the polypropylene is carried out by dissolving the polypropylene in toluene or xylene and, in the presence of a radical generator, an acid anhydride of an α, β-unsaturated carboxylic acid and / or an α, β-unsaturated carboxylic acid and / or 1 The reaction can be performed using a compound having one or more double bonds per molecule. Alternatively, using an apparatus capable of raising the temperature to a temperature not lower than the softening temperature or melting point of polypropylene, in the presence or absence of a radical generator, α, β-unsaturated carboxylic acid and / or α, β-unsaturated The reaction can be carried out using a carboxylic acid anhydride and / or a compound having one or more double bonds per molecule. In the case where the modification reaction of polypropylene is carried out in a solution state in an organic solvent such as toluene and / or xylene, or in the case of a reaction in a heterogeneous dispersion system carried out in a non-solvent such as an aqueous system, nitrogen replacement is sufficiently performed. There is a need. Thus, an acid-modified polypropylene can be prepared.

  Examples of the radical generator include peroxide and azonitrile. Examples of the above azonitrile include di-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyethyl hexanoate, tert-butyl Butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide and the like are included. Examples of the azonitrile include azobisisobutyronitrile and azobisisopropionitrile. The amount of the radical generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the polypropylene. Also, particularly preferably, it is 0.5 to 30 parts by mass.

  Examples of α, β-unsaturated carboxylic acids or anhydrides include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, and anhydride. Contains aconitic 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 the compound having one or more double bonds per molecule include (meth) acrylic acid-based monomers and styrene-based monomers. Examples of the (meth) acrylic acid-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Ethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, (meth) Benzyl acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, (di) ethylene glycol di (meth) acrylate, di (meth) acrylate ) Acrylic acid-1,4-butanediol, di (meth) acrylic acid-1,6-hexanediol , 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 styrene monomer include styrene, α-methylstyrene, paramethylstyrene, chloromethylstyrene, and the like. Further, a vinyl monomer such as divinylbenzene, vinyl acetate, or a vinyl ester of versatic acid can be used in combination with the above compound.

  The compound having one or more double bonds per molecule may be one kind or more. The compounding amount of the compound is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the polypropylene. Particularly preferably, it is 0.5 to 30 parts by mass.

(Polyurethane resin)
The polyurethane resin is a polymer compound containing a polyurethane skeleton and the hydrogen bonding functional group. Examples of the polyurethane resin include a 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 adhesiveness to the metal base material can be obtained. Further, the polyurethane-based resin may further include 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 effects of the present invention can be obtained.

  PC-containing polyurethane has a polycarbonate unit in the molecular chain. The “polycarbonate unit” refers to a structure shown below in the molecular chain of the 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 from 15 to 80% by mass based on the mass of all the resins in the organic resin layer, which means that both the adhesiveness to the metal base material and the weldability to the object to be joined are obtained. From the viewpoint of increasing the If the content of the polycarbonate unit is less than 15% by mass, the organic resin layer may not adhere to the metal base material with sufficient strength. May not weld with sufficient strength. The ratio of the mass of the polycarbonate unit to the mass of all resins 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, an organic polyisocyanate, a polycarbonate polyol, and a polyol having a tertiary amino group or a carboxyl group are reacted to generate a urethane prepolymer. In addition, within the range where the effects of the present invention can be obtained, it is possible to use a polyol other than the polycarbonate polyol, for example, a polyester polyol or a polyether polyol in combination.

  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 polyurethane containing a cationic polycarbonate unit can be produced. Alternatively, the carboxyl group of the urethane prepolymer is neutralized with a basic compound such as triethylamine, trimethylamine, diethanol monomethylamine, diethylethanolamine, caustic soda, caustic potassium, and the like to be converted to carboxylic acid salts. 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 type of the organic polyisocyanate is not particularly limited. Examples of the organic polyisocyanate 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 include isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. The organic polyisocyanate may be one kind or more.

  The polycarbonate polyol is obtained by reacting a carbonate compound with a diol compound. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and the like. 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. The polycarbonate polyol may be a compound whose chain is extended by an isocyanate compound. The polycarbonate polyol may be one kind or more.

  The polyol having a tertiary amino group or a carboxyl group can be obtained, for example, by subjecting an alkanolamine to a dicarboxylic acid to an acid-base reaction or dehydration condensation 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. And the like. 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, N-methylaniline and the like. Examples of the alkanolamines include monoethanolamine and diethanolamine. Examples of the above dicarboxylic acids include adipic acid and phthalic acid. The polyol having a tertiary amino group or a carboxyl group may be a compound whose chain is extended by an isocyanate compound. The polyol having a tertiary amino group or a carboxyl group may be one kind or more.

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

  The rust preventive improves the corrosion resistance of the coated metal material and, as a result, improves the corrosion resistance of the composite. The rust inhibitor may be one kind or more. 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 in the organic resin layer can be appropriately determined according to the type of the rust preventive from the range in which the rust preventive effect of the rust preventive and the effect of the present invention can be obtained.

  Examples of the metal compound-based rust preventive include oxides and 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 as long as the function of the metal oxide is exhibited. For example, from the viewpoint of the corrosion resistance, the content of the rust inhibitor in the organic resin layer is such that the content in terms of Si is 0.5% by mass or more, the content in terms of Ti is 0.005% by mass or more, and the content in terms of Zr is Is preferably 0.05% by mass or more, the Mo equivalent content 0.005% by mass or more, and the V equivalent content 0.02% by mass or more. 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 the 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, and the content in terms of V is less than 3.0% by mass.

  Examples of the nonmetallic compound-based rust preventive include phosphoric acid compounds such as diammonium hydrogen phosphate and thiol compounds such as thiourea.

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

  The lubricant can suppress the occurrence of galling on the surface of the coated metal material. The lubricant may be one kind or more, and the kind of the lubricant is not particularly limited. Examples of the lubricant include organic waxes such as fluorine-based, polyethylene-based, styrene-based, and polypropylene-based, 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 based on 100 parts by mass of the total amount of the organic resin and the other resin in the organic resin layer. When the amount of the lubricant is less than 1 part by mass, the occurrence of galling may not be sufficiently suppressed. On the other hand, when the amount of the lubricant is more than 20 parts by mass, the effect of suppressing the generation of galling reaches a plateau, and the lubricity is too high, so that the handleability may be poor.

  The antifoaming agent suppresses the generation of bubbles during the preparation of an organic resin paint described below. The antifoaming agent may be one kind or more. The type of the antifoaming agent is not particularly limited. As the defoaming agent, an appropriate amount of a known defoaming agent such as a silicone antifoaming agent may be added.

  The etching agent activates the surface of the metal base material, thereby improving the adhesion of the organic resin layer to the metal base material. Examples of the etching agent include fluorides such as hydrofluoric acid, ammonium fluoride, zirconium hydrogen fluoride, and titanium hydrogen fluoride.

  The inorganic compound densifies the organic resin layer and improves water resistance. 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 coloring material gives a predetermined color tone to the organic resin layer. Examples of the coloring material include an inorganic pigment, an organic pigment, an organic dye, and the like.

(Properties of organic resin layer)
The amount of the organic resin to be adhered to the organic resin layer may be an amount that allows sufficient adhesion to a hot melt film described later. From the viewpoint of further increasing the corrosion resistance of the coated metal material, the amount of the organic resin attached is preferably 0.2 g / m ² or more. The upper limit of the amount of the organic resin attached is not particularly limited, but can be determined from the viewpoint of the above effects reaching a peak, productivity, cost, and the like. For example, the amount of the organic resin attached is preferably about 20 g / m ² or less.

The adhesion amount of the organic resin layer may be an adhesion amount sufficient for adhesion to a hot melt film described later, and is preferably 0.2 g / m ² or more. When the adhesion amount of the organic resin layer is less than 0.2 g / m ² , the bonding strength of the hot melt film to the coated metal base material may be insufficient. When the amount of the organic resin layer attached is less than 0.2 g / m ² , the function of the additive contained in the organic resin layer (for example, the rust-preventive action of the rust-preventive agent) becomes insufficient. There is. The upper limit of the amount of the organic resin layer attached is not particularly limited, but can be determined from the viewpoint of the above-mentioned effects reaching a peak, the viewpoint of productivity, the viewpoint of cost, and the like. For example, adhesion of the organic resin layer is preferably 10 g / ^{m 2} or less, 3 g / ^{m 2} or less is more preferable.

  The organic resin layer is composed of a composition containing the above-described organic resin and any of the above-described additives. The melting point of the composition is preferably equal to or less than that of the object to be joined, and is preferably, for example, 60 to 160 ° C. When the melting point of the composition is lower 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 joining property of the coated metal base material to the article to be joined 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 organic resin layer is to be formed on the surface of the metal base material, or may be dispersed in the region and cover the surface of the metal base material. .

1-2. Hot-melt film A type of hot-melt film is a film composed of components that are melted by heating and express various members and bonding strength, produced by existing methods such as stretching or extrusion molding of a thermoplastic resin composition. Or if it is a sheet form, it will not be specifically limited.

  The melting point of the hot melt film is preferably from 50 ° C to 200 ° C. When the melting point of the hot melt film is lower than 50 ° C., the hot melt film is softened at a relatively low temperature, so that the hot melt films may stick to each other during storage or the like, Due to the softening, there is a possibility that the joined objects may fall off. If the melting point is higher than 200 ° C., an excessive amount of heat is required to soften the hot melt film, which is not practical. Examples of hot melt films having a melting point of 50 ° C. or more and 200 ° C. or less include polyurethane-based, polyester-based, polyolefin-based, polyamide-based, and ethylene / vinyl acetate copolymer (EVA) -based hot melt films. These hot-melt films may be commercially available, or may be used by synthesizing a film having desired characteristics. The melting point is measured according to JIS K 0064.

1-3. Bonded body In the composite of the present invention, the bonded body is formed on the surface of the above-described coated metal material, more precisely, the organic resin layer of the above-mentioned coated metal material, via the hot melt film. Are joined. The shape of the article to be joined is not particularly limited, and can be appropriately selected depending on the application. In addition, from the viewpoint of further increasing the adhesion to the hot melt film, it is preferable that at least a part of the surface to be joined to the hot melt film is coated with the organic resin. The type of the organic resin material is not particularly limited as long as it covers at least a part of the surface of the object to be joined and can be dried. For example, the type is included in the organic resin layer used for the coated metal base material. Organic resin.

  The type of the material to be joined is not particularly limited as long as it can be joined to the hot melt film.

  Examples of such materials include metals, thermoplastic compositions, thermoset compositions, paper, carbon fibers, processed and unprocessed plant pieces, and inorganic compositions.

  Examples of the joined body using a metal as a material include a ferrous metal, a non-ferrous metal, and a metal element formed from various plating materials. In addition, from the viewpoint of further increasing the adhesiveness with the hot melt film, the metal base material is preferably coated with an organic resin on at least a part of the bonding surface with the hot melt film. It is preferable that the coated metal base material has the same.

  Examples of the joined body using the thermoplastic resin composition as a material include cloth, fiber, woven fabric, and fiber-reinforced plastics (FRTP, CFRTP, and the like). In addition, from the viewpoint of further increasing the adhesiveness with the hot melt film, the bonded body using these thermoplastic resin compositions has at least a part of the bonding surface with the hot melt film coated with the organic resin. Is preferred.

  Examples of the joined body using the thermosetting resin composition as a material include cloth, fiber, woven fabric, and fiber-reinforced plastics (FRP, CFRP, and the like). In addition, from the viewpoint of further increasing the adhesiveness with the hot melt film, the bonded body using these thermosetting resin compositions is such that at least a part of the bonding surface with the hot melt film is coated with an organic resin. Is preferred.

  Examples of an object to be joined using a plant piece as a material include an object to be joined formed from petals, leaves, and other woody materials. In addition, from the viewpoint of further increasing the adhesiveness with the hot melt film, it is preferable that at least a part of the bonding surface with the hot melt film is covered with the organic resin in the joined body using these plant pieces. .

  Examples of the object using the inorganic composition as the material include an object formed from glass, ceramics, and minerals. In addition, from the viewpoint of further increasing the adhesiveness with the hot melt film, the bonded body using these inorganic compositions may have at least a part of the bonding surface with the hot melt film coated with an organic resin. preferable.

  Among these, from the viewpoint of expanding the use of the composite to a wider field, the joined object preferably includes a molded body formed of a material such as a ferrous metal, a non-ferrous metal, an organic resin, or glass.

  Further, a joined body using a thermoplastic resin composition or a thermosetting resin composition containing an organic resin as a material is preferable because the adhesion with a hot melt film is higher.

2. Method for Producing Composite The method for producing the coated metal element according to the present invention is not particularly limited. For example, the coated metal material according to the present invention can be manufactured by the following method.

  An exemplary method for manufacturing the composite of the present invention is as follows: 1) disposing the joined object so as to be in contact with the hot melt film with respect to a laminate including the coated metal base material and the hot melt film; And 2) a step of welding the hot melt film and the organic resin layer to the object. An exemplary method for producing the composite of the present invention further comprises: 3) disposing the hot melt film of the metal base material having an organic resin layer formed thereon so as to be in contact with the organic resin layer; The step of forming a body may be included before the step 1). The exemplary method for producing the composite of the present invention may further include a step 4) forming an organic resin layer on the metal base material before the step 3).

(1) A step of arranging the object to be joined so as to be in contact with the hot melt film In this step, the coated metal base material and the hot melt film arranged so as to be in contact with the organic resin layer of the coated metal base material The object to be bonded is disposed so as to be in contact with the hot melt film disposed so as to be in contact with the organic resin layer. The laminate may be manufactured by the following steps 3) and 4) or may be separately prepared.

  For example, the object to be joined is such that at least a portion to be joined of the object to be joined and a portion to be joined of the painted metal base material are in contact with each other via the hot melt film, It is placed on the surface of the profile. In this step, the part to be joined of the object to be joined and the part to be joined of the coated metal base material are in contact with each other via the hot melt film at least at the time of performing the step 2) described later. Just do it. At this time, it is preferable from the viewpoint of preventing displacement or the like that the object to be joined and the coated metal preform are pressed and adhered to each other by a fixing jig or the like. In addition, the hot melt film may be arranged at least in a part of a portion to be brought into contact with the member to be joined in step 3) described later.

(2) A step of welding the hot melt film to the object to be joined In this step, the hot melt film is heated and fused to the organic resin layer and the object to be joined via the hot melt film. The object to be joined is joined to the painted metal base material. Heating may be performed on at least a part of the surface where the object to be bonded and the hot melt film are in contact with each other, but from the viewpoint of further improving the adhesion, the heating is performed on the entire surface of the contacting surface. Is preferred.

  The heating method is not particularly limited, and may be appropriately selected from known methods. Examples of such heating methods include direct heating with a flame or the like, heater heating, ultrasonic heating, electromagnetic induction heating, and laser heating.

  At this time, for example, by heating so that the reached plate temperature is equal to or higher than the melting point of the hot melt film, the article to be bonded and the coated metal material can be closely bonded via the hot melt film. . The upper limit of the adhesion amount of the ultimate plate temperature is not particularly limited, but can be determined from the viewpoint of the above-mentioned effects reaching a plateau or suppressing the decomposition of the hot melt film or the organic resin layer. It can be:

(3) Step of Arranging Hot Melt Film in Contact with Organic Resin Layer In this step, a hot melt film is arranged on the painted metal base material so as to be in contact with the organic resin layer. The coated metal base material may be manufactured by the step 4) described later or may be separately prepared. The method for arranging the hot melt film is not particularly limited, and may be appropriately selected from known methods. Examples of such a method include a method in which a hot-melt film resin previously formed into a film shape is adhered to the surface of a coated metal base material by a hot roll or the like, and a hot-melt film resin supplied from an extruder. Is laminated on a painted metal base material in a layered form, and cooled and fixed by a cooling roller or the like. Alternatively, a sheet-shaped hot melt film formed in advance may be provided so as to be in contact with the organic resin layer without being bonded or fixed.

(4) Step of forming an organic resin layer on a metal element In this step, a metal element serving as a coating base material is prepared, an organic resin layer is formed on the metal element, and a painted metal element is formed. And When forming a chemical conversion treatment film, a chemical conversion treatment is performed on the metal base material before forming the organic resin layer. When a chemical conversion coating is not formed, an organic resin layer is formed as it is.

  When forming a chemical conversion treatment film on the surface of a metal base material, the chemical conversion treatment film can be formed by applying a chemical conversion treatment solution to the surface of the metal base material and drying it. The method of applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method, and the like. Drying conditions for the chemical conversion treatment liquid may be appropriately set according to the composition of the chemical conversion treatment liquid and the like. For example, the metal shaped material coated with the chemical conversion treatment liquid is put into a drying oven without washing, and heated so that the reached plate temperature is in the range of 80 to 250 ° C., so that the surface of the metal shaped material is heated. A uniform chemical conversion treatment film can be formed.

  The organic resin layer can be formed, for example, by applying a paint containing the above-described organic resin to the surface of the metal base material (or the chemical conversion treatment film) and baking the applied paint. The method for applying the paint is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method, and the like. The conditions for baking the paint may be appropriately set according to the composition of the paint and the like. For example, the metal base material (or the chemical conversion treatment) is put into a drying oven with the paint applied, and dried with a hot-air dryer so that the reached plate temperature is in the range of 110 to 200 ° C. A uniform organic resin layer can be formed on the surface of the film.

  As described above, in the coated metal material according to the present invention, the organic resin layer enhances the adhesion between the metal material and the hot melt film. Excellent adhesion. Further, the coated metal base material according to the present invention can be easily manufactured simply by applying and baking a paint containing an organic resin.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

1. Production of coated metal plate (1) Metal plate As a hot-dip Zn-Al-Mg alloy-plated steel plate, a hot-dip Zn-6 mass% Al-3 mass% Mg alloy-plated steel plate with a coating weight per side of 45 g / m ² is used. did. As a base steel plate, a cold-rolled steel plate (SPCC) having a thickness of 1.6 mm was used.

(2) Preparation of Organic Resin Paint An emulsion of an organic resin, 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, a urethane resin emulsion and a polypropylene resin emulsion were used. As the urethane-based resin emulsion, a commercially available polyurethane resin emulsion containing a polycarbonate unit (Adekabon Titer HUX-386: ADEKA CORPORATION, also simply referred to as “UE”) was used. A commercially available acid-modified polypropylene resin emulsion (Hardlen NZ-1005: Toyobo Co., Ltd., simply referred to as “PPE”) was used as the polypropylene resin emulsion.

  As the polyethylene wax, a commercially available polyethylene wax (E-9015: Toho Chemical Industry Co., Ltd.) was used. The addition amount of the polyethylene wax is 3.0 parts by mass based on 100 parts by mass of the total amount of the organic resin.

  A commercially available epoxy-based crosslinking agent (HUX-XW3: ADEKA CORPORATION) was used as the crosslinking agent. The amount of the crosslinking agent added is 3.0 parts by mass based on 100 parts by mass of the total amount of the organic resin.

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

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

As the metal compound (B1), oxides of Si, Ti, Zr, V and Mo were used. 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 (also referred to as “B13” by Daiichi Rare Element Chemical Co., Ltd.) was used. V ₂ O ₅ (also referred to as “B14”, Taiyo Kokko Co., Ltd.) was used as the V oxide. The Mo oxide _was used _{(NH 4) 6 Mo 7 O} 24 · 4H 2 O ( Kishida Chemical Co., also referred to as "B15"). The above metal compounds were added alone or in combination.

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

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

  A commercially available silicone-based antifoaming resin (KM-73: Shin-Etsu Chemical Co., Ltd.) was used as the antifoaming agent. The amount of the defoamer added is 0.05% by mass based on the total mass of the organic resin.

  Organic resin paints 1 to 9 were prepared using the above materials in the types and amounts shown in Tables 1 and 2 below.

(3) Evaluation of Stability of Organic Resin Paint The storage stability of the nine prepared organic resin paints was evaluated. Each organic resin paint placed in a closed container was stored in a constant temperature bath at 40 ° C., and the state of the organic resin paint was observed. Regarding each organic resin paint, those that were stable for 30 days or more were evaluated as “O”, and those that were thickened or solidified in less than 30 days were evaluated as “X”. The results are shown in Tables 1 and 2.

  In Tables 1 and 2, the content of the rust inhibitor is the 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 described together with the numerical value of the content of the rust inhibitor. "P" is phosphorus, "SH" is (thiol component), "Zr" is zirconium, "V" is vanadium, "Si" is silicon, "Ti" is titanium, and "Mo" is molybdenum. Are respectively shown. In the column of the content of the rust preventive B31 in the organic resin paint 5 and the organic resin paint 8, the content of B31 is shown.

  As shown in Tables 1 and 2, the organic resin paints 2 to 6 and 8 contained a metal compound rust inhibitor, but exhibited good storage stability. This is because the content of the rust inhibitor of the metal compound is as follows: Ti: less than 0.6% by mass, Zr: less than 12.0% by mass, Mo: less than 3.0% by mass, V: less than 3.0% by mass. It is considered that there was.

  In addition, since the organic resin coatings 1 and 7 did not contain a rust inhibitor, they exhibited good storage stability. In addition, the storage stability of the organic resin paint 9 was insufficient. This is considered to be because the content of the rust inhibitor of the metal compound was at least 0.6% by mass of Ti and at least 12.0% by mass of Zr.

(4) Formation of Organic Resin Layer The above metal plate was immersed in an alkaline degreasing aqueous solution (SD-270; Nippon Paint Co., Ltd.) at a liquid temperature of 40 ° C. and pH 12 for 1 minute to degrease the surface. Next, the organic resin coating material 1 prepared in the above (2) is applied to the surface of the degreased metal plate with a roll coater, and dried with a hot-air drier so that the reached plate temperature becomes 150 ° C. Was formed. Thus, a coated metal plate 1 was obtained. Also, coated metal plates 2 to 9 were obtained in the same manner except that each of organic resin coatings 2 to 9 was used instead of organic resin coating 1.

  Also, a coated metal plate 10 was obtained in the same manner except that the organic resin paint was not applied and dried.

Table 3 shows the types of the original coating plates, the types of the organic resin paint, and the amounts of the organic resin layers attached to the coated metal plates 1 to 10. It is considered that (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ exists in the organic resin layer in a state of ZrO. It is considered that V ₂ O ₅ exists in the state 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 form of _Mo 7 _{O 24} is an organic resin layer.

Evaluation of corrosion resistance The coated metal plate 1 was cut out into a width of 70 mm x a length of 150 mm, and the end face was sealed all around the circumference to prepare a sample 1. Next, the sample 1 was put into a salt water spray tester, a white rust generation area ratio after 72 hours was obtained, and the corrosion resistance of the coated metal sheet 1 was evaluated from the white rust generation area rate. The case where the white rust generation area ratio after 72 hours of salt water spraying was less than 10% was evaluated as “○”, 10% or more and less than 30% as “Δ”, and 30% or more as “X”. The corrosion resistance of the coated metal plates 2 to 10 was evaluated in the same manner except that each of the coated metal plates 2 to 12 was used instead of the coated metal plate 1. Table 3 shows the results.

As shown in Table 3, each of the coated metal plates 1 to 9 exhibited corrosion resistance having no practical problem. Among them, the coated metal plates 5, 8, and 9 exhibited good corrosion resistance. This is because the adhesion amount of the organic resin layer is 0.2 g / m ² or more, the content of the rust inhibitor of the metal compound is Ti: 0.005% by mass or more, Zr: 0.05% by mass or more, and Mo: This is probably because 0.005% by mass or more and V: 0.02% by mass or more.

On the other hand, the coated metal plates 1 to 4, 6 and 7 showed no problem in practical use, but exhibited lower corrosion resistance than the corrosion resistance of the coated metal plates 5, 8 and 9. The reason is considered to be that the coated metal plates 1 to 4 contain only some of the rust-preventive components of the metal compounds such as Ti, Zr, Mo, and V. In the coated metal plate 6, the content of the rust inhibitor of the metal compound is Ti: less than 0.005% by mass, Zr: less than 0.05% by mass, Mo: less than 0.005% by mass, V: 0.02% by mass. %, It is considered that the coating amount of the organic resin layer of the coated metal plate 7 was less than 0.2 g / m ² .

  Furthermore, the corrosion resistance of the coated metal plate 10 was insufficient. It is considered that the reason is that the organic resin layer is not formed.

2. Evaluation and Preparation of the complex (1) cutting the respective coated metal formed and fabricated material coated metal plate 10, the width _(W 11) 25 mm × length _(L 12) 100 mm coated metal formed and fabricated material 1 dimensions 10 were prepared (see FIGS. 1A and 1B). The thickness of each of the painted metal base materials 1 to 10 is 1.6 mm.

(2) Object to be joined (2-1) Painted metal plate As a painted metal plate, a metal plate similar to the painted metal plates 1 to 10 used in Example 1 is prepared, and the same as the painted metal plates 1 to 10 described above. It was cut to be joined bodies 1 to 10, respectively.

(2-2) Wood piece A 9 mm-thick cypress material was prepared as a wood piece, and was used as a body 11 to be joined. Further, the above-mentioned piece of wood was brush-coated with the organic resin paint 4 prepared in Example 1, and dried in a drying oven at 60 ° C for 1 hour to form an organic resin layer.

(2-3) Glass Plate A float plate glass having a thickness of 6 mm was prepared as a glass plate, and was used as a bonded body 13.

(2-4) CFRP
A 0.2 mm-thick epoxy resin-impregnated prepreg (manufactured by Toray, trading card 3255S-25) was prepared as the CFRP, and the bonded body 14 was obtained.

(2-5) CFRTP
As the CFRTP, a prepreg impregnated with a polypropylene resin having a thickness of 2 mm (SA-3203PT1 manufactured by Sakai Obec Co., Ltd.) was prepared.

(2-6) Paper A piece of A-flute corrugated cardboard having a thickness of 5 mm was prepared as paper, and was used as a bonded body 16.

(3) Hot melt film As a hot melt film, a polyurethane (hereinafter also referred to as “PU”) hot melt film, a polyester (hereinafter also referred to as “PE”) hot melt film, and a polyamide (hereinafter also referred to as “PA”). ) -Based hot melt films, polyurethane elastomer (hereinafter also referred to as “PU-E”)-based hot melt films, and polypropylene (hereinafter also referred to as “PP”)-based hot melt films.

  SHM107-PUR (Seed Co., Ltd.) having a thickness of 70 μm was used as the PU-based hot melt film. The melting point of the PU hot melt film was 110 ° C.

  Eselan SHM244-PES (Seed Co., Ltd.) having a thickness of 200 μm was used as the PE-based hot melt film. The melting point of the PE-based hot melt film was 120 ° C.

  Elfant NT120 (Nippon Matai Co., Ltd.) having a thickness of 100 μm was used as the PA hot melt film. The melting point of the PA hot melt film was 120 ° C.

  Eselan SHM605-CDR (Nippon Mattai Co., Ltd.) having a thickness of 200 μm was used as the PU-E hot melt film. The melting point of the PU-E hot melt film was 190 ° C.

  Admer QE060 (Mitsui Chemicals Tosello Co., Ltd.) having a thickness of 40 μm was used for the PP-based hot melt film. The melting point of the PP hot melt film was 139 ° C.

[Example 1]
A PU-based hot-melt film 30 having a width (W ₁₁ ) of 25 mm and a length (L ₁₁ ) of 12.5 mm is applied to an organic resin on a piece in the longitudinal direction of the coated metal plate 1 (25 mm × 100 mm) as the coated metal base material 10. The coated metal plate 1 (25 mm × 100 mm) as the member to be joined 20 was overlapped and adhered so as to be in contact with the layer and sandwich the PU-based hot melt film (FIGS. 3A and 3B).

  A sample in which the hot melt film 30 was sandwiched between the coated metal base material 10 and the two coated metal plates 1 as the objects to be bonded 20 was placed on a plate 500 heated to 200 ° C., and heated to 200 ° C. from above. A sample for a tensile test was produced by sandwiching the plate with another fixed plate 500 and pressing it at 2.4 MPa for 15 seconds using a press machine.

[Examples 2 to 15 and Comparative Examples 1 to 4]
A sample for a tensile test was produced in the same manner as in Example 1 except that the types of the coated metal base material, the hot melt film, and the joined object were changed as shown in Table 4 below.

(4) Evaluation of bonding strength of composite The coated metal plate in the sample for the tensile test obtained in Examples 1 to 15 and Comparative Examples 1 to 4 was installed on an Autograph AG-IS manufactured by Shimadzu Corporation and was heated at room temperature. Then, both ends of the sample were pulled at a pulling speed of 5 mm / min, and a value (N / mm ² = MPa) obtained by dividing the maximum load (N) at the time when the joint was broken by the joint area was calculated as the shear strength. . The direction in which the sample was pulled was parallel to the joining surface and opposite to each other (X direction in FIG. 3A), and the pulling speed was 100 mm / min.

  "X" when the joining force is less than 10 MPa, "△" when the joining force is 10 MPa or more and less than 15 MPa, "O" when the joining force is 15 MPa or more and less than 20 MPa, A case of 20 MPa or more was evaluated as “◎”. Table 4 shows the measurement results and evaluation results of the bonding strength (shear strength) of each sample (composite).

  In all of the composites according to Examples 1 to 15, the bonding strength was as good as 10 MPa or more. This is presumably because the object to be joined was joined using a laminate in which the hot melt film was laminated on the painted metal plate on which the organic resin layer was formed as the painted metal base material.

  In Example 4 in which the bonded object 12 which was a piece of wood having an organic resin layer was bonded, the evaluation of the bonding strength was higher than in Example 2 in which the bonded body 11 was a piece of wood which did not have an organic resin layer. In addition, although both the bonded body 14 made of CFRP and the bonded body 15 made of CFRTP contain an organic resin, in Examples 8 and 10 in which these were bonded, the shear strength tended to be high.

  On the other hand, in the composites according to Comparative Examples 1 to 4, the bonding strength was insufficient. This is presumably because the object to be joined was joined to a combination of a metal base material having no organic resin layer and a hot melt film.

  Since the composite of the present invention has excellent adhesion between the coated metal material and the object to be joined, it can be used, for example, in various electronic devices, household appliances, medical devices, automobile bodies, vehicle-mounted articles, building materials, and the like. It is preferably used.

REFERENCE SIGNS LIST 10 painted metal base material 20, 40 bonded object 30 hot melt film 100, 200, 300 composite 102 metal base material 104 organic resin layer 402 recess 404 rim 500 base plate

Claims (11)

A coated metal member including a metal member and an organic resin layer formed on the surface of the metal member,
Hot melt film,
To be joined,
A composite having
The organic resin layer contains an acid-modified polypropylene or a polycarbonate-containing polyurethane,
The composite, wherein the hot melt film is welded to the organic resin layer and the object. The deposition amount of the organic resin layer is 0.2 g / ^{m 2} or more, the composite body according to claim 1. The melting point of the hot melt film is 50 to 200 ° C., composite according to claim 1 or 2. The composite according to any one of claims 1 to 3 , wherein the joined body includes a molded body of one or more materials selected from the group consisting of a ferrous metal, a non-ferrous metal, an organic resin, and glass. body. The organic resin layer contains a rust inhibitor complex according to any one of claims 1 to 4. A laminate having a metal base material and a coated metal base material including an organic resin layer formed on the surface of the metal base material, and a hot melt film disposed so as to be in contact with the organic resin layer On the other hand, a step of arranging the joined body so as to be in contact with the hot melt film,
A step of heating at least a part of the hot melt film in contact with the joined body, and welding the hot melt film to the organic resin layer and the joined body;
Only including,
The organic resin layer includes an acid-modified polypropylene or a polycarbonate-containing polyurethane,
A method for producing a composite. The method for producing a composite according to claim 6 , further comprising a step of arranging the hot melt film so as to be in contact with the organic resin layer of the painted metal base material to form the laminate. The method for producing a composite according to claim 6 , wherein the amount of the organic resin layer attached is 0.2 g / m ² or more. The method for producing a composite according to any one of claims 6 to 8 , wherein the melting point of the hot melt film is 50 to 200 ° C. The composite according to any one of claims 6 to 9 , wherein the joined body includes a molded body of one or more materials selected from the group consisting of a ferrous metal, a non-ferrous metal, an organic resin, and glass. How to make the body. The method for producing a composite according to any one of claims 6 to 10 , wherein the organic resin layer contains a rust inhibitor.

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