WO2018121493A1 - Resin composition for bonding metal, product formed by bonding metal with resin composition, and manufacturing method - Google Patents

Abstract

The present invention provides a resin composition for bonding metal, a product formed by bonding metal with the resin composition, and a manufacturing method. The composition mainly consists of: a component (I) (which is at least one selected from polyether ketone, polyether ether ketone, or polyether ketone ketone); a component (II) (which is polyphenylene sulfide); a component (III) (which is at least one selected from polyetherimide, polyimide, polyamideimide, or polysulfone resin) which is added according to needs; and (IV) an inorganic filler. The composition is obtained by means of corresponding melt-mixing in a known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixer. The resin composition for bonding metal in the present invention has an excellent metal bonding property, and is suitable for use in motor vehicle parts and electronic products, such as laptop computers and mobile phones, that need metal bonding.

Description

Metal bonding resin composition and metal-bonded molded article and method of manufacturing same Technical field

The present invention relates to the field of high molecular polymer materials, and mainly relates to a resin composition for metal joining, a metal bonded product thereof, and a method for producing the same.

Background technique

In recent years, the demand for lightweight vehicles has increased, and the promotion of aluminum, magnesium, titanium alloys, resins, composite materials and other materials with low density and light weight has become an effective countermeasure. Furthermore, due to the emergence of new power units, the use of steel, aluminum, and copper as their main materials is increasing dramatically. In response to such a situation, the demand for related dissimilar material bonding techniques has gradually increased, and new dissimilar material bonding techniques with a resin as a core have attracted attention.

The existing metal-resin bonding technique is mainly to treat the surface of the metal with a chemical agent or to irradiate with a laser (see International Patent Application Publication No. WO2004/041532, WO2013/077277), and the metal-bonding resin composition used in these techniques is polyphenylene sulfide. Ether composition, polybutylene terephthalate composition, polyamide composition, and the like.

Further, there is also a method of manufacturing a composite material of CFRTP and resin bonding in the prior art (Japanese Patent Application Publication No. 2016-150547A). However, the resin composition used in this technique is a polyetheretherketone composition or a polyetheretherketone and a polyetherimide alloy composition, and a polyetheretherketone and a polyphenylene sulfide alloy resin composition are not used. .

Furthermore, it has been reported that by adding polyetherimide to polyetheretherketone and polyphenylene sulfide alloy compositions, the tensile strength, impact resistance and heat distortion temperature of the composition are improved (Chinese patent) Application Publication No. CN101668814A). However, this document does not describe that the above composition has better bonding properties than the polyetheretherketone monomer metal.

Summary of the invention

In order to solve the above-mentioned problem of lightweighting of a motor vehicle, the inventors have proposed a corresponding metal and resin joining solution.

The present inventors have found that (I) at least one of polyether ketone, polyether ether ketone or polyether ketone ketone and (II) polyphenylene sulfide form an alloy polymer than component (I) or component (II) alone Better metal bondability.

That is, the technical solution of the present invention is:

A resin composition for metal bonding, comprising a component (I) and a component (II);

Wherein component (I) is at least one selected from the group consisting of polyether ketone, polyether ether ketone or polyether ketone ketone; and component (II) is polyphenylene sulfide.

2. The resin composition for metal bonding according to the above 1, wherein the component (II) is added in an amount of from 1 to 9,900 parts by weight based on 100 parts by weight of the component (I).

3. The resin composition for metal bonding according to the above 1, wherein the resin composition for metal bonding further comprises a component (III) selected from the group consisting of polyetherimide and polyamido. At least one of an amine, a polyamideimide or a polysulfone resin.

4. The resin composition for metal bonding according to the above 3, wherein the component (III) is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (I) and (II).

5. The resin composition for metal bonding according to the above-mentioned item 4, wherein the component (III) is added in an amount of 0.1 part by weight or more and less than 3 based on 100 parts by weight of the total of the components (I) and (II). Parts by weight.

6. The resin composition for metal bonding according to the above 1, wherein the resin composition for metal bonding further contains an inorganic filler (IV), and inorganic with respect to a total of 100 parts by weight of the components (I) and (II). The filler (IV) is added in an amount of 5 to 300 parts by weight.

7. The metal-bonding resin composition according to the above 6, wherein the inorganic filler (IV) is selected from the group consisting of glass fibers, carbon fibers, glass beads, mica flakes, calcium carbonate, magnesium carbonate, silica, talc or At least one of wollastonite.

The resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 1 part by weight or more and less than 66.7 parts by weight based on 100 parts by weight of the component (I).

9. The resin composition for metal bonding according to the above 8, wherein the component (II) has an average dispersed particle diameter of 1.0 μm or less.

The resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 150 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the component (I).

The resin composition for metal bonding according to the above 10, wherein the component (I) has a dispersed particle diameter of 5.0 μm or less.

The resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 66.7 parts by weight or more and less than 150 parts by weight based on 100 parts by weight of the component (I).

The resin composition for metal bonding according to the above 12, wherein at least the dispersed phase component (II) having a dispersed particle diameter of 1.0 μm or less is present.

A molded article obtained by joining a metal composition for resin bonding according to any one of the above 1 to 13 to a metal.

The method of producing a molded article according to any one of the above-mentioned items 1 to 13, wherein the resin composition for metal bonding according to any one of the above 1 to 13 is heated and melted, and then injection-molded with a metal previously placed in a mold to form a mold. Curing at a temperature of 120-250 °C.

The metal bonding resin composition of the present invention has excellent metal bondability, and is suitable not only for automotive parts that require metal bonding, but also for electronic products such as notebook computers and mobile phones.

DRAWINGS

Fig. 1 is a schematic view showing the front side of a joint molded product of metal and resin.

Fig. 2 is a schematic view showing the side surface of a joint molded product of metal and resin.

detailed description

The specific embodiments of the present invention are described below:

Metal material

The present invention relates to a resin composition for metal bonding, wherein the material of the metal is not particularly limited, and examples thereof include gold, platinum (platinum), silver, aluminum, magnesium, titanium, iron, tin, zinc, lead, chromium, and manganese. Copper, stainless steel, cobalt or alloys of the above materials are all within the scope of protection. The microporous or concave-convex structure may be etched by chemical treatment on the metal surface by metal surface treatment, or may be formed by anodizing to form micropores, or may be formed by plating, or the metal surface may be irradiated by laser irradiation. After the etching treatment, the metal is placed in a mold in advance, and the metal bonding resin of the present invention is subjected to injection molding to cause the resin to intrude into the pores or the uneven structure of the metal surface to form a physical bond. Further, the resin composition of the present invention can also be used in a chemical bonding technique in which a metal surface is subjected to an activation treatment with a chemical reagent, and then the resin and the metal are chemically reacted to form a film by the above-described injection molding method.

The metal surface treatment method according to the present invention may be a treatment method used in NMT (Nano Molding Technology) technology, for example, T (Dacheng Plas's first letter) processing method developed by Dacheng Plath Co., Ltd. and East Asian electrochemical type Metal surface treatment technology such as the TRI treatment method developed by the company or the C treatment method developed by Japan Corona Industrial Co., Ltd. The corrosive liquid used for the corrosion of the chemical agent includes an alkaline aqueous solution (pH>7), an acidic aqueous solution (pH<7), an aqueous solution of a nitrogen-containing compound, and the like. The alkaline aqueous solution may be an aqueous solution of sodium hydroxide, potassium hydroxide or sodium carbonate. The acidic aqueous solution may be an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid. The nitrogen-containing compound may be ammonia, hydrazine, or a water-soluble amine. The water-soluble amine may be methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, propylamine, ethanolamine, diethanolamine, triethanolamine, aniline or other amines. Class of compounds.

The anodic oxidation of the metal surface of the present invention refers to a method of forming an oxide film on a metal surface by a current acting on the metal using the metal as an anode. For example, water-soluble ammonia can be used as an electrolyte to anodize the metal surface.

The chemical reagent for forming a reactive coating film between the metal and the resin according to the present invention may be a compound such as ammonia, hydrazine, a water-soluble amine or a triazine thiol derivative.

The triazine thiol derivative, specifically, 1,3,5-triazine-2,4,6-trithiol (TT), 1,3,5-triazine-2, 4 , 6-trithiol monosodium (TTN), 1,3,5-triazine-2,4,6-trithiol triethanolamine (F-TEA), 6-anilino-1,3,5-three Pyrazine-2,4-dithiol (AF), 6-anilino-1,3,5-triazine-2,4-dithiol monosodium (AFN), 6-dibutylamino-1,3 , 5-triazine-2,4-dithiol (DB), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN), 6-diene Propylamino-1,3,5-triazine-2,4-dithiol (DA), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium (DAN), 1,3,5-triazine-2,4,6-trithiol-bis(tetrabutylammonium) (F2A), 6-dibutylamino-1,3,5-triazine -2,4-dithiol-tetrabutylammonium salt (DBA), 6-dithiooctylamino-1,3,5-triazine-2,4-dithiol (DO), 6-di Thiooctylamino-1,3,5-triazine-2,4-dithiol monosodium (DON), 6-dilaurylamino-1,3,5-triazine-2,4-disulfide Alcohol (DL), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN), 6-stearylamino-1,3,5-triazine- 2,4-dithiol (ST), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK), 6-oleylamino-1,3, Triazine thiol derivative such as 5-triazine-2,4-dithiol (DL) and 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK) Salt and so on.

The present invention relates to a method of plating a metal surface to form micropores, including a method of depositing another metal on a treated metal surface by electrical treatment or a method of forming a deposited layer by chemical treatment, which may be gold or silver. , nickel, chromium and other metals.

The laser metal surface etching according to the present invention may be a technique in which micropores are etched on a metal surface by a laser, such as DLAMP technology developed by Daicel Corporation of Daicel and Daicel Plastics.

The metal surface nano-scale concavo-convex structure according to the present invention refers to a micron- to nano-scale pore existing on a metal surface observed by a scanning electron microscope. The average pore diameter is preferably from 10 to 100 nm, more preferably from 10 to 80 nm.

2. Ingredients (I)

The component (I) used in the resin composition for metal bonding of the present invention is at least one selected from the group consisting of polyether ketone, polyether ether ketone, and polyether ketone ketone.

A typical repeating unit in the chemical structure of the polyether ketone is represented by the formula (1), and the repeating unit represented by the formula (I) accounts for 70 mol% or more, more preferably 90 mol% or more of the polyether ketone polymer.

A typical repeating unit in the chemical structure of the polyetheretherketone is represented by the formula (2), and the repeating unit represented by the formula (2) accounts for 70% by mole or more, and more preferably 90% by mole or more of the polyetheretherketone polymer. May be used, for example, Victrex PEEK ^(TM) manufactured by VICTREX, made of SOLVAY Ketaspire ^TM, Avaspire ^TM, Evonik manufactured

Manufactured by Jilin Zhongyan Polymer Materials Co., Ltd.

"Fengfulong Chemical Co., Ltd."

PEEK" and so on.

A typical repeating unit in the chemical structure of the polyetherketoneketone is represented by the formula (3), and the repeating unit represented by the formula (3) accounts for 70% by mole or more, and more preferably 90% by mole or more of the polyetherketoneketone polymer.

In the present invention, a polyether ketone, a polyetheretherketone or a polyetherketoneketone having good fluidity is preferred, and a melt volume flow rate (MVR) measured by a melt indexer under a test condition of 380 ° C and a load of 5 Kgf is preferred. The polyether ketone, polyether ether ketone or polyether ketone ketone at 5 cm ³ / 10 min or more is more preferably 15 cm ³ /10 min or more, and most preferably 60 cm ³ /10 min or more. On the other hand, in order to maintain the toughness of the resin composition for metal bonding of the present invention, it is preferred that the polyether ketone, polyetheretherketone or polyetherketoneketone has a melt volume flow rate (MVR) of 300 cm ³ / 10 min or less.

3. Composition (II)

The component (II) used in the resin composition for metal bonding of the present invention is polyphenylene sulfide. The polyphenylene sulfide polymer is a polymer having a repeating unit represented by the following formula (4), and the repeating unit represented by the formula (4) accounts for 70% by mole or more, more preferably 90% by mole based on the polyphenylene sulfide polymer. the above. For example, it can be manufactured by Toray Industries, Inc.

Manufactured by SOLVAY

Made by American GE

Made by Ticona, USA

Wait.

In the polyphenylene sulfide polymer, the repeating unit other than the repeating unit represented by (4) is selected from the repeating units (5), (6), (7), (8), (9), and the following structures. One or more of (10), or (11).

When the polyphenylene sulfide polymer has one or more of the above repeating units (5) to (11), the polyphenylene sulfide polymer has a low melting point, which is more advantageous from the viewpoint of molding. At the same time, since the crystallization property is also lowered, the molding shrinkage of the molded article is also lowered.

The polyphenylene sulfide polymer used in the present invention is more preferably a high melt index from the viewpoint of obtaining excellent fluidity. For example, it is preferable that the melt index is from 200 g/10 minutes or more, and further preferably 500 g/10 minutes or more, and the resin composition for metal bonding of the present invention is preferably 5,000 g/10 minutes or less.

Further, in order to balance fluidity, toughness and modulus, as the polyphenylene sulfide, a mixture of polyphenylene sulfides having various chemical structures is preferably used.

The polyphenylene sulfide used in the present invention is not limited to the production method. The polyphenylene sulfide polymer having a structure of the above (5) to (11) can be used for a method for obtaining high fluidity as described in JP-A-45-3368 or JP-A-52-12240. Prepared by a method that achieves lower fluidity. The former differs from the latter in whether or not there is a polymerization aid alkali metal carboxylate in the polymerization system. In the former method, the alkali metal carboxylate is not added to the polymerization system, and the fluidity is high. In the latter method, the alkali metal carboxylate is added to the polymerization system, and the fluidity is low, thereby contributing to the toughness of the resin. . Therefore, the polyphenylene sulfide polymers prepared by the two methods can be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.

Further, by subjecting the polyphenylene sulfide polymer prepared above as a capping treatment, a polyphenylene sulfide polymer having a lower chlorine content can be obtained. For example, by capping with 2-mercaptobenzimidazole under basic conditions, a blocked polyphenylene sulfide polymer having a lower chlorine content can be obtained.

4. Composition of components (I) and (II)

In the present invention, the amount of the component (II) to be added is preferably from 1 to 9,900 parts by weight based on 100 parts by weight of the component (I). In the present invention, it is necessary to suppress shrinkage of the resin which enters the micropores or the uneven structure of the metal surface. In order to achieve this, the components (I) and (II) are mixed, and the two resin components mutually inhibit crystallization. In the present invention, the component (II) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 15 parts by weight or more based on 100 parts by weight of the component (I). On the other hand, the amount of the component (II) to be added is preferably 1900 parts by weight or less, more preferably 900 parts by weight or less, and most preferably 570 parts by weight or less.

5. Ingredient (III)

The component (III) used in the resin composition for metal bonding of the present invention is at least one of polyetherimide, polyimide, polyamideimide or polysulfone resin.

The polyetherimide is a polymer having a repeating unit represented by the following formula (12), and the repeating unit represented by the formula (12) accounts for 70% by mole or more, more preferably 90% by weight of the polyetherimide polymer. More than mol%.

In the above formula (12), R ₁ is a divalent aromatic residue having 6 to 30 carbon atoms, R ₂ is a divalent organic group selected from the group consisting of 6 to 30 carbon atoms a divalent aromatic residue, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polyorganosiloxane terminated by an alkylene group having 2 to 8 carbon atoms Alkyl composition. The above R ₁ and R _{2 are} preferably the chemical groups shown below.

The polyimide is a polymer having a repeating unit represented by the following formula (13), and the repeating unit represented by the formula (13) accounts for 70% by mole or more, more preferably 90% by mole based on the polyimide polymer. the above.

In the above formula (13), R ₃ is a direct bond or is -SO ₂ -, -CO-, -C(CH ₃ ) ₂ -, C(CF ₃ ) ₂ -, -S-. Further, R ₄ is one or more selected from the following structures.

The polyamideimide is a polymer having a repeating unit represented by the following formula (14), and the repeating unit represented by the formula (14) accounts for 70% by mole or more, more preferably 90% by weight of the polyamideimide polymer. More than mol%.

In the above formula (14), R ₅ is a divalent aromatic and/or aliphatic group, R ₆ is hydrogen, a methyl group or a phenyl group, and Ar is a trivalent aromatic group containing at least one six-membered ring.

More specifically, the repeating structural unit represented by the above formula (14) and the repeating structural unit represented by the following formula (15) and/or (16) may be aggregated together.

Here, R _{7 is} also applicable to the above description for R ₅ , and Ar′ represents a divalent aromatic group containing one or two or more carbon 6-membered rings or a divalent alicyclic group.

Here, R ₈ also applies to the above description for R ₅ , and Ar” represents a tetravalent carbonyl group-containing aromatic group containing one or two carbon 6-membered rings.

In the above, the imide bond structure of the structural units (14) and (16) may retain the closed-loop front structure as shown in the structural unit (17).

The polysulfone resin is a polymer having a repeating unit represented by the following formula (18) or (19), and the repeating unit represented by the formula (18) or (19) accounts for 70% by mole or more, more preferably 90% by weight of the polysulfone resin. More than mol%.

6. Composition of component (III)

The amount of the component (III) to be added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the components (I) and (II). Since the component (III) may affect the mixing property of the components (I) and (II), and thereby inhibit the crystallization of the components (I) and (II), the component (III) is added in a relative amount (I) and (II) 100 parts by weight is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, most preferably less than 3 parts by weight, and further preferably 0.5 parts by weight or more, more preferably 1 part by weight or more.

7. Inorganic filler (IV) and its ratio

The ratio of the inorganic filler (IV) of the present invention is preferably 5 to 300 parts by weight based on 100 parts by weight of the components (I) and (II). In the range of the amount of addition, the resin composition for metal bonding of the present invention can impart a good fluidity to the resin composition while reducing the shrinkage ratio. The inorganic filler (IV) is preferably added in an amount of 10 parts by weight or more, more preferably 20 parts by weight or more, and most preferably 30 parts by weight or more. Further, it is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, and most preferably 70 parts by weight or less.

The inorganic filler of the present invention refers to a filler used in the resin which is used in the prior art. For example, glass fiber, carbon fiber, potassium titanate whisker, zinc whisker oxide, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, silicon Gray stone, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, graphite, aluminosilicate, alumina, silica, Magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride , silicon carbide or wollastonite. It is also possible that the inorganic filler is hollow in structure, and further, two or more kinds of these inorganic fillers may be used in combination.

In particular, in order to obtain a metal bonding resin composition excellent in performance, in view of low molding shrinkage ratio and fluidity, the inorganic filler is preferably at least one of glass fiber or carbon fiber. The glass fiber is not particularly limited and may be a glass fiber used in the prior art. The glass fiber may be a fiber of a shape such as a chopped strand of a fixed length, a coarse sand, or a ground fiber. In general, it is preferred to use glass fibers having an average diameter of 5 to 15 μm. In the case of using chopped strands, the length is not particularly limited, and it is preferred to use a standard 3 mm-length fiber suitable for extrusion kneading.

On the other hand, in order to obtain a better product appearance, at least one of glass beads, mica, calcium carbonate, magnesium carbonate, silica, talc or wollastonite is preferred.

The average diameter of the inorganic filler is not particularly limited, and is preferably 0.001 to 20 μm, and in this range, better fluidity and a better appearance can be obtained.

In order to obtain better performance, the inorganic filler is preferably an inorganic filler previously treated with a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound, or an epoxy compound.

8. Dispersed particle size of component (I) and component (II)

In the present invention, depending on the ratio of the component (I) and the component (II), the dispersion state of each component varies. Further, the addition of the component (III) also changes the morphology of the dispersion. When the amount of the component (II) is 1 part by weight or more and less than 66.7 parts by weight based on 100 parts by weight of the component (I), the component (I) is formed as the sea phase and the component (II) as the island phase. In this case, the smaller the dispersed particle diameter of the component (II), the higher the bonding property with the metal, which is preferable. In this case, the average dispersed particle diameter of the component (II) is preferably 1.0 μm or less, more preferably 0.50 μm or less, still more preferably 0.40 μm or less, and most preferably 0.2 μm or less.

In addition, when the component (II) is 150 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the component (I), the component (I) is formed as an island phase and the component (II) is used as a sea phase. . In this case, the smaller the dispersed particle diameter of the component (I), the higher the bonding property with the metal, which is preferable. In this case, the average dispersed particle diameter of the component (I) is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 2.0 μm or less.

In addition, when the component (II) is 66.7 parts by weight or more and less than 150 parts by weight based on 100 parts by weight of the component (I), the component (I) is formed as the sea phase and the component (II) is used as the island phase. In addition, the component (I) has a structure in which the island phase and the component (II) are simultaneously present as a sea phase. In this case, the component (II) which is an island phase has a small dispersed particle diameter and tends to have improved metal bonding properties. Therefore, the dispersed particle diameter of the dispersed phase of the component (II) is preferably 1.0 μm or less, and the dispersed particle diameter of the component (II) is preferably 1.0 μm or less, and more preferably, the dispersed particle diameter is 0.6 μm or less, and more preferably The dispersed particle diameter is 0.40 μm or less, and most preferably, the dispersed particle diameter is 0.3 μm or less.

Here, the dispersed particle diameter of each component can be tested by the following method. The resin composition for metal bonding of the present invention was cut by an automatic sheet cutter, and then observed with a JEM-2100 transmission electron microscope manufactured by JEOL. The obtained electron microscope photograph was processed using Image-ProPlus, an image analysis software of Media Cybernetics, and the area of 100 dispersed phases was calculated. The area was calculated into the area of a circle, and the diameter was calculated to obtain an average dispersed particle diameter. However, when the component (II) is 150 parts by weight or more and 900 parts by weight or less based on 100 parts by weight of the component (I), 100 PPS dispersed phases are randomly selected from the obtained electron micrograph, and the smallest is measured. Dispersed particle size.

9. Other additives

The metal bonding resin composition of the present invention may further comprise other thermoplastic polymers in addition to the components (I) to (III), for example, polyamide, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, liquid crystal. Polymer, ABS resin, SAN resin, polystyrene, or polytetrafluoroethylene. In order to improve the toughness of the resin composition for metal bonding of the present invention, a (co)modified polyolefin polymer obtained by polymerizing an olefin compound and/or a conjugated diene compound is preferable.

In addition, an antioxidant can be added to the resin composition for metal bonding of the present invention in a range that does not impair the effects of the present invention, whereby the heat resistance and thermal stability of the resin composition can be further improved. The antioxidant preferably contains at least one selected from the group consisting of a phenol antioxidant and a phosphorus antioxidant. When a phenolic antioxidant and a phosphorus-based antioxidant are used in combination, heat resistance and heat stability can be efficiently maintained, so that the combination of both is preferable.

As the phenolic antioxidant, a hindered phenol compound is preferably used. Specific examples are: triethylene glycol bis(3-tert-butyl-(5-methyl-4-hydroxybenzyl)propionate), N,N'-hexamethylene double (3,5-di-tert Butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene-3-(3',5'-di-tert-butyl-4'-hydroxybenzyl)propionate)methane, pentaerythritol tetrakis(3- (3',5'-di-tert-butyl)-4'-hydroxybenzyl)propionate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s -Triazine-2,4,6-(1H,3H,5H)-trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4 4'-butylidene bis(3-methyl-6-tert-butylphenyl), n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy)-1,1-dimethylethyl)-2,4, 8,10-Tetraoxaspiro(5,5)undecane, or 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl Base) benzene, etc. Among them, an ester type polymer is preferably a hindered phenol type, and specifically, tetrakis(methylene-3-(3',5'-di-tert-butyl-4'-hydroxybenzyl)propionate)methane or pentaerythritol IV is preferably used. 3-(3',5'-di-tert-butyl)-4'-hydroxybenzyl)propionate), or 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-)- 5-methylphenyl)propanoyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.

Examples of the phosphorus-based antioxidant include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol-two. Phosphite, bis(2,4-dicumylphenyl)pentaerythritol-diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butyl) Phenyl)-4,4'-bisphenylene phosphite, distearyl pentaerythritol-diphosphite, triphenylphosphite, or 3,5-dibutyl-4-hydroxybenzylphosphoric acid Ethyl ester and the like.

The amount of the antioxidant added is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, most preferably 0.1 to 1 part by weight based on 100 parts by weight of the relative components (I) and (II).

In addition, a release agent (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearic acid amide, amide, biuret or polyethylene wax, etc., in which, in order to reduce during the molding process, can also be used. Gas generation, preferably amide), pigment (cadmium sulfide, phthalocyanine, or colored carbon black masterbatch, etc.), dye (aniline black, etc.), crystallization agent (talc, titanium dioxide, kaolin, clay, etc.), plasticizer ( Octyl-p-hydroxybenzoate, or N-butylbenzenesulfonamide, etc., antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan Nonionic antistatic agent such as monostearate or ampicillin amphoteric antistatic agent), flame retardant (for example, red phosphorus, phosphate, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, more Ammonium phosphate, brominated polystyrene, brominated polyphenylene ether, polycarbonate bromide, brominated epoxy resin or a combination of these bromine-containing flame retardants and antimony trioxide, etc., one or more of which may be selected With the use of.

10. Manufacture of metal joint compositions

The method for producing a metal composition for metal bonding of the present invention is to use the main components (I) and (II) and the components (III) and (IV) to be added as needed in a known melt kneader such as a single screw or a double. A screw extruder, a Banbury mixer, a kneader, and a kneader are obtained in accordance with a corresponding melt-kneading method.

11. Manufacture of metal bonded molded articles

The metal bonding resin composition is heated and melted, and then injection-molded with a metal previously placed in a mold. details as follows:

A metal piece is inserted into the mold in advance, and the metal bond molding product is obtained by injection molding the resin composition for metal bonding of the present invention. The mold temperature is preferably in the range of 120 ° C or more and 250 ° C or less, and the molten metal bonding resin composition can intrude into the micropores or the uneven structure of the metal surface under the conditions of 120 ° C or higher. The mold temperature is preferably 130 ° C or higher, more preferably 140 ° C or higher; and for the formulation in which the component (I) is more than the component (II), the mold temperature is preferably 180 ° C or higher, and most preferably 200 ° C or higher. On the other hand, when the mold temperature is 250 ° C or lower, the resin composition for metal bonding can be cured in a mold, and the mold temperature is preferably 240 ° C or lower, more preferably 230 ° C or lower. In the case of molding a formulation having a larger ratio of the component (II) to the component (I), the mold temperature is preferably 170 ° C or lower, and most preferably 160 ° C or lower.

The metal bonding resin composition of the present invention has high bonding strength and is suitable for use in a housing of an electronic component such as an automobile component, a notebook computer, or a mobile phone that requires metal bonding.

The invention is further illustrated by the following specific examples. The following examples are illustrative of the embodiments of the present invention, in which detailed embodiments and specific procedures are described, but the scope of the invention is not limited to the embodiments described below.

Example

Metal

Aluminum sheet A6061 (45mm*10mm*1.5mm): Kunshan Xinda Mould Co., Ltd.;

Stainless steel SUS361 (45mm*10mm*1.5mm): Shanghai Jingyu Trading Co., Ltd.

Brass (45mm*10mm*1.5mm): Shanghai Jingyu Trading Co., Ltd.

A company entrusted with T treatment of aluminum sheets: Shenzhen Baoyuanjin Co., Ltd.;

The company commissioned to deal with aluminum sheet TRI: Shenzhen Jinhongxin Technology Co., Ltd.

Company commissioned to coat stainless steel and brass: Shenzhen Ruichangsheng Precision Technology Co., Ltd.

2. Raw materials of the resin composition

Polyetheretherketone PEEK1: VICTREX ^TM 450PF;

Polyetheretherketone PEEK2: PFLUON manufactured by Pengfulong Chemical Co., Ltd.

8800G (melt volume flow rate (MVR): 70cm ³ /10min)

Polyetheretherketone PEEK3: PFLUON manufactured by Pengfulong Chemical Co., Ltd.

8900G (melt volume flow rate (MVR): 120cm ³ /10min)

Polyphenylene sulfide PPS: Toray Co., Ltd.

M2888;

Polyetherimide PEI: SABIC ULTEM ^TM PEI1010;

Polysulfone resin PES: Jiangmen Youju New Material Co., Ltd. F2150

Glass fiber: Nitto Spin CSG 3PA-830.

3. Metal bondability of resin composition

A molded article obtained by injection molding of a resin composition and a metal is obtained, and its shape is as shown in FIG. After molding, the formulation having a higher PPS content was annealed at 130 ° C for 1 hour. Formulations with a higher PEEK content and formulations with the same PEEK and PPS content were annealed at 170 °C for 1 hour. After standing for 24 hours, the test was carried out under the conditions of a temperature of 23 ° C and a humidity of 50% RH using an AG-IS1KN apparatus of Shimadzu Corporation of Japan, and the shearing force was measured at a tensile speed of 5 mm/min and a clamp distance of 3 mm. strength.

4. Bending performance

In the examples and comparative examples shown in Table 6, the bending properties described were molded by a Nissei NEX-50 molding machine at a mold temperature of 140 degrees, and the flexural modulus and bending of the molded article were tested in accordance with the ISO178 standard. strength.

5. Dispersed particle size of each component

The resin portion of the molded article in which the resin composition and the T-treated metal were joined was sliced with an automatic sheet slicer, and observed with a JEM-2100 transmission electron microscope manufactured by JEOL. The results of the observation were processed by the processing software of Media Cybernetics, and the area of the 100 particles of the dispersed phase was converted into the area of the circle to calculate the diameter, thereby obtaining the average dispersed particle diameter. However, the results of Examples 23 to 28 are the smallest dispersed particle diameters calculated by randomly selecting 100 PPS dispersed phase particle diameters from electron micrographs.

Examples 1 to 32, Comparative Examples 1 to 6

The raw materials were weighed as shown in Tables 1 to 6. The granulation was carried out using a TEX30α-type twin-screw extruder (L/D=45.5) manufactured by Nippon Steel Works Co., Ltd., which has two sets of charging devices with measuring instruments and vacuum evacuation equipment. The raw materials other than the glass fiber are mixed in a high-speed mixer, and then added to the main feed port of the extruder, and the glass fiber is fed from the extruder side feed port, and the extruder temperature is set as shown in Tables 1 to 6. After the obtained resin composition for metal bonding was dried in an oven at 130 ° C for 12 hours, the above-mentioned treated metal was placed in a mold, and injection molding was completed in a Nisse NEX-50 molding machine to obtain a resin composition and a metal. The joint molded product, the molding temperature and the mold temperature are shown in Tables 1 to 6.

Table 1

From the comparison of Example 1 with Comparative Example 1, it can be seen that the addition of PPS to PEEK increases the shear strength. From the comparison of Example 1 and Examples 2 to 4, it can be seen that PEI is added to the formulation of PEEK1/PPS=80/20, so that the shear strength is increased.

Table 2

As can be seen from Comparative Example 2, metal bonding could not be achieved using a glass fiber reinforced pure PEEK1 formulation at a mold temperature of 160 °C. As can be seen from Example 6, metal joining was achieved due to the addition of PPS. As can be seen from Example 7, the addition of PEI resulted in an increase in shear strength.

Comparing Examples 6 to 7 with Examples 9 to 10, it can be seen that the mold temperature was raised to 220 ° C and the shear strength was improved.

table 3

As can be seen from the comparison between Example 11 and Comparative Example 4, in the formulation in which PPS was added to PEEK2, the shear strength was improved. As can be seen from Examples 11 to 16, the shear strength was improved by adding PEI to the formulation of PEEK2/PPS = 80/20. In addition, the average dispersed particle size of the PPS is made smaller by the addition of PEI.

Table 4

As can be seen from the comparison of Example 17 and Comparative Example 5, the shear strength was improved by using a formulation in which PEEK2 was added to PPS. As can be seen from Examples 17 to 20, the shear strength was improved by adding PEI to the formulation of PEEK2/PPS = 20/80. In addition, the average dispersed particle size of PEEK is reduced because of the addition of PEI.

table 5

From the comparison of Example 23 and Comparative Examples 4 and 5, it can be seen that in the formulation in which PEEK2 and PPS are used together, the shear strength is improved. As can be seen from Examples 23 to 27, PEI polyetherimide was added to the formulation of PEEK2/PPS = 50/50 to increase the shear strength. In addition, the minimum dispersed particle size of the PPS is made smaller by the addition of PEI.

Table 6

A comparison of Example 14 and Example 29, Example 20 and Example 30, Example 26 and Example 31 shows that the shear strength is improved in the formulation of PEEK3 which is relatively large in melt volume flow rate (MVR).

Claims (15)

1. A resin composition for metal bonding, characterized in that the resin composition comprises component (I) and component (II);

   Wherein component (I) is at least one selected from the group consisting of polyether ketone, polyether ether ketone or polyether ketone ketone; and component (II) is polyphenylene sulfide.
2. The resin composition for metal bonding according to claim 1, wherein the component (II) is added in an amount of from 1 to 9,900 parts by weight based on 100 parts by weight of the component (I).
3. The resin composition for metal bonding according to claim 1, wherein the resin composition for metal bonding further contains a component (III) selected from the group consisting of polyetherimide and polyacyl group. At least one of an imine, a polyamideimide or a polysulfone resin.
4. The resin composition for metal bonding according to claim 3, wherein the component (III) is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (I) and (II).
5. The resin composition for metal bonding according to claim 4, wherein the component (III) is added in an amount of 0.1 part by weight or more and less than 3 parts by weight based on 100 parts by weight of the total of the components (I) and (II). Share.
6. The resin composition for metal bonding according to claim 1, wherein the resin composition for metal bonding further contains an inorganic filler (IV), and based on 100 parts by weight of the total of components (I) and (II), The inorganic filler (IV) is added in an amount of 5 to 300 parts by weight.
7. The resin composition for metal bonding according to claim 6, wherein the inorganic filler (IV) is selected from the group consisting of glass fibers, carbon fibers, glass beads, mica flakes, calcium carbonate, magnesium carbonate, and silica. At least one of talc or wollastonite.
8. The resin composition for metal bonding according to claim 2, wherein the component (II) is added in an amount of 1 part by weight or more and less than 66.7 parts by weight based on 100 parts by weight of the component (I).
9. The resin composition for metal bonding according to claim 8, wherein the component (II) has an average dispersed particle diameter of 1.0 μm or less.
10. The resin composition for metal bonding according to claim 2, wherein the component (II) is added in an amount of 150 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the component (I).
11. The resin composition for metal bonding according to claim 10, wherein the component (I) has a dispersed particle diameter of 5.0 μm or less.
12. The resin composition for metal bonding according to claim 2, wherein the component (II) is added in an amount of 66.7 parts by weight or more and less than 150 parts by weight based on 100 parts by weight of the component (I).
13. The resin composition for metal bonding according to claim 12, wherein at least a dispersed phase component (II) having a dispersed particle diameter of 1.0 μm or less is present.
14. A molded article obtained by joining a resin composition for metal bonding according to any one of claims 1 to 13 to a metal.
15. A method of producing a molded article according to any one of claims 1 to 13, wherein the resin composition for metal bonding according to any one of claims 1 to 13 is heated and melted, and then injection-molded with a metal previously placed in a mold. Curing at a mold temperature of 120-250 °C.

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