WO2017061062A1 - Complex and method for manufacturing same - Google Patents

Abstract

The purpose of the present invention is to provide a complex including a metal shaped material and a bonded body, the complex being excellent in adhesion and capable of being easily manufactured even if various materials are bonded together. The complex comprises: a coated metal shaped material including a metal shaped material and an organic resin layer formed on a surface of the metal shaped material; a hot melt film; and a bonded body. In the complex, the hot melt film is welded to the organic resin layer and the bonded body.

Description

Composite and production method thereof

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

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

When manufacturing a composite body by insert molding, it is important to improve the adhesion between the metal base material and the molded body of the resin composition. As a method for improving the adhesion between the metal shaped material and the molded body of the resin composition, for example, it is proposed to roughen the surface of the metal shaped material before performing insert molding (patent) Reference 1 to 3). In the methods of Patent Documents 1 to 3, the surface of the aluminum alloy is roughened to improve the bondability between the aluminum alloy and the 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 laminate in which a hot melt film is laminated, after a material containing a thermoplastic resin is disposed 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 thermoplastic resin molded body are joined to produce a composite.

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

The composites produced by the methods described in Patent Documents 1 to 3 have a problem that the adhesion between the metal shaped material and the molded body of the resin composition is not sufficient because they are joined by the anchor effect. In addition, the methods for producing composites described in Patent Documents 1 to 3 have a problem that the surface of the metal base material is roughened, so that the production process becomes complicated and the production cost increases.

In addition, in the composite manufactured by the method described in Patent Document 4, it cannot be said that the adhesiveness between the thermoplastic resin molded body and the metal base material is sufficiently high, and a composite with higher adhesiveness is desired. It was.

In addition, the methods described in Patent Documents 1 to 4 are for joining a molded body of a resin composition to a metal base material. In order to broaden the application of the composite, when trying to produce a composite in which a material other than the resin composition is bonded to the metal base material, the method described in Patent Documents 1 to 4 uses a method other than the resin composition. It was unclear whether sufficient adhesion occurred between the material and the metal profile.

The present invention has been made in view of such a point, and even if various materials are bonded, a metal shaped material and an object to be bonded that are excellent in adhesion and can be easily manufactured. It aims at providing the composite_body | complex containing and its manufacturing method.

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 painted metal base material including an organic resin layer formed on a surface of the metal base material, a hot melt film, and a joined body, The said hot-melt film is the composite_body | complex which is welded to the said organic resin layer and the said to-be-joined body.
[2] The composite according to [1], wherein the organic resin layer includes a polypropylene resin.
[3] The composite according to [1], wherein the organic resin layer includes a polyurethane resin.
[4] The composite according to any one of [1] to [3], wherein an adhesion amount of the organic resin layer is 0.2 g / m ² or more.
[5] The composite according to any one of [1] to [4], wherein the hot-melt film has a melting point of 50 to 200 ° C.
[6] The joined body includes a molded body of one or more materials selected from the group consisting of ferrous metals, non-ferrous metals, organic resins, and glass. The complex described.
[7] The composite according to any one of [1] to [6], wherein the organic resin layer contains a rust inhibitor.
[8] A painted metal shape material including a metal shape material and an organic resin layer formed on a surface of the metal shape material, and a hot melt film disposed so as to be in contact with the organic resin layer A step of disposing a body to be in contact with the hot melt film with respect to the laminate, and heating at least a part of the hot melt film in contact with the body to be bonded, And a step of welding to the organic resin layer and the joined body.
[9] The method for producing a composite according to [8], further including a step of forming the laminate by disposing the hot melt film so as to contact the organic resin layer of the metal base material. .
[10] The method for producing a composite according to [8] or [9], wherein the organic resin layer includes a polypropylene resin.
[11] The method for producing a composite according to [8] or [9], wherein the organic resin layer includes a polyurethane-based resin.
[12] The method for producing a composite according to any one of [8] to [11], wherein the adhesion amount of the organic resin layer 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 joined body includes a molded body of one or more materials selected from the group consisting of ferrous metals, non-ferrous metals, organic resins, and glass. The manufacturing method of the composite_body | complex described.
[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, the composite_body | complex containing the metal shape material and to-be-joined body which is excellent in the adhesiveness and can be manufactured easily, and its manufacturing method are provided. 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 taken along line 1B-1B in FIG. 1A. 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 taken along line 2B-2B in FIG. 2A. FIG. 3A is a plan view of a sample for a tensile test produced in 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 painted metal shape 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 shape member and the object to be joined, and joins the painted metal shape material and the object 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. As shown in FIGS. 1A and 1B, the composite 100 has a painted metal base material 10, a hot melt film 30, and a joined body 20. The painted metal base material 10 includes a metal base material 102 and an organic resin layer 104. In the composite body 100, the hot melt film 30 is welded to both the organic resin layer 104 and the joined body 20, whereby the painted metal shape member 10 and the joined body 20 are joined.

2A and 2B show a complex according to another embodiment of the present invention. As shown in FIGS. 2A and 2B, the composite 200 has a painted metal raw material 10, a hot melt film 30, and a joined body 40. The joined 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 hot melt film 30 in the composite 200 has the same shape as the collar portion 404 of the joined body 40, and the hot melt film 30 is welded to both the collar portion 404 and the organic resin layer 104 of the joined body 40. Thus, the painted metal shape member 10 and the joined body 40 are joined.

1-1. Painted metal material The painted metal material according to the present invention includes a metal material and an organic resin layer. The organic resin layer is formed on the surface of the metal base material. The coated metal preform may have a chemical conversion treatment film formed between the metal preform and the organic resin layer. However, the painted metal preform according to the present invention includes an organic resin layer, a hot melt film, Therefore, it is not necessary to have a chemical conversion film. Hereinafter, each element of the painted metal shape material will be described.

(1) Metal shape material The metal shape material is a shape obtained by applying heat or force to a metal. The metal base material used as the coating substrate is a metal plate, a press-molded product thereof, or a metal member formed by casting, forging, cutting, powder metallurgy, or the like. The type of the metal base material is not particularly limited. Examples of the metal shape member include a metal plate, a pressed product of the metal plate, a metal member, and the like. Examples of the metal plate include galvanized steel sheet, Zn—Al alloy plated steel sheet, Zn—Al—Mg alloy plated steel sheet, Zn—Al—Mg—Si alloy plated steel sheet, aluminum plated steel sheet, stainless steel sheet (austenite, martensite). Site, ferrite, and ferrite-martensite two-phase), 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, and powder metallurgy including aluminum die casting and zinc die casting. The metal shaped material may be subjected to known coating pretreatments such as degreasing and pickling as necessary.

(2) Chemical conversion treatment film As mentioned above, as for the coating metal raw material, the chemical conversion treatment film may be formed between the metal raw material and the organic resin layer. The chemical conversion treatment film 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 film may be formed on at least a region (bonding surface) to be bonded to the object to be bonded, which will be described later, on the surface of the metal shape material, but from the viewpoint of facilitating film formation, It is preferably formed on the entire surface of the material.

The kind of chemical conversion treatment for forming a chemical conversion treatment film is not particularly limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, and phosphate treatment. The adhesion amount of the chemical conversion treatment film formed by chemical conversion treatment is not particularly limited as long as it is within a range effective for improving the adhesion between the metal raw material and the organic resin layer and the corrosion resistance of the metal raw material. 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 coating amount of the Ti—Mo composite film is 10 to 500 mg / m ² , and the fluoroacid-based film has a fluorine conversion adhesion amount or a total metal element conversion adhesion amount of 3 to 100 mg / m ² . What is necessary is just to adjust the adhesion amount so that it may become in the range. Also, if the phosphate film, the adhesion amount of the coating may be adjusted to adhesion amount such that 0.1 ~ 5g / 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 treatment film. As the organic resin layer is welded to the hot melt film, in the composite according to the present invention, the metal base material and the object to be joined are more firmly adhered to each other through the organic resin layer and the hot melt film.

The type of organic resin contained in the organic resin layer is particularly limited as long as it has a functional group (hydrogen-bonding functional group) that forms a hydrogen bond with the metal shape material and has a weldability to a hot melt film. Not. 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 weldability to a hot melt film include epoxy resin, polyolefin resin, phenol resin, acrylic resin, polyester resin, and polycarbonate unit-free polyurethane. System resin is included. These resins may be used alone or in combination of two or more.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and the like. Examples of the olefin resin include polyethylene resin and polypropylene resin. The phenolic resin includes novolac type resin, resol type resin and the like. The polyurethane resin is obtained by copolymerizing a diol and a diisocyanate. Examples of the diol are other than polycarbonate diol, and include bisphenol A, 1,6-hexanediol, 1,5-pentanediol, and the like. Examples of the isocyanate include aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like.

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

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

From the viewpoint of further improving the adhesion between the hot melt film described later, the organic resin that is the material of the organic resin layer is preferably a polypropylene resin or a polyurethane resin. The polyurethane resin preferably contains a polycarbonate unit-containing polyurethane resin. Similar to the chemical conversion treatment film, the organic resin layer may be formed on at least a part of the bonding surface with the object to be bonded among the surfaces of the metal raw material, but from the viewpoint of further improving the adhesion, The organic resin layer is preferably 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 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 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 painted metal shape material and the hot melt film. Thereby, sufficient joining force of the painted metal shape member to the joined body 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. In the case where the melt viscosity is less than 1000 mPa · s, the organic resin layer may flow during welding with the joined body. For this reason, an organic resin layer does not weld to a to-be-joined body, but the joining force of the coating metal shape material with respect to the to-be-joined body may become inadequate. On the other hand, when the melt viscosity is more than 10,000 mPa · s, the weldability of the organic resin layer to the hot melt film may be lowered and become insufficient. For this reason, the joining force of the coated metal shaped member to the joined body may be insufficient. 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.

The melting point of the acid-modified polypropylene is preferably 60 to 120 ° C., and the crystallinity of the acid-modified polypropylene is preferably 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 bonded body may be lowered.

It should be noted that the melting point and crystallinity of the acid-modified polypropylene hardly change between the state contained in the organic resin coating (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 isotacticity, atacticity, syndiotactic, hemi-isotactic and stereotactic tacticity. The stereoregularity of the polypropylene in the acid-modified polypropylene is preferably isotactic from the viewpoint of mechanical properties such as rigidity and impact strength or durability.

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

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

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

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

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

The above 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 polypropylene. Particularly preferred is 0.5 to 30 parts by mass.

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

PC-containing polyurethane has a polycarbonate unit 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 total mass of the resin in the organic resin layer. From the viewpoint of increasing When the content of the polycarbonate unit is less than 15% by mass, the organic resin layer may not adhere to the metal shape material with sufficient strength. When the content is more than 80% by mass, the organic resin layer is bonded. May not weld with sufficient strength to the body. The ratio of the mass of the polycarbonate unit to the mass of the total resin can be determined by nuclear magnetic resonance spectroscopy (NMR analysis) using a sample in which the organic resin layer is dissolved in chloroform.

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

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

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

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

(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, rust inhibitors, phosphorus compounds, lubricants, antifoaming agents, etching agents, inorganic compounds, and coloring materials.

The above rust preventive improves the corrosion resistance of the painted metal profile, and as a result, improves the corrosion resistance of the composite. One or more rust inhibitors may be used. Examples of the rust inhibitor include a metal compound rust inhibitor, a non-metal compound rust inhibitor, and an organic compound rust inhibitor. The content of the rust preventive agent in the organic resin layer can be appropriately determined from the range in which the rust preventive effect of the rust preventive agent and the effect of the present invention can be obtained according to the type of the rust preventive agent.

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

The content of the anticorrosive agent in the organic resin layer can be appropriately determined as long as the function of the metal oxide is expressed. For example, the content of the rust inhibitor in the organic resin layer is 0.5 mass% or more in terms of Si, 0.005 mass% or more in terms of Ti, and Zr content in terms of corrosion resistance. Is 0.05% by mass or more, the Mo equivalent content is 0.005% by mass or more, and the V equivalent content is preferably 0.02% by mass or more. In addition, the content of the rust inhibitor in the organic resin layer is such that the content in terms of Si is less than 23.5% by mass, the content in terms of Ti is less than 0.6% by mass, from the viewpoint of storage stability of the organic resin paint. It is preferable that the content in terms of Zr is less than 12.0% 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 non-metallic compound-based rust preventive include phosphate compounds such as diammonium hydrogen phosphate and thiol compounds such as thiourea.

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

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

The above-mentioned etching agent improves the adhesion of the organic resin layer to the metal base material by activating the surface of the metal base material. Examples of the etching agent include fluorides such as hydrofluoric acid, ammonium fluoride, zircon hydrogen fluoride, and titanium hydrogen fluoride.

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

(Properties of organic resin layer)
The adhesion amount of the organic resin in the organic resin layer may be an amount that provides sufficient adhesion with a hot melt film described later. From the viewpoint of further improving the corrosion resistance of the painted metal shape material, the adhesion amount of the organic resin is preferably 0.2 g / m ² or more. The upper limit value of the organic resin adhesion amount 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 adhesion amount of the organic resin is preferably about 20 g / m ² or less.

The adhesion amount of the organic resin layer may be an adhesion amount that provides sufficient adhesion with the 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 painted metal shape material may be insufficient. Moreover, when the adhesion amount of the organic resin layer 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 value of the adhesion amount of the organic resin layer is not particularly limited, but can be determined from the viewpoint that the above effect reaches a peak, the productivity viewpoint, the cost viewpoint, 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 including the organic resin described above and the additive that is optionally blended. The melting point of the composition is preferably equal to or less than that of the above-mentioned bonded body, 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. If the melting point of the composition is higher than 160 ° C., the bondability of the coated metal shaped material to the bonded body may be insufficient. The melting point of the resin composition can be adjusted by the type of organic resin and the use of additives.

The organic resin layer may uniformly cover a region where the organic resin layer is to be formed in the surface of the metal base material, or may be dispersed in the region to cover the surface of the metal base material. .

1-2. Hot melt film The type of hot melt film is a film made of an existing method such as stretching or extrusion molding of a thermoplastic resin composition, which is composed of components that melt by heating and develop various members. Or if it is a sheet-like thing, it will not specifically limit.

The melting point of the hot melt film is preferably 50 ° C. or higher and 200 ° C. or lower. 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, Due to the softening, the bonded objects to be bonded may fall off. When the melting point is higher than 200 ° C., an excessive amount of heat is required to soften the hot melt film, which is not realistic. Examples of hot melt films having a melting point of 50 ° C. or higher and 200 ° C. or lower 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 synthesized and used having desired characteristics. The melting point is measured according to JIS K0064.

1-3. To-be-joined body In the composite of the present invention, the to-be-joined body passes through the hot melt film on the surface of the above-mentioned painted metal preform, more precisely, the organic resin layer of the above-mentioned painted metal preform. Are joined. The shape of the object to be joined is not particularly limited and can be appropriately selected depending on the application. In addition, from a viewpoint of improving adhesiveness with a hot-melt film, it is preferable that the to-be-joined body is coat | covered with the organic resin at least one part of the joining surface with a hot-melt film. The type of the organic resin is not particularly limited as long as it can cover and dry at least a part of the surface of the object to be joined. For example, the organic resin material is included in the organic resin layer used for the painted metal shape material. It can be an organic resin.

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

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

Examples of objects to be joined using metals as materials include ferrous metals, non-ferrous metals, and metal shapes formed from various plating materials. From the viewpoint of further improving the adhesion to the hot melt film, it is preferable that at least a part of the bonding surface with the hot melt film is coated with an organic resin in the metal shaped material, and the organic resin layer is It is preferable that it is the coating metal shape material which has.

Examples of the joined body using the thermoplastic resin composition as a material include cloth, fiber, woven fabric, and fiber reinforced plastics (such as FRTP and CFRTP). From the viewpoint of further improving the adhesion with the hot melt film, at least a part of the joining surface with the hot melt film is coated with an organic resin in the joined body using these thermoplastic resin compositions. It is preferable.

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 improving the adhesion with the hot melt film, to-be-joined bodies using these thermosetting resin compositions have at least a part of the bonding surface with the hot melt film coated with an organic resin. Preferably it is.

Examples of joined bodies using plant pieces as materials include joined bodies formed from petals, leaves, and other woody materials. In addition, from the viewpoint of further improving the adhesion to the hot melt film, it is preferable that at least a part of the bonding surface with the hot melt film is coated with an organic resin in the bonded body using these plant pieces. .

Examples of the joined body using an inorganic composition as a material include a joined body formed from glass, ceramics, and mineral. In addition, from the viewpoint of further improving the adhesion with the hot melt film, it is preferable that at least a part of the bonding surface with the hot melt film is coated with an organic resin in the bonded body using these inorganic compositions. preferable.

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

In addition, a bonded body using a thermoplastic resin composition or a thermosetting resin composition containing an organic resin as a material is preferable because it has higher adhesion to a hot melt film.

2. Manufacturing method of composite The manufacturing method of the coating metal shape material which concerns on this invention is not specifically limited. For example, the painted metal profile according to the present invention can be manufactured by the following method.

In an exemplary method for producing a composite according to the present invention, 1) the object to be joined is disposed so as to be in contact with the hot melt film with respect to a laminate including the painted metal preform and the hot melt film. And 2) a step of welding the hot melt film and the organic resin layer to the joined body. The exemplary production method of the composite according to the present invention further includes: 3) arranging the hot melt film so as to contact the organic resin layer of the metal shaped material on which the organic resin layer is formed; A step of forming a body may be included before the step 1). The exemplary manufacturing method of the composite of the present invention may further include 4) a step of forming an organic resin layer on the metal base material before 3) the step.

(1) The process of arrange | positioning a to-be-joined body so that it may contact | connect a hot-melt film In this process, the said hot-melt film arrange | positioned so that the said coating metal shape material and the organic resin layer of a coating metal shape material may be touched The bonded body 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 processes 3) and 4) described later, or may be prepared separately.

For example, the object to be bonded is coated metal element so that at least the part to be bonded of the object to be bonded and the part to be bonded of the painted metal shape member are in contact via the hot melt film. Arranged on the surface of the profile. In this process, the part to be joined of the object to be joined and the part to be joined of the painted metal shape material are in contact with each other via a hot melt film at the time of performing step 2) described later. Just do it. At this time, it is preferable from the viewpoint of preventing misalignment that the object to be joined and the painted metal shape member are pressed and adhered to each other by a fixing jig or the like. Moreover, what is necessary is just to arrange | position a hot-melt film in at least one part of the site | part made to contact with a to-be-joined body at the process 3) mentioned later.

(2) Step of welding a hot melt film to the joined body In this step, the hot melt film is heated and heat-fused to the organic resin layer and the joined body, and the hot melt film is interposed therebetween. A to-be-joined body is joined to the above-mentioned paint metal shape 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, but from the viewpoint of further improving the adhesion, the heating should be performed on the entire surface of the surface in contact. 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 ultimate plate temperature is equal to or higher than the melting point of the hot melt film, the object to be bonded and the coated metal shaped material can be closely bonded via the hot melt film. . The upper limit value of the amount of adhesion of the ultimate plate temperature is not particularly limited, but can be determined from the viewpoint that the above effect reaches a peak or the viewpoint of suppressing the decomposition of the hot melt film or the organic resin layer. It can be as follows.

(3) The process of arrange | positioning a hot-melt film so that an organic resin layer may be contacted In this process, a hot-melt film is arrange | positioned so that the organic resin layer may be contact | connected with respect to a coating metal shape material. The painted metal shape material may be manufactured by the step 4) described later, or may be prepared separately. 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 for bonding a resin for hot melt film previously formed into a film shape to the surface of a painted metal base material by a hot roll or the like, and a resin for hot melt film supplied from an extruder And a method of laminating a layer on a painted metal shape material and cooling and fixing with a cooling roller or the like. Moreover, you may install so that the sheet-like hot-melt film previously shape | molded may contact | connect an organic resin layer, without adhere | attaching or adhering.

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

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

The organic resin layer can be formed, for example, by applying and baking a paint containing the above-described organic resin on the surface of a metal base material (or chemical conversion film). The method for applying the paint is not particularly limited and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. The baking condition of the paint may be set as appropriate according to the composition of the paint. For example, a metal shape material (or chemical conversion treatment) is applied by putting a metal shape material coated with paint into a drying oven and drying it with a hot air drier so that the ultimate 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 painted metal preform according to the present invention, the organic resin layer enhances the adhesion between the metal preform and the hot melt film. Excellent adhesion. In addition, the painted metal shape 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. As the manufacturing (1) metal plate hot-dip Zn-Al-Mg alloy plated steel sheet coated metal plate, the coating weight per one side using a melt Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet of 45 g / ^{m 2} did. The base steel plate was a cold rolled steel plate (SPCC) having a thickness of 1.6 mm.

(2) Preparation of organic resin coating Organic resin emulsion, polyethylene wax and cross-linking agent were added to water to prepare an organic resin coating with a non-volatile component of 20% by mass.

For the emulsion of organic resin, urethane resin emulsion and polypropylene resin emulsion were used. As the urethane resin emulsion, a commercially available polyurethane resin emulsion (Adekabon titer HUX-386: ADEKA Corporation, also simply referred to as “UE”) containing a polycarbonate unit was used. 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 Industry Co., Ltd.) was used. The addition amount of the polyethylene wax is 3.0 parts by mass with respect to 100 parts by mass of the total mass of the organic resin.

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

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

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

As the metal compound (B1), Si, Ti, Zr, V, and Mo oxides were used. As the Si oxide, SiO ₂ (Nissan Chemical Industry Co., Ltd., colloidal silica ST-N, also referred to as “B11”) was used. TiO ₂ (IV) (Kishida Chemical Co., Ltd., also referred to as “B12”) was used as the Ti oxide. 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. 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 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 citrate (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 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 coating The storage stability of the nine types of 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, “SH” is (thiol component), “Zr” is zirconium, “V” is vanadium, “Si” is silicon, “Ti” is titanium, “Mo” is molybdenum Are shown respectively. In addition, in the column of content of the rust preventive agent 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 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 paints 1 and 7 do not contain a rust preventive agent, they showed good storage stability. In addition, the storage stability of the organic resin paint 9 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 above metal plate was immersed in an alkaline degreasing aqueous solution (SD-270; Nippon Paint Co., Ltd.) having a liquid temperature of 40 ° C. and pH 12 for 1 minute to degrease the surface. Next, the organic resin paint 1 prepared in (2) above is applied to the surface of the degreased metal plate with a roll coater and dried with a hot air dryer so that the ultimate plate temperature becomes 150 ° C. 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 the organic resin paints 2 to 9 was used in place of the organic resin paint 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 coating original plates, the types of organic resin paints, and the adhesion amounts of the organic resin layers of the coated metal plates 1 to 10. 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”. Further, the corrosion resistance of the coated metal plates 2 to 10 was evaluated in the same manner except that each of the painted metal plates 2 to 12 was used instead of the painted metal plate 1. The results are shown in Table 3.

As shown in Table 3, each of the coated metal plates 1 to 9 exhibited corrosion resistance with no practical problem. Among these, the coated metal plates 5, 8 and 9 showed 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 metal compound rust inhibitor is Ti: 0.005 mass% or more, Zr: 0.05 mass% or more, Mo: It is thought that it was 0.005 mass% or more and V: 0.02 mass% or more.

On the other hand, the coated metal plates 1 to 4, 6 and 7 had no practical problem, but exhibited corrosion resistance lower than the corrosion resistance of the coated metal plates 5, 8 and 9. The reason is considered that the coated metal plates 1 to 4 contain only a part of the rust preventive components of metal compounds such as Ti, Zr, Mo and V. The coated metal plate 6 has a metal compound rust inhibitor content of Ti: less than 0.005 mass%, Zr: less than 0.05 mass%, Mo: less than 0.005 mass%, and V: 0.02 mass%. because there was less than%, considered, coated metal plate 7 is probably because amount of adhering the organic resin layer is less than 0.2 g / m ^2.

Furthermore, the corrosion resistance of the coated metal plate 10 was insufficient. This is probably because the organic resin layer is not formed.

2. Fabrication and evaluation of composite (1) Painted metal preform 1 to 10 Each of the painted metal sheets 1 to 10 is cut to have a width (W ₁₁ ) of 25 mm × length (L ₁₂ ) of 100 mm. 10 were prepared (see FIG. 1A and FIG. 1B). The thickness of each of the painted metal preforms 1 to 10 is 1.6 mm.

(2) To-be-joined body (2-1) Painted metal plate As a coated metal plate, the same metal plate as the coated metal plates 1 to 10 used in Example 1 was prepared, and the same as the above coated metal plates 1 to 10. It cut | disconnected and it was set as the to-be-joined bodies 1-10, respectively.

(2-2) Wood Piece As a piece of wood, a cypress material having a thickness of 9 mm was prepared and used as the joined body 11. Moreover, the organic resin coating material 4 prepared in Example 1 was brushed on the above wood pieces, and dried in a drying oven at 60 ° C. for 1 hour to form an organic resin layer.

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

(2-4) CFRP
As a CFRP, an epoxy resin-impregnated prepreg having a thickness of 0.2 mm (Torayca 3255S-25 manufactured by Toray Industries, Inc.) was prepared and used as the bonded body 14.

(2-5) CFRTP
As CFRTP, a polypropylene resin-impregnated prepreg (SA-3203PT1 manufactured by Sakai Obec Co., Ltd.) having a thickness of 2 mm was prepared and used as the bonded body 15.

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

(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, a polyamide (hereinafter also referred to as “PA”). ) Hot melt film, polyurethane elastomer (hereinafter also referred to as “PU-E”) hot melt film, and polypropylene (hereinafter also referred to as “PP”) hot melt film.

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

For the PE hot melt film, 200 μm thick Ecelan SHM244-PES (Seadam Co., Ltd.) was used. The melting point of the PE hot melt film was 120 ° C.

Elfan NT120 (Nihon Matai Co., Ltd.) having a thickness of 100 μm was used for the PA-based hot melt film. The melting point of the PA-based hot melt film was 120 ° C.

For the PU-E hot melt film, 200 μm thick Ecelan SHM605-CDR (Nippon Matai Co., Ltd.) was used. The melting point of the PU-E hot melt film was 190 ° C.

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

[Example 1]
A PU 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 one piece in the longitudinal direction of a painted metal plate 1 (25 mm × 100 mm) as a painted metal shape member 10. The coating metal plate 1 (25 mm × 100 mm) as the bonded body 20 was stacked and adhered so as to be in contact with the layers and sandwich the PU hot melt film (FIGS. 3A and 3B).

A sample in which the hot melt film 30 is sandwiched between the coated metal base material 10 and the two coated metal plates 1 as the joined bodies 20 is placed on a fixed plate 500 heated to 200 ° C., and heated to 200 ° C. from the top. A sample for tensile test was prepared by sandwiching with another plate 500 and applying pressure 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 painted metal shape material, the hot melt film, and the joined body were changed as shown in Table 4 below.

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

The case where the joining force is less than 10 MPa is “x”, the case where the joining force is 10 MPa or more and less than 15 MPa is “Δ”, the case where the joining force is 15 MPa or more and less than 20 MPa is “◯”, and the joining force is The 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 the composites according to Examples 1 to 15, all had good bonding strength of 10 MPa or more. This is presumably because the object to be joined was joined using a laminated body in which a hot melt film was laminated on a painted metal plate on which an organic resin layer was formed as a painted metal shape material.

Example 4 which joined the to-be-joined body 12 which is a piece of wood which has an organic resin layer evaluated the joining force higher than Example 2 which joined the to-be-joined body 11 which is a piece of wood which does not have an organic resin layer. Moreover, although the to-be-joined body 14 which is CFRP, or the to-be-joined body 15 which is CFRTP contains organic resin, the tendency for shear strength to become high was seen in Example 8 and 10 which joined these.

On the other hand, in the composites according to Comparative Examples 1 to 4, the bonding force 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.

This application claims priority based on Japanese Patent Application No. 2015-200500 filed on Oct. 9, 2015, and the contents described in the claims, specification and drawings of this application are Incorporated into the application.

The composite of the present invention is excellent in adhesion between the painted metal base material and the object to be joined. For example, in various electronic devices, household appliances, medical devices, automobile bodies, vehicle-mounted products, building materials, etc. Preferably used.

DESCRIPTION OF SYMBOLS 10 Painted metal shaped material 20, 40 To-be-joined body 30 Hot- melt film 100, 200, 300 Composite 102 Metal shaped material 104 Organic resin layer 402 Concave part 404 Brim part 500 Surface plate

Claims (15)

1. A metal metal material and a painted metal material comprising an organic resin layer formed on the surface of the metal material; and
   Hot melt film,
   To-be-joined,
   A complex having
   The said hot-melt film is the composite_body | complex which is welded to the said organic resin layer and the said to-be-joined body.
2. The composite according to claim 1, wherein the organic resin layer includes a polypropylene resin.
3. The composite according to claim 1, wherein the organic resin layer includes a polyurethane resin.
4. The composite according to any one of claims 1 to 3, wherein an adhesion amount of the organic resin layer is 0.2 g / m ² or more.
5. The composite according to any one of claims 1 to 4, wherein the hot-melt film has a melting point of 50 to 200 ° C.
6. The composite according to any one of claims 1 to 5, wherein the joined body includes a molded body of one or a plurality of materials selected from the group consisting of ferrous metals, non-ferrous metals, organic resins, and glass. body.
7. The composite according to any one of claims 1 to 6, wherein the organic resin layer contains a rust inhibitor.
8. A laminate having a metal base material and a painted metal base material including an organic resin layer formed on a 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, the step of arranging the object to be bonded so as to contact the hot melt film,
   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;
   The manufacturing method of the composite_body | complex containing.
9. Furthermore, the process of arrange | positioning the said hot-melt film so that the said organic resin layer of the said coating metal shape material may contact | connect, and forming the said laminated body is included before the said process to arrange | position. A method for producing the composite.
10. The said organic resin layer is a manufacturing method of the composite_body | complex of Claim 8 or 9 containing a polypropylene resin.
11. The method for producing a composite according to claim 8 or 9, wherein the organic resin layer contains a polyurethane resin.
12. The method for producing a composite according to any one of claims 8 to 11, wherein the adhesion amount of the organic resin layer is 0.2 g / m ² or more.
13. The method for producing a composite according to any one of claims 8 to 12, wherein the melting point of the hot melt film is 50 to 200 ° C.
14. The composite according to any one of claims 8 to 13, wherein the joined body includes a molded body of one or more materials selected from the group consisting of ferrous metals, non-ferrous metals, organic resins, and glass. Body manufacturing method.
15. The method for producing a composite according to any one of claims 8 to 14, wherein the organic resin layer contains a rust inhibitor.

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