JP2020132917A - Shaped metal material surface treatment liquid, method for manufacturing composite, and treatment solution applicator - Google Patents

Abstract

To provide a shaped metal material surface treatment liquid capable of easily bonding the shaped metal material to a resin composition molding.SOLUTION: The shaped metal material surface treatment liquid for forming a surface treated layer capable of bonding a resin composition molding to one shaped metal material on the surface of the one shaped metal material comprises: a phosphoric acid compound; an adhesion auxiliary agent being a metal oxide selected from a group consisting of Ti, Zr, V and Mo, a hydroxide or a fluoride; an organic solvent included by an amount of 5 mass% or more and 35 mass% or less to the total mass; and a resin, and has a viscosity of 2 mPa s or more and 50 mPa s and less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a surface treatment liquid for a metal shape material, a method for producing a composite, and a treatment liquid imparting tool.

A metal plate or a press-molded product thereof, or a so-called metal element molded by casting, forging, cutting, powder metallurgy, etc., is used in various industrial products such as automobiles. When these metal base materials are used as parts, a composite of the metal base materials or the metal base material and the molded product of the resin composition is often used.

A composite in which a metal molding material and a molded body of a resin composition are joined is lighter than a metal-only part and stronger than a resin-only part, and is therefore used in various industrial products. Has been done. Conventionally, such a composite has been manufactured by fitting a metal molding material and a molded body of a resin composition. Furthermore, in recent years, a method of producing a composite by insert molding or bonding with an adhesive has attracted attention. However, the method for producing a composite by fitting, insert molding, adhesive, or the like has a large number of work steps and low productivity.

Therefore, as a method of joining the metal molding material and the molded product of the resin composition, which are excellent in workability and adhesion, a surface treatment liquid containing an organic resin is applied to the surface of the metal base material, dried, and organic. A method for forming a resin layer has been developed (Patent Document 1 and the like).

Japanese Patent No. 5335126

According to the method described in Patent Document 1 and the like, the metal molding material and the molded product of the resin composition can be easily and adhereably joined to each other. Therefore, further development of a method that makes the method easier is desired.

The present invention has been made in view of the above points, and is a surface treatment liquid for a metal molding material capable of easily joining a metal molding material and a molded product of a resin composition, and a composite using the surface treatment liquid. It is an object of the present invention to provide a method for producing a body and a treatment liquid applying tool for applying the surface treatment liquid to the surface of a metal molding material.

One aspect of the present invention for solving the above-mentioned problems is to form a surface-treated layer on the surface of the above-mentioned metal-shaped material, which can bond a molded body of the resin composition to the one metal-shaped material. The present invention relates to a surface treatment liquid for a metal shape material. The surface treatment liquid is based on a phosphoric acid compound, an adhesion aid which is an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V and Mo, and a total mass thereof. It contains an organic solvent contained in an amount of 5% by mass or more and 35% by mass or less and an emulsion of a resin, and has a viscosity of 2 mPa · s or more and 50 mPa · s or less.

Another aspect of the present invention for solving the above problems is a step of applying the surface treatment liquid to the surface of one metal molding material and drying it to form a surface treatment layer, and the above one metal molding material. A composite comprising a step of arranging a molded body of the resin composition so as to be in contact with the surface-treated layer and a step of heating a contact portion between the surface-treated layer and the molded body of the resin composition with respect to the material. Regarding the manufacturing method of the body.

Another aspect of the present invention for solving the above problems is a step of applying the surface treatment liquid to the surface of one metal molding material and drying it to form a surface treatment layer, and forming the surface treatment layer. A step of inserting the above-mentioned one metal element into the injection molding die and a step of injecting the molten thermoplastic resin composition into the inside of the above-mentioned injection molding die into which the above-mentioned one metal element is inserted. And, the present invention relates to a method for producing a complex having.

Another aspect of the present invention for solving the above problems relates to a treatment liquid imparting tool having a container and a surface treatment liquid for the metal body material housed inside the container. The container has an accommodating portion for accommodating the surface treatment liquid for the metal shape material, and an imparting unit for applying the surface treatment liquid contained in the accommodating portion to the metal shape material.

According to the present invention, a surface treatment liquid for a metal shape material capable of easily joining a metal shape material and a molded product of a resin composition, a method for producing a composite using the surface treatment liquid, and the surface treatment. A treatment liquid applying tool for applying the liquid to the surface of the metal shape material is provided.

FIG. 1 is a schematic cross-sectional view showing an example of a treatment liquid applying tool according to an embodiment of the present invention.

1. 1. Surface treatment liquid for metal element material In one embodiment of the present invention, a surface treatment layer capable of bonding a molded body of a resin composition to one metal element material is formed on the above metal element material. The present invention relates to a surface treatment liquid for a metal shape material (hereinafter, also simply referred to as “surface treatment liquid”) that can be easily formed on the surface. Specifically, the surface treatment liquid is applied to the surface of the above-mentioned metal element, and is naturally dried or heat-dried to form the surface treatment layer. Then, the surface treatment liquid can bond the molded product of the resin composition to the metal element shape material of the above one more firmly through the formed surface treatment layer.

The surface treatment liquid can be easily carried by being housed in a treatment liquid imparting tool or the like, which will be described later, and can be placed on the surface of the metal profile material at any time and place without a special device or the like. It is possible to easily form a treatment layer. Further, as will be described later, the above-mentioned surface treatment liquid includes a metal base material coated with rust preventive oil, processing oil, etc. (hereinafter, also simply referred to as "oil surface metal base material"), stainless steel, and aluminum. The surface treatment layer can be easily formed on the surface of a metal shape material (hereinafter, also simply referred to as “difficult-to-adhere metal shape material”) to which an organic resin such as magnesium is difficult to adhere. The molded body of the resin composition can be bonded to the surface of the oil-level metal base material or the difficult-to-adhere metal base material with good adhesion.

1-1. Metal element The metal element is a metal plate, its press-molded product, or a metal that is shaped by casting, forging, cutting, powder metallurgy, etc., or by applying force. To say. The types of these metal shape materials are not particularly limited. For example, cold-rolled steel sheet, galvanized steel sheet, Zn-Al alloy plated steel sheet, Zn-Al-Mg alloy plated steel sheet, Zn-Al-Mg-Si alloy plated steel sheet, aluminum plated steel sheet, stainless steel sheet (austenite type, martensite type). , Ferrite type, and ferrite / martensite two-phase type), aluminum plate, aluminum alloy plate, magnesium plate, magnesium alloy plate, metal plate such as copper plate, and press-molded products thereof. It also includes metal parts formed by casting, forging, cutting, powder metallurgy and the like, including aluminum die casting, zinc die casting and magnesium die casting.

The metal shape material may have a chemical conversion treatment film formed on the surface of the metal shape material. The chemical conversion coating improves the corrosion resistance of the metal profile. The chemical conversion treatment film may be formed on at least the region where the surface treatment liquid is applied on the surface of the metal base material, but from the viewpoint of facilitating film formation, the chemical conversion treatment film is formed on the entire surface of the metal shape material. It is preferably formed.

The type of chemical conversion treatment for forming the chemical conversion treatment film is not particularly limited. For example, chromate treatment, chromium-free treatment and phosphate treatment are included. 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 corrosion resistance of the metal shape material. For example, in the case of chromate treatment, the Cr equivalent adhesion amount may be adjusted to be 5 mg / m ² or more and 100 mg / m ² or less. In the case of chromium-free treatment, the adhesion amount of the Ti-Mo composite film is 10 mg / m ² or more and 500 mg / m ² or less, and that of the fluoroacid film is 3 mg / m ² or more and 100 mg / m ² or less. It should be adjusted as follows. Further, in the case of a phosphate film, the adhesion amount may be adjusted to be 0.1 mg / m ² or more and 5 g / m ² or less.

An anodic oxide film may be formed on the surface of the metal shape material. The anodic oxide film improves the corrosion resistance and abrasion resistance of the metal profile. The anodic oxide film can be formed by a known method of anodic oxidation in an electrolytic solution of an aqueous solution containing, for example, nitric acid, sulfuric acid, chromic acid, etc., and is widely formed particularly for metals such as aluminum and magnesium. ..

1-2. Surface treatment liquid The surface treatment liquid contains a phosphoric acid compound, an adhesion aid, an organic solvent, and a resin emulsion.

1-2-1. Phosphoric acid compound The phosphoric acid compound enhances the adhesion between the surface treatment layer and the metal body material. The phosphoric acid group of the phosphoric acid compound exhibits a strong affinity with a metal (a metal profile material or an inorganic element during chemical conversion treatment) and forms a complex. By forming this complex, the phosphoric acid compound enhances the wettability of the surface treatment liquid on the surface of the oil-based metal profile material coated with rust preventive oil or processing oil, and adheres strongly to the metal profile material. A surface treatment layer can be formed. In addition, the phosphoric acid compound enhances the affinity of the surface treatment liquid with the oxide film formed on the surface of stainless steel, aluminum, magnesium, etc. by forming this complex. The wettability of the surface treatment liquid to the surface can be enhanced to form a surface treatment layer that is strongly adhered to the metal shape material. As a result, the phosphoric acid compound can eliminate or simplify the pretreatment of the surface of the metal profile, and facilitate the formation of the surface treatment layer.

Examples of the above-mentioned phosphoric acid compounds include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate and Includes magnesium hydrogen phosphate and the like.

The content of the phosphoric acid compound contained in the surface treatment liquid is appropriately determined within a range in which the adhesion of the surface treatment layer to the surface of the oil surface metal base material and the poorly adherent metal base material can be sufficiently enhanced. be able to. For example, the content of the phosphoric acid compound contained in the surface treatment liquid is such that the content of the phosphoric acid compound in the surface treatment layer (the content of the phosphoric acid compound with respect to the total amount of solids) is 0.05% by mass in terms of P atom. The amount is preferably less than 3.0% by mass.

1-2-2. Adhesion Auxiliary Adhesive Auxiliary is a metal oxide, hydroxide or fluoride selected from the group consisting of Ti, Zr, V and Mo. Since the adhesive auxiliary has a low surface free energy, it tends to be selectively concentrated in the vicinity of the surface of the metal profile material in the inside of the surface treatment layer formed by the application and drying of the surface treatment liquid. .. Due to this thickening action, the adhesion aid further enhances the wettability of the surface treatment liquid to the surface of the oil surface metal base material or the difficult-to-adhere metal base material, and makes the metal base material with the phosphoric acid compound. Helps improve the adhesion of the surface treatment layer.

Further, the metal contained in the adhesion aid can improve the corrosion resistance of the metal shape material. In particular, the fluoride of the metal can be expected to suppress corrosion in the defective portion of the surface treatment layer by the self-repairing action.

The content of the adhesion aid contained in the surface treatment liquid is appropriately set within a range in which the adhesion of the surface treatment layer to the surfaces of the oil-level metal base material and the difficult-to-adhere metal base material can be sufficiently enhanced. You can decide. For example, the content of the adhesion aid contained in the surface treatment liquid is such that the content of the adhesion aid in the surface treatment layer (the content of the adhesion aid with respect to the total solid content) is 0 in terms of Ti atoms. 005 mass% or more and less than 0.6 mass%, Zr atom equivalent 0.05 mass% or more and less than 12.0 mass%, V atom equivalent 0.02 mass% or more and less than 3.0 mass%, Mo atom equivalent 0 The amount is preferably .005% by mass or more and less than 3.0% by mass.

The above content can be confirmed by elemental analysis with an electron microanalyzer (EPMA). Specifically, a cross section is processed by Ar milling, and then a thin piece having a thickness of about 500 nm is produced by focused ion beam (FIB) processing, and the obtained cross section is vapor-deposited with osmium. Then, for example, EPMA analysis is performed at an acceleration voltage of 15 kV and an irradiation current of 100 nA to determine the ratio of each element amount to the total amount of elements contained in the surface treatment layer.

1-2-3. Organic solvent The organic solvent adjusts the wettability of the surface treatment liquid with respect to the surface of the metal shape material.

Further, the organic solvent volatilizes relatively early after the surface treatment liquid is applied to the surface of the metal shape material, so that the organic solvent is applied to the surface of the metal shape material. Can be dried early. As a result, the organic solvent makes it possible to form the surface treatment layer even in an environment where there is no equipment for drying or the like.

The organic solvent is not particularly limited, but from known solvents such as aliphatic solvents, alicyclic solvents, aromatic solvents, alcohol solvents, ketone solvents, ester solvents, ether solvents and amide solvents. Those that do not react with each component of the surface treatment liquid can be used alone or in combination.

The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent is not particularly limited, and is, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanediol, tert-butyl alcohol, isobutyl alcohol, n-pentanol, 2-pentanol. , 3-Pentanol, tert-pentyl alcohol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Alcoholic or polyhydric alcohol solvents such as butanediol, 1,2-pentanediol, 1,5-pentanediol and glycerin, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone and N- Examples thereof include amide-based solvents such as methyl-2-pyrrolidone.

The content of the organic solvent contained in the surface treatment liquid is 5% by mass or more and 35% by mass from the viewpoint of enhancing the wettability of the surface treatment liquid on the surface of the oil surface metal base material or the poorly adherent metal base material. It is as follows. From the viewpoint of improving the stability of the surface treatment liquid and reducing the burden on the environment, the content of the organic solvent is more preferably 5% by mass or more and 30% by mass or less.

1-2-4. Resin emulsion The resin may be any material that can adhere to the metal shape material. For example, the resin can have a functional group (hydrogen-bonding functional group) that hydrogen-bonds to the metal body shape material. Examples of the hydrogen-bonding functional group include a carboxyl group and an amino group. Examples of resins having a hydrogen-bonding functional group include epoxy-based resins, polyolefin-based resins, phenol-based resins, acrylic-based resins, polyester-based resins, and polyurethane-based resins. These resins may be used alone or in combination of two or more.

These resins are emulsions. From the viewpoint of improving the adhesion of the surface treatment layer to the surface of the oil surface metal shape material and the difficult-to-adhere metal base material, and adjusting the viscosity of the surface treatment liquid to the range described later, the above resin emulsion The average particle size measured by the light scattering method is preferably 5 nm or more and 500 nm or less, and more preferably 10 nm or more and 400 nm or less.

Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin and the like. Examples of polyolefin-based resins include polyethylene resins and polypropylene resins. Phenolic resins include novolak-type resins, resol-type resins, and the like. The polyurethane resin is obtained by copolymerizing a diol and a diisocyanate. Examples of diols include bisphenol A, 1,6-hexanediol, 1,5-pentanediol and the like. Examples of isocyanates include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like.

The above resin can be obtained as a commercially available product. Further, the presence of the resin in the surface treatment liquid can be confirmed by ordinary analytical instruments such as NMR, IR, and GC-MS.

Further, the resin may be crosslinked. Cross-linking of the resin can be carried out, for example, by a cross-linking agent having a cross-linking functional group that reacts with a hydrogen-bonding functional group in the resin. Cross-linking the resin is preferable from the viewpoint of improving the strength of the surface treatment layer. As the cross-linking agent, a known cross-linking agent used for cross-linking the resin can be used. Examples of cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, melamine-based cross-linking agents, carbodiimide-based cross-linking agents, and cross-linking agents having metal salts. The amount of the cross-linking agent used is appropriately determined within a range in which both the adhesion of the surface-treated layer to the metal profile and the effect of cross-linking in the surface-treated layer can be obtained.

From the viewpoint of further enhancing the adhesion of the resin to the molded product described later, the resin contained in the surface treatment liquid is preferably a polyurethane resin or a polypropylene resin. The polyurethane resin preferably contains a polycarbonate unit-containing polyurethane resin.

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

The PC-containing polyurethane has a polycarbonate unit in the molecular chain. The "polycarbonate unit" refers to the structure shown below in the molecular chain of polyurethane. The carbonate group may be present individually or continuously in the PC-containing polyurethane. The content of the polycarbonate unit in the surface treatment liquid should be 15% by mass or more and 80% by mass or less with respect to the mass of the total resin in the surface treatment liquid, that is, the adhesion to the metal molding material and the adhesion of the resin to the molded product. It is preferable from the viewpoint of enhancing both sex. If the content of the polycarbonate unit is less than 15% by mass, the surface treatment layer may not adhere to the metal molding material with sufficient strength, and if it is more than 80% by mass, the surface treatment layer is made of resin. It may not adhere to the molded product with sufficient strength. The ratio of the mass of the polycarbonate unit to the mass of the total resin can be determined by nuclear magnetic resonance spectroscopy (NMR analysis).

The PC-containing polyurethane can be prepared by a known method and is not particularly limited. For example, it can be prepared by the following steps. First, an organic polyisocyanate, a polycarbonate polyol, and a polyol having a tertiary amino group or a carboxyl group are reacted to produce a urethane prepolymer. It is possible to use a polyol other than the polycarbonate polyol, for example, a polyester polyol or a polyether polyol, in combination within the range in which the effect of the present invention can be obtained.

Then, 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. In this way, a cationic polycarbonate unit-containing polyurethane can be produced. Alternatively, the carboxyl group of the urethane prepolymer is neutralized with a basic compound such as triethylamine, trimethylamine, diethanol monomethylamine, diethylethanolamine, sodium hydroxide, or potassium hydroxide to convert it into a salt of a carboxylic acid. In this way, an anionic polycarbonate unit-containing polyurethane can be produced. The PC-containing polyurethane may be a cationic polycarbonate unit-containing polyurethane or an anionic polycarbonate unit-containing polyurethane.

The type of the organic polyisocyanate is not particularly limited. Examples of organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-Diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylenediocyanate, 1,5-naphthalenediocyanate, 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. The organic polyisocyanate may be one kind or more.

The above-mentioned polycarbonate polyol is obtained by reacting a carbonate compound with a diol compound. Examples of the carbonate compounds include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate and the like. Examples of the above diol compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4. -Butandiol, 1,4-cyclohexanediol, 1,6-hexanediol and the like are included. The polycarbonate polyol may be a compound whose chain is extended by an isocyanate compound. The above-mentioned polycarbonate polyol may be one kind or more.

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

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

The content of the acid-modified polypropylene should be 40% by mass or more with respect to the total resin in the surface treatment liquid, and the adhesion between the metal base material and the molded product of another metal base material or resin composition. It is preferable from the viewpoint of enhancing. The upper limit of the content of the acid-modified polypropylene can be appropriately determined within the range in which the effect of the present invention can be obtained.

The acid value of the acid-modified polypropylene is preferably 1 mgKOH / g or more and 500 mgKOH / g or less. When the acid value of the acid-modified polypropylene is within the above range, the acid-modified polypropylene itself acts as a surfactant by neutralizing the acid-modified polypropylene when producing the emulsion described later.

It is preferable that the melting point of the acid-modified polypropylene is 60 ° C. or higher and 120 ° C. or lower, and the crystallinity of the acid-modified polypropylene is 5% or more and 20% or less. The acid-modified polypropylene having the above melting point and crystallinity has high wettability to the surface of the metal body material. Therefore, it is preferable from the viewpoint of adhesion of the surface treatment layer. When the melting point is less than 60 ° C. or the crystallinity is less than 5%, the surface treatment layer is softened at a relatively low temperature, so that, for example, the blocking resistance of the metal profile is insufficient during storage. There is.

The melting point and crystallinity of the acid-modified polypropylene hardly change between the state contained in the surface treatment liquid and the state of the surface treatment layer (after drying). Therefore, the crystallinity of the acid-modified polypropylene in the surface-treated layer can be examined by measuring the surface-treated liquid containing the acid-modified polypropylene by X-ray diffraction by the Ruland method.

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

Polypropylene is known for its isotactic, atactic, syndiotactic, hemiisotactic and stereotactic stereoregularities. The stereoregularity of polypropylene in acid-modified polypropylene is preferably isotactic from the viewpoint of mechanical properties such as rigidity and impact strength or durability.

The weight average molecular weight of the polypropylene is preferably 1000 or more and 300,000 or less, and more preferably 5000 or more and 100,000 or less. When the weight average molecular weight of polypropylene is 1000 or more, the strength of the surface treatment layer can be further increased. On the other hand, when the weight average molecular weight of polypropylene is 300,000 or less, the decrease in workability due to the increase in viscosity when the polypropylene is acid-modified is suppressed.

Acid modification of polypropylene involves dissolving polypropylene in toluene or xylene and in the presence of a radical generator, acid anhydrides and / or 1 of α, β-unsaturated carboxylic acids and / or α, β-unsaturated carboxylic acids. This can be done using compounds having one or more double bonds per molecule. Alternatively, using an instrument capable of raising the temperature above the softening temperature or melting point of polypropylene, in the presence or absence of a radical generator, α, β-unsaturated carboxylic acid and / or α, β-unsaturated. It can be carried out using an acid anhydride of a carboxylic acid and / or a compound having one or more double bonds per molecule. Sufficient nitrogen substitution is performed when the polypropylene modification reaction is carried out in a solution state in an organic solvent such as toluene and / or xylene, or when the reaction is carried out in a non-uniform dispersion system such as an aqueous system. Is desirable. In this way, acid-modified polypropylene is prepared.

Examples of the radical generators include peroxides and azonitriles. Examples of the above azonitriles include di-tert-butylperphthalate, tert-butylhydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyethyl hexanoate, tert-. Includes butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide and the like. Examples of the above azonitrile include azobisisobutyronitrile, azobisisopropionitrile and the like. The blending amount of the radical generator is preferably 0.1 part by mass or more and 50 parts by mass or less, and more preferably 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of polypropylene.

Examples of α, β-unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, and anhydrous. Contains aconitic acid. The α, β-unsaturated carboxylic acid or its acid anhydride may be one kind or more. When two or more of the above α, β-unsaturated carboxylic acids or acid anhydrides thereof are used in combination, the physical properties of the surface treatment layer are often improved.

Examples of the above-mentioned compounds having one or more double bonds per molecule include (meth) acrylic acid-based monomers and styrene-based monomers. Examples of the above (meth) acrylic acid-based monomers include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid, and -2-hydroxy (meth) acrylic acid. Ethyl, -2-hydroxypropyl (meth) acrylate, -4-hydrokibutyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, (meth) Benzyl acrylate, -2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, di (meth) acrylate (di) ethylene glycol, di (meth) ) Acrylic acid-1,4-butanediol, di (meth) acrylic acid-1,6-hexanediol, tri (meth) acrylate trimethylolpropane, di (meth) glycerate glycerin, (meth) acrylic acid-2 -Includes ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, and acrylamide. Examples of the styrene-based monomer include styrene, α-methylstyrene, paramethylstyrene, chloromethylstyrene and the like. Further, vinyl-based monomers such as divinylbenzene, vinyl acetate, and vinyl ester of versatic acid can be used in combination with the above compounds.

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

1-2-5. Other Additives The surface treatment liquid 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, lubricants, defoamers, etching agents, inorganic compounds, coloring materials and the like.

The rust inhibitor improves the corrosion resistance of the metal profile. The rust inhibitor may be one kind or more. Examples of rust inhibitors include metal compound rust inhibitors, non-metal compound rust inhibitors, and organic compound rust inhibitors. The content of the rust preventive agent in the surface treatment liquid 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 preventive include metal oxides, hydroxides or fluorides selected from the group consisting of Si, Cr, Hf, Nb, Ta, W, Mg and Ca.

Examples of the non-metal compound rust preventive include thiol compounds such as thiourea.

Examples of the organic compound-based rust preventives include inhibitors and chelating agents. Examples of such inhibitors include carboxylic acids such as oleic acid, dimer acid and naphthenic acid, metal carboxylic acid soaps (lanolin Ca, Zn naphthenic acid, oxide wax Ca, Ba salts, 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 above chelating agents include EDTA (ethylandiaminetetraacetic acid), gluconic acid, NTA (nitrilotriacetic acid), HEDTA (hydroxyethyl, ethylenediaminetriacetic acid), DTPA (diethylenetriaminepentaacetic acid), and Na citrate. included.

The above-mentioned lubricant can suppress the occurrence of galling on the surface of the metal shape material. The type of lubricant may be one type 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 surface treatment liquid is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin in the surface treatment liquid. If the amount of the 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 occurrence 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 surface treatment liquid. The defoaming agent may be one kind or more. The type of antifoaming agent is not particularly limited. As the defoaming agent, an appropriate amount of a known defoaming agent such as a silicone-based defoaming agent may be added.

The etching agent activates the surface of the metal shape material to improve the adhesion of the surface treatment 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 surface treatment layer to improve water resistance. Examples of inorganic compounds include inorganic oxide sol such as silica, alumina and zirconia.

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

1-2-6. Physical properties of the surface treatment liquid The surface treatment liquid has a viscosity of 2 mPa · s or more and 50 mPa · s or less. When the viscosity of the surface treatment liquid is 2 mPa · s or more and 50 mPa · s or less, excellent wettability to the metal base material can be obtained, and the surface of the oil surface metal base material and the difficult-to-adhere metal base material can be used. On the other hand, the surface treatment liquid spreads evenly and uniformly, and a surface treatment layer having good adhesion can be formed. The viscosity of the surface treatment liquid is a value measured by a method specified in JISZ-8803 (2011) using a Brookfield type viscometer in an environment of 20 ° C. after defoaming.

Further, when the viscosity is 2 mPa · s or more and 50 mPa · s or less, a treatment liquid applying tool used for applying the surface treatment liquid to the surface of the metal shape material by a spray method, brush coating, stationery coating or the like. When applied to, it suppresses clogging of treatment liquid application tools (clogging of sprays, nozzle heads, etc.), and resin compositions and felts made of fiber aggregates such as brush hair bundles and marker nibs. Excellent impregnation property. Further, since the surface treatment liquid has a viscosity of 2 mPa · s or more, so-called direct current phenomena such as dropping of the liquid from these treatment liquid application tools and bleeding after application are unlikely to occur. Further, since the surface treatment liquid has a viscosity of 50 mPa · s or less, clogging of these treatment liquid application tools, rubbing at the time of application, and dry-up due to volatilization of liquid components (improper application due to drying of the treatment liquid application tool). ) Is unlikely to occur. From these viewpoints, the viscosity of the surface treatment liquid is more preferably 5 mPa · s or more and 35 mPa · s or less.

The viscosity of the surface treatment liquid can be adjusted by adjusting the content of the resin solid content in the surface treatment liquid or the addition of a viscosity modifier. Examples of viscosity modifiers include polymeric polysaccharides, water-soluble acrylic resins and inorganic mineral forms. The content of the viscosity adjusting agent in the surface treatment liquid can be appropriately determined from the range in which the thickening effect and the effect of the present invention can be obtained, depending on the type of the viscosity adjusting agent.

2. 2. Method of manufacturing the complex (contact and heating)
Another embodiment of the present invention relates to a method for producing a composite using the above-mentioned surface treatment liquid. Specifically, the surface treatment liquid includes (1) a step of applying the above-mentioned surface treatment liquid to the surface of one metal molding material and drying it to form a surface treatment layer, and (2) the above-mentioned one. A step of arranging a molded body of the resin composition so as to be in contact with the surface treatment layer on the metal shape material, and (3) a step of heating a contact portion between the surface treatment layer and the molded body of the resin composition. Can be used to produce a complex with and.

2-1. Formation of surface treatment layer First, the above-mentioned surface treatment liquid is applied to the surface of one metal shape material and dried to form a surface treatment layer.

The above surface treatment liquid can be applied by a known method such as a roll coating method, a curtain flow method, a spin coating method, a spray method, or a dipping pulling method. In addition, the surface treatment liquid may be applied by brush coating and stationery coating using a writing tool such as a felt-tip pen, a marker pen, a brush pen, and a marker.

Of these, the spray method, brush coating, and stationery coating are preferable, and brush coating and stationery coating are preferable from the viewpoint of being able to partially surface-treat only the necessary parts without the need for large-scale equipment and having excellent workability. More preferred.

The amount of the surface treatment liquid applied is preferably such that the film thickness of the surface treatment layer formed by drying is 0.5 μm or more. When the thickness of the surface treatment liquid to be formed is 0.5 μm or more, the bonding force of the molded body of the resin composition to the metal element shape material is sufficiently increased, and the surface treatment liquid is contained in the surface treatment layer. The function of the additive (for example, the rust preventive action of the rust preventive) is also fully exhibited. The upper limit of the thickness of the surface treatment layer to be formed is not particularly limited, but can be determined from the viewpoint of the above-mentioned effects reaching a plateau and the viewpoint of cost. For example, the thickness of the surface treatment layer to be formed is preferably 20 μm or less, more preferably 10 μm or less.

The applied surface treatment liquid may be dried naturally or by heating. These drying conditions may be appropriately selected according to the composition of the surface treatment liquid and the like. For example, when the applied surface treatment liquid is dried by heating, the metal shape material coated with the surface treatment liquid is put into a drying oven without washing with water, and the reaching plate temperature is 80 ° C. or higher and 250 ° C. or lower. It may be heated so as to be within the range.

2-2. Arrangement of the molded body of the resin composition Next, the molded body of the resin composition is arranged so as to be in contact with the surface-treated layer with respect to one metal base material on which the surface-treated layer is formed.

For example, in the molded product of the resin composition, at least the portion to be joined and the portion to be joined of the above-mentioned metal element shape material are in contact with each other via the above-mentioned surface treatment layer. It is placed against the metal shape material of. In the step, the portion of the molded body of the resin composition to be joined and the portion of the one metal element to be joined are formed by forming the surface treatment layer at least at the time of performing the heating step described later. It suffices if they are in contact with each other. At this time, it is preferable that the above-mentioned metal element and the molded product of the above-mentioned resin composition are pressed against each other by a fixing jig or the like and adhere to each other from the viewpoint of preventing misalignment.

The molded body of the resin composition may be a molded body having a shape that is in close contact with the surface of the above-mentioned metal element shape material.

The resin composition constituting the molded product of the resin composition is preferably a thermoplastic resin composition because it has high weldability to the surface treatment layer. Examples of the thermoplastic resin composition include an acrylonitrile-butadiene-styrene (ABS) -based resin composition, a polyethylene terephthalate (PET) -based resin composition, a polybutylene terephthalate (PBT) -based resin composition, and a polycarbonate (PC) -based resin. Included are resin compositions, polyamide (PA) -based resin compositions, polyphenylene terephthale (PPS) -based resin compositions, polypropylene (PP) -based resin compositions, and combinations thereof. The type of the thermoplastic resin composition can be determined according to the weldability with the surface treatment layer.

The molding shrinkage of the thermoplastic resin composition is preferably 1.1% or less from the viewpoint of suppressing deformation due to temperature changes during production of the composite. The molding shrinkage rate is preferably 0.9% or less, and more preferably 0.7% or less, from the viewpoint of further enhancing the bonding force of the coated metal element to the molded body. The molding shrinkage of the thermoplastic resin composition can be adjusted by a known method. For example, the molding shrinkage ratio can be adjusted by adding a filler to the thermoplastic resin composition, mixing the crystalline resin and the non-crystalline resin in the thermoplastic resin composition, and the like. The non-crystalline resin is, for example, PVC or PMMA. The crystalline resin is, for example, PE, PP, POM, or the like. The molding shrinkage ratio can be lowered, for example, by increasing the content of the filler or increasing the mixing ratio of the non-crystalline resin with respect to the crystalline resin.

The molding shrinkage rate (%) is determined by setting the volume of the molten thermoplastic resin composition (for example, the volume of the thermoplastic resin composition having the melting point of the thermoplastic resin or the cavity of the injection molding mold) to Va, and the molten state. When the volume of the thermoplastic resin composition (for example, the thermoplastic resin composition at room temperature (20 ° C.)) solidified by cooling from the above is Vb, it is calculated by the following formula.
{(Va-Vb) / Va} x 100

Further, it is preferable that αp / αm is 6 or less from the viewpoint of suppressing deformation due to a temperature change during production of the composite. αp is the coefficient of linear expansion of the thermoplastic resin composition, and αm is the coefficient of linear expansion of the metal profile. If αp / αm is larger than 6, the coated metal element may not be sufficiently firmly bonded to the molded product. αp / αm is preferably 4.5 or less from the viewpoint of further enhancing the bonding force of the coated metal molding material to the molded body. αm and αp are obtained by measuring the amount of dimensional change due to temperature change of the material, for example, by TMA (Thermal Mechanical Analysis). αp decreases, for example, when the content of the filler in the thermoplastic resin composition is large.

The thermoplastic resin composition may further contain components other than the above-mentioned organic resin as long as the effects of the present invention can be obtained. Examples of such other components include fillers and thermoplastic elastomers.

The filler reduces the molding shrinkage rate of the molded product and improves the rigidity of the molded product. The type of filler is not particularly limited, and known substances can be used. The filler may be one kind or more. Examples of fillers are fiberglass, carbon fiber and fiber-based fillers such as aramid resin, carbon black, calcium carbonate, calcium silicate, magnesium carbonate, silica, talc, glass, clay, lignin, mica, quartz powder and glass spheres. Such as powder fillers, as well as crushed carbon fibers and aramid fibers are included. Above all, glass fiber is more preferable from the viewpoint of maintaining the light transmittance of the molded product. From the above viewpoint, the content of the filler in the thermoplastic resin composition is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

The thermoplastic elastomer improves the impact resistance of the molded product. The type of the thermoplastic elastomer is not particularly limited, and the thermoplastic elastomer may be one kind or more. Examples of thermoplastic elastomers include polyolefin resins, polystyrene resins, and combinations thereof.

2-3. Heating of the contact portion Next, the contact portion between the surface treatment layer and the molded product of the resin composition is heated to weld them. As a result, the above-mentioned metal element and the molded product of the above-mentioned resin composition are joined via the above-mentioned surface treatment layer.
The heating may be performed on at least a part of the surface where the surface treatment layer and the molded product of the resin composition are in contact with each other, but from the viewpoint of further improving the adhesion, the entire surface of the contacting surface may be performed. It is preferable to carry out.

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

At this time, for example, by heating so that the ultimate temperature becomes equal to or higher than the melting point of the resin contained in the surface treatment layer, the molded product of the above-mentioned metal element and the above-mentioned resin composition is passed through the above-mentioned surface treatment layer. Can be closely joined. The upper limit of the ultimate temperature is not particularly limited, but can be determined from the viewpoint that the above effect reaches a plateau, the viewpoint of suppressing the decomposition of the surface treatment layer, and the like, and can be, for example, 250 ° C. or lower.

3. 3. Complex manufacturing method (injection molding)
Another embodiment of the present invention relates to another method for producing a composite using the surface treatment liquid described above. Specifically, the surface treatment liquid includes (1) a step of applying the above-mentioned surface treatment liquid to the surface of one metal molding material and drying it to form a surface treatment layer, and (2) a surface treatment layer. The step of inserting the above-mentioned one metal molding material into the injection molding mold, and (3) the thermoplastic resin composition melted inside the injection molding mold into which the above-mentioned one metal molding material was inserted. Can be used in the process of injecting and for the production of composites.

3-1. Formation of surface treatment layer First, the above-mentioned surface treatment liquid is applied to the surface of one metal shape material and dried to form a surface treatment layer. Since this step can be performed by the method described above, duplicate description will be omitted.

3-2. Insertion into the injection molding die Next, the above-mentioned metal element having the surface treatment layer formed is inserted into the injection molding die.

3-3. Injection of the thermoplastic resin composition Next, the molten thermoplastic resin composition is injected into the injection molding die into which the above-mentioned metal element is inserted. The thermoplastic resin composition can be the same as the thermoplastic resin composition constituting the molded product of the resin composition described above.

At this time, it is preferable to inject the thermoplastic resin composition at a high pressure. Further, it is preferable that the injection molding die is provided with a degassing so that the thermoplastic resin composition can flow smoothly. The molten thermoplastic resin composition comes into contact with the surface treatment layer formed on the surface of the above-mentioned metal element. The temperature of the injection molding die is preferably close to the melting point of the thermoplastic resin composition.

4. Treatment Liquid Applying Tool Another embodiment of the present invention relates to a treatment liquid applying tool for applying the surface treatment liquid to the above-mentioned metal element shape material. The treatment liquid imparting tool is preferably portable.

FIG. 1 is a schematic cross-sectional view showing an example of a treatment liquid applying tool according to the present embodiment.

FIG. 1A is a schematic cross-sectional view showing an example of a spray-type treatment liquid applying tool. As shown in FIG. 1A, the treatment liquid imparting tool 100a includes a container 110a and the above-mentioned surface treatment liquid 120a. The container 110a has an accommodating portion 112a for accommodating the surface treatment liquid 120a, and an imparting portion 114a for applying the surface treatment liquid 120a contained in the accommodating portion 112a to the surface of the above-mentioned metal element.

In the treatment liquid applying tool 100a, the applying portion 114a has a nozzle 115a and a valve 116a. When the nozzle head 117a in which the nozzle 115a is arranged is pushed into the accommodating portion 112a, the valve 116a is released and the surface treatment liquid 120a inside the accommodating portion 112a is pushed out by the pressure of the gas contained inside the accommodating portion 112a. It is ejected from the nozzle 115a. As a result, the applying portion 114a pushes the nozzle head 117a against the accommodating portion 112a with the nozzle 115a facing the surface of the above-mentioned metal element, so that the surface treatment liquid 120a ejected from the nozzle 115a Can be applied to the surface of the above-mentioned metal element shape material.

FIG. 1B is a schematic cross-sectional view showing an example of a felt-tip pen type treatment liquid applying tool. As shown in FIG. 1B, the treatment liquid imparting tool 100b has a container 110b and the above-mentioned surface treatment liquid 120b. The container 110b has an accommodating portion 112b for accommodating the surface treatment liquid 120b, and an imparting portion 114b for applying the surface treatment liquid 120b contained in the accommodating portion 112b to the surface of the above-mentioned metal element.

In the treatment liquid applying tool 100b, the applying portion 114b is an aggregate of fibers such as a fiber aggregate, felt and a non-woven fabric. The imparting portion 114b passes through the aggregate of the fibers to the surface treatment liquid 120b that has moved from the accommodating portion 112b due to gravity or pressing against the accommodating portion 112b in a state of being in contact with the surface of the above-mentioned one metal shape material. By doing so, the surface treatment liquid 120b can be applied to the surface of the above-mentioned metal element shape material.

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. Metal base material As a metal base material, an aluminum plate, which is a difficult-to-adhere metal base material, was prepared. As the aluminum plate, an Al6061 alloy (JISH 4000 (2014)) having a plate thickness of 1.0 mm was used. The Al6061 alloy was used without pretreatment such as degreasing and pickling.

2. 2. Surface treatment liquid As the emulsion of the resin in the surface treatment liquid, a polyurethane resin or a polypropylene resin emulsion was used. Superflex E-4800 (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the emulsion of the polyurethane resin. As the polypropylene-based resin emulsion, MGP-1650 (Maruyoshi Chemical Co., Ltd.) containing an acid-modified polypropylene-based resin was used.

A phosphoric acid compound, an adhesion aid and an organic solvent were added to the obtained surface treatment solution.

As the phosphoric acid compound in the surface treatment liquid, diammonium hydrogen phosphate (Kishida Chemical Co., Ltd.) was used. The content of the phosphoric acid compound in the surface treatment liquid was adjusted to an amount such that the P conversion content in the formed surface treatment layer was 0.25% by mass.

Oxides of Ti, Zr, V and Mo were used as the adhesion aid in the surface treatment liquid. As the Ti oxide, titanium oxide (IV) (Kishida Chemical Co., Ltd.) was used. As the Zr oxide, ammonium zirconium carbonate (Daiichi Rare Element Chemical Industry Co., Ltd.) was used. As the V oxide, vanadium pentoxide (Taiyo Koko Co., Ltd.) was used. As the Mo oxide, hexaammonium hexaammonium tetrahydrate (Kishida Chemical Co., Ltd.) was used. Adhesion aids were added alone or in combination. The content of the adhesion aid in the surface treatment liquid is such that the Ti conversion content in the formed surface treatment layer is 0.25% by mass, the Zr conversion content is 0.5% by mass, and the V conversion content is V. The amounts were adjusted to 0.25% by mass and the Mo conversion content was 0.5% by mass.

Ethanol (Kishida Chemical Co., Ltd.) was used as the organic solvent in the surface treatment liquid. The content of the organic solvent in the surface treatment liquid was adjusted to an amount of 5% by mass or more and 35% by mass or less.

The viscosity of the surface treatment liquid was adjusted to the value shown in Table 1 by changing the amount of the viscosity modifier (ADEKANOL UH550: ADEKA Corporation) added.

3. 3. Formation of surface treatment layer A marker pen (Cutter 15 Empty marker: GROG) equipped with a felt-shaped pen tip was used as a treatment liquid applying tool. The surface treatment liquid is sealed in the cylinder tip (accommodation part) of the treatment liquid applying tool, the pen tip (applying part) is impregnated with the surface treatment liquid, and then applied to the surface of the metal shape material without pretreatment (writing). ) And air-dried to form a surface-treated layer having a thickness of 0.5 μm or more.

4. Evaluation of coatability of surface treatment liquid After forming the surface treatment layer, cissing and bleeding were visually confirmed to evaluate the coatability of the surface treatment liquid. When no repelling of the coated part (handwriting) was seen, no bleeding was seen, and the edge of the coated part was clear, the evaluation was evaluated as ⊚. If no repellency was observed on the coated portion, no bleeding was observed, and the edge of the coated portion was clear, but uneven coating was observed, the evaluation was evaluated as ◯. When both or either of the occurrence of cissing in the coated portion and the blurring of the edge of the coated portion due to bleeding were observed, the evaluation was evaluated as x.

5. Joining the molded body of the resin composition The molded body of the resin composition was joined to the metal molding material on which the surface treatment layer was formed. As the molded product of the resin composition, a polycarbonate (PC) -based resin and a polypropylene (PP) -based resin, which are thermoplastic resin compositions, were used. Iupiron GSH2030FT (Mitsubishi Engineering Plastics Co., Ltd.) was used as the PC resin. Prime Polypro R-350 (Prime Polymer Co., Ltd.) was used as the PP resin.

To join the metal shape material to the molded body of the resin composition, insert the metal shape material into the mold of the injection molding machine and inject the molten resin composition, or the surface of the metal shape material. This was done by pressing the thermoplastic resin composition and heating the metal molding material. When the resin composition was injected, the resin composition was cooled and solidified in a mold to obtain a composite in which the metal molding material and the molded body of the resin composition were joined. When pressing the resin composition to heat the metal shape material, use a heating device using a heater tip (pulse heat unit NA-154: Nippon Avionics Co., Ltd.) and adjust the current value to heat the heating temperature. Was controlled. The shape of the composite was a type B test piece defined in ISO 19095-2.

6. Evaluation of Adhesion of Surface Treatment Layer After joining the molded bodies of the resin composition, the joint is broken by the tensile shear test method specified in ISO19095-3, and the adhesion of the surface treatment layer is observed by observing the fracture surface. Was evaluated. When 80% or more of the surface treatment layer remained on the metal profile side, the evaluation was evaluated as ⊚. When a surface treatment layer of 40% or more and less than 80% remained on the metal profile side, the evaluation was evaluated as ◯. When less than 40% of the surface treatment layer remained on the metal profile side, the evaluation was evaluated as x.

7. Evaluation Results Examples 1 to 14 and Comparative Examples 1 to 15 were carried out by changing the components and viscosities contained in the molded product of the resin composition and the surface treatment liquid. Table 1 shows the combination of conditions of Examples and Comparative Examples and the evaluation results.

In Examples 1 to 2, 4 to 6 and 9 to 10, a phosphoric acid compound and an adhesion aid are contained, and since the organic solvent and the viscosity are within the range satisfying the present invention, they are applied in all the examples. Good properties and adhesion.

In Examples 3 and 7 to 8, although uneven coating (difference in coating amount) was observed in the coated portion, it contained a phosphoric acid compound and an adhesion aid, and the organic solvent and viscosity satisfied the present invention. Therefore, the coatability and adhesion were good in all the examples.

In Examples 11 to 14, the phosphoric acid compound and the adhesion aid are contained, and since the organic solvent and the viscosity are within the range satisfying the present invention, the coatability and the adhesion are good in all the examples. It was.

In Comparative Examples 1 and 2, the content of the organic solvent was less than the lower limit of the range, the wettability of the surface treatment liquid on the metal shape material was inferior, and some repellent was observed. Therefore, the coating property was inferior.

In Comparative Examples 3 to 4, the content of the organic solvent was larger than the upper limit of the range, and the wettability of the surface treatment liquid on the metal shape material was good, but the adhesion was poor. It is presumed that this is because the stability of the surface treatment liquid was lowered due to the increased content of the organic solvent.

In Comparative Examples 5 to 6, the viscosity was lower than the lower limit of the range, and bleeding was observed, so that the coatability was inferior. In addition, the viscosity was out of the range, resulting in poor adhesion of the surface treatment layer.

In Comparative Examples 7 to 8, the viscosity was higher than the upper limit of the range, and repelling was observed, so that the coatability was inferior. In addition, the viscosity was out of the range, resulting in poor adhesion of the surface treatment layer.

In Comparative Examples 9 to 10, the content of the organic solvent was less than the lower limit of the range, the wettability of the surface treatment liquid on the metal shape material was inferior, and some repellent was observed. Therefore, the coating property was inferior.

In Comparative Examples 11 to 12, the content of the organic solvent was larger than the upper limit of the range, and the wettability of the surface treatment liquid on the metal shape material was good, but the adhesion was poor. It is presumed that this is because the stability of the surface treatment liquid was lowered due to the increased content of the organic solvent.

In Comparative Examples 13 to 15, the organic solvent and the viscosity were within the range, but the coating property and the adhesiveness were inferior. This is because it did not contain either or both of the phosphoric acid compound and the adhesion aid, which have the effect of improving coatability and adhesion.

The surface treatment liquid of the present invention has a viscosity suitable for a portable treatment liquid imparting tool, and has excellent adhesion to an oil surface metal base material and a poorly adherent metal base material without pretreatment. , Various electronic devices, household electric appliances, medical devices, automobile bodies, vehicle-mounted products, building materials, etc.

100a, 100b Treatment liquid applying tool 110a, 110b Container 112a, 112b Accommodating part 114a, 114b Applying part 115a Nozzle 116a Valve 117a Nozzle head 120a, 120b Surface treatment liquid

Claims (8)

A surface treatment liquid for a metal base material for forming a surface treatment layer capable of bonding a molded body of a resin composition to the surface of the metal base material. hand,
Phosphoric acid compound and
Adhesion aids that are oxides, hydroxides or fluorides of metals selected from the group consisting of Ti, Zr, V and Mo.
An organic solvent contained in an amount of 5% by mass or more and 35% by mass or less with respect to the total mass of the surface treatment liquid.
With resin emulsion,
Including
Viscosity is 2 mPa · s or more and 50 mPa · s or less,
Surface treatment liquid for metal shape materials. The surface treatment liquid for a metal shape material according to claim 1, wherein the resin contains a polyurethane resin. The surface treatment liquid for a metal shape material according to claim 1, wherein the resin contains a polypropylene-based resin. A step of applying the surface treatment liquid according to any one of claims 1 to 3 to the surface of one metal shape material and drying it to form a surface treatment layer.
A step of arranging a molded body of the resin composition so as to be in contact with the surface treatment layer with respect to the one metal shape material.
A step of heating the contact portion between the surface treatment layer and the molded product of the resin composition, and
A method for producing a complex. A step of applying the surface treatment liquid according to any one of claims 1 to 3 to the surface of one metal shape material and drying it to form a surface treatment layer.
The step of inserting the above-mentioned one metal shape material on which the surface treatment layer is formed into the injection molding die, and
A step of injecting a molten thermoplastic resin composition into the injection molding die into which the one metal molding material is inserted, and a step of injecting the molten thermoplastic resin composition.
A method for producing a complex. With the container
The surface treatment liquid for a metal shape material according to any one of claims 1 to 3 contained in the container.
Have,
The container is
An accommodating portion for accommodating the surface treatment liquid for the metal shape material, and
An applying portion for applying the surface treatment liquid contained in the accommodating portion to the metal shape material,
A treatment liquid imparting tool having. The applying portion applies the surface treatment liquid to the metal shape material by spraying or spraying the surface treatment liquid from the nozzle head.
The treatment liquid applying tool according to claim 6. The applying portion imparts the surface treatment liquid to the metal shape material by passing the surface treatment liquid through an aggregate of fibers in contact with the metal shape material.
The treatment liquid applying tool according to claim 6.

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