JP7035699B2 - Method for manufacturing coated metal profiles, complexes and composites for injection molding adhesion - Google Patents

Description

The present invention relates to a coated metal element, a composite, and a method for manufacturing the composite.

The so-called "metal element", which is a metal plate or a press-molded product thereof, or a metal member formed by casting, forging, cutting, powder metallurgy, etc., is used in various industrial products such as automobiles. .. In addition, the composite in which the metal shape material and the molded body of the resin composition are joined is lighter than the parts made only of metal and has higher strength than the parts made only of resin, so that it is a mobile phone or a personal computer. It is used in various electronic devices such as computers. Conventionally, such a composite has been manufactured by fitting a metal molding material and a molded body of a resin composition. However, the method for manufacturing a complex by fitting has a large number of work steps and low productivity. Therefore, in recent years, it is common to join a metal profile material and a molded body of a resin composition by insert molding to produce a composite.

When a composite is manufactured by insert molding, it is important to improve the adhesion between the metal profile and the molded body of the resin composition. As a method for improving the adhesion between the metal shape material and the molded body of the resin composition, for example, it has been proposed to roughen the surface of the metal shape material before performing insert molding (patented). Refer to Documents 1 to 4). In the methods of Patent Documents 1 to 4, the surface of the aluminum alloy is roughened to form ultrafine irregularities, and the resin composition is allowed to penetrate into the formed ultrafine irregularities, whereby the aluminum alloy and the resin composition are prepared. The bondability with the molded body is improved.

An organic resin layer containing a polycarbonate unit-containing polyurethane resin such that the ratio of the mass of the polycarbonate unit to the total mass of the resin is 15 to 80% by mass is formed on the surface of the metal molding material, and the formed organic resin layer is used. It has been proposed to improve the adhesion between the metal shape material and the molded body of the resin composition (see Patent Document 5).

Japanese Unexamined Patent Publication No. 2006-027018 Japanese Unexamined Patent Publication No. 2004-054088 Japanese Unexamined Patent Publication No. 2005-342895 Japanese Unexamined Patent Publication No. 2013-24725 International Publication No. 2013/145712

The composites produced by the methods described in Patent Documents 1 to 4 have a problem that the adhesion and thermal impact resistance between the metal molding material and the molded product of the resin composition are not sufficient. Further, in the method for producing a complex described in Patent Documents 1 to 4, since the surface of the metal shape material is roughened, there is a problem that the production process becomes complicated and the production cost increases.

INDUSTRIAL APPLICABILITY The present invention has been made in view of these points, and is a coated metal element, a coated metal element and a thermoplastic resin composition having excellent adhesion to a molded body of the thermoplastic resin composition and heat and impact resistance. It is an object of the present invention to provide a composite to which the molded body of the above is bonded and a method for producing the same.

The present invention relates to the following coated metal element, composite and method for manufacturing the composite.
[1] The organic resin layer has a metal element and an organic resin layer formed on the surface of the metal element, and the organic resin layer contains a polyurethane resin containing a polyether unit, and is contained in the organic resin layer. A coated metal molding material in which the ratio of the mass of the polyether unit to the total mass of the resin is 5% by mass or more and 85% by mass or less, and the thickness of the organic resin layer is 0.5 μm or more.
[2] The coated metal element according to [1], wherein the polyether unit-containing polyurethane resin further contains a polyester unit or a polycarbonate unit.
[3] The organic resin layer contains a metal oxide, a hydroxide or a fluoride selected from the group consisting of Ti, Zr, V, Mo and W, or a combination thereof, [1] or [2]. ] Described in the coated metal element.
[4] A thermoplastic resin composition bonded to the coated metal element according to any one of [1] to [3] and the surface on which the organic resin layer of the coated metal element is formed. A composite having a molded body of an object.
[5] At the interface between the organic resin layer and the molded body, there is a compatible layer in which the polyurethane resin containing a polyether unit and the thermoplastic resin are incompatible, and the thickness of the compatible layer is 25 nm. The complex according to [4], which is 500 nm or less.
[6] The thermoplastic resin composition is an acrylic nitrile-butadiene-styrene resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, or a combination thereof. The complex according to [4] or [5].
[7] A method for producing a composite in which a coated metal molding material and a molded body of a thermoplastic resin composition are joined, wherein the step of preparing the coated metal molding material and the coated metal molding material are used. The step of inserting into an injection molding die and the thermoplastic resin composition being injected into the injection molding die to form a molded body of the thermoplastic resin composition bonded to the surface of the coated metal molding material. The coated metal element has a metal element and an organic resin layer formed on the surface of the metal element, and the organic resin layer contains a polyether unit. The ratio of the mass of the polyether unit to the total mass of the resin in the organic resin layer containing the polyurethane resin is 5% by mass or more and 85% by mass or less, and the thickness of the organic resin layer is 0.5 μm or more. , How to make a complex.

According to the present invention, a coated metal base material having excellent adhesion to a molded body of a thermoplastic resin composition and heat impact resistance, and a composite in which a painted metal base material and a molded body of a thermoplastic resin composition are joined. Can provide a body.

FIG. 1 shows the bonding surface between the organic resin layer and the molded body of the thermoplastic resin composition when the coated metal element according to the embodiment of the present invention and the molded body of the PPS-based resin are joined. This is an example of the analysis result obtained by elemental analysis of the including cross section with an electron microanalyzer (EPMA).

1. 1. Painted metal element shape material The coated metal element shape material according to the embodiment of the present invention has a metal element shape material and an organic resin layer formed on the surface of the metal element shape material. Further, in the coated metal shape material, a chemical conversion treatment film may be formed between the metal shape material and the organic resin layer. Hereinafter, each element of the coated metal shape material will be described.

(1) Metal element shape material A metal element shape material is a metal that has been given a shape by applying heat or force to it. The metal base material used as the coating base material 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 shape material is not particularly limited. Examples of metal profile materials include metal plates, stamped products of metal plates, metal members, and the like. Examples of the above metal plates include galvanized steel sheets, Zn-Al alloy plated steel sheets, Zn-Al-Mg alloy plated steel sheets, Zn-Al-Mg-Si alloy plated steel sheets, aluminum plated steel sheets, and stainless steel sheets (austenite-based, martenite). Includes site-based, ferrite-based, and ferrite-martensite two-phase systems), aluminum plates, aluminum alloy plates, copper plates, and the like. The metal plate may be a rolled steel plate such as a cold-rolled steel plate. Examples of the metal members include various metal members formed by casting, forging, cutting, powder metallurgy, etc., including aluminum die casting and zinc die casting. If necessary, the metal shape material may be subjected to known pre-painting treatment such as degreasing and pickling.

(2) Chemical conversion treatment film As described above, in the coated metal element shape material, a chemical conversion treatment film may be formed between the metal element shape 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-treated film may be formed on at least a region (bonding surface) of the surface of the metal element to be bonded to the object to be bonded, which will be described later, but from the viewpoint of facilitating film formation, the metal element is formed. It is preferably formed on the entire surface of the material.

The type of chemical conversion treatment for forming the chemical conversion treatment film is not particularly limited. Examples of chemical conversion treatments include chromate treatments, chromium-free treatments, and phosphate treatments. The amount of adhesion of the chemical conversion treatment film formed by the chemical conversion treatment is not particularly limited as long as it is within an effective range 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 Cr equivalent adhesion amount is 5 to 100 mg / m ² . In the case of a chromium-free film, the adhesion amount of the Ti-Mo composite film is 10 to 500 mg / m ² , and that of the fluoroacid film is 3 to 100 mg / m ² in terms of fluorine or total metal element. The amount of adhesion may be adjusted so as to be within the range. Further, in the case of a phosphate film, the adhesion amount may be adjusted so that the adhesion amount of the film is 0.1 to 5 g / m ² .

(3) Organic Resin Layer The organic resin layer is a layer containing a polyurethane resin containing a polyether unit, and improves the adhesion of the molded body of the thermoplastic resin composition to the metal profile material. As will be described later, the organic resin layer may further contain a resin containing no polyether unit as an optional component. The organic resin layer may uniformly cover the region of the surface of the metal base material on which the organic resin layer should be formed, or may be dispersed in the above region to cover the surface of the metal base material. The organic resin layer may be formed on the joint surface of the surface of the metal base material as in the case of the chemical conversion treatment film, but is usually formed on the entire surface of the metal base material (or the chemical conversion treatment film). There is.

The film thickness of the organic resin layer is not particularly limited as long as it is 0.5 μm or more. When the film thickness of the organic resin layer is 0.5 μm or more, the adhesion of the molded product of the thermoplastic resin composition to the metal profile can be sufficiently improved. The upper limit of the film thickness of the organic resin layer is not particularly limited, but is about 20 μm. Even if the film thickness of the organic resin layer exceeds 20 μm, further improvement in adhesion cannot be expected.

The polyether unit-containing polyurethane resin has a polyether unit in the molecular chain. The "polyester unit" refers to the structure shown below in the molecular chain of the polyurethane resin. The polyether unit, also called a soft segment, imparts flexibility and extensibility to the polyurethane resin. Further, since the polyether unit has high molecular mobility, when the thermoplastic resin composition is insert-molded into the coated metal profile material, the polyurethane resin containing the polyether unit is compatible with the thermoplastic resin. These are tightly coupled. Therefore, by including the polyurethane resin containing a polyether unit in the organic resin layer, the adhesion of the molded product of the thermoplastic resin composition to the organic resin layer can be improved.

The polyether unit-containing polyurethane resin can be prepared, for example, by the following steps. A urethane prepolymer is produced by reacting an organic polyisocyanate as a hard segment component, a polyether polyol as a soft segment component, and a polyol having a tertiary amino group or a carboxyl group. This urethane prepolymer can be used as it is as a polyurethane resin containing a polyether unit. From the viewpoint of improving the adhesion of the thermoplastic resin composition to the molded body and the compatibility of the organic resin layer with the thermoplastic resin, the urethane resin containing a polyether unit is a polyol other than the polyether polyol compound, for example, a polyester polyol. It is possible to use or a polycarbonate polyol in combination.

Further, 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 to produce a polyurethane resin containing a cationic polycarbonate unit. be able to.

In addition, the carboxyl group of the produced urethane prepolymer is neutralized with a basic compound such as triethylamine, trimethylamine, diethanolmonomethylamine, diethylethanolamine, caustic soda, and caustic potassium to convert it into a carboxylic acid salt, thereby being anionic. A polyurethane resin containing a polycarbonate unit can be produced.

The polyether polyol is a compound obtained by condensing various alcohols under an acid catalyst. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and other polyalkylene ether glycols. The polyether polyol may be chain-extended by an isocyanate compound. These polyether polyols may be used alone or in combination of two or more.

Polyester polyols include dicarboxylic acid compounds including isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, etc., and 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, and 1,6-hexanediol, etc. It can be a compound obtained by reacting with a diol compound containing. These polyester polyols may be used alone or in combination of two or more.

Polycarbonate polyols include carbonate compounds containing dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and the like, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, methylpentanediol, dimethylbutanediol and butylethylpropane. A compound obtained by reacting with a diol compound containing diol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,6-hexanediol and the like. be able to. The polycarbonate polyol may be chain-extended with an isocyanate compound. These polycarbonate polyols may be used alone or in combination of two or more.

The type of organic polyisocyanate is not particularly limited. Examples of organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-Diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenedi isocyanate, 3,3'-dichloro-4,4'-biphenylenediocyanate, 1,5-naphthalenedi isocyanate, 1,5-tetrahydro Naphthalenediocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexamethylene diisocyanate, 1,4-cyclohexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Includes hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. These organic polyisocyanates may be used alone or in combination of two or more.

The organic resin layer may further contain a resin containing no polyether unit as an optional component from the viewpoint of further improving the adhesion of the organic resin layer to the metal profile material. The type of the resin containing no polyether unit is not particularly limited as long as it does not contain the polyether unit in the molecular chain, but from the viewpoint of improving the adhesion of the organic resin layer to the metal profile material, a polar group may be used. Those containing are preferable. Examples of the type of resin containing no polyether unit include epoxy-based resin, acid-modified polyolefin-based resin, phenol-based resin and the like. 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 acid-modified olefin resin include an acid-modified polyethylene resin and an acid-modified polypropylene resin. Phenolic resins include novolak-type resins and resol-type resins.

The ratio of the mass of the polyether unit to the total mass of the resin is 5% by mass or more and 85% by mass or less. When the ratio of the mass of the polyether unit is 5% by mass or more, the organic resin layer and the thermoplastic resin are sufficiently compatible with each other, and the adhesion of the molded product of the thermoplastic resin composition to the organic resin layer is sufficient. Can be enhanced. On the other hand, when the ratio of the mass of the polyether unit is 75% by mass or less, by introducing a sufficient amount of hard segments into the polyurethane resin containing the polyether unit, the molded body of the thermoplastic resin composition adheres to the organic resin layer. The sex can be sufficiently enhanced. The ratio of the mass of the polyether unit to the total mass of the resin can be determined by nuclear magnetic resonance spectroscopy (NMR analysis) using a sample in which the organic resin layer is dissolved in chloroform. From the above viewpoint, the ratio of the mass of the polyether unit to the total mass of the resin is preferably 5% by mass or more and 85% by mass or less, more preferably 10% by mass or more and 75% by mass or less, and further preferably 15% by mass or more. It is particularly preferably 65% by mass or less, and particularly preferably 20% by mass or more and 65% by mass or less.

The organic resin layer may further contain additives as long as the effects of the present invention can be obtained. Examples of such additives include metal oxides, rust inhibitors, phosphorus compounds, lubricants, defoamers, etching agents, inorganic compounds, coloring materials and the like.

The rust inhibitor improves the corrosion resistance of the coated metal profile, and as a result, improves the corrosion resistance of the complex. The rust inhibitor may be one kind or more. Examples of rust preventives include metal compound-based rust inhibitors, non-metal compound-based rust inhibitors, and organic compound-based rust inhibitors. 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, depending on the type of the rust preventive agent.

Examples of the metal compound-based rust inhibitor include oxides, hydroxides or fluorides of metals (valve metals) selected from the group consisting of Ti, Zr, V, Mo and W. These metal compound-based rust preventives can further improve the corrosion resistance of the metal profile material. In particular, the fluorides of these valve metals can be expected to suppress corrosion in the film defect portion by the self-repairing action.

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

Examples of the non-metal compound-based rust preventive agent include a phosphoric acid compound such as diammonium hydrogen phosphate and a thiol compound such as thiourea.

Examples of the organic compound-based rust preventives include inhibitors and chelating agents. Examples of the inhibitor include carboxylic acids such as oleic acid, dimer acid and naphthenic acid, carboxylic acid metal soaps (lanolin Ca, Zn naphthenate, oxide wax Ca, Ba salt, etc.) and sulfonates (Na, Ca, Ba). Sulfonates), amine salts, and esters (such as glycerin esters of higher fatty acids, sorbitan monoisostearates, sorbitan monoolates, etc.). Examples of the chelating agent include EDTA (ethyrandiaminetetraacetic acid), gluconic acid, NTA (nitrilotriacetic acid), HEADA (hydroxyethyl, ethylenediaminetriacetic acid), DTPA (diethylenetriaminepentaacetic acid), and Na citrate. included.

The above-mentioned lubricant can suppress the generation of galling on the surface of the coated metal shape material. The type of lubricant may be one or more, and the type of lubricant is not particularly limited. Examples of lubricants 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 with respect to 100 parts by mass of the total amount of the organic resin and the other resins in the organic resin layer. If the amount of lubricant is less than 1 part by mass, it may not be possible to sufficiently suppress the occurrence of galling. 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 plateau, and the lubricity is too high and the handleability may be inferior.

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

The etching agent activates the surface of the metal shape material to improve the adhesion of the organic resin layer to the metal shape material. Examples of etching agents include fluorides such as hydrofluoric acid, ammonium fluoride, zircon hydrogen fluoride, titanium hydrogen fluoride.

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

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

The method for producing the coated metal element is not particularly limited. For example, the coated metal element can be produced by the following method.

First, a metal profile material to be used as a coating base material is prepared. When forming a chemical conversion treatment film, the chemical conversion treatment is performed before forming the organic resin layer. When the chemical conversion treatment film is not formed, the organic resin layer is formed as it is.

When a chemical conversion treatment film is formed on the surface of the metal element shape material, the chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid to the surface of the metal element shape material and drying it. The method for applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods. Examples of the coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping pulling method and the like. The drying conditions of 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 surface of the metal profile material coated with the chemical conversion treatment liquid is placed in a drying oven without washing with water and heated so that the reaching plate temperature is within the range of 80 to 250 ° C. A uniform chemical conversion treatment film can be formed.

The organic resin layer can be formed by applying a paint containing the above-mentioned polyether unit-containing polyurethane resin to the surface of a metal shaping material (or a chemical conversion treatment film) and baking it. The method for applying the paint is not particularly limited, and a known method may be appropriately selected. Examples of the coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping pulling method and the like. The baking conditions of the paint may be appropriately set according to the composition of the paint and the like. For example, a metal profile material coated with paint is placed in a drying oven and dried with a hot air dryer so that the reaching plate temperature is within the range of 110 to 200 ° C., whereby the metal profile material (or chemical conversion treatment) is applied. A uniform organic resin layer can be formed on the surface of the film).

As described above, the coated metal profile material according to the present embodiment can be easily manufactured only by applying and baking a paint containing a polyurethane resin containing a polyether unit.

2. 2. Composite The composite according to another embodiment of the present invention is a molding of a thermoplastic resin composition bonded to the above-mentioned coated metal element and the surface on which the organic resin layer of the above-mentioned coated metal element is formed. Has a body.

The molded body of the thermoplastic resin composition is bonded to the surface of the above-mentioned coated metal element (more accurately, the surface of the organic resin layer). The shape of the molded product of the thermoplastic resin composition is not particularly limited and may be appropriately selected depending on the intended use.

The type of the thermoplastic resin constituting the molded product of the thermoplastic resin composition is not particularly limited. Examples of thermoplastic resins include acrylic nitrile-butadiene-styrene (ABS) -based resins, polyethylene terephthalate (PET) -based resins, polybutylene terephthalate (PBT) -based resins, polycarbonate (PC) -based resins, and polyamide (PA) -based resins. , Polyphenylene terephide (PPS) based resins or combinations thereof. Among these, PET resin and PBT resin are particularly preferable. When the polyurethane resin containing a polyether unit is synthesized by using a polycarbonate polyol or the like in combination, a thermoplastic resin having a benzene ring is preferable, and a PBT-based resin and a PPS-based resin are particularly preferable.

The thermoplastic resin composition may contain an inorganic filler, a thermoplastic polymer, and the like from the viewpoint of lowering the molding shrinkage rate and increasing the material strength, mechanical strength, scratch resistance, and the like.

The inorganic filler improves the rigidity of the molded product of the thermoplastic resin composition. The type of the inorganic filler is not particularly limited, and known substances can be used. Examples of inorganic fillers include fiber-based fillers such as glass fiber, carbon fiber, and aramid resin, carbon black, calcium carbonate, calcium silicate, magnesium carbonate, silica, talc, glass, clay, lignin, mica, quartz powder, etc. And powder fillers such as glass spheres, as well as crushed carbon and aramid fibers. The blending amount of the inorganic filler is not particularly limited, but is preferably in the range of 5 to 50% by mass. The inorganic filler may be used alone or in combination of two or more.

The thermoplastic polymer improves the impact resistance of the molded product of the thermoplastic resin composition. The type of the thermoplastic polymer is not particularly limited, and may be a thermoplastic polymer having a benzene ring or a thermoplastic polymer having no benzene ring. Examples of the thermoplastic polymer having a benzene ring include acrylic nitrile-butadiene-styrene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, polyphenylene ether resin and the like. Further, examples of the thermoplastic polymer having no benzene ring include a polyolefin resin and the like. The thermoplastic polymer may be used alone or in combination of two or more.

On the joint surface between the organic resin layer and the molded body of the thermoplastic resin composition, an organic resin such as a polyether unit-containing polyurethane resin contained in the organic resin layer and the thermoplasticity constituting the molded body of the thermoplastic resin composition are formed. A compatible layer is formed in which the resin and the resin are compatible with each other. When the organic resin layer contains a polyether unit of 5% by mass or more and 85% by mass or less, the organic resin and the thermoplastic resin are compatible with each other to form a compatible layer having a sufficient thickness. The compatible layer can enhance the adhesion and thermal impact resistance between the organic resin layer and the molded product of the thermoplastic resin composition.

When the cross section of the composite including the joint surface between the organic resin layer and the molded body of the thermoplastic resin composition is elementally analyzed, the compatible layer changes from the atomic composition peculiar to the organic resin layer to the thermoplastic resin composition. It is a layer whose atomic composition changes to a unique atomic composition. The compatible layer has a composition closer to that of the organic resin layer as it approaches the organic resin layer, and has a composition closer to that of the thermoplastic resin composition as it approaches the molded product of the thermoplastic resin composition. Therefore, the compatible layer reduces the difference between the linear expansion rate of the organic resin layer and the linear expansion rate of the molded body of the thermoplastic resin composition, and alleviates the thermal fatigue applied to the interface due to repeated high and low temperatures. It is considered that the decrease in bonding force due to the above thermal fatigue can be suppressed.

On the other hand, when the metal element and the resin composition are directly bonded as in the composites described in Patent Documents 1 to 4, the difference in linear expansion rate between the metal and the resin is large, so that the temperature is increased. Due to thermal fatigue due to changes, the bonding force between the metal profile and the resin composition tends to decrease. On the other hand, it is also possible to add a filler to the resin composition to reduce the difference in the linear expansion rate. However, in the composites described in Patent Documents 1 to 4, the size of the ultrafine irregularities formed by roughening the surface of the aluminum alloy is as small as several hundred nm to several tens of μm, so that the ultrafine irregularities are between the ultrafine irregularities. It is difficult for the filler to penetrate, and it is difficult to sufficiently reduce the difference in the linear expansion rate. Therefore, in the complexes described in Patent Documents 1 to 4, voids are likely to be generated between the ultrafine irregularities and the resin composition when the temperature changes due to the difference in linear expansion rate, and the voids reduce the thermal shock resistance. It's easy to do.

The thickness of the compatible layer is 25 nm or more and 500 nm or less from the viewpoint of sufficiently enhancing the adhesion and thermal impact resistance between the organic resin layer and the molded product of the thermoplastic resin composition. When the thickness of the compatible layer is 25 nm or more, the molecular chains of the organic resin and the molecular chains of the thermoplastic resin are sufficiently entangled, the compatibility is sufficiently enhanced, and one of the molecular chains is not easily pulled out. Therefore, the adhesion between the organic resin layer and the molded body of the thermoplastic resin composition is enhanced, and the thermal impact resistance can be sufficiently enhanced by the above action. Although the upper limit of the thickness of the compatible layer is not particularly limited, it is preferably 500 nm or less because the thermal impact resistance is rather lowered if the thickness is too large. From the above viewpoint, the thickness of the compatible layer is preferably 50 nm or more and 450 nm or less, more preferably 40 nm or more and 400 nm or less, and particularly preferably 50 nm or more and 350 nm or less. The thickness of the compatible layer can be adjusted by the amount of the polyether unit contained in the organic resin layer, the bonding temperature at the time of bonding, and the like.

FIG. 1 shows the organic resin layer and thermoplasticity when a coated metal molding material containing a polyether unit having an organic resin layer of 5% by mass or more and 85% by mass or less and a PPS-based resin molded product are bonded to each other. This is an example of the analysis result obtained by elemental analysis of the cross section of the resin composition including the joint surface with the molded product by an electronic microanalyzer (EPMA). The left side of the figure is the organic resin layer, the right side is the molded body of the thermoplastic resin composition, and the bonding surface has an atomic composition (FIG. 1 shows the intensities obtained for wavelengths corresponding to N, C, and S). However, the compatible layer changes from the atomic composition peculiar to the organic resin layer (many N derived from urethane bonds) to the atomic composition peculiar to the thermoplastic resin composition (many S derived from PPS). It can be seen that is formed.

3. 3. Method for Producing Composite The method for producing a composite according to another embodiment of the present invention is the above-mentioned method for manufacturing a composite, which is 1) a first step of preparing a coated metal molding material and 2) a coated metal element. It has a second step of inserting a profile into an injection molding die and a third step of joining a molded body of a thermoplastic resin composition to the surface of a coated metal element.

Hereinafter, each step of this embodiment will be described.

(1) First step Prepare a coated metal shape material by the above procedure.

(2) Second step In the second step, the coated metal shape material prepared in the first step is inserted into the injection molding die. The coated metal shape material may be processed into a desired shape by press working or the like.

(3) Third Step In the third step, the high-temperature thermoplastic resin composition is injected at high pressure into the injection molding die into which the coated metal element is inserted in the second step. At this time, it is preferable to provide a gas vent in the injection molding die so that the thermoplastic resin composition can flow smoothly. The high-temperature thermoplastic resin composition comes into contact with the organic resin layer formed on the surface of the coated metal profile material, and the organic resin such as the polyether unit-containing polyurethane resin contained in the organic resin layer and the thermoplastic resin composition are formed. It is compatible with the constituent thermoplastic resin. Then, by cooling, the thermoplastic resin composition is molded into the shape of an injection molding die, and the molded body of the thermoplastic resin composition bonded to the surface of the coated metal element is molded. The temperature of the injection molding die is preferably near the melting point of the thermoplastic resin composition.

After the injection is completed, the mold is opened and released to obtain a complex. The composite obtained by injection molding may be annealed after molding to eliminate internal strain due to molding shrinkage.

By the above procedure, the complex of the present invention can be produced.

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

1. 1. Preparation of Painted Metal Plate (1) Metal Plate Prepare a molten Zn-6% by mass Al-3% by mass Mg alloy plated steel plate with a plating adhesion amount of 45 g / m ² per side as a coating base material for a painted metal element. did. As the base steel sheet, a cold rolled steel sheet (SPCC) having a thickness of 0.8 mm was used.

(2) Preparation of organic resin paint A polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., DK polyol 3776) was added as a soft segment component to a flask equipped with a gas introduction tube, a cooling tube, a thermometer and a stirrer, and the temperature was 90 ° C. After heating for 10 minutes in, it was kept at a temperature of 75 ° C. Next, an organic polyisocyanate (Mitsui Chemicals, Inc., Cosmonate PH (“Cosmonate” is a registered trademark of the same company)) and a catalyst are added to the flask, reacted at 90 ° C for 3 hours, and then cooled to 50 ° C. Urethane prepolymer was manufactured.

The obtained urethane prepolymer was diluted by dropping acetone, reacted at 60 ° C. for another 1 hour, and then triethylamine was added to neutralize the carboxyl group of the urethane prepolymer for 30 minutes.

Water was added dropwise to the neutralized urethane prepolymer solution for emulsification. A chain extender was added dropwise to this emulsified urethane prepolymer solution to carry out a chain extension reaction. After the reaction, acetone and water were removed by vacuum distillation using a rotary evaporator. An appropriate amount of water was added to adjust the solid content to obtain a polyurethane resin (polyurethane emulsion) containing a polyether unit. The ratio of the mass of the polyether unit to the polyurethane resin containing the polyether unit determined by nuclear magnetic resonance spectroscopy (NMR analysis) was 85% by mass.

Polyurethane resin containing a polyether unit and polyurethane resin not containing a polyether unit (Sanyo Kasei Kogyo Co., Ltd., U-Coat UWS-145) so that the ratio of the mass of the polyether unit to the total mass of the resin is the predetermined ratio shown in Table 1. And various additives were added to water to prepare a paint having a non-volatile component of 20% (see Table 1). The paint contains 0.5% by mass of ammonium fluoride (Morita Chemical Industries, Ltd.) as an etching agent, 2% by mass of collodyl silica (Nissan Chemical Industries, Ltd.) as an inorganic compound, and phosphoric acid (Kishida Chemical Industries, Ltd.). ) Was compounded in an amount of 0.5% by mass. Both were mixed to adjust the ratio of the mass of the polyether unit to the total mass of the resin.

(3) Formation of Organic Resin Layer The coated original plate was immersed in an alkaline degreasing aqueous solution (pH: 12) having a liquid temperature of 60 ° C. for 1 minute to degreas the surface. Next, the paint was applied to the surface of the degreased coating substrate with a roll coater, and dried with a hot air dryer so that the ultimate plate temperature reached 150 ° C. to obtain an organic resin layer having the film thickness shown in Table 1. The coated metal element shape material 1 to the coated metal element shape material 8 to be possessed were formed.

2. 2. Preparation of Composite (1) Painted Metal Element Shape Material No. of Painted Metal Element Shape Material of Example 1. 1 to 8 were prepared.

(2) Thermoplastic Resin Composition The thermoplastic resin composition shown in Table 2 was prepared. For each thermoplastic resin composition shown in Table 2, the acrylic nitrile-butadiene-styrene (ABS) -based resin composition used was Excelloy CK10G20 (no clear melting point was observed) manufactured by Techno Polymer Co., Ltd. As the polyethylene terephthalate (PET) -based resin composition, a free sample from a resin manufacturer (melting point 230 ° C.) was used. As the polybutylene terephthalate (PBT) -based resin composition, Novaduran 5710F40 (melting point 230 ° C.) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. As the polycarbonate (PC) -based resin composition, Europin GS-2030MR2 (melting point 250 ° C.) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. As the polyamide (PA) -based resin composition, Amylan CM3511G50 (melting point 216 ° C.) manufactured by Toray Industries, Inc. was used. As the polyphenylene sulfide (PPS) -based resin composition, 1130MF1 (melting point 280 ° C.) manufactured by Polyplastics Co., Ltd. was used. Each thermoplastic resin composition contains various fillers shown in Table 2 (the numerical values in parentheses indicate the blending amount of the fillers). The molding shrinkage rate indicates a value measured in the flow direction.

(3) Joining of Molded Body of Thermoplastic Resin Composition A coated metal molding material was inserted into an injection molding die, and the molten thermoplastic resin composition was injected into the injection molding die. The volume of the portion of the injection molding die into which the thermoplastic resin composition flows is 30 mm in width × 100 mm in length × 4 mm in thickness, and the coating film and the thermoplastic resin composition are formed in a region of 30 mm in width × 30 mm in length. Are in contact. After injecting the thermoplastic resin composition into the injection molding die, the thermoplastic resin composition was solidified to obtain a composite of a coated metal molding material and a molded body of the thermoplastic resin composition.

The combinations of the coated metal profile material and the thermoplastic resin composition were changed to prepare the complexes 1 to 21 shown in Table 3.

3. 3. Evaluation of the composite (1) Thickness of the compatible layer The thickness of the compatible layer was confirmed by elemental analysis of the obtained composite with an electron microanalyzer (EPMA). As a pretreatment, the cross section of the composite was processed by Ar milling, and then a thin section having a thickness of about 500 nm was produced by focused ion beam (FIB) processing, and the obtained cross section was vapor-deposited with audium. The EPMA analysis was performed using EPMA-8050G manufactured by Shimadzu Corporation at an acceleration voltage of 15 kV and an irradiation current of 100 nA. The atomic composition was confirmed by the line profile, and the thickness was calculated assuming that the portion where the atomic composition peculiar to the organic resin layer changes to the atomic composition peculiar to the thermoplastic resin composition is the compatible layer.

(2) Thermal impact resistance The thermal impact resistance was evaluated by a cold impact test. In the thermal shock test, the temperature of the complex is changed by alternately repeating the environment between the low temperature state and the high temperature state, and the stress caused by the difference in the expansion rate of the joints of different materials due to the expansion and contraction accompanying the temperature change. This is a method for evaluating peeling and the like. Here, 120 ° C x 1 hour and -40 ° C x 1 hour are set as one cycle, and a 90 ° peel test (peeling test) is performed before and after the cold shock test of 500 cycles to determine the thermal shock resistance of the complex as follows. evaluated.
⊚: Peel strength after the thermal impact test was 80% or more before the test ○: Peel strength after the thermal impact test was 50% or more and less than 80% before the test ×: After the thermal impact test Peel strength was less than 50% before the test

Table 3 shows the combination of the coated metal profile material used for producing the complexes 1 to 21 and the thermoplastic resin composition, and the measured thickness of the compatible layer and the results of thermal shock resistance.

As shown in Table 3, an organic resin containing a polyurethane resin containing a polyether unit, having a ratio of the mass of the polyether unit to the total mass of the resin of 5% by mass or more and 85% by mass or less and a film thickness of 0.5 μm or more. When a composite was prepared by joining a coated metal profile material having a layer and a thermoplastic resin composition, a compatible layer having a thickness of 25 nm or more and 500 nm or less was formed, and heat impact resistance was also enhanced. ..

Since the composite of the present invention has excellent adhesion and thermal shock resistance between the coated metal profile material and the object to be joined, for example, various electronic devices, household electrical appliances, medical devices, automobile bodies, vehicle-mounted products, etc. It is suitably used for building materials and the like. In particular, since the complex of the present invention has excellent thermal shock resistance, it is suitably used for electronic devices and the like where it is important to withstand the influence of the external environment and temperature fluctuations due to heat generated from the main body of the electronic device.

Claims (6)

Metal element and
It has an organic resin layer formed on the surface of the metal shape material, and has.
The organic resin layer contains a polyurethane resin containing a polyether unit and contains
The ratio of the mass of the polyether unit to the total mass of the resin in the organic resin layer is 5% by mass or more and 85% by mass or less.
The film thickness of the organic resin layer is 0.5 μm or more.
Painted metal element for injection molding adhesion . The coated metal element for injection molding bonding according to claim 1, wherein the polyether unit-containing polyurethane resin further includes a polyester unit or a polycarbonate unit. The injection according to claim 1 or 2, wherein the organic resin layer contains an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V, Mo and W, or a combination thereof. Painted metal element for molding and bonding . The coated metal element for injection molding bonding according to any one of claims 1 to 3 and
A molded body of a thermoplastic resin composition bonded by injection molding to the surface on which the organic resin layer of the coated metal element for injection molding adhesion was formed.
Has a complex. At the interface between the organic resin layer and the molded body, there is a compatible layer in which the polyurethane resin containing the polyether unit and the thermoplastic resin are compatible with each other.
The molded body is a molded body of a thermoplastic resin composition containing at least one thermoplastic resin selected from the group consisting of a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, and a polyphenylene sulfide resin. can be,
The thickness of the compatible layer is 25 nm or more and 500 nm or less.
The complex according to claim 4. It is a method for manufacturing a composite in which a coated metal element for injection molding adhesion and a molded body of a thermoplastic resin composition are joined.
The process of preparing a painted metal profile material for injection molding adhesion ,
The process of inserting the coated metal shape material into the injection molding die, and
A step of injecting a molten thermoplastic resin composition into the injection molding die to form a molded body of the thermoplastic resin composition bonded to the surface of the coated metal element for injection molding adhesion. , Has,
The coated metal element shape material for injection molding adhesion has a metal element shape material and an organic resin layer formed on the surface of the metal element shape material.
The organic resin layer contains a polyurethane resin containing a polyether unit and contains
The ratio of the mass of the polyether unit to the total mass of the resin in the organic resin layer is 5% by mass or more and 85% by mass or less.
The film thickness of the organic resin layer is 0.5 μm or more.
How to make a complex.

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