TW201627435A - Treatment liquid for shaped metallic materials - Google Patents

Abstract

This treatment liquid for shaped metallic materials includes a polyurethane resin containing a polycarbonate unit. The polycarbonate unit content proportion of the total mass of resin in the treatment liquid for shaped metallic materials is within the range of 5%-80% by mass.

Description

Metallic material processing liquid

The present invention relates to a treatment liquid for a metal material for forming a coating film for bonding a metal body material and a molded body of a thermoplastic resin composition on a surface of a metal material.

A metal plate or a press-formed product thereof, or a so-called "metal element" formed by casting, forging, cutting, powder metallurgy or the like is an indispensable member for manufacturing all industrial products including automobiles. The composite in which the metal element is bonded to the molded body of the resin composition is lighter than the metal-only part, and on the other hand, is stronger than the part containing only the resin. Therefore, the composite is used in electronic devices such as mobile phones or personal computers. Previously, such a composite was produced by fitting a metal material to a molded body of a resin composition. However, since the manufacturing method using the chimeric composite has a large number of work steps, productivity is low. Therefore, in recent years, a composite of a metal material and a molded body of a resin composition is generally joined by insert molding.

In the case where the composite is produced by insert molding, it is important to improve the adhesion between the metal material and the molded body of the resin composition. In the method of improving the adhesion between the metal element and the molded article of the resin composition, for example, it is proposed to roughen the surface of the metal element before insert molding (see Patent Documents 1 to 3). . In the methods described in Patent Document 1 to Patent Document 3, fine irregularities by chemical etching are provided on the surface of the aluminum alloy, and the bonding property between the aluminum alloy and the molded body of the resin composition is achieved by an anchor effect ( Adhesion) is improved. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. 2000-176.

[Problems to be solved by the invention]

In the method for producing a composite according to Patent Document 1 to Patent Document 3, the metal material is bonded to the molded body of the resin composition by the anchoring effect of the unevenness formed on the surface of the metal material. Therefore, when the metal element is slid by the processing after the roughening treatment or the like, the unevenness formed by the roughening treatment collapses, and the anchoring effect cannot be obtained. Further, since the size and depth of the concavities and convexities formed by the chemical etching are not uniform, when the molded body of the resin composition is joined, the molded article of the metal element and the resin composition is easily formed by thermal contraction of the resin composition. A fine gap is formed between them. Therefore, in the method for producing a composite according to Patent Document 1 to Patent Document 3, the bondability (adhesiveness) of the molded article of the metal element and the resin composition is insufficient.

An object of the present invention is to provide a coating liquid for a metal element which is formed on a surface of a metal material to form a coating film in which a metal body material and a molded body of a thermoplastic resin composition are joined together with excellent adhesion. [Means for solving the problem]

The inventors of the present invention have found that the above problems can be solved by using a polyurethane resin containing a polycarbonate unit in a predetermined ratio, and the present invention has been further studied.

That is, the present invention relates to the following treatment liquid for a metal element. [1] A treatment liquid for a metal element, which is a metal material for forming a coating film for joining the metal element and the molded body of the thermoplastic resin composition on the surface of the metal material. a treatment liquid comprising a polyurethane resin containing a polycarbonate unit, and the ratio of the polycarbonate unit to the total mass of the resin in the treatment liquid for the metal material is 5% by mass to 80% Within the range of mass %. [2] The treatment liquid for a metal element according to [1], which further contains an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V, Mo, and W Or a combination of these. [3] The treatment liquid for a metal element according to [1], wherein the treatment liquid for the metal element further contains an acrylic resin, an epoxy resin, a urethane. One or two or more kinds of resins not containing a polycarbonate unit, such as a resin, a polyolefin resin, a phenol resin, a polyester resin, a copolymer of these, and a modified product thereof . [4] The treatment liquid for a metal element according to any one of [1], wherein the thermoplastic resin composition is an acrylonitrile-butadiene-styrene resin or a polyparaphenylene An ethylene dicarboxylate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, or a combination thereof. [Effects of the Invention]

According to the invention, the metal body material and the molded body of the thermoplastic resin composition can be joined by excellent adhesion.

1. Treatment liquid for metal element material The treatment liquid for metal element material (hereinafter also referred to simply as "treatment liquid") of the present invention can be used to form a metal element and a thermoplastic resin composition on the surface of the metal element. The molded body is bonded to the coating film with excellent adhesion. As described later, the coated metalloid material produced by using the treatment liquid of the present invention can be joined to the molded body of the thermoplastic resin composition with excellent bonding strength.

The treatment liquid of the present invention contains a predetermined amount of a polycarbonate unit-containing polyurethane resin (hereinafter referred to as "polycarbonate resin-containing resin") as an essential component. Further, the treatment liquid of the present invention may further contain a resin not containing a polycarbonate unit as an optional component. Further, the treatment liquid of the present invention may contain a solvent, a rust preventive, an etchant, an inorganic compound, a lubricant, a stabilizer, a coloring pigment, a dye, and an antifoaming agent, which will be described later, as needed. Hereinafter, each component will be described.

(Polyurethane resin containing polycarbonate unit) The polyurethane resin containing a polycarbonate unit has a polycarbonate unit in a molecular chain. Here, the "polycarbonate unit" means a structure as described below in the molecular chain of the polyurethane resin. The polycarbonate resin containing a polycarbonate unit and the thermoplastic resin contained in the molded body of the thermoplastic resin composition described later have a similar skeleton (for example, a benzene ring) and a functional group. Therefore, in the case of thermocompression bonding a thermoplastic resin composition to a coated metal material, the polycarbonate unit-containing polyurethane resin is compatible with the thermoplastic resin composition and firmly bonded. Therefore, by including a polyurethane resin containing a polycarbonate unit in advance in the coating film, the adhesion of the molded body of the thermoplastic resin composition to the coating film can be improved.

[Chemical 1]

The polyurethane resin containing a polycarbonate unit can be produced, for example, by the following procedure. The organic polyisocyanate, the polycarbonate polyol, and a polyol having a tertiary amino group or a carboxyl group are reacted to form a urethane prepolymer. Further, a polyol other than the polycarbonate polyol compound, for example, a polyester polyol or a polyether polyol, may be used in combination within the range not impairing the object of the present invention.

Further, the tertiary amine group of the resulting urethane prepolymer is neutralized by an acid, or after quaternization by a quaternary ammonizing agent, chain elongation by water Thereby, a cationic polyurethane resin-containing polyurethane resin can be produced.

Further, the carboxyl group of the resulting urethane prepolymer is neutralized by a basic compound such as triethylamine or trimethylamine, diethanol monomethylamine, diethylethanolamine, caustic soda or caustic potash to be converted into A salt of a carboxylic acid can thereby form an anionic polycarbonate resin containing a polycarbonate unit.

The polycarbonate polyol can be obtained by using a carbonate compound such as dimethyl carbonate or diethyl carbonate, ethyl carbonate, or propyl carbonate, with ethylene glycol or diethylene glycol, propylene glycol, dipropylene glycol, and neopentyl Alcohol, methyl pentanediol, dimethyl butanediol, butyl ethyl propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,4-cyclohexane It is obtained by reacting a diol compound such as a diol or 1,6-hexanediol. The polycarbonate polyol may also be chain extended by an isocyanate compound.

The type of the organic polyisocyanate is not particularly limited. Examples of the organic polyisocyanate include: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophthalic diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dichloro-4,4' -biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, Trimethylhexamethylene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, phthaldimethyl diisocyanate, tetramethyl dimethyl diisocyanate, hydrogenated benzyl Diisocyanate, quaternary acid diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate. These organic polyisocyanates may be used singly or in combination of two or more.

The treatment liquid contains a polycarbonate unit-containing polyurethane resin so that the ratio of the polycarbonate unit to the total mass of the resin in the treatment liquid is in the range of 5 mass% to 80 mass%. When the ratio of the polycarbonate unit is less than 5% by mass, there is a problem that the molded body of the thermoplastic resin composition cannot sufficiently obtain the adhesion to the coating film. On the other hand, when the ratio of the polycarbonate unit exceeds 80% by mass, the adhesion of the coating film to the metal material may not be sufficiently obtained. The ratio of the polycarbonate unit to the total mass of the resin can be determined by a nuclear magnetic resonance spectroscopy (NMR analysis) using a sample obtained by dissolving a coating film in chloroform. Here, the "mass total mass" means the total mass of a polycarbonate-containing polyurethane and a resin which does not contain a polycarbonate unit to be described later.

(Polyurethane resin not containing a polycarbonate unit) As described above, the treatment liquid may further contain a resin not containing a polycarbonate unit as an optional component. The resin which does not contain a polycarbonate unit further improves the adhesiveness of a coating film to a metal-form material. The type of the resin which does not contain a polycarbonate unit is not particularly limited as long as it does not contain a polycarbonate unit in the molecular chain, but from the viewpoint of further improving the adhesion of the coating film to the metal element, It is better to have a polar base. Examples of the type of the resin not containing the polycarbonate unit include an epoxy resin, a polyolefin resin, a phenol resin, an acrylic resin, a polyester resin, and an urethane system not containing a polycarbonate unit. Resin. These resins may be used singly or in combination of two or more.

Examples of the type of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin. Examples of the type of the polyolefin resin include a polyethylene resin and a polypropylene resin. Examples of the kind of the phenol resin include a novolak type resin and a resol type resin. A polyurethane resin which does not contain a polycarbonate unit can be obtained by copolymerizing a diol with a diisocyanate. Examples of the kind of the diol include bisphenol A, 1,6-hexanediol, and 1,5-pentanediol other than the polycarbonate diol. Examples of the kind of isocyanate include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate.

(Other components) As described above, the treatment liquid of the present invention may contain a solvent, a rust preventive or an etchant, an inorganic compound, a lubricant, a coloring pigment, a dye, a stabilizer, an antifoaming agent, and the like.

The solvent is a liquid which is obtained by uniformly dissolving or dispersing various components in the treatment liquid and evaporating in the formation step of the coating film. The type of the solvent is not particularly limited, but it is preferred that the solvent be water. At this time, the treatment liquid is an aqueous emulsion.

The rust preventive agent improves the corrosion resistance of the coated metal sheet. The type of the rust inhibitor is not particularly limited. Examples of the kind of the rust inhibitor include oxides, hydroxides or fluorides of metals (valve metals) selected from the group consisting of Ti, Zr, V, Mo, and W, or the like combination. By dispersing the metal compounds in the coating film, the corrosion resistance of the coated metalloid material can be further improved. In particular, it is also expected that the fluoride of the metal suppresses corrosion of the defective portion of the coating film by self-repairing action.

From the viewpoint of corrosion resistance, the amount of the rust inhibitor in the treatment liquid is preferably Ti: 0.005 mass% or more, Zr: 0.05 mass% or more, V: 0.02 mass% or more, and Mo: 0.005 mass% or more. Further, from the viewpoint of storage stability of the treatment liquid, the amount of the rust inhibitor in the treatment liquid is preferably Ti: less than 0.6% by mass, Zr: less than 12.0% by mass, Mo: less than 3.0% by mass, and V: insufficient 3.0% by mass.

The treatment liquid of the present invention may further contain a soluble metal phosphate or a complex phosphate or a poorly soluble metal phosphate or complex phosphate. The soluble metal phosphate or complex phosphate complements the self-healing action of the fluoride of the metal, thereby further improving the corrosion resistance of the metal form. Further, the poorly soluble metal phosphate or composite phosphate is dispersed in the coating film to increase the strength of the coating film. For example, a soluble metal phosphate or a complex phosphate, or a poorly soluble metal phosphate or complex phosphate is a salt of Al or Ti, Zr, Hf, Zn or the like.

The etchant improves the adhesion of the coating film to the metal sheet by activating the surface of the metal sheet. Examples of the type of the etchant include fluorides such as hydrofluoric acid, ammonium fluoride, zirconic hydrogen fluoride, and titanium hydrogen fluoride.

The inorganic compound densifies the coating film to improve water resistance. Examples of the inorganic compound include inorganic oxide sols such as cerium oxide, aluminum oxide, and zirconium oxide; phosphates such as sodium phosphate, calcium phosphate, manganese phosphate, and magnesium phosphate.

The lubricant suppresses the occurrence of scratches on the surface of the coated metallized material. The type of the lubricant is not particularly limited. Examples of the type of the lubricant include organic waxes such as fluorine-based or polyethylene-based, polystyrene-based, and polypropylene-based; and inorganic lubricants such as molybdenum disulfide or talc.

Further, a predetermined color tone can be imparted to the coating film by blending an inorganic pigment, an organic pigment, an organic dye, or the like.

The antifoaming agent is difficult to generate bubbles at the time of preparation of the treatment liquid. The type of the antifoaming agent is not particularly limited, and for example, an appropriate amount of a known antifoaming agent such as an anthrone may be added.

(Method for Producing Treatment Liquid for Metallic Material) The method for producing the treatment liquid of the present invention is not particularly limited. For example, a polyurethane resin containing a polycarbonate unit and a resin not containing a polycarbonate unit may be added to water and diluted to a desired concentration. Further, other components (for example, rust inhibitors, lubricants, stabilizers, and antifoaming agents) may be added as needed. As described above, the amount of each component added is adjusted so that the ratio of the polycarbonate unit to the total mass of the resin in the treatment liquid of the present invention is in the range of 5 mass% to 80 mass%.

2. Method for Producing Coated Metallic Material The treatment liquid of the present invention can be used to produce a coated metallic material having a coating film formed thereon, which can be joined to a molded body of a thermoplastic resin composition with excellent adhesion. For example, the coated metal form can be produced by the following sequence.

First, a metal form is prepared as a coated original plate. The metallization material may also be subjected to a known coating pretreatment such as degreasing, pickling, and roughening treatment as needed. Alternatively, a metal form having been subjected to coating pretreatment may be prepared.

The type of the metal element is not particularly limited. Examples of the metal material include cold rolled steel sheets, zinc plated steel sheets, Zn-Al alloy plated steel sheets, Zn-Al-Mg alloy plated steel sheets, aluminum plated steel sheets, and stainless steel sheets (including austenite). Department, martensite (martensite), ferrite iron (ferrite), fat iron-matian bulk two-phase system), aluminum plate, aluminum alloy plate, copper plate and other metal plates or their pressed products, or aluminum die casting (die cast ), casting/forging such as zinc die casting, or various metal members formed by cutting, powder metallurgy, or the like.

Further, from the viewpoint of improving the adhesion between the metal material and the coating film and the corrosion resistance of the coated metal material, a chemical conversion treatment film may be formed on the surface of the metal material. The chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid to the surface of the metal element and drying it. The coating method of the chemical conversion treatment liquid is not particularly limited, and can be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method, and the like. The drying conditions of the chemical conversion treatment liquid can be appropriately set depending on the composition of the chemical conversion treatment liquid and the like. For example, the metal element coated with the chemical conversion treatment liquid may be introduced into the drying oven without being washed with water, and heated so that the sheet temperature becomes 50° C. to 250° C., whereby the metal element can be heated. The surface of the profile forms a uniform chemical conversion treatment film.

The type of the chemical conversion treatment for forming the chemical conversion treatment film is not particularly limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, phosphate treatment, and the like. The amount of the chemical conversion treatment film formed by the chemical conversion treatment is not particularly limited as long as it is effective in improving the adhesion between the coating film and the corrosion resistance. For example, in the case of a chromate film, the adhesion amount can be adjusted so that the amount of adhesion in all Cr conversion amounts is 5 mg/m ² to 100 mg/m ² . Moreover, in the case of a chrome-free film, it is 10 mg/m ² to 500 mg/m ² in the Ti-Mo composite film, and in the fluoro acid film, the amount of adhesion or total metal can be converted in terms of fluorine. The adhesion amount is adjusted so that the amount of the element conversion is in the range of 3 mg/m ² to 100 mg/m ² . Further, in the case of a phosphate film, the amount of adhesion can be adjusted so as to be 0.1 g/m ² to 5 g/m ² .

Next, the treatment liquid of the present invention is applied to a metal material and dried to form a coating film. At this time, the coating film may be formed on a surface of the surface of the metal element which is bonded to at least the molded body of the thermoplastic resin composition. The coating film may be formed only on one side of the metal sheet, or the coating film may be formed on both sides.

The coating film is disposed on the surface of the metal material (or the chemical conversion coating film) to improve the adhesion between the metal material and the molded body of the thermoplastic resin composition. The coating film formed using the treatment liquid of the present invention contains a polycarbonate unit-containing polyurethane resin so that the ratio of the polycarbonate unit to the total mass of the resin is in the range of 5 mass% to 80 mass%. .

The coating method of the treatment liquid is not particularly limited, and can be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping and pulling method, and the like.

The coating amount of the treatment liquid can be appropriately adjusted depending on the film thickness of the formed coating film. The film thickness of the coating film is not particularly limited, but is preferably 0.2 μm or more. When the film thickness of the coating film is less than 0.2 μm, it becomes difficult to uniformly cover the surface of the metal element. Therefore, when the film thickness is less than 0.2 μm, a fine gap is formed between the metal material and the molded body of the thermoplastic resin composition, and the bonding force between the metal element and the molded body of the thermoplastic resin composition is applied. Reduce the embarrassment. Further, when fine voids are formed, the sealing property in the composite is lowered. On the other hand, the upper limit of the film thickness of the coating film is not particularly limited, but the film thickness is preferably 20 μm or less. Even if the film thickness exceeds 20 μm, no significant performance improvement is found, and it is disadvantageous in terms of both manufacturing and cost.

The method of drying the treatment liquid is not particularly limited as long as it can volatilize the solvent (water) in the treatment liquid, and can be appropriately set depending on the composition of the treatment liquid and the like. For example, the metal material coated with the treatment liquid may be washed into a drying oven without being washed with water. The drying temperature is not particularly limited, and it is preferred that the sheet temperature reached during drying is 250 ° C or lower. By setting the obtained sheet temperature to 250 ° C or lower, a coating film which is in close contact with each other can be formed on the surface of the metal element (or the chemical conversion treatment film). Further, the drying time is also not particularly limited. When the drying temperature is low, by making the drying time longer, a coating film which is in close contact with each other can be formed on the surface of the metal element (or the chemical conversion treatment film). On the other hand, when the drying temperature is high, the drying time is shortened by using a drying oven or the like, and a coating film which is in close contact with each other can be formed on the surface of the metal element (or chemical conversion coating film).

As described above, the coated metal sheet having the coating film formed thereon can be produced by using the treatment liquid of the present invention, and the coating film can have excellent adhesion to the molded body of the metal material and the thermoplastic resin composition. Engage.

3. Method for Producing Composite The composite can be produced by contacting a heated thermoplastic resin composition with a surface of a coated metal sheet produced by using the treatment liquid of the present invention, in the form of a coated metal form. The surface of the material is bonded to a molded body of a thermoplastic resin composition. The coated metal form may be processed into a desired shape by press working or the like. A molded body of a thermoplastic resin composition may be formed only on one side of the metal element, or a molded body of a thermoplastic resin composition may be formed on both surfaces.

Specifically, after the coated metallic material is inserted into the inside of the injection molding die, the molten thermoplastic resin composition can be injected under high pressure into the inside of the injection molding die. At this time, it is preferable to provide degassing in the injection molding die to smoothly flow the thermoplastic resin composition. The molten thermoplastic resin composition is compatible with the coating film formed on the surface of the coated metal sheet. At this time, the temperature of the injection molding die is preferably near the melting point of the thermoplastic resin composition. Further, the composite obtained by injection molding may be annealed after molding to eliminate internal strain due to molding shrinkage.

Further, other examples of the method of producing the composite include a thermocompression bonding method, a laser welding method, and the like. The thermocompression bonding method can be carried out by heating the coated metallocene material to a temperature equal to or higher than the melting point of the bonded thermoplastic resin composition, and press-welding the thermoplastic resin composition. The laser welding method can be carried out by superposing a coated metal element and a thermoplastic resin composition, and thermally bonding the interface between the coated metal element and the thermoplastic resin composition by the heat of the laser.

The type of the thermoplastic resin constituting the molded body is not particularly limited. Examples of the type of the thermoplastic resin include an Acrylonitrile-butadiene-styrene (ABS) resin, a polyethylene terephthalate (PET) resin, and a polyterephthalic acid. a polybutylene terephthalate (PBT) resin, a polycarbonate (PC) resin, a polyamide (PA) resin, a polyphenylene sulfide (PPS) resin, and the like The combination. Among these, a thermoplastic resin having a benzene ring which also contains a polycarbonate unit is preferable, and a PBT resin or a PPS resin is particularly preferable. Further, the shape of the molded body of the thermoplastic resin composition is not particularly limited, and can be appropriately selected depending on the use. The shape of the molded body of the thermoplastic resin composition is not particularly limited, and can be appropriately selected depending on the use.

The PBT-based resin can be obtained, for example, by condensing 1,4-butanediol with terephthalic acid, and has the following structure.

[Chemical 2]

The PPS-based resin can be obtained, for example, by condensing p-dichlorobenzene with sodium sulfide in a guanamine-based solvent, and has the following structure.

[Chemical 3]

The thermoplastic resin composition may contain an inorganic filler, a thermoplastic polymer or the like from the viewpoints of mold shrinkage, material strength, mechanical strength, and scratch resistance. Particularly in the case of using a thermoplastic resin which does not have a benzene ring, it is preferred to formulate a thermoplastic polymer having a benzene ring.

The inorganic filler can increase the rigidity of the molded body of the thermoplastic resin composition. The type of the inorganic filler is not particularly limited and can be selected from known substances. Examples of the type of the inorganic filler include fiber-based fillers such as glass fiber, carbon fiber, and aromatic polyamide resin; carbon black, calcium carbonate, calcium silicate, magnesium carbonate, cerium oxide, talc, glass, clay, lignin, mica Powder filler such as quartz powder or glass ball; pulverized material of carbon fiber or aromatic polyamide fiber. The inorganic fillers may be used singly or in combination of two or more.

The thermoplastic polymer improves the impact resistance of the molded body of the thermoplastic resin composition. The type of the thermoplastic polymer is not particularly limited. Examples of the thermoplastic polymer having a benzene ring include an acrylonitrile-butadiene-styrene resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polycarbonate resin, Polystyrene resin or polyphenylene ether resin. Moreover, examples of the thermoplastic polymer having no benzene ring include polyolefin-based resins. The thermoplastic polymer may be used singly or in combination of two or more.

By the above procedure, a composite in which a molded body of a coated metal element and a thermoplastic resin composition is joined with excellent adhesion can be produced.

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

[Experiment 1] 1. Preparation of a treatment liquid for a metal element material A polyurethane resin containing a polycarbonate (PC) unit, a resin not containing a polycarbonate unit, and a rust preventive agent are added to water. 18 treatment liquids having a nonvolatile content of 20% were prepared. In addition, when a plurality of resins which do not contain a PC unit are used, the content of the resin which does not contain a PC unit becomes the same.

(Polyurethane-containing Polyurethane Resin) As a polycarbonate (PC)-containing polyurethane resin, a PC containing 50% by mass, 70% by mass, 80% by mass, and 90% by mass is used. The unit, or PC unit, is 100% by mass of five resins.

As a PC unit-containing polyurethane resin containing 50% by mass of a PC unit, SF-420 (First Industrial Pharmaceutical Co., Ltd.) was used.

As a PC unit-containing polyurethane resin containing 70% by mass of a PC unit, SF-470 (First Industrial Pharmaceutical Co., Ltd.) was used.

As a PC unit-containing polyurethane resin containing 80% by mass of a PC unit, HUX-386 (ADEKA Co., Ltd.) was used.

As a resin containing a PC unit containing 90% by mass of a PC unit, a resin prepared as a prototype by a resin manufacturer was used.

A 100% by mass PC-containing polyurethane resin was prepared by the following procedure. First, a PC board (Takiron Co., Ltd.) having a thickness of 2.0 mm was cut into about 5 mm × 5 mm to obtain a PC sheet. Next, a PC sheet of 30 g was placed in 200 g of methylene chloride, and while stirring at a liquid temperature of 40 ° C, the PC sheet was dissolved for 3 hours.

(Resin which does not contain a polycarbonate unit) As a resin which does not contain a polycarbonate unit, a polyurethane resin, an epoxy resin, a polyolefin resin, and a phenol resin which do not contain a polycarbonate unit are used. These four resins.

As the polyurethane resin not containing a polycarbonate unit, HUX-232 (ADEKA Co., Ltd.) or SF-170 (First Industrial Pharmaceutical Co., Ltd.) was used.

As the epoxy resin, Adeka Resin EM-0461N (ADEKA Co., Ltd.) or Super Ester E650 (Arakawa Chemical Industries Co., Ltd.) was used.

As the polyolefin-based resin, HARDLEN NZ-1005 (Toyobo Co., Ltd.) or MGP1650 (Maruhide Chemical Co., Ltd.) is used.

As the phenol resin, TAMANOL E-100 (Arakawa Chemical Industries Co., Ltd.) or IG-1002 (Di Ai Sheng (DIC) Co., Ltd.) was used.

(Anti-rust agent) As a rust preventive agent, a Ti compound, a Zr compound, a V compound, a Mo compound, a P compound, or a combination thereof is added. (Ni ₄ ) ₂ TiF ₆ (Mori Chemical Industry Co., Ltd.) is used for the Ti compound, (NH ₄ ) ₂ ZrO(CO ₃ ) ₂ (First Dilute Element Chemical Industry Co., Ltd.) is used for the Zr compound, and V compound is used for the V compound. ₂ O ₅ (Solar Steel Co., Ltd.), Mo compound used (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O (Kishida Chemical Co., Ltd.), P compound used (NH ₄ ) ₂ HPO ₄ (Kishida Chemical Co., Ltd.) Limited).

In the coating film, (NH ₄ ) ₂ TiF ₆ exists in the state of TiF ₄ , (NH ₄ ) ₂ ZrO(CO ₃ ) ₂ exists in the state of ZrO ₂ , and V ₂ O ₅ exists in the state of V ₂ O ₅ . On the other hand, (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O exists in the state of MoO ₃ or Mo ₇ O ₂₁ .

2. Investigation of storage stability of the treatment liquid The 18 treatment liquids prepared were placed in a closed container and stored in a thermostat at 40 ° C to evaluate the storage stability. The case where the stability was 30 days or more was evaluated as "○", and the case where the thickening or solidification was less than 30 days was evaluated as "x".

The treatment liquid No., the type of the (polyurethane) resin containing the PC unit, the ratio of the PC unit to the total mass of the resin, the type of the resin not containing the PC unit, and the rust preventive agent. The evaluation results of the types, contents, and storage stability are shown in Table 1-1 and Table 1-2.

[Table 1] Table 1-1 Table 1-2 Polyurethane resin A containing PC unit: Polyurethane resin containing 50% by mass of PC unit (SF-420) B: Polyurethane containing 70% by mass of PC unit Resin (SF-470) C: Polyurethane resin (HUX-386) containing 80% by mass of PC unit D: Polyurethane resin E: PC unit containing 90% by mass of PC unit 100% by mass of resin · Resin not containing PC unit a: Polyurethane resin (HUX-232) not containing PC unit b: Polyurethane resin (SF-170) not containing PC unit c: epoxy resin (Adeka Resin EM-0461N) d: epoxy resin (Super Ester E650) e: polyolefin resin (HARDLEN NZ-1005) f: polyolefin resin (MGP1650) g: phenol resin (TAMANOL E-100) h: phenolic resin (IG-1002)

As shown in Table 1-2, the treatment liquid of No. 11 had too much content of Zr, so the storage stability was poor. Since the treatment liquid of No. 12 has too much content of Mo, storage stability is inferior. Since the treatment liquid of No. 13 has too much Ti content, storage stability is inferior. Since the treatment liquid of No. 14 has too much content of V, storage stability is inferior.

On the other hand, as shown in Table 1-1 and Table 1-2, the treatment liquids of No. 1 to No. 10 and No. 15 to No. 18 are stored in the desired range because of the content of the rust inhibitor. Excellent stability.

[Experiment 2] 1. Preparation of coated metallized material (1) Preparation of metallic material A stainless steel plate, a molten Zn-Al-Mg alloy plated steel plate, a molten Al-plated steel plate, and a molten metal plate were prepared as a metal material. Five kinds of substrates, such as a molten Zn-plated steel sheet and an electrically-conductive Zn-plated steel sheet. Regarding each of the plated steel sheets, the base steel sheet is a steel plate cold rolled commercial (SPCC) having a thickness of 0.8 mm.

As a stainless steel plate, a steel plate containing SUS430 processed by No. 4 was prepared.

As the molten Zn-Al-Mg alloy plated steel sheet, a molten Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet having a plating adhesion amount of 45 g/m ² per one surface was prepared.

As the molten Al-plated steel sheet, a molten Al-9 mass% Si alloy plated steel sheet having a plating adhesion amount of 45 g/m ² per one surface was prepared.

As the molten Zn-plated steel sheet, a molten Zn alloy-plated steel sheet having a plating adhesion amount of 45 g/m ² per one surface was prepared.

As the electrically conductive Zn-plated steel sheet, an electric Zn-plated steel sheet having a plating adhesion amount of 20 g/m ² per one surface was prepared.

(2) Formation of coating film The coated substrate was immersed in an alkali degreasing aqueous solution (SD-270; Nippon Paint Co., Ltd., pH = 12) having a liquid temperature of 40 ° C for 1 minute to carry out degreasing. Next, any treatment liquid of No. 1 to No. 18 prepared in Experiment 1 was applied onto the surface of the degreased coated substrate by a roll coater, and dried by a hot air dryer. A coating film was formed in such a manner that the sheet temperature reached 150 °C.

2. Evaluation of the coated metallized material The composite of the molded metal body of the thermoplastic resin composition was prepared for each of the coated metal materials, and the bonding force with the molded body of the thermoplastic resin composition was carried out using the composite. the study.

As the thermoplastic resin composition, an acrylonitrile-butadiene-styrene (ABS) resin composition, a polyethylene terephthalate (PET) resin composition, and polybutylene terephthalate (PBT) are used. A resin composition, a polycarbonate (PC) resin composition, a polyamide (PA) resin composition, and a polyphenylene sulfide (PPS) resin composition.

As the ABS resin composition, EXCELLOY CK-10G20 (Techno Polymer Co., Ltd.) containing 20% by mass of glass fiber was used.

As a PET-based resin composition, Rynite 935 (DuPont Co., Ltd.) having a molding shrinkage ratio of 0.4 and containing 35 mass% of glass fibers was used.

As a PBT-based resin composition, NOVADURAN 5710F40 (Mitsubishi Engineering Plastics Co., Ltd.) containing 40% by mass of glass fibers was used.

As a PC-based resin composition, Iupilon GSH2030FT (Mitsubishi Engineering Plastic Co., Ltd.) containing 30% by mass of glass fibers was used.

As a PA-based resin composition, AMILAN CM3511G50 (Toray Industries, Inc.) containing 50% by mass of glass fibers was used.

As a PPS resin composition, Fortron 1140T11 (Polyplastics Co., Ltd.) containing 40% by mass of glass fibers was used.

FIG. 1 is a schematic view showing a configuration of a composite for measuring a joint strength. As shown in Fig. 1, a test piece having a width of 30 mm × a length of 100 mm was cut out from each of the coated metallic materials. The test piece is inserted into an injection molding die, and the molten thermoplastic resin composition is injected to the cavity of the injection molding die. The shape of the cavity is 30 mm wide x 100 mm long x 4 mm thick. Further, the thermoplastic resin composition was brought into contact with the coated metallic material in an area of 30 mm in width × 30 mm in length. After the thermoplastic resin composition was injected into a cavity, it was cooled and solidified to obtain a composite for evaluation.

With respect to each composite, the coated metal sheet and the molded body of the thermoplastic resin composition were stretched at a speed of 100 mm/min in the opposite directions on the same plane, and the strength at the time of fracture (peel strength) was measured. . When the peeling strength was less than 1.0 kN, the case where the peeling strength was 1.0 kN or more and less than 1.5 kN was evaluated as "△", and the peeling strength of 1.5 kN or more and less than 2.0 kN was evaluated as "○". The case where the peeling strength was 2.0 kN or more was evaluated as "◎". The "x" composite having a peel strength of less than 1.0 kN was not practical and was judged to be unacceptable.

The evaluation results of the classification, the ratio of the treatment liquid No., the ratio of the PC unit to the total mass of the resin, the type of the metal element, the type of the thermoplastic resin composition, and the bondability with the molded body of the thermoplastic resin composition are shown in the table. 2 in.

[Table 2] Table 2 Coating base material A: stainless steel plate (SUS430) B: molten Zn-6 mass% Al-3 mass% Mg alloy plated steel sheet C: molten Al-9 mass% Si alloy plated steel sheet D: molten Zn alloy plating Steel plate E: Electrically Zn-plated steel sheet, type of thermoplastic resin composition a: ABS resin composition (EXCELLOY CK-10G20) b: PET resin composition (Rynite 935) c: PBT resin composition (NOVADURAN 5710F40 d: PC resin composition (Iupilon GSH2030FT) e: PA resin composition (AMILAN CM3511G50) f: PPS resin composition (Fortron 1140T11)

As shown in Table 2, in the coated metal sheet of Comparative Example 1 and Comparative Example 2, since the ratio of the PC unit to the total mass of the resin in the treatment liquid is small, the bonding strength between the coating film and the resin molded body is insufficient. As a result, the bonding strength between the metal material and the resin molded body is insufficient. In the coated metal sheet of Comparative Example 3 and Comparative Example 4, since the ratio of the PC unit to the total mass of the resin in the treatment liquid is large, the bonding strength between the metal element and the coating film is insufficient, and as a result, the metal form is obtained. The bonding strength with the resin molded body is insufficient. On the other hand, all of the coated metal materials of Examples 1 to 14 are excellent in the bonding strength between the coating film and the resin molded body.

According to the above results, it is understood that the coating liquid of the present invention can form a coating film on which the metal body material and the thermoplastic resin composition can be joined to each other with excellent adhesion. [Industrial availability]

The treatment liquid for a metal element material of the present invention can form a coating film which can bond the metal element material and the molded body of the thermoplastic resin composition with excellent adhesion, and thus is, for example, used in various electronic devices, household electric appliances, medical equipment, and the like. It is preferably used in the fields of automobile bodies, vehicle-mounted articles, building materials, and the like.

no

FIG. 1 is a schematic view showing a configuration of a composite for measuring a bonding strength of a molded body of a coated metal element and a thermoplastic resin composition.

no

Claims (4)

A treatment liquid for a metal element, which is a treatment liquid for a metal material for forming a coating film which can bond the metal material and the molded body of the thermoplastic resin composition on the surface of the metal material. Further, the method comprises a polyurethane resin containing a polycarbonate unit, and the ratio of the polycarbonate unit to the total mass of the resin in the treatment liquid for the metal material is 5% by mass to 80% by mass. Within the scope. The treatment liquid for a metal element according to claim 1, further comprising an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V, Mo, and W. Or a combination of these. The treatment liquid for a metal element according to the first aspect of the invention, wherein the treatment liquid for a metal element further contains an acrylic resin, an epoxy resin, an urethane resin, and a poly One or two or more kinds of resins containing no olefin resin, phenol resin, polyester resin, copolymers, and modified substances thereof. The treatment liquid for a metal element according to any one of the first to third aspect, wherein the thermoplastic resin composition is an acrylonitrile-butadiene-styrene resin or a polyparaphenylene An ethylene dicarboxylate resin, a polybutylene terephthalate resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, or a combination thereof.