JP2016179546A - COATED Al-CONTAINING METAL SHAPED MATERIAL, COMPLEX, AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated AL-containing metal shaped material used for a complex having superior bondability and sealability between an AL-containing metal shaped material and a molding of a thermoplastic resin composition.SOLUTION: The coated AL-containing metal shaped material has an AL-containing metal shaped material comprising aluminum or aluminum alloy, and an acid-modified polypropylene layer that is arranged on the AL-containing metal shaped material and contains 40 mass% or more of acid-modified polypropylene. The melt viscosity of the acid-modified polypropylene layer is 1,000-10,000 Pa s. The film thickness of the acid-modified polypropylene layer is 0.2 μm or more.SELECTED DRAWING: None

Description

  The present invention relates to a painted Al-containing metal preform, a composite in which a painted Al-containing metal preform and a molded body of a thermoplastic resin composition are joined, and a method for producing them.

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

  When producing a composite by insert molding, it is important to improve the adhesion between the metal base material and the molded body of the resin composition. As a method for improving the adhesion between the metal shaped material and the molded body of the resin composition, for example, it is proposed to roughen the surface of the metal shaped material before performing insert molding (patent) References 1-3). In the methods of Patent Documents 1 to 3, the surface of the Al alloy is roughened to improve the bondability between the Al alloy and the molded body of the resin composition.

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

  In the composites described in Patent Documents 1 to 3, the surface of the Al alloy shaped material is roughened in order to use the anchor effect. As described above, when fine irregularities are formed on the surface of the Al alloy shaped material for the purpose of anchor effect, a fine gap is easily formed between the Al alloy shaped material and the molded body of the resin composition. For this reason, in the composites described in Patent Documents 1 to 3, the sealability between the Al alloy shaped material and the molded resin composition is low, and the Al alloy shaped material and the molded resin composition There was a risk of gas or liquid leaking from between.

  The present invention has been made in view of the above points, and provides a composite excellent in bondability and sealability between a painted Al-containing metal preform and a molded article of a thermoplastic resin composition, and a method for producing the same. The purpose is to provide. It is another object of the present invention to provide a coated Al-containing metal shape material used for manufacturing the composite and a method for manufacturing the same.

  The present inventors have found that the above-mentioned problems can be solved by forming an acid-modified polypropylene layer on the surface of an Al-containing metal shape material using a predetermined acid-modified polypropylene, and further studies are made to complete the present invention. I let you.

That is, the present invention relates to the following painted Al-containing metal profile and composite.
[1] having an Al-containing metal element made of aluminum or an aluminum alloy, and an acid-modified polypropylene layer disposed on the Al-containing metal element and containing 40% by mass or more of acid-modified polypropylene, The melt-modified viscosity of the acid-modified polypropylene layer is 1000 to 10,000 mPa · s, and the film thickness of the acid-modified polypropylene layer is 0.2 μm or more.
[2] The degree of distortion (Rsk) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is arranged in the Al-containing metal profile is −1.0 or more, and in the Al-containing metal profile The painted Al-containing metal profile according to [1], wherein the surface roughness curve of the surface on which the acid-modified polypropylene layer is disposed has a kurtosis (Rku) of less than 200.
[3] The melting point of the acid-modified polypropylene layer is in the range of 60 to 120 ° C., and the crystallinity of the acid-modified polypropylene layer is in the range of 5 to 20%. [1] or [2] Painted Al-containing metal preform as described in 1.
[4] The molded body of the thermoplastic resin composition bonded to the surface of the painted Al-containing metal profile according to any one of [1] to [3] and the painted Al-containing metal profile. And having a complex.
[5] The composite according to [4], wherein the thermoplastic resin composition has a molding shrinkage of 1.1% or less.

Moreover, this invention relates to the manufacturing method of the following coating Al containing metal raw material, and the manufacturing method of a composite_body | complex.
[6] A preparation step of preparing an Al-containing metal preform made of aluminum or an aluminum alloy, and an acid-modified polypropylene having a melt viscosity in the range of 1000 to 10,000 mPa · s on the surface of the Al-containing metal preform. A coating Al-containing metal element having a coating step of forming an acid-modified polypropylene layer containing 40% by mass or more of acid-modified polypropylene and having a film thickness of 0.2 μm or more. A method of manufacturing the material.
[7] The degree of distortion (Rsk) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is formed in the Al-containing metal profile is −1.0 or more, and in the Al-containing metal profile The method for producing a coated Al-containing metal profile according to [6], wherein the surface roughness curve of the surface on which the acid-modified polypropylene layer is formed has a kurtosis (Rku) of less than 200.
[8] The melting point of the acid-modified polypropylene layer is in the range of 60 to 120 ° C., and the crystallinity of the acid-modified polypropylene layer is in the range of 5 to 20%. [6] or [7] The manufacturing method of the coating Al containing metal raw material of description.
[9] A method for producing a composite in which an Al-containing metal base material and a molded body of a thermoplastic resin composition are joined, the coating Al-containing material according to any one of [1] to [3] A step of preparing a metal raw material, and a surface of the coated Al-containing metal raw material is brought into contact with a heated thermoplastic resin composition; Joining a molded article of the product.
[10] The method for producing a composite according to [9], wherein the thermoplastic resin composition has a molding shrinkage of 1.1% or less.

  According to the present invention, a composite excellent in bondability and sealing property between a painted Al-containing metal shape material and a molded body of a thermoplastic resin composition, and a painted Al-containing metal shape material used therefor Can be provided.

FIG. 1A is a schematic diagram of a composite for measuring bonding strength, and FIG. 1B is a schematic diagram of a composite for measuring gas sealing properties. FIG. 2 is a schematic diagram of measurement of the leak amount of helium gas.

1. Composite The composite according to the present invention comprises a painted Al-containing metal shaped material according to the present invention and a molded body of a thermoplastic resin composition bonded to the surface of the painted Al-containing metal shaped material according to the present invention. Have. Hereafter, each component of the composite_body | complex which concerns on this invention is demonstrated.

(1) Painted Al-containing metal profile The painted Al-containing metal profile according to the present invention includes an Al-containing metal profile (A) and an acid-modified polypropylene layer disposed on the surface of the Al-containing metal profile. (C). In the coated Al-containing metal element, the surface treatment film (B) may be disposed between the Al-containing metal element and the acid-modified polypropylene layer. Hereinafter, each component of the painted Al-containing metal profile will be described.

A. Al-containing metal material The type of the Al-containing metal material used as the coating substrate is not particularly limited as long as it is made of an Al-containing metal selected from Al and an Al alloy. Examples of the Al-containing metal shaped material include rolled products such as plate materials and extruded shapes, and die-cast products formed by casting, forging, cutting, powder metallurgy, and the like. The Al-containing metal shape material may be subjected to known coating pretreatments such as degreasing and pickling as necessary.

  The degree of distortion (Rsk) of the surface roughness curve on the surface of the Al-containing metal profile is preferably −1.0 or more. When Rsk is less than −1.0, since the concave portion on the surface of the Al-containing metal shape member is small (the width of the concave portion is narrow), the flow of acid-modified polypropylene may be hindered and gas sealing performance may be reduced. . In the Al-containing metal profile, only the surface on which the acid-modified polypropylene layer is disposed may be a predetermined Rsk, or both surfaces may be a predetermined Rsk.

  The kurtosis (Rku) of the surface roughness curve on the surface of the Al-containing metal profile is preferably less than 200. When Rku is 200 or more, the convex portion has a sharp shape, and there is a possibility that a portion not covered with the acid-modified polypropylene layer may be generated. Thereby, there exists a possibility that the joining force of the coating Al containing metal raw material and the molded object of a thermoplastic resin composition may fall. In the Al-containing metal profile, only the surface on which the acid-modified polypropylene layer is disposed may be a predetermined Rku, or both surfaces may be a predetermined Rku.

  Rsk and Rku are defined in JIS B 0601-2001. Rsk and Rku are measured using a contact-type surface roughness meter (ET4000AK31; Kosaka Laboratory Ltd.).

  The method for adjusting Rsk and Rku on the surface of the Al-containing metal profile is not particularly limited. Examples of methods for adjusting Rsk and Rku on the surface of the Al-containing metal profile include adjustment of roll roughness during temper rolling, and blasting such as grit blasting, garnet blasting, sand blasting and shot blasting. In addition, when the Al-containing metal shape material is a plating material, Rsk and Rku on the surface of the Al-containing metal shape material can be adjusted by adjusting the surface state of the material before plating.

B. Surface Treatment Film The coated Al-containing metal shape material may have a chemical conversion treatment film or an alumite film formed between the Al-containing metal shape material and the acid-modified polypropylene layer. The chemical conversion treatment film is disposed on the surface of the Al-containing metal profile, and improves the adhesion between the Al-containing metal profile and the acid-modified polypropylene layer and the corrosion resistance of the painted Al-containing metal profile. In addition, the anodized film can improve the corrosion resistance and wear resistance of the Al-containing metal material, and can also have other functions such as decoration. These films may be formed on the entire surface of the surface of the Al-containing metal shape member, or may be formed on only a part of the surface.

The kind of chemical conversion treatment which forms a chemical conversion treatment film is not specifically limited. Examples of the chemical conversion treatment include chromate treatment, chromium-free treatment, phosphate treatment and the like. The adhesion amount of the chemical conversion treatment film formed by chemical conversion treatment is not particularly limited as long as it is within a range effective for improving coating film adhesion and corrosion resistance. For example, in the case of a chromate film, the adhesion amount may be adjusted so that the total Cr conversion adhesion amount is 5 to 100 mg / m ² . Further, in the case of a chromium-free coating, the Ti-Mo composite coating has a range of 10 to 500 mg / m ² , and the fluoroacid-based coating has a fluorine equivalent or total metal element equivalent deposit of 3 to 100 mg / m ^2. The adhesion amount may be adjusted. Moreover, what is necessary is just to adjust the adhesion amount so that it may become 0.1-5 g / m < ² > in the case of a phosphate membrane | film | coat.

Examples of the alumite treatment include a method of performing electrolysis using Al as an anode in a treatment bath containing dilute sulfuric acid, oxalic acid, or the like. Thereby, the surface of Al is electrochemically oxidized, and a porous film of aluminum oxide (Al ₂ O ₃ ) can be formed. Another example of the alumite treatment includes a method of treating Al with an acid having a low dissolving power with respect to Al oxide such as boric acid. As a result, a thin oxide layer having a thickness of several tens to several hundreds of nanometers can be formed on the surface of Al. Further, if necessary, the alumite film may be sealed. Examples of the sealing treatment include pore inactivation by a chemical reaction and pore filling by a polymer. For example, the alumite film may be β-aluminated by hydration with a high-temperature liquid such as boiling water or nickel acetate solution, or pressurized steam, and the pore wall may be hydrated and expanded for sealing. Further, the alumite film may be colored by adsorbing a metal salt, an organic dye or the like to the porous using the porous property of the alumite film.

C. Acid-modified polypropylene layer The acid-modified propylene layer is disposed on the surface of the Al-containing metal profile (or surface treatment film) and is a layer containing 40% by mass or more of acid-modified polypropylene. The acid-modified polypropylene layer improves the adhesion between the coated Al-containing metal shape material and the molded body of the thermoplastic resin composition. When the acid-modified polypropylene content in the acid-modified polypropylene layer is less than 40% by mass, the compatibility between the acid-modified polypropylene layer and the molded article of the thermoplastic resin composition is lowered. Thereby, there exists a possibility that the joining force of the coating Al containing metal raw material and the molded object of a thermoplastic resin composition may not be acquired. For the acid-modified polypropylene layer, a coating containing acid-modified polypropylene having a melting point and a crystallinity within a predetermined range is applied to the surface of an Al-containing metal profile (or surface treatment film), and the solvent (water) is heated and dried. It is formed by evaporating.

  The melt viscosity of the acid-modified polypropylene layer containing 40% by mass or more of acid-modified polypropylene is in the range of 1000 to 10,000 mPa · s. When the melt viscosity of the acid-modified polypropylene is less than 1000 mPa · s, the acid-modified polypropylene layer flows during bonding with the molded article of the thermoplastic resin composition, and compatibility with the thermoplastic resin composition occurs. Therefore, there is a possibility that the bonding strength between the painted Al-containing metal element and the molded product of the thermoplastic fat composition cannot be obtained. On the other hand, when the melt viscosity of the acid-modified polypropylene exceeds 10,000 mPa · s, the compatibility between the acid-modified polypropylene layer and the molded body of the thermoplastic resin composition decreases, so that the coated Al-containing metal base material and the thermoplastic fat There is a possibility that the bonding strength of the composition to the molded body may not be obtained. The melt viscosity of the acid-modified polypropylene layer is measured with a Brookfield viscometer.

  The acid-modified polypropylene layer in the coated Al-containing metal profile according to the present invention contains an acid-modified polypropylene having a melting point in the range of 60 to 120 ° C. and a crystallinity in the range of 5 to 20%. It is preferable. The acid-modified polypropylene having a melting point and a crystallinity within the above ranges have high wettability with respect to the surface of the Al-containing metal shape material, Become. When the melting point of the acid-modified polypropylene is less than 60 ° C. or the crystallinity is less than 5%, the acid-modified polypropylene layer is softened at a relatively low temperature. May be inferior. On the other hand, when the melting point of the acid-modified polypropylene exceeds 120 ° C. or the degree of crystallinity exceeds 20%, the bondability between the coated Al-containing metal element and the molded article of the thermoplastic resin composition may be lowered. Note that the melting point and crystallinity of the acid-modified polypropylene hardly change between the state contained in the paint (before baking) and the state of the acid-modified polypropylene layer (after baking). Therefore, the degree of crystallinity of the acid-modified polypropylene in the acid-modified polypropylene layer can be examined by measuring a paint described later containing the acid-modified polypropylene by X-ray diffraction by the Ruland method.

  The film thickness of the acid-modified polypropylene layer is 0.2 μm or more. When the film thickness of the acid-modified polypropylene layer is less than 0.2 μm, the surface of the Al-containing metal shaped material cannot be uniformly covered. For this reason, the composite having an acid-modified polypropylene layer with a film thickness of less than 0.2 μm is coated with Al by forming a fine gap between the Al-containing metal profile and the molded body of the thermoplastic resin composition. There is a possibility that the bonding strength between the metal-containing material and the molded body of the thermoplastic resin composition is lowered. Moreover, when a fine space | gap arises, there exists a possibility that the sealing performance in the above-mentioned composite body may fall. On the other hand, the upper limit of the film thickness of the acid-modified polypropylene layer is not particularly limited, but the film thickness is preferably 3 μm or less. Even if the film thickness exceeds 3 μm, no significant performance improvement is observed, and it is disadvantageous from the viewpoint of manufacturing and cost.

  The composition of the coating applied to the surface of the Al-containing metal profile is not particularly limited as long as it contains the acid-modified polypropylene. For example, the paint applied to the surface of an Al-containing metal base material is an acid-modified polypropylene-based aqueous emulsion, a non-acid-modified water-based resin emulsion, a crosslinking agent, a rust inhibitor, a lubricant, a stabilizer, and an antifoaming agent. Containing. Hereinafter, each component will be described.

  The acid-modified polypropylene emulsion can be prepared by preparing an acid-modified polypropylene and then dispersing the acid-modified polypropylene in water. The acid-modified polypropylene emulsion may contain various surfactants as an emulsifier. The amount of the acid-modified polypropylene in the paint can be prepared by blending an acid-modified polypropylene emulsion and a non-acid-modified aqueous resin emulsion.

  Polypropylene is known for the stereoregularity of isotactic, tactic, syndiotactic, hemi-isotactic and stereotactic. The stereoregularity of polypropylene is preferably isotactic from the viewpoint of mechanical properties such as rigidity and impact strength required after molding or durability.

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

  The acid modification of polypropylene involves dissolving polypropylene in toluene or xylene, and in the presence of a radical generator, an α, β-unsaturated carboxylic acid and / or an acid anhydride of α, β-unsaturated carboxylic acid and / or 1 This can be done using compounds having one or more double bonds per molecule. Alternatively, using an apparatus capable of raising the temperature to the softening temperature or melting point of polypropylene, the α, β-unsaturated carboxylic acid and / or α, β-unsaturated in the presence or absence of a radical generator. Carboxylic acid anhydrides and / or compounds having one or more double bonds per molecule can be used.

  Examples of the radical generator include di-tert-butyl perphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyethyl hexano. Peroxides such as ate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide; azonitriles such as azobisisobutyronitrile and azobisisopropionitrile. It is preferable that the compounding quantity of a radical generator exists in the range of 0.1-50 mass parts with respect to 100 mass parts of polypropylene. Moreover, it is particularly preferably within the range of 0.5 to 30 parts by mass.

  Examples of types of α, β-unsaturated carboxylic acids or acid anhydrides include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid and Aconitic anhydride is included. These compounds may be used alone or in combination of two or more. When two or more compounds are used in combination, the properties of the acid-modified polypropylene layer are often improved.

  Examples of compounds having one or more double bonds per molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryl Isobornyl acid, benzyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, di (meth) acrylic acid (di) Ethylene glycol, di (meth) acrylic acid-1,4-butanediol, (dimeth) acrylic acid-1,6-he Such as sundiol, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, acrylamide, etc. ) Acrylic acid monomer; Styrene monomers such as styrene, α-methyl styrene, paramethyl styrene, chloromethyl styrene are included. Furthermore, in addition to the compound, vinyl monomers such as divinylbenzene, vinyl acetate, and vinyl ester of versatic acid can be used in combination.

  These compounds having a double bond may be used alone or in combination of two or more. It is preferable that the compounding quantity of the compound which has these double bonds exists in the range of 0.1-50 mass parts with respect to 100 mass parts of polypropylene. Especially preferably, it exists in the range of 0.5-30 mass parts.

  The acid value of the acid-modified polypropylene is preferably 1 to 500 mg · KOH / g or less. If it is a predetermined acid value, the compound polymer itself which has a double bond acts as surfactant by neutralizing at the time of the below-mentioned emulsification. When this modification reaction is performed in a solution state in an organic solvent such as toluene and / or xylene, or in a non-uniform dispersion system performed in a non-solvent such as an aqueous system, sufficient nitrogen substitution is required. There is. In this way, acid-modified polypropylene can be prepared.

  The aqueous resin emulsion can be prepared by blending and dispersing water in the acid-modified polypropylene prepared as described above. A surfactant may be added to the aqueous resin emulsion. The kind of surfactant is not specifically limited. Examples of surfactant types include nonionic surfactants, anionic surfactants, and cationic surfactants. In place of these surfactants, polymer emulsifiers or dispersants may be used. These surfactants may be used alone or in combination of two or more. The blending amount of the surfactant is preferably in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the modified polypropylene.

  The water-based resin emulsion not modified with acid can be prepared by dispersing a predetermined resin in water. Examples of resins used in non-acid-modified aqueous resin emulsions include acrylic resins, acrylic / styrene resins, vinyl acetate, EVA (ethylene-vinyl acetate copolymer resins), fluorine resins, urethane resins, esters Resin, olefin resin, or a combination thereof.

  Return to the description of each component contained in the paint. The crosslinking agent crosslinks the acid-modified polypropylene and improves the strength of the film. The type of the crosslinking agent is not particularly limited. Examples of types of crosslinking agents include those having isocyanate, epoxy, oxazoline, melamine, or metal salts. It is preferable that the compounding quantity of the crosslinking agent in a coating material exists in the range of 1-30 mass parts with respect to 100 mass parts of acid-modified polypropylene. When the crosslinking agent is less than 1 part by mass, the acid-modified polypropylene may not be sufficiently crosslinked. On the other hand, when the crosslinking agent exceeds 30 parts by mass, there is a risk of thickening and solidifying the treatment liquid.

  The rust inhibitor improves the corrosion resistance of the coated Al-containing metal profile according to the present invention and the composite according to the present invention. The kind of rust preventive agent is not specifically limited. Examples of types of rust preventives include oxides, hydroxides or fluorides of metals (valve metals) selected from the group consisting of Ti, Zr, V, Mo and W, or combinations thereof. preferable. By dispersing these metal compounds in the chemical conversion film, the corrosion resistance of the coated Al-containing metal profile can be further improved. In particular, these metal fluorides can also be expected to suppress corrosion at film defects by a self-repairing action.

  The acid-modified polypropylene layer may further contain a soluble metal phosphate or complex phosphate, or a hardly soluble metal phosphate or complex phosphate. Soluble metal phosphates and composite phosphates further improve the corrosion resistance of the Al-containing metal profile by complementing the self-healing action of the metal fluorides. Further, the hardly soluble metal phosphate and composite phosphate are dispersed in the acid-modified polypropylene layer to improve the film strength. For example, the soluble metal phosphate or complex phosphate, or the poorly soluble metal phosphate or complex phosphate is a salt of Al, Ti, Zr, Hf, Zn or the like.

  The lubricant can suppress galling on the surface of the coated Al-containing metal profile according to the present invention. The type of lubricant is not particularly limited. Examples of types of lubricants include organic waxes such as fluorine-based, polyethylene-based, styrene-based, and polypropylene-based materials; and inorganic lubricants such as molybdenum disulfide and talc. The blending amount of the lubricant in the paint is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the acid-modified polypropylene. When the lubricant is less than 1 part by mass, the generation of galling may not be sufficiently suppressed. On the other hand, when the amount of the lubricant exceeds 20 parts by mass, no significant improvement is observed in the effect of suppressing the generation of galling, and the lubricity is too high and the handleability may be poor.

  The antifoaming agent makes it difficult for bubbles to be generated during preparation of the paint. The type of the antifoaming agent is not particularly limited, but an appropriate amount of a known silicone-based antifoaming agent may be added as necessary.

(2) Molded body of thermoplastic resin composition The molded body of the thermoplastic resin composition is joined to the surface of the coated Al-containing metal profile (more precisely, the surface of the acid-modified polypropylene layer). The thermoplastic resin composition constituting the molded body is a non-crystalline resin composition such as a polyvinyl chloride (PVC) resin composition, a methacrylic acid (PMMA) resin composition, or a polyethylene (PE) resin. A crystalline resin composition such as a composition, a polypropylene (PP) resin composition, a polyacetal (POM) resin composition, or a combination thereof. The shape of the molded article of the thermoplastic resin composition is not particularly limited and can be appropriately selected depending on the application.

  The molding shrinkage of the molded article of the thermoplastic resin composition is preferably 1.1% or less. The molding shrinkage of the thermoplastic resin composition can be adjusted by a known method. For example, the molding shrinkage can be adjusted by adding an inorganic filler or the like to the thermoplastic resin composition containing (A) a thermoplastic elastomer. The molding shrinkage can also be adjusted by changing the mixing ratio of (B) crystalline resin and amorphous resin.

A. Adjustment of Mold Shrinkage Ratio by Addition of Inorganic Filler The thermoplastic elastomer improves the impact resistance of the molded article of the thermoplastic resin composition. The kind of thermoplastic elastomer is not particularly limited. Examples of thermoplastic elastomers include polyolefin resins, polystyrene resins, and combinations thereof. The inorganic filler reduces the molding shrinkage of the molded article of the thermoplastic resin composition and improves the rigidity. The kind of inorganic filler is not particularly limited, and a known substance can be used. Examples of inorganic fillers include fiber fillers such as glass fiber, carbon fiber, and aramid resin; carbon black, calcium carbonate, calcium silicate, magnesium carbonate, silica, talc, glass, clay, lignin, mica, quartz powder, glass Powder fillers such as spheres; pulverized products of carbon fibers and aramid fibers are included. An inorganic filler may be used independently and may be used in combination of 2 or more type. The filler content in the thermoplastic resin composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 40% by mass.

B. Adjustment of Molding Shrinkage Ratio by Mixing Crystalline Resin and Amorphous Resin Molding shrinkage ratio of the thermoplastic resin composition can also be adjusted by mixing the crystalline resin and the amorphous resin. Generally, the molding shrinkage rate of the crystalline resin is larger than the molding shrinkage rate of the amorphous resin. Therefore, if the mixing ratio of the amorphous resin to the crystalline resin is increased, the molding shrinkage rate of the thermoplastic resin composition can be decreased.

2. Manufacturing method of composite body The manufacturing method of the composite body according to the present invention includes (1) a first step of preparing a coated Al-containing metal shape material according to the present invention, and (2) a surface of the painted Al-containing metal shape material. And a second step of bringing the molded body of the thermoplastic resin composition into contact with the surface of the coated Al-containing metal shaped material by contacting the heated thermoplastic resin composition. Hereinafter, each step will be described.

(1) First Step In the first step, a coated Al-containing metal shape material according to the present invention is prepared. As described above, the coated Al-containing metal profile according to the present invention is a method in which a coating containing a predetermined acid-modified polypropylene is applied to the surface of the Al-containing metal profile and dried to form an acid-modified polypropylene layer. Formed with. Before forming the acid-modified polypropylene layer, a surface treatment film such as a chemical conversion film or an alumite film may be formed.

  In the case of forming a chemical conversion treatment film on the surface of the Al-containing metal raw material, the chemical conversion treatment film can be formed by applying a chemical conversion treatment liquid to the surface of the Al-containing metal raw material and drying it. The method for applying the chemical conversion liquid is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. What is necessary is just to set suitably the drying conditions of a chemical conversion liquid according to the composition of a chemical conversion liquid, etc. For example, an Al-containing metal element coated with a chemical conversion treatment solution is placed in a drying oven without being washed with water, and heated so that the ultimate plate temperature is in the range of 80 to 250 ° C. A uniform chemical conversion coating can be formed on the surface of the profile.

  The acid-modified polypropylene layer is formed by applying a paint containing the above-mentioned acid-modified polypropylene to the surface of the Al-containing metal shape member (or surface treatment film) and drying it. The method for applying the paint is not particularly limited, and may be appropriately selected from known methods. Examples of such a coating method include a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method. The drying method is not particularly limited, and the solvent (water) in the acid-modified polypropylene layer may be volatilized. For example, the Al-containing metal profile coated with acid-modified polypropylene is dried without being washed with water. The drying temperature is not particularly limited, but it is preferable that the ultimate plate temperature at the time of drying is 250 ° C. or lower and the melting point of the acid-modified polypropylene or higher. By setting the ultimate plate temperature to 250 ° C. or less, it is possible to form an acid-modified polypropylene layer that is in close contact with the surface of the Al-containing metal shaped material (or chemical conversion film) without any gap. Further, by setting the drying temperature to be equal to or higher than the melting point of the acid-modified polypropylene, the emulsion particles of the acid-modified polypropylene are melted and the acid-modified polypropylene tends to be in a film form. Also, the drying time is not particularly limited. When the drying temperature is low, it is possible to form an acid-modified polypropylene layer that is in close contact with the surface of the Al-containing metal shaped material (or the chemical conversion film) by increasing the drying time. On the other hand, when the drying temperature is high, the drying time is shortened using a drying oven or the like, and the decomposition of the acid-modified polypropylene is suppressed, and the Al-containing metal shape material (or chemical conversion film) is closely adhered to the surface. An acid-modified polypropylene layer can be formed.

(2) Second Step In the second step, the surface of the painted Al-containing metal shape material is brought into contact with the heated thermoplastic resin composition, and the surface of the painted Al-containing metal shape material is contacted with the thermoplastic resin composition. Join the compact. The painted Al-containing metal shape material may be processed into a desired shape by pressing or the like.

  For example, after inserting the coated Al-containing metal profile according to the present invention prepared in the first step into the injection mold, the molten thermoplastic resin composition is injected into the injection mold at a high pressure. do it. At this time, it is preferable to provide a gas vent in the injection mold so that the thermoplastic resin composition flows smoothly. The molten thermoplastic resin composition is compatible with the organic resin layer formed on the surface of the Al-containing metal profile. At this time, the temperature of the injection mold is preferably near the melting point of the thermoplastic resin composition. In addition, the composite obtained by injection molding may be annealed after molding to eliminate internal distortion due to molding shrinkage.

  In addition, after setting the coated Al-containing metal shape material according to the present invention prepared in the first step and the thermoplastic resin composition in a thermocompression press machine, these painted Al-containing metal shape material and thermoplastic resin Heat and pressure may be applied to the composition. At this time, heating and pressurization may be performed on all or part of the painted Al-containing metal profile and the thermoplastic resin composition. It is necessary to heat and press at least the joint surfaces of the painted Al-containing metal profile and the thermoplastic resin composition. Part of the heated and pressurized acid-modified polypropylene layer and part of the thermoplastic resin composition are melted and compatible. The method for heating and pressurizing the painted Al-containing metal profile and the thermoplastic resin composition are not particularly limited. Examples of the heating method include heater heating, electromagnetic induction heating, and ultrasonic heating. Examples of the pressurizing method include pressurization by human power, pressurization using a vise and the like.

  By the above procedure, the composite of the present invention can be produced by joining the molded body of the thermoplastic resin composition to the surface of the painted Al-containing metal profile.

  As described above, when producing the coated Al-containing metal profile according to the present invention, a coating containing acid-modified polypropylene having a melting point and a crystallinity within a predetermined range is applied to the surface of the Al-containing metal profile. By applying and drying, the paint is brought into intimate contact with the surface of the Al-containing metal shape member to form an acid-modified polypropylene layer. Since this acid-modified polypropylene layer is compatible with the thermoplastic resin composition, the acid-modified polypropylene layer can be firmly bonded to the molded body of the thermoplastic resin composition without any gap. For this reason, in the composite according to the present invention, the Al-containing metal element and the molded body of the thermoplastic resin composition are joined without a gap. As described above, the composite containing the coated Al-containing metal preform according to the present invention joins the Al-containing metal preform and the molded body of the thermoplastic resin composition without gaps, so that gas and liquid can be sealed. Excellent stopping properties.

  Hereinafter, although this invention is demonstrated in detail with reference to the Example at the time of using an Al alloy plate for Al containing metal shape material, this invention is not limited by these Examples.

[Example 1]
In Example 1, the blocking resistance of the coated Al-containing metal profile was examined.

1. Preparation of painted Al-containing metal shape material (1) Al-containing metal shape material Paint substrate 1
A1050 with an alumite treatment thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 1 was 6.5, and Rku was 72.2.

B. Paint base 2
A1050 having an alumite treatment with a plate thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 2 was 11.7, and Rku was 191.1.

C. Paint base 3
A2017 uncoated alumite with a thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 3 was 3.3, and Rku was 14.4.

D. Paint base 4
A2017 was prepared by sandblasting with a plate thickness of 0.5 mm. The Rsk of the surface of the coated substrate 4 was 14.4, and Rku was 206.1.

E. Paint base 5
A5052 not prepared by anodizing with a plate thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 5 was 6.0, and Rku was 49.6.

F. Paint base 6
A6063 which is not anodized and has a thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 6 was −0.3, and Rku was 1.8.

G. Paint base material 7
A6063 which processed alumite with a plate thickness of 0.5 mm was prepared. The Rsk of the surface of the coated substrate 7 was −1.2, and Rku was 4.6.

(2) Preparation of paint Acid-modified polypropylene resin (A), polyurethane-based resin (B), polyethylene wax (C), epoxy-based crosslinking so that the ratio of acid-modified polypropylene to the total mass of the resin is as shown in Table 1. Agent (D) was added to water to prepare a paint having a non-volatile component of 20%. In addition, for coating materials, ammonium molybdate (Kishida Chemical Co., Ltd.): 0.5% by mass, zirconium carbonate (zircazole; Daiichi Rare Element Chemical Co., Ltd.): 0.5% by mass as a rust preventive agent, silicone type Antifoaming agent (KM-73; Shin-Etsu Chemical Co., Ltd.): 0.05% by mass was blended.

A. Acid-modified polypropylene resin Male acid-modified polypropylene resin having an acid value of 5 mg · KOH / g, crystallinity of 3% and 50% was obtained from a resin manufacturer. An acid-modified polypropylene resin having a crystallinity of 3% and 50% is blended at a predetermined ratio, respectively, and an acid having a crystallinity of 3%, 5%, 10%, 15%, 18%, 20% and 25% A modified polypropylene resin was prepared.

B. Polyurethane resin A polyurethane resin emulsion (HUX-232; ADEKA Corporation) was used as a polyurethane resin for adjusting the ratio of acid-modified polypropylene to the total resin mass.

C. Polyethylene wax Polyethylene wax (E-9015; Toho Chemical Industry Co., Ltd.) was added in an amount of 5% by mass based on the total mass of the resin.

D. Epoxy-based crosslinking agent Epoxy resin (EM-0461N; ADEKA Corporation) was added in an amount of 5% by mass based on the total mass of the resin.

(3) Formation of acid-modified polypropylene layer The coated substrate was immersed in an alkaline degreasing aqueous solution (SD-270; Nippon Paint Co., Ltd., pH = 12) at a liquid temperature of 40 ° C. for 1 minute to degrease the surface. Next, a paint is applied to the surface of the degreased coated substrate with a roll coater and dried with a hot air drier so that the ultimate plate temperature is 150 ° C., and the acid-modified polypropylene layer having the film thickness shown in Table 1 is obtained. Formed.

  For each painted Al-containing metal profile, the painted Al-containing metal profile No. Table 1 shows the type of coating substrate, the ratio of acid-modified polypropylene, the melt viscosity, melting point, crystallinity and film thickness of the acid-modified polypropylene layer.

2. Evaluation (1) Evaluation of blocking resistance Two test pieces (50 mm x 50 mm) were cut out from each coated Al-containing metal element, and each acid-modified polypropylene layer was opposed to each other and stacked at a pressure of 0.1 MPa ( Crimped). Each of the painted Al-containing metal shapes stacked was left in an atmosphere of 45 ° C. and a relative humidity of 80% for 24 hours. After standing for 24 hours, the stack of each painted Al-containing metal profile was unwound and the adhesion between the acid-modified polypropylene layers was evaluated. The case where adhesion between the acid-modified polypropylene layers was observed was evaluated as “x”, and the case where adhesion was not observed was evaluated as “◯”. Table 2 shows the painted Al-containing metal profile and the evaluation results of blocking resistance.

(2) Result No. The coated Al-containing metal shapes 1 to 12, 14, 16 to 20 have a melting point of the acid-modified polypropylene layer of 60 ° C. or higher and a crystallinity of 5% or higher. Excellent blocking resistance between materials. On the other hand, no. No. 13, the coated Al-containing metal profile, the melting point of the acid-modified polypropylene layer is less than 60 ° C. The 15 coated Al-containing metal preform had a crystallinity of the acid-modified polypropylene layer of less than 5%, so the blocking resistance between the painted Al-containing metal preforms was inferior.

[Example 2]
In Example 2, the bonding strength of the composite and the gas sealing property of the composite were examined.

1. Preparation of composite (1) Painted Al-containing metal profile No. 1 as in Example 1 1 to 20 painted Al-containing metal profiles were prepared.

(2) Thermoplastic resin composition As a polyethylene (PE) resin composition, Nipolon Hard 1000 (melting point 134 ° C; Tosoh Corporation) was used. Prime Polypro R-350G (melting point 150 ° C .; Prime Polymer Co., Ltd.) was used as the polypropylene (PP) resin composition. Kane Vinyl S-400 (melting point 159 ° C .; Kaneka Corporation) was used as the polyvinyl chloride (PVC) resin composition. As a methacrylic acid (PMMA) resin composition, Parapet GF (melting point: 110 ° C .; Kuraray Co., Ltd.) was used. As a polyacetal (POM) resin composition, Duracon TF-30 (melting point: 165 ° C .; Polyplastics Co., Ltd.) was used.

(3) Joining of Painted Al-containing Metal Shaped Material and Thermoplastic Resin Composition FIG. 1A is a schematic view of a composite for measuring bonding force, and FIG. 1B is a schematic view of a composite for measuring gas sealing properties. FIG.

A. Joining of coated Al-containing metal mold and thermoplastic resin composition for measuring bonding force Insert the coated Al-containing metal mold into the injection mold and insert the molten thermoplastic resin composition into the injection mold. Injected into the cavity. As shown in FIG. 1A, the shape of the cavity is 30 mm wide × 100 mm long × 4 mm thick. Further, the thermoplastic resin composition and the coated Al-containing metal shape material are in contact with each other in an area of one width 30 mm × length 30 mm. After injecting the thermoplastic resin composition into the cavity, it was cooled and solidified to obtain a composite of a coated Al-containing metal profile for measuring the bonding force and a molded body of the thermoplastic resin composition. Table 3 shows combinations of the painted Al-containing metal element and the thermoplastic resin composition.

B. Bonding of coated Al-containing metal profile for measuring gas sealing property and molded body of thermoplastic resin composition As shown in FIG. 1B, a hole of φ100 mm and φ10 mm in the center is formed in the injection mold. The coated Al-containing metal profile was inserted and the molten thermoplastic resin composition was injected into an injection mold. The shape of the cavity of the injection mold is φ12 mm × thickness 2 mm. After injecting the thermoplastic resin composition into the injection mold, it is cooled and solidified to obtain a composite of the coated Al-containing metal shape material for measuring the gas sealing property and the molded body of the thermoplastic resin composition. It was. The molded body of the painted Al-containing metal profile and the thermoplastic resin composition is in contact with a width of 1 mm around a hole of φ10 mm provided in the center of the painted Al-containing metal profile. Moreover, the combination of the coating Al-containing metal shape material and the thermoplastic resin composition in the composite prepared for gas sealing property measurement is in the composite prepared for bonding force measurement. This is the same as the combination of the painted Al-containing metal profile and the thermoplastic resin composition (see Table 3).

2. Evaluation (1) Measurement of bonding force About each of the produced composites, the coated Al-containing metal raw material and the molded body of the thermoplastic resin composition were pulled at a speed of 100 mm / min in opposite directions on the same plane. The strength when peeled (peel strength) was measured. A case where the peel strength is less than 1.0 kN is evaluated as “x”, a case where the peel strength is 1.0 kN or more and less than 1.5 kN is evaluated as “Δ”, and the peel strength is 1.5 kN or more and 2. The case of less than 0 kN was evaluated as “◯”, and the case where the peel strength was 2.0 kN or more was evaluated as “◎”. The binding strength of the composite was determined to be acceptable in the case of “Δ”, “◯”, or “◎”.

(2) Measurement of gas sealing performance FIG. 2 is a schematic diagram of measurement of the leak amount of helium gas. As shown in FIG. 2, the prepared composite was placed in a sealed container made of SUS, helium gas was injected at 0.3 MPa for 3 minutes, and the amount of leaked helium gas at the junction was measured by a sniffer method. The case where the leak amount of helium gas is 10 Pa · m ³ / s or more is evaluated as “×”, and the case where it is 10 ⁻³ Pa · m ³ / s or more and less than 10 Pa · m ³ / s is evaluated as “△”. The case where 10 ⁻⁵ Pa · m ³ / s or more and less than 10 ⁻³ Pa · m ³ / s is evaluated as “◯”, and the helium gas leakage is less than 10 ⁻⁵ Pa · m ³ / s Was evaluated as “◎”. The gas sealing property of the composite was determined to be acceptable in the case of “Δ”, “◯”, or “◎”.

  For the prepared composite, the classification, composite no. , Painted Al-containing metal element No. Table 3 shows the type of the resin composition, the ratio of the glass fiber, the molding shrinkage, the bonding strength, and the gas sealing property.

(3) Result No. In the composites 1 to 18, the amount of the acid-modified polypropylene layer in the acid-modified polypropylene layer is 40% by mass or more, the melt viscosity of the acid-modified polypropylene layer is in the range of 1000 to 10,000 mPa · s, and the film thickness is 0.00. Since it was 2 μm or more, the bonding strength and gas sealing property of the painted Al-containing metal element and the resin composition were excellent.

  On the other hand, no. In No. 19, the acid-modified polypropylene layer had a film thickness of less than 0.2 μm, so that the bonding strength and gas sealing property between the coated Al-containing metal element and the molded body of the thermoplastic resin composition were inferior. It was. No. In No. 20 composite, the amount of acid-modified polypropylene in the acid-modified polypropylene layer was less than 40% by mass, so that the bonding strength between the coated Al-containing metal element and the molded body of the thermoplastic resin composition was inferior. No. No. 21 complex and no. In the composite of No. 22, the melt viscosity of the acid-modified polypropylene layer was not within the predetermined range, so that the bonding strength between the coated Al-containing metal element and the molded article of the thermoplastic resin composition was inferior.

  Since the composite containing the coated Al-containing metal profile of the present invention is excellent in gas and liquid sealing properties, it can block humidity, corrosive gas, etc., and can be used for automobile inverter cases and ECUs (engines). This is useful for control unit) cases and precision electronic parts cases for electrical products.

Claims (10)

An Al-containing metal profile made of aluminum or an aluminum alloy;
An acid-modified polypropylene layer comprising 40% by mass or more of acid-modified polypropylene disposed on the Al-containing metal profile;
The acid-modified polypropylene layer has a melt viscosity of 1000 to 10,000 mPa · s,
The acid-modified polypropylene layer has a thickness of 0.2 μm or more.
Painted Al-containing metal profile. The skewness (Rsk) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is disposed in the Al-containing metal profile is −1.0 or more,
The kurtosis (Rku) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is arranged in the Al-containing metal profile is less than 200.
The coated Al-containing metal profile according to claim 1. The melting point of the acid-modified polypropylene layer is in the range of 60 to 120 ° C.,
The crystallinity of the acid-modified polypropylene layer is in the range of 5 to 20%.
The coated Al-containing metal shape material according to claim 1 or 2. The coated Al-containing metal profile according to any one of claims 1 to 3,
A molded body of a thermoplastic resin composition bonded to the surface of the painted Al-containing metal profile,
Having a complex.   The composite body according to claim 4, wherein the thermoplastic resin composition has a molding shrinkage of 1.1% or less. A preparatory step of preparing an Al-containing metal preform made of aluminum or an aluminum alloy;
A coating containing acid-modified polypropylene having a melt viscosity in the range of 1000 to 10000 mPa · s is applied to the surface of the Al-containing metal profile, and dried to contain 40% by mass or more of acid-modified polypropylene, and a film A forming step of forming an acid-modified polypropylene layer having a thickness of 0.2 μm or more;
Having
Method for producing painted Al-containing metal profile. The skewness (Rsk) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is formed in the Al-containing metal profile is −1.0 or more,
The kurtosis (Rku) of the surface roughness curve of the surface on which the acid-modified polypropylene layer is formed in the Al-containing metal profile is less than 200.
The manufacturing method of the coating Al containing metal shape material of Claim 6. The melting point of the acid-modified polypropylene layer is in the range of 60 to 120 ° C.,
The crystallinity of the acid-modified polypropylene layer is in the range of 5 to 20%.
The manufacturing method of the coating Al containing metal raw material of Claim 6 or Claim 7. A method for producing a composite in which an Al-containing metal profile and a molded body of a thermoplastic resin composition are joined,
Preparing a painted Al-containing metal profile according to any one of claims 1-3;
Bringing a heated thermoplastic resin composition into contact with the surface of the painted Al-containing metal profile, and joining the molded body of the thermoplastic resin composition to the surface of the painted Al-containing metal profile;
Having
A method for producing a composite. The manufacturing method of the composite_body | complex of Claim 9 whose mold shrinkage rate of the said thermoplastic resin composition is 1.1% or less.

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