JP7265124B2 - SURFACE TREATMENT LIQUID FOR METAL MATERIALS, COMPOSITE MANUFACTURING METHOD AND TREATMENT LIQUID DISPENSER - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface treatment liquid for metal materials, a method for producing a composite, and a treatment liquid applicator.

BACKGROUND ART Metal sheets, press-formed products thereof, or so-called metal preforms formed by casting, forging, cutting, powder metallurgy, etc. are used in various industrial products such as automobiles. When these metal preforms are used as parts, composites are often used in which metal preforms are bonded together or metal preforms and a molded body of a resin composition are bonded together.

Composites, in which metal preforms and moldings of resin compositions are joined, are lighter than parts made only of metal and stronger than parts made only of resin, so they are used in various industrial products. It is Conventionally, such a composite has been produced by fitting a metal preform and a molded article of a resin composition. Furthermore, in recent years, attention has been paid to a method of manufacturing a composite by insert molding or bonding with an adhesive. However, these methods of manufacturing composites by fitting, insert molding, adhesives, etc. have a large number of work steps and low productivity.

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

Japanese Patent No. 5335126

According to the method described in Patent Literature 1 and the like, it is possible to easily join a metal preform and a molded article of a resin composition with good adhesion. Therefore, further development of a method that allows the method to be performed more easily is desired.

The present invention has been made in view of the above points, and provides a surface treatment liquid for a metal material and a molded product of a resin composition that can be easily joined together, and a composite material using the surface treatment liquid. It is an object of the present invention to provide a body manufacturing method and a treatment liquid applicator for applying the surface treatment liquid to the surface of a metal material.

One aspect of the present invention for solving the above-mentioned problems is to form a surface treatment layer on the surface of the one metal material for bonding a molded body of a resin composition to the one metal material. It is related with the surface-treatment liquid for the metal preforms for doing. The surface treatment liquid contains a phosphoric acid compound, an adhesion aid that is an oxide, hydroxide or fluoride of a metal selected from the group consisting of Ti, Zr, V and Mo, and 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 preform and drying it to form a surface treatment layer; a step of placing a molded body of the resin composition on a material 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. It relates to 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 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 preform into an injection mold, and a step of injecting a molten thermoplastic resin composition into the inside of the above-mentioned injection mold into which the one above-mentioned metal preform has been inserted. and a method for manufacturing a composite.

Another aspect of the present invention for solving the above problems relates to a treatment liquid applicator having a container and a surface treatment liquid for the metal material, which is housed inside the container. The container has a storage section for storing the surface treatment liquid for the metal material, and an application section for applying the surface treatment liquid stored in the storage section to the metal material.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a surface treatment liquid for a metal preform capable of easily joining a metal preform and a molded body of a resin composition, a method for producing a composite using the surface treatment liquid, and the surface treatment. A treatment liquid applicator is provided for applying a liquid to the surface of a metal workpiece.

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

1. Surface Treatment Liquid for Metal Forming Material In one embodiment of the present invention, a surface treatment layer capable of bonding a molded body of a resin composition is applied to one metal forming material. The present invention relates to a surface treatment liquid for metal materials (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 one metal material and dried naturally or by heating to form the surface treatment layer. Then, the surface treatment liquid can adhere and bond the molded body of the resin composition more firmly to the one metal material through the formed surface treatment layer.

The surface treatment liquid can be stored in a treatment liquid applicator, which will be described later, and can be easily carried. It is possible to easily form a treated layer. In addition, as will be described later, the surface treatment liquid may be a metal material to which rust preventive oil, processing oil, or the like is applied (hereinafter simply referred to as "oil-surface metal material"), stainless steel, aluminum, or the like. The surface treatment layer can be easily formed on the surface of a metal material to which an organic resin such as magnesium is difficult to adhere (hereinafter also simply referred to as a "difficult-to-bond metal material"). The molding of the resin composition can be adhered with good adhesion to the surface of the oily surface metal material and the surface of the difficult-to-adhere metal material.

1-1. Metal raw materials Metal raw materials are metal sheets, their press-formed products, or objects that have been given a shape by forming or applying force to metal by casting, forging, cutting, powder metallurgy, etc. Say. The types of these metal preforms 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 (austenitic, martensitic) , ferritic, and ferrite-martensite two-phase), metal plates such as aluminum plates, aluminum alloy plates, magnesium plates, magnesium alloy plates and copper plates, and press-formed products thereof. It also includes metal members formed by casting, forging, cutting, powder metallurgy, etc., including aluminum die casting, zinc die casting and magnesium die casting.

A chemical conversion treatment film may be formed on the surface of the metal material. The chemical conversion coating improves the corrosion resistance of the metal stock. The chemical conversion treatment film may be formed on at least the region to which the surface treatment liquid is applied on the surface of the metal material, but from the viewpoint of facilitating the formation of the film, is preferably formed.

The type of chemical conversion treatment for forming the chemical conversion film is not particularly limited. Examples include chromate treatment, chromium-free treatment and phosphate treatment. The adhesion amount 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 material. For example, in the case of chromate treatment, the Cr-equivalent adhesion amount may be adjusted to 5 mg/m ² or more and 100 mg/m ² or less. In addition, in the case of chromium-free treatment, the adhesion amount is 10 mg/m ² or more and 500 mg/m ² or less for the Ti—Mo composite film, and the fluorine conversion adhesion amount is 3 mg/m ² or more and 100 mg/m ² or less for the fluoroacid-based film. should be adjusted as follows. Also, in the case of a phosphate coating, the coating amount may be adjusted to 0.1 mg/m ² or more and 5 g/m ² or less.

The metal preform may have an anodized film formed on its surface. The anodized film improves the corrosion resistance, wear resistance, etc. of the metal material. The anodized film can be formed, for example, by a known method of anodizing in an aqueous electrolytic solution containing nitric acid, sulfuric acid, chromic acid, etc., and is widely formed particularly on 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. Phosphate compound The phosphate compound enhances the adhesion between the surface treatment layer and the metal material. The phosphate group of the phosphate compound exhibits a strong affinity with metals (metallic materials or inorganic elements during chemical conversion) to form complexes. Through this complex formation, the phosphoric acid compound enhances the wettability of the surface treatment liquid with respect to the surface of the oil-surface metal material coated with rust preventive oil, processing oil, etc., and strongly adheres to the metal 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 this complex formation, so that these hard-to-bond metal materials are used. By increasing the wettability of the surface treatment liquid to the surface, it is possible to form a surface treatment layer that strongly adheres to the metal material. As a result, the phosphoric acid compound can eliminate or simplify the pretreatment of the surface of the metal material, facilitating the formation of the surface treatment layer.

Examples of the above 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 Magnesium hydrogen phosphate and the like are included.

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 material and the difficult-to-adhere metal 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 relative to the total solid content) is 0.05% by mass in terms of P atoms. It is preferable that the amount is more than or equal to less than 3.0% by mass.

1-2-2. Adhesion Aid The adhesion aid is a metal oxide, hydroxide or fluoride selected from the group consisting of Ti, Zr, V and Mo. Since the adhesion aid has a low surface free energy, it tends to selectively concentrate near the surface of the metal material within the surface treatment layer formed by applying and drying the surface treatment liquid. . The adhesion aid enhances the wettability of the surface treatment liquid to the surface of the oil surface metal material and the hard-to-adhere metal material due to this thickening action, and the phosphate compound adheres to the metal material. helps the effect of improving the adhesion of the surface treatment layer.

Also, the metal contained in the adhesion aid can improve the corrosion resistance of the metal material. In particular, the metal fluorides are expected to suppress corrosion at defective portions of the surface treatment layer due to their self-repairing action.

The content of the adhesion aid contained in the surface treatment liquid is appropriately within a range that can sufficiently improve the adhesion of the surface treatment layer to the surface of the oil surface metal material and the difficult-to-adhere metal material. 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 0.00 in terms of Ti atoms. 005% by mass or more and less than 0.6% by mass, 0.05% by mass or more and less than 12.0% by mass in terms of Zr atoms, 0.02% by mass or more and less than 3.0% by mass in terms of V atoms, 0 in terms of Mo atoms The amount is preferably 0.005% by mass or more and less than 3.0% by mass.

The above content can be confirmed by elemental analysis with an electronic microanalyzer (EPMA). Specifically, a cross section is processed by Ar milling, 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. Thereafter, 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 the amount of each element 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 to the surface of the metal workpiece.

In addition, the organic solvent evaporates relatively quickly after the surface treatment liquid is applied to the surface of the metal material. can be dried early. As a result, the organic solvent enables the surface treatment layer to be formed even in an environment where there is no drying facility.

Organic solvents include, but are not limited to, known solvents such as aliphatic solvents, alicyclic solvents, aromatic solvents, alcohol solvents, ketone solvents, ester solvents, ether solvents and amide solvents. Those which do not react with each component of the surface treatment liquid can be used singly or in combination.

The organic solvent is preferably a water-soluble organic solvent. Water-soluble organic solvents include, but are not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, 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- Alcohol or polyhydric alcohol solvents such as butanediol, 1,2-pentadiol, 1,5-pentanediol and glycerin, N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone and N- Amide solvents such as methyl-2-pyrrolidone can be mentioned.

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 increasing the wettability of the surface treatment liquid to the surface of the oil surface metal material or the difficult-to-adhere metal material. Below. From the viewpoint of enhancing the stability of the surface treatment liquid and reducing the load 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. Emulsion of resin Any resin can be used as long as it can adhere to the metal material. For example, the resin may have functional groups that form hydrogen bonds with the metal preform (hydrogen-bonding functional groups). Examples of the hydrogen-bonding functional groups include carboxyl groups and amino groups. Examples of resins having hydrogen-bonding functional groups 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 enhancing the adhesion of the surface treatment layer to the surface of the oil surface metal material and the hard-to-adhere metal material and adjusting the viscosity of the surface treatment liquid within the range described later, the emulsion of the resin is used. The average particle size measured by a light scattering method is preferably 5 nm or more and 500 nm or less, more preferably 10 nm or more and 400 nm or less.

Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and the like. Examples of polyolefin resins include polyethylene resins, polypropylene resins, and the like. Phenolic resins include novolac type resins, resol type resins, and the like. A 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 resins are commercially available. Moreover, the presence of the resin in the surface treatment liquid can be confirmed by ordinary analytical instruments such as NMR, IR, and GC-MS.

Furthermore, the resin may be crosslinked. Crosslinking of the resin can be performed, for example, with a crosslinker having a crosslinkable functional group that reacts with the hydrogen-bonding functional group in the resin. Crosslinking 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 resins 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 with metal salts. The amount of the cross-linking agent to be used is appropriately determined within a range in which both the adhesion of the surface treatment layer to the metal material and the cross-linking effect of the surface treatment layer can be obtained.

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

A polyurethane-based resin is a polymer compound containing a polyurethane skeleton and the hydrogen-bonding functional groups described above. 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-based resin is appropriately determined within a range in which sufficient adhesion to the metal material can be obtained. In addition, the polyurethane-based resin may further contain functional groups other than the hydrogen-bonding functional groups. Moreover, the weight average molecular weight of the polyurethane-based resin is not particularly limited as long as the effects of the present invention can be obtained.

PC-containing polyurethanes have polycarbonate units in the molecular chain. "Polycarbonate unit" refers to the structure shown below in the molecular chain of polyurethane. The carbonate groups may exist individually or continuously in the PC-containing polyurethane. The content of the polycarbonate unit in the surface treatment liquid is 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. It is preferable from the viewpoint of enhancing both the property and the property. If the content of the polycarbonate unit is less than 15% by mass, the surface treatment layer may not adhere to the metal material with sufficient strength. It may not adhere to the compact 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 should be noted that it is possible to use polyols other than polycarbonate polyols, such as polyester polyols and polyether polyols, within the range in which the effects of the present invention can be obtained.

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

The type of the organic polyisocyanate is not particularly limited. Examples of organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydro naphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Included are hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. One or more organic polyisocyanates may be used.

The polycarbonate polyol is obtained by reacting a carbonate compound and 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 -butanediol, 1,4-cyclohexanediol, and 1,6-hexanediol. The polycarbonate polyol may be a compound chain-extended with an isocyanate compound. One or more polycarbonate polyols may be used.

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 dicarboxylic acid in the presence of an initiator. Examples of such initiators include ammonia, primary or secondary monoamines, primary or secondary aliphatic polyamines, and primary or secondary aromatic mono- or aromatic polyamines. types, 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 alkanolamines include monoethanolamine and diethanolamine. Examples of the dicarboxylic acids include adipic acid and phthalic acid. The polyol having a tertiary amino group or a carboxyl group may be a compound chain-extended with an isocyanate compound. One or more polyols having a tertiary amino group or a carboxyl group may be used.

A 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 above acid-modified polypropylene is a polypropylene in which a carboxyl group or an anhydride group thereof is introduced into the constitutional units 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 material can be obtained. In addition, the polypropylene-based resin may further contain functional groups other than the hydrogen-bonding functional groups.

The content of the acid-modified polypropylene is 40% by mass or more with respect to the total resin in the surface treatment liquid. is preferable from the viewpoint of increasing The upper limit of the above content of the acid-modified polypropylene can be appropriately determined within the range in which the effects 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. If the acid value of the acid-modified polypropylene is within the above range, the acid-modified polypropylene itself acts as a surfactant by neutralizing the acid-modified polypropylene when preparing the emulsion described below.

Preferably, the acid-modified polypropylene has a melting point of 60° C. or higher and 120° C. or lower, and a crystallinity of 5% or higher and 20% or lower. The acid-modified polypropylene having the above melting point and crystallinity has high wettability with respect to the surface of the metal casting. Therefore, it is preferable from the viewpoint of adhesion of the surface treatment layer. If the melting point is less than 60°C or the crystallinity is less than 5%, the surface treatment layer softens at a relatively low temperature. There is

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

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

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

The weight average molecular weight of the polypropylene is preferably 1000 or more and 300000 or less, more preferably 5000 or more and 100000 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 an increase in viscosity during acid modification of polypropylene is suppressed.

Acid modification of polypropylene is carried out by dissolving polypropylene in toluene or xylene and adding an α,β-unsaturated carboxylic acid and/or an acid anhydride of an α,β-unsaturated carboxylic acid and/or 1 in the presence of a radical generator. It can be done with compounds having more than one double bond per molecule. Alternatively, using a device that can raise the temperature to the softening temperature or melting point of polypropylene or higher, 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 carboxylic acid anhydrides and/or compounds having one or more double bonds per molecule. When the modification reaction of polypropylene is carried out in a solution state in an organic solvent such as toluene and/or xylene, or in the case of a reaction in a heterogeneous dispersion system carried out in a non-solvent such as an aqueous system, sufficient nitrogen substitution is performed. is desirable. Thus, an acid-modified polypropylene is prepared.

Examples of such radical generators include peroxides and azonitriles. Examples of the above azonitriles include di-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyethylhexanoate, tert- butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and the like. Examples of the above azonitriles include azobisisobutyronitrile, azobisisopropionitrile, and the like. The content of the radical generator is preferably 0.1 parts by mass or more and 50 parts by mass or less, 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 their anhydrides include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic anhydride, and Contains aconitic acid. The α,β-unsaturated carboxylic acid or its acid anhydride may be one or more. When two or more of the α,β-unsaturated carboxylic acids or their acid anhydrides are used in combination, the physical properties of the surface treatment layer are often improved.

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

One or more compounds having one or more double bonds per molecule may be used. The compounding amount of the compound is preferably 0.1 parts by mass or more and 50 parts by mass or less, 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, antirust agents, lubricants, antifoaming agents, etching agents, inorganic compounds, coloring materials, and the like.

The rust preventive agent improves the corrosion resistance of the metal material. One or more rust inhibitors may be used. Examples of rust inhibitors include metallic compound rust inhibitors, non-metallic compound rust inhibitors, and organic compound rust inhibitors. The content of the rust preventive agent in the surface treatment liquid can be appropriately determined according to the type of the rust preventive agent from the range in which the rust preventive effect of the rust preventive agent and the effect of the present invention can be obtained.

Examples of the metal compound-based antirust agents 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-metallic compound rust inhibitor include thiol compounds such as thiourea.

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

The lubricant can suppress galling on the surface of the metal material. One or more lubricants may be used, and the type of lubricant is not particularly limited. Examples of lubricants include fluorine-based, polyethylene-based, styrene-based, polypropylene-based organic waxes, 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 as the total amount of the resin in the surface treatment liquid. If the amount of the lubricant is less than 1 part by mass, galling may not be sufficiently suppressed. On the other hand, when the amount of the lubricant exceeds 20 parts by mass, the effect of suppressing the occurrence of galling hits a ceiling, and the lubricity is too high, resulting in poor handleability.

The antifoaming agent suppresses the generation of air bubbles during the preparation of the surface treatment liquid. One or more antifoaming agents may be used. The type of antifoaming agent is not particularly limited. As for the antifoaming agent, an appropriate amount of known antifoaming agent such as a silicone antifoaming agent may be added.

The etchant improves the adhesion of the surface treatment layer to the metal material by activating the surface of the metal material. Examples of etchants include fluorides such as hydrofluoric acid, ammonium fluoride, zircon hydrofluoride, titanium hydrofluoride.

The inorganic compound densifies the surface treatment layer to improve water resistance. Examples of inorganic compounds include inorganic oxide sols such as silica, alumina, and zirconia.

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

1-2-6. Physical Properties of Surface Treatment Liquid The viscosity of the surface treatment liquid is 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 material can be obtained, and the surface of the oil surface metal material and the difficult-to-adhere metal material can be obtained. On the other hand, the surface treatment liquid spreads evenly and uniformly, and a surface treatment layer with good adhesion can be formed. The viscosity of the surface treatment liquid is a value measured by the method specified in JISZ-8803 (2011) using a Brookfield 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 applicator used for applying the surface treatment liquid to the surface of a metal material by a spray method, brush coating, stationery coating, or the like. When applied to , it suppresses clogging of treatment liquid applicators (clogging of sprays, nozzle heads, etc.), and resin compositions and felts made of fiber aggregates such as tufts of brushes and pen tips of markers. Excellent impregnation. In addition, since the surface treatment liquid has a viscosity of 2 mPa·s or more, so-called direct current phenomenon such as dripping of the liquid from the treatment liquid applicator and bleeding after application are less likely to occur. In addition, since the surface treatment liquid has a viscosity of 50 mPa·s or less, clogging of the treatment liquid applicator, rubbing during application, and dry-up due to volatilization of the liquid component (improper application due to drying of the treatment liquid applicator) may occur. ) is less likely to occur. From these points of view, 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 resin solid content in the surface treatment liquid or adding a viscosity modifier. Examples of viscosity modifiers include polymeric polysaccharides, water-soluble acrylic resins, inorganic mineral forms, and the like. The content of the viscosity modifier in the surface treatment liquid can be appropriately determined according to the type of the viscosity modifier within a range in which the thickening effect and the effect of the present invention can be obtained.

2. Composite manufacturing method (contact and heating)
Another embodiment of the present invention relates to a 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 casting and drying it to form a surface treatment layer; (3) a step of heating a contact portion between the surface-treated layer and the resin composition molded article; and can be used in the manufacture of composites.

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

Application of the surface treatment liquid can be performed by a known method such as a roll coating method, a curtain flow method, a spin coating method, a spray method, or an immersion lifting method. In addition, application of the surface treatment liquid may be carried out by brush coating, or stationery coating using writing implements such as felt-tip pens, marker pens, calligraphy pens, and markers.

Of these, the spray method, brush coating, and stationery coating are preferred because they do not require large-scale equipment and allow partial surface treatment only where necessary, and from the viewpoint of excellent workability, and brush coating and stationery coating are preferred. more preferred.

The amount of the surface treatment liquid to be 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 strength of the molding of the resin composition to the one metal material is sufficiently increased, and the liquid is contained in the surface treatment layer. The function of the additive (for example, the antirust action of the anticorrosive agent) is also fully exhibited. Although the upper limit of the thickness of the surface treatment layer to be formed is not particularly limited, it can be determined from the viewpoint of reaching the ceiling of the above effects 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.

Drying of the applied surface treatment liquid may be natural drying or drying by heating. These drying conditions may be appropriately selected according to the composition of the surface treatment liquid. For example, when the applied surface treatment liquid is dried by heating, the metal shaped material coated with the surface treatment liquid is put into a drying oven without being washed with water, and the plate temperature reaches 80 ° C. or higher and 250 ° C. or lower. It is sufficient to heat within the range.

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

For example, the molded body of the resin composition is arranged such that at least the part to be joined and the part to be joined of the one metal material are in contact with each other through the surface treatment layer. is placed against the metal stock. In this step, the part to be joined of the molded body of the resin composition and the part to be joined of the one metal material are separated from each other by the surface treatment layer at least at the time of performing the heating step described later. contact through At this time, it is preferable from the viewpoint of preventing misalignment that the one metal material and the resin composition molding are pressed against each other by a fixing jig or the like.

The molded body of the resin composition may be a molded body having a shape that adheres to the surface of the one metal material.

The resin composition forming the molded body of the resin composition is preferably a thermoplastic resin composition because of its high adhesion to the surface treatment layer. Examples of the thermoplastic resin composition include acrylonitrile-butadiene-styrene (ABS)-based resin composition, polyethylene terephthalate (PET)-based resin composition, polybutylene terephthalate (PBT)-based resin composition, polycarbonate (PC)-based Resin compositions, polyamide (PA)-based resin compositions, polyphenylene sulfide (PPS)-based resin compositions, polypropylene (PP)-based resin compositions, combinations thereof, and the like are included. 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, more preferably 0.7% or less, from the viewpoint of further increasing the bonding strength of the coated metal material to the molded body. The molding shrinkage of the thermoplastic resin composition can be adjusted by a known method. For example, the mold shrinkage rate can be adjusted by adding a filler to the thermoplastic resin composition, or by adjusting the mixing ratio of the crystalline resin and the non-crystalline resin in the thermoplastic resin composition. Amorphous resins are, for example, PVC and PMMA. The crystalline resin is, for example, PE, PP, POM, or the like. The mold shrinkage rate can be lowered by, for example, increasing the content of the filler or increasing the mixing ratio of the non-crystalline resin to the crystalline resin.

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

In addition, it is preferable that αp/αm is 6 or less from the viewpoint of suppressing deformation due to 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 preform. If αp/αm is greater than 6, the coated metal material may not be sufficiently strongly bonded to the compact. αp/αm is preferably 4.5 or less from the viewpoint of further increasing the bonding strength of the coated metal material to the compact. αm and αp are each obtained by measuring the amount of dimensional change associated with temperature change of the material by, for example, TMA (Thermal Mechanical Analysis). αp becomes small, for example, when the filler content in the thermoplastic resin composition is large.

The thermoplastic resin composition may further contain components other than the above organic resin within the range where the effects of the present invention can be obtained. Examples of such other ingredients include fillers and thermoplastic elastomers.

The filler reduces the molding shrinkage of the molded article and improves the rigidity of the molded article. The type of filler is not particularly limited, and known substances can be used. One or more fillers may be used. Examples of fillers include fibrous fillers such as glass fibers, carbon fibers and aramid resins, carbon black, calcium carbonate, calcium silicate, magnesium carbonate, silica, talc, glass, clay, lignin, mica, quartz powder and glass spheres. and pulverized carbon fiber and aramid fiber. Among them, glass fiber is more preferable from the viewpoint of maintaining the light transmittance of the molded article. The content of the filler in the thermoplastic resin composition is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, from the above viewpoint.

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

2-3. Heating of Contact Portion Next, the contact portion between the surface treatment layer and the molded body of the resin composition is heated to fuse them together. As a result, the one metal preform and the molded body of the resin composition are joined via the surface treatment layer.
The heating may be performed on at least a part of the surface where the surface-treated layer and the molded article of the resin composition are in contact. It is preferable to perform

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

At this time, for example, by heating so that the reaching temperature is equal to or higher than the melting point of the resin contained in the surface treatment layer, the molded body of the one metal material and the resin composition is formed through the surface treatment layer. can be closely bonded. The upper limit of the temperature to be reached is not particularly limited, but can be determined from the viewpoint that the above effects reach a ceiling or from the viewpoint of suppressing decomposition of the surface treatment layer, and can be set to 250° C. or less, for example.

3. Composite manufacturing method (injection molding)
Another embodiment of the present invention relates to another method of manufacturing a composite using the surface treatment liquid described above. Specifically, the surface treatment liquid includes (1) a step of applying the above-described surface treatment liquid to the surface of one metal material and drying it to form a surface treatment layer, and (2) a surface treatment layer. (3) a molten thermoplastic resin composition inside the injection mold into which the one metal cast is inserted; can be used to manufacture composites by injecting and

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

3-2. Insertion into Mold for Injection Molding Next, the above-mentioned one metal material having the surface treatment layer formed thereon is inserted into a mold for injection molding.

3-3. Injection of Thermoplastic Resin Composition Next, a melted thermoplastic resin composition is injected into the injection mold into which the one metal material has been inserted. The thermoplastic resin composition can be the same as the thermoplastic resin composition that constitutes the molded article of the resin composition described above.

At this time, the thermoplastic resin composition is preferably injected at high pressure. In addition, it is preferable to provide a gas vent in the injection mold 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 one metal preform. The temperature of the injection mold is preferably near the melting point of the thermoplastic resin composition.

4. Treatment Liquid Applicator Another embodiment of the present invention relates to a treatment liquid applicator for applying the surface treatment liquid to the metal material. The treatment liquid applicator is preferably portable.

FIG. 1 is a schematic cross-sectional view showing an example of a treatment liquid applicator according to this embodiment.

FIG. 1A is a schematic cross-sectional view showing an example of a spray-type treatment liquid applicator. As shown in FIG. 1A, the treatment liquid applicator 100a has a container 110a and the above-described surface treatment liquid 120a. The container 110a has a storage portion 112a that stores a surface treatment liquid 120a, and an application portion 114a that applies the surface treatment liquid 120a stored in the storage portion 112a to the surface of the one metal material.

In the treatment liquid applicator 100a, the applicator 114a has a nozzle 115a and a valve 116a. When the nozzle head 117a having the nozzle 115a arranged therein is pushed into the containing portion 112a, the valve 116a is released, and the surface treatment liquid 120a inside the containing portion 112a is pushed out by the pressure of the gas contained inside the containing portion 112a. and jetted from the nozzle 115a. As a result, the applying unit 114a pushes the nozzle head 117a into the storage unit 112a with the nozzle 115a facing the surface of the one metal material, thereby supplying the surface treatment liquid 120a sprayed from the nozzle 115a. can be applied to the surface of the one metal preform.

FIG. 1B is a schematic cross-sectional view showing an example of a felt-tip pen type treatment liquid applicator. As shown in FIG. 1B, the treatment liquid applicator 100b has a container 110b and the above-described surface treatment liquid 120b. The container 110b has a storage portion 112b that stores the surface treatment liquid 120b, and an application portion 114b that applies the surface treatment liquid 120b stored in the storage portion 112b to the surface of the one metal material.

In the treatment liquid applicator 100b, the applicator portion 114b is a fiber aggregate such as a fiber aggregate, felt, and non-woven fabric. The imparting portion 114b, in a state of being in contact with the surface of the one metal material, allows the surface treatment liquid 120b, which has moved from the accommodating portion 112b due to gravity or pressure to the accommodating portion 112b, to pass through the assembly of the fibers. By doing so, the surface treatment liquid 120b can be applied to the surface of the one metal material.

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

1. Metal Forming Material As a metal forming material, an aluminum plate, which is a hard-to-bond metal forming material, was prepared. The aluminum plate used was an Al6061 alloy (JISH 4000 (2014)) with a plate thickness of 1.0 mm. The Al6061 alloy was used without pretreatment such as degreasing or pickling.

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

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

Diammonium hydrogen phosphate (Kishida Chemical Co., Ltd.) was used as the phosphoric acid compound in the surface treatment liquid. The content of the phosphoric acid compound in the surface treatment liquid was adjusted so that the P-converted content in the surface treatment layer to be formed was 0.25% by mass.

Ti, Zr, V and Mo oxides were used as adhesion aids in the surface treatment liquid. Titanium (IV) oxide (Kishida Chemical Co., Ltd.) was used as the Ti oxide. Zirconium ammonium carbonate (Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was used as the Zr oxide. As the V oxide, vanadium pentoxide (Taiyo Koko Co., Ltd.) was used. As the Mo oxide, hexaammonium heptamolybdate tetrahydrate (Kishida Chemical Co., Ltd.) was used. Adhesion aids were added singly or in combination. The content of the adhesion aid in the surface treatment liquid is 0.25% by mass in terms of Ti, 0.5% by mass in terms of Zr, and 0.5% by mass in terms of V in the surface treatment layer to be formed. The content was adjusted to 0.25% by mass and the Mo content was adjusted to 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 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 added amount of a viscosity modifier (ADEKA NOL UH550: ADEKA Corporation).

3. Formation of surface treatment layer A marker pen (Cutter 15 Empty marker: GROG) with a felt-like pen tip attached was used as a treatment liquid applicator. The surface treatment liquid is sealed in the tube tip (accommodating part) of the treatment liquid applicator, and the pen tip (applying part) is impregnated with the surface treatment liquid. ) and air-dried to form a surface treatment layer having a thickness of 0.5 μm or more.

4. Evaluation of Applicability of Surface Treatment Liquid After forming the surface treatment layer, cissing and bleeding were visually observed to evaluate the applicability of the surface treatment liquid. When no cissing of the applied portion (handwriting) was observed, no bleeding was observed, and the edge of the applied portion was clear, the evaluation was made as ⊚. When no cissing or bleeding was observed in the applied portion and the edge of the applied portion was clear, but unevenness in coating was observed, the evaluation was given as ◯. When both or one of the occurrence of cissing in the applied portion and the smearing of the edge of the applied portion due to blurring was observed, the evaluation was made as x.

5. Bonding with Molded Body of Resin Composition A molded body of the resin composition was bonded to the metal preform on which the surface treatment layer was formed. Polycarbonate (PC)-based resins and polypropylene (PP)-based resins, which are thermoplastic resin compositions, were used for molded bodies of resin compositions. Iupilon GSH2030FT (Mitsubishi Engineering-Plastics Co., Ltd.) was used as the PC-based resin. Prime Polypro R-350 (Prime Polymer Co., Ltd.) was used as the PP resin.

The metal casting and resin composition molding can be joined by inserting the metal casting into the mold of an injection molding machine and injecting the melted resin composition, or by It was carried out by pressing the thermoplastic resin composition into the metal preform and heating it. When the resin composition was injected, the resin composition was cooled and solidified in the mold to obtain a composite in which the molded metal material and the resin composition were joined together. When heating the metal material by pressing the resin composition, a heating device using a heater chip (Pulse Heat Unit NA-154: Nippon Avionics Co., Ltd.) is used, and the heating temperature is adjusted by adjusting the current value. controlled. The shape of the composite was a type B test piece defined in ISO19095-2.

6. Adhesion evaluation of the surface treatment layer After joining the molded body 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. evaluated. When 80% or more of the surface treatment layer remained on the metal material side, the evaluation was made as ⊚. When 40% or more and less than 80% of the surface treatment layer remained on the metal material side, the evaluation was made as ◯. When less than 40% of the surface treatment layer remained on the metal material side, the evaluation was made as x.

7. Evaluation Results Examples 1 to 14 and Comparative Examples 1 to 15 were carried out by changing the components and the viscosity of the molded article of the resin composition and the surface treatment liquid. Table 1 shows the combinations of conditions and the evaluation results of Examples and Comparative Examples.

Examples 1 to 2, 4 to 6 and 9 to 10 contain a phosphoric acid compound and an adhesion aid, and the organic solvent and viscosity are within the range satisfying the present invention. The properties and adhesion were good.

In Examples 3 and 7 to 8, uneven coating (difference in coating amount) was observed in the coated part, but the phosphoric acid compound and adhesion aid were contained, and the organic solvent and viscosity were in the range satisfying the present invention. Therefore, the coatability and adhesion were good in all the examples.

In Examples 11 to 14, a phosphoric acid compound and an adhesion aid were contained, and the organic solvent and viscosity were within the ranges satisfying the present invention. rice field.

In Comparative Examples 1 and 2, the content of the organic solvent was less than the lower limit of the range, and the wettability of the surface treatment liquid to the metal material was inferior, and repelling was partially observed. Therefore, the result was that the coatability was inferior.

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

In Comparative Examples 5 and 6, the viscosities were lower than the lower limit of the range, and bleeding was observed, resulting in poor applicability. In addition, since the viscosity was out of the range, the adhesion of the surface treatment layer was also inferior.

In Comparative Examples 7 and 8, the viscosity was higher than the upper limit of the range, and cissing was observed, so the applicability was inferior. In addition, since the viscosity was out of the range, the adhesion of the surface treatment layer was also inferior.

In Comparative Examples 9 and 10, the content of the organic solvent was less than the lower limit of the range, and the wettability of the surface treatment liquid to the metal material was inferior, and repelling was partially observed. Therefore, the result was that the coatability was inferior.

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

In Comparative Examples 13 to 15, although the organic solvent and viscosity were within the ranges, the results were poor in coatability and adhesion. This is because neither the phosphoric acid compound nor the adhesion aid, or both, which are effective in improving coatability and adhesion, were contained.

The surface treatment liquid of the present invention has a viscosity suitable for a portable treatment liquid applicator, and has excellent adhesion to oil surface metal materials and difficult-to-adhere metal materials without pretreatment. , various electronic devices, household electrical appliances, medical devices, automobile bodies, vehicle-mounted goods, construction materials, and the like.

100a, 100b treatment liquid applying tool 110a, 110b container 112a, 112b storage section 114a, 114b applying section 115a nozzle 116a valve 117a nozzle head 120a, 120b surface treatment liquid

Claims (8)

For forming a metal material for forming on the surface of the one metal material a surface-treated layer capable of being in contact with and bonding the molded article of the resin composition to the one metal material. A surface treatment liquid of
a phosphoric acid compound in an amount such that the content relative to the total solid content is 0.05% by mass or more and less than 3.0% by mass in terms of P atoms ;
an adhesion aid that is an oxide, hydroxide or fluoride of a metal 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;
a resin emulsion;
(excluding those in which the water-soluble organic resin and/or water-dispersible organic resin content is 0 to 15% by mass in the total solid content),
Viscosity is 2 mPa s or more and 50 mPa s or less,
Surface treatment liquid for metal materials. 2. The surface treatment liquid for metal castings according to claim 1, wherein said resin includes a polyurethane-based resin. 2. The surface treatment liquid for metal castings according to claim 1, wherein said resin includes a polypropylene resin. A step of applying the surface treatment liquid according to any one of claims 1 to 3 to the surface of one metal material and drying it to form a surface treatment layer;
A step of disposing a molded body of the resin composition so as to be in contact with the surface treatment layer on the one metal preform;
a step of heating a contact portion between the surface treatment layer and the molded body of the resin composition;
A method for producing a composite. A step of applying the surface treatment liquid according to any one of claims 1 to 3 to the surface of one metal material and drying it to form a surface treatment layer;
a step of inserting the one metal material on which the surface treatment layer is formed into an injection mold;
a step of injecting a molten thermoplastic resin composition into the injection mold into which the one metal material is inserted;
A method for producing a composite. a container;
a surface treatment liquid for metal forming materials according to any one of claims 1 to 3, which is contained in the container;
has
The container is
a storage unit that stores a surface treatment liquid for the metal material;
an application unit for applying the surface treatment liquid stored in the storage unit to the metal material;
A treatment liquid applicator. The application unit applies the surface treatment liquid to the metal material by spraying or ejecting the surface treatment liquid from a nozzle head.
The treatment liquid applicator according to claim 6. The applying unit applies the surface treatment liquid to the metal material by passing the surface treatment liquid through an assembly of fibers in contact with the metal material.
The treatment liquid applicator according to claim 6.

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