JP2008162115A - Method of manufacturing metal/resin composite material - Google Patents

Method of manufacturing metal/resin composite material Download PDF

Info

Publication number
JP2008162115A
JP2008162115A JP2006353914A JP2006353914A JP2008162115A JP 2008162115 A JP2008162115 A JP 2008162115A JP 2006353914 A JP2006353914 A JP 2006353914A JP 2006353914 A JP2006353914 A JP 2006353914A JP 2008162115 A JP2008162115 A JP 2008162115A
Authority
JP
Japan
Prior art keywords
metal
film
thermoplastic resin
resin
containing film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2006353914A
Other languages
Japanese (ja)
Other versions
JP5058593B2 (en
Inventor
Shozo Yamamoto
尚三 山本
Keiko Yamagata
恵子 山形
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YKK Corp
Original Assignee
YKK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by YKK Corp filed Critical YKK Corp
Priority to JP2006353914A priority Critical patent/JP5058593B2/en
Publication of JP2008162115A publication Critical patent/JP2008162115A/en
Application granted granted Critical
Publication of JP5058593B2 publication Critical patent/JP5058593B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which is feasible in safe working circumstances and enables integrated formation of a metal material and a thermoplastic resin with sufficient bonding strength and manufacture of a metal/resin composite material at low costs. <P>SOLUTION: The method comprises injecting a thermoplastic resin onto the surface of a metal having a micro-porous hydroxy-containing film to integrate the metal with the thermoplastic resin via the film. The hydroxy-containing film can be formed easily at low cost by treating the surface of the metal with warm water. The film can also be considered as a hydroxylated and/or a hydrated film, or a film containing a hydroxide and/or hydrated oxide of the metal. Preferably, the micro-porous hydroxy-containing film is at least 5 nm thick, more preferably 5-100 nm thick, is formed on the surface of the metal. The warm water treatment preferably comprises immersing the metal in warm water at 50°C or higher for 30 sec or longer, more preferably in warm water at 60-90°C for 1-30 min. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、金属と樹脂の複合体の製造方法に関し、さらに詳しくは、微多孔質の水酸基含有皮膜が形成された金属の表面に熱可塑性樹脂を射出し、上記皮膜を介して金属と熱可塑性樹脂とを一体化する金属と樹脂の複合体の製造方法に関する。   The present invention relates to a method for producing a composite of a metal and a resin, and more specifically, a thermoplastic resin is injected onto the surface of a metal on which a microporous hydroxyl group-containing film is formed, and the metal and the thermoplastic are passed through the film. The present invention relates to a method for producing a composite of a metal and a resin that integrates a resin.

金属と合成樹脂を一体化する技術は、自動車部品、家庭電化製品や産業機器の各種部品、内外装用部材等の広い分野において求められている。また、昨今の携帯電話、携帯用パソコンなど携帯用電子機器の発展と市場拡大は、より軽量丈夫で外観の優れた構造を求めており、アルミニウムやマグネシウム等の軽合金製や薄いステンレスシート製の外装部と、これと素材が全く異なる高強度樹脂製シャーシの合理的な接合手段が求められている。金属と合成樹脂の接合には、一般に接着剤が使用され、このために多くの接着剤が開発されている。しかしながら、接着剤は経時的に強度低下を伴い、固着力が安定的でない上、作業の繁雑さを伴う。また、ねじ止め等の一体化方法も従来から広く行われ、周知であるが、軽量化の要望に充分に応えることはできず、また量産を伴う製造においては、必ずしも能率的であるとはいえない。   Technology for integrating metal and synthetic resin is required in a wide range of fields such as automobile parts, home appliances, various parts of industrial equipment, and interior and exterior members. In addition, the development and market expansion of portable electronic devices such as mobile phones and personal computers in recent years are demanding structures that are lighter, more durable and have a better appearance, and are made of light alloys such as aluminum and magnesium and thin stainless steel sheets. There is a need for a rational means for joining an exterior part and a chassis made of high-strength resin, which is completely different from the material. Adhesives are generally used for joining metal and synthetic resin, and many adhesives have been developed for this purpose. However, the adhesive is accompanied by a decrease in strength over time, the fixing force is not stable, and the work is complicated. Also, integration methods such as screwing have been widely used and are well known, but they cannot fully meet the demand for weight reduction, and are not necessarily efficient in production involving mass production. Absent.

そこで、接着剤を使用しない、より合理的な接合方法について従来から研究されてきた。このような目的に合う最も容易な接合手段としてまず考えられるのは、インサート成形法である。即ち、金属板等を曲げ、切断、絞り加工等のプレス加工、ミーリング等の切削加工等の加工法により、所望の形状に金属材を加工し、これを射出成形金型に挿入した後、溶融した熱可塑性樹脂を射出する方法である。しかしながら、金属と熱可塑性樹脂では線膨張率等の物性で大きな差があり、充分な接合強度で金属と熱可塑性樹脂を一体化することは困難である。   Therefore, a more rational joining method that does not use an adhesive has been studied. An insert molding method is first considered as the easiest joining means for such purposes. That is, a metal material is processed into a desired shape by a bending method such as bending, cutting, drawing processing, etc., cutting processing such as milling, etc., and inserted into an injection mold, and then melted. This is a method of injecting a thermoplastic resin. However, there is a large difference in physical properties such as linear expansion coefficient between metal and thermoplastic resin, and it is difficult to integrate the metal and thermoplastic resin with sufficient bonding strength.

上記のような問題を解決するために、従来、金属と樹脂の複合体をインサート成形するに先立って、予め金属表面をヒドラジン等の水溶性還元剤で処理し、この表面処理された金属表面に、ポリアルキレンテレフタレートやポリフェニレンサルファイドを含む熱可塑性樹脂組成物を射出し、一体化する方法が提案されている（特許文献１〜６参照）。
特開２００３−１０３５６３公報（特許請求の範囲） 特開２００３−２００４５３号公報（特許請求の範囲） 特開２００３−２５１６５４号公報（特許請求の範囲） 特開２００４−５０４８８号公報（特許請求の範囲） 特開２００５−１１９００５号公報（特許請求の範囲） 特開２００５−１１９２３７号公報（特許請求の範囲） In order to solve the above problems, prior to insert molding of a metal-resin composite, the metal surface is previously treated with a water-soluble reducing agent such as hydrazine, and this surface-treated metal surface is applied. A method of injecting and integrating a thermoplastic resin composition containing polyalkylene terephthalate or polyphenylene sulfide has been proposed (see Patent Documents 1 to 6).
JP 2003-103563 A (Claims) JP 2003-200453 A (Claims) JP 2003-251654 A (Claims) JP 2004-50488 A (Claims) Japanese Patent Laying-Open No. 2005-119005 (Claims) JP 2005-119237 A (Claims)

上記のような予め金属表面をヒドラジン等の水溶性還元剤で処理し、この表面処理された金属表面に、ポリブチレンテレフタレートやポリフェニレンサルファイドを含む熱可塑性樹脂組成物を射出し、一体化する方法により、ある程度充分な接合強度で金属と樹脂を一体的に接合することは可能である。
しかしながら、ヒドラジンは作業環境への影響の面から使用方法と取扱いに注意が必要である。従って、このような薬品の使用は実際の工業的使用の面で問題があり、またコストアップの要因となる。また、射出処理にて接合できる樹脂は上記ＰＢＴとＰＰＳの２種類が挙げられ、他の樹脂にも適用可能かどうかは不明である。 By previously treating the metal surface with a water-soluble reducing agent such as hydrazine as described above, and injecting and integrating a thermoplastic resin composition containing polybutylene terephthalate or polyphenylene sulfide on the surface-treated metal surface. It is possible to integrally bond the metal and the resin with a sufficiently high bonding strength.
However, hydrazine requires attention in usage and handling from the viewpoint of impact on the working environment. Accordingly, the use of such chemicals is problematic in terms of actual industrial use and increases costs. In addition, two types of resins, PBT and PPS, are mentioned as the resins that can be joined by the injection process, and it is unclear whether they can be applied to other resins.

従って、本発明の目的は、従来の水溶性還元剤を用いることなく、安全な作業環境での従事が可能であり、しかも充分な接合強度で金属材と熱可塑性樹脂とを一体成形でき、低コストで金属と樹脂の複合体を製造できる方法を提供することにある。   Therefore, the object of the present invention is to be able to engage in a safe working environment without using a conventional water-soluble reducing agent, and to be able to integrally form a metal material and a thermoplastic resin with sufficient bonding strength. The object is to provide a method capable of producing a composite of metal and resin at low cost.

前記目的を達成するために、本発明によれば、微多孔質の水酸基含有皮膜が形成された金属の表面に、熱可塑性樹脂を射出し、上記皮膜を介して金属と熱可塑性樹脂とを一体化することを特徴とする金属と樹脂の複合体の製造方法が提供される。
ここで、水酸基含有皮膜は、金属の表面に温水処理を施すことにより容易に且つ低コストで形成でき、水酸化皮膜及び／又は水和皮膜ということもでき、金属の水酸化物及び／又は水和酸化物を含む皮膜ということができる。好適な態様においては、前記金属の表面に少なくとも５ｎｍ以上の厚さ、好ましくは５ｎｍ〜１００ｎｍの厚さの微多孔質の水酸基含有皮膜が形成されている。 In order to achieve the above object, according to the present invention, a thermoplastic resin is injected onto the surface of a metal on which a microporous hydroxyl group-containing film is formed, and the metal and the thermoplastic resin are integrated through the film. A method for producing a composite of a metal and a resin is provided.
Here, the hydroxyl group-containing film can be easily formed at a low cost by subjecting a metal surface to hot water treatment, and can also be referred to as a hydroxide film and / or a hydrated film. It can be said that the film contains a hydrated oxide. In a preferred embodiment, a microporous hydroxyl-containing film having a thickness of at least 5 nm, preferably 5 nm to 100 nm, is formed on the surface of the metal.

好適な態様においては、前記金属は、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅又は銅合金のいずれかの金属である。特に好適には、陽極酸化皮膜が形成されたアルミニウム又はアルミニウム合金である。
前記金属の表面に微多孔質の水酸基含有皮膜を形成する手段としては、温水処理を施す方法が好適である。温水処理は、金属を５０℃以上の温水に３０秒以上浸漬する処理、好ましくは金属を６０〜９０℃の温水に１〜３０分浸漬する処理が好ましい。 In a preferred embodiment, the metal is any one of aluminum, aluminum alloy, magnesium, magnesium alloy, copper, and copper alloy. Particularly preferred is aluminum or an aluminum alloy on which an anodized film is formed.
As a means for forming a microporous hydroxyl group-containing film on the surface of the metal, a method of performing hot water treatment is suitable. The hot water treatment is preferably a treatment of immersing a metal in hot water of 50 ° C. or higher for 30 seconds or more, preferably a treatment of immersing the metal in hot water of 60 to 90 ° C. for 1 to 30 minutes.

一方、前記熱可塑性樹脂としては、ポリアルキレンテレフタレート、ポリアルキレンサルファイド又はポリフェニレンサルファイドを含む樹脂、好ましくはポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンサルファイド或いはこれらを主とする樹脂、特に好ましくは熱可塑性エラストマーを添加した樹脂を有利に用いることができる。
より具体的な態様としては、金型内に前記微多孔質の水酸基含有皮膜が形成された金属を配し、上記金属表面の水酸基含有皮膜と金型内周面とによって形成される空間に熱可塑性樹脂を射出するインサート成形法が好ましい。 On the other hand, as the thermoplastic resin, a resin containing polyalkylene terephthalate, polyalkylene sulfide or polyphenylene sulfide, preferably polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide or a resin mainly containing these, particularly preferably a thermoplastic elastomer is added. The resin obtained can be used advantageously.
More specifically, a metal in which the microporous hydroxyl group-containing film is formed is arranged in a mold, and heat is generated in a space formed by the hydroxyl group-containing film on the metal surface and the inner peripheral surface of the mold. An insert molding method in which a plastic resin is injected is preferable.

本発明の金属と樹脂の複合体の製造方法によれば、微多孔質の水酸基含有皮膜が形成された金属の表面に、熱可塑性樹脂を射出し、上記皮膜を介して金属と熱可塑性樹脂とを一体化するものであるため、上記微多孔質の水酸基含有皮膜のアンカー効果と化学的な作用により、金属と熱可塑性樹脂とを充分な接合強度で一体化することができる。また、このような水酸基含有皮膜は、従来のヒドラジンを用いることなく、金属の表面に温水処理を施すことにより容易に且つ低コストで形成できるので、悪臭を伴うことも無く、所望の形状に成形された金属材と熱可塑性樹脂とが一体成形された複合体を低コストで安全に製造することができる。   According to the metal / resin composite production method of the present invention, a thermoplastic resin is injected onto the surface of a metal on which a microporous hydroxyl group-containing film is formed, and the metal and the thermoplastic resin are injected through the film. Therefore, the metal and the thermoplastic resin can be integrated with sufficient bonding strength by the anchor effect and chemical action of the microporous hydroxyl group-containing film. Further, such a hydroxyl group-containing film can be formed easily and at low cost by subjecting the metal surface to hot water treatment without using conventional hydrazine, so that it does not cause bad odor and is formed into a desired shape. The composite body in which the formed metal material and the thermoplastic resin are integrally molded can be manufactured safely at low cost.

また、本発明の方法は、前記微多孔質の水酸基含有皮膜を形成できる金属であれば全て適用可能であり、特定の金属に限定されることが無いという利点を有する。特に、陽極酸化皮膜が形成されたアルミニウム又はアルミニウム合金の場合、耐食性に優れるため、上記水酸基含有皮膜が剥がれても優れた耐食性を維持できると共に、既存アルマイトラインをそのまま使用し、射出温度・時間の低減も可能であり、製造工程の簡素化を図ることができ、コストダウンが可能である。また、接合する熱可塑性樹脂としても、各種樹脂に適用可能であるという利点を有し、また、熱可塑性エラストマーを添加した熱可塑性樹脂組成物を使用した場合、樹脂組成物の過冷却領域を広げ、比較的低温でも樹脂組成物に流動性を持たせることが可能となる。それにより、金属と樹脂の射出成形時に、比較的低温で短時間射出することによっても、流動性の良い半溶融状態の樹脂となるため、前記微多孔質の水酸基含有皮膜との接触面積が拡大し、金属と樹脂の接合強度を高めることができる。   The method of the present invention can be applied to any metal that can form the microporous hydroxyl group-containing film, and has the advantage that it is not limited to a specific metal. In particular, in the case of aluminum or aluminum alloy on which an anodized film is formed, it has excellent corrosion resistance. Reduction is also possible, the manufacturing process can be simplified, and the cost can be reduced. Also, the thermoplastic resin to be joined has the advantage that it can be applied to various resins, and when a thermoplastic resin composition to which a thermoplastic elastomer is added is used, the supercooling region of the resin composition is expanded. It becomes possible to impart fluidity to the resin composition even at relatively low temperatures. As a result, even during injection molding of metal and resin, it becomes a resin in a semi-molten state with good fluidity even by injecting at a relatively low temperature for a short time, so the contact area with the microporous hydroxyl-containing film is expanded. In addition, the bonding strength between the metal and the resin can be increased.

さらに、金型内に前記微多孔質の水酸基含有皮膜が形成された金属を配し、上記金属表面の水酸基含有皮膜と金型内周面とによって形成される空間に熱可塑性樹脂を射出することにより、金属−樹脂複合成形体を低コストで安全に製造することができ、製品の軽量化を達成できる。また、２種以上の所望の形状に成形された金属材を各々温水処理後、組み合わせて金型内に配し、射出成形することで、異なる物性を有する金属材と樹脂とを一体成形することもできる。さらに、製品廃棄時には、アルカリ浸漬を行うことで容易に金属と樹脂の分離が可能であり、製品のリサイクル性にも優れている。   Further, a metal having the microporous hydroxyl group-containing film formed therein is arranged in a mold, and a thermoplastic resin is injected into a space formed by the hydroxyl group-containing film on the metal surface and the inner peripheral surface of the mold. Thus, the metal-resin composite molded body can be manufactured safely at low cost, and the weight of the product can be reduced. Also, two or more kinds of metal materials molded into desired shapes are each treated with warm water, combined and placed in a mold, and injection molded to integrally form metal materials and resins having different physical properties. You can also. Furthermore, when the product is discarded, it is possible to easily separate the metal and the resin by soaking in alkali, and the product is excellent in recyclability.

本発明者らは、前記目的を達成するために鋭意研究した結果、微多孔質の水酸基含有皮膜が形成された金属の表面に、熱可塑性樹脂を射出すれば、上記皮膜を介して金属と熱可塑性樹脂とを充分な接合強度で一体化できること、及び、このような水酸基含有皮膜は、従来のヒドラジンを用いることなく、金属の表面に温水処理を施すことにより容易に且つ低コストで形成できることを見出し、本発明を完成するに至ったものである。   As a result of intensive studies to achieve the above object, the present inventors have found that when a thermoplastic resin is injected onto the surface of a metal on which a microporous hydroxyl group-containing film is formed, the metal and the heat can be transferred through the film. The plastic resin can be integrated with sufficient bonding strength, and such a hydroxyl group-containing film can be formed easily and at low cost by performing hot water treatment on the metal surface without using conventional hydrazine. The headline and the present invention have been completed.

このように、微多孔質の水酸基含有皮膜が形成された金属の表面に熱可塑性樹脂を射出すれば、金属と熱可塑性樹脂とを充分な接合強度で一体化できる理由としては、現時点では必ずしも明らかになっているとはいい難いが、上記微多孔質の水酸基含有皮膜のアンカー効果と化学的な作用によるものと考えられる。すなわち、金属の表面に温水処理を施すことにより形成される水酸基含有皮膜は、水酸化皮膜及び／又は水和皮膜ということもでき、金属の水酸化物及び／又は水和酸化物を含む皮膜ということができる。また、微多孔質構造は、その孔が金属面に対して網目状に入り込んで、どちらかといえば毛羽立った構造を有している。従って、このような微多孔質構造に射出された熱可塑性樹脂が入り込み、アンカー効果を発揮することができる。また、上記水酸基含有皮膜は、金属の水酸化物及び／又は水和酸化物を含む皮膜であり、電気的に陰性を帯びた（δ−で表示される）水酸基もしくは酸素原子を含むため、樹脂の電気的に陽性を帯びた（δ＋で表示される）水素原子と引き合い、その化学的な作用が水酸基含有皮膜と樹脂の接合強度向上に大きく寄与しているものと考えられる。   As described above, the reason why the metal and the thermoplastic resin can be integrated with sufficient bonding strength by injecting the thermoplastic resin onto the surface of the metal on which the microporous hydroxyl group-containing film is formed is not always clear at present. Although it is difficult to say, the anchor effect and chemical action of the microporous hydroxyl group-containing film are considered. That is, the hydroxyl group-containing film formed by performing hot water treatment on the metal surface can also be referred to as a hydroxide film and / or a hydrated film, or a film containing a metal hydroxide and / or hydrated oxide. be able to. In addition, the microporous structure has a structure in which the pores enter a network shape with respect to the metal surface, and is rather fuzzy. Therefore, the thermoplastic resin injected into such a microporous structure enters and can exert an anchor effect. The hydroxyl group-containing film is a film containing a metal hydroxide and / or a hydrated oxide and contains an electrically negative hydroxyl group (indicated by δ-) or an oxygen atom. It is considered that the chemical action is greatly contributed to the improvement of the bonding strength between the hydroxyl group-containing film and the resin by attracting to the electrically positive hydrogen atom (indicated by δ +).

従って、本発明の方法は、前記微多孔質の水酸基含有皮膜を形成できる金属であれば全て適用可能であり、特定の金属に限定されることが無いが、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅又は銅合金のいずれかの金属に好適に適用できる。特に、陽極酸化皮膜が形成されたアルミニウム又はアルミニウム合金の場合、耐食性に優れるため、上記水酸基含有皮膜が剥がれても優れた耐食性を維持できると共に、既存アルマイトラインをそのまま使用可能である。なお、必要な形状、構造に加工された金属材は、樹脂を接合すべき面に油脂が付着していたり、厚く酸化されていないことが必要であり、必要に応じて、脱脂、水洗、中和等の前処理を施すことが望ましい。また、長期間の自然放置で表面に錆の存在が明らかなものは、研磨等により取り除くことが必要である。また、２種以上の所望の形状に成形された金属材を各々温水処理後、組み合わせて金型内に配し、射出成形することで、異なる物性を有する金属材料と樹脂とを一体成形することもできる。   Therefore, the method of the present invention can be applied to any metal that can form the microporous hydroxyl group-containing film, and is not limited to a specific metal, but aluminum, aluminum alloy, magnesium, magnesium alloy It can be suitably applied to any metal of copper or copper alloy. In particular, in the case of aluminum or an aluminum alloy on which an anodized film is formed, the corrosion resistance is excellent, so that excellent corrosion resistance can be maintained even if the hydroxyl group-containing film is peeled off, and an existing anodized line can be used as it is. It should be noted that the metal material processed into the necessary shape and structure requires that the surface to which the resin is to be bonded has oil or fat not thickly oxidized, and if necessary, degrease, water wash, It is desirable to perform a pretreatment such as sum. In addition, it is necessary to remove the rust on the surface that has been clearly left standing for a long time by polishing or the like. In addition, two or more kinds of metal materials molded into desired shapes are each treated with warm water, combined and placed in a mold, and injection molded to integrally form metal materials and resins having different physical properties. You can also.

前記熱可塑性樹脂としては、特定の種類のものに限定されるものではないが、ポリアルキレンテレフタレート、ポリアルキレンサルファイド又はポリフェニレンサルファイドを含む樹脂、好ましくはポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリフェニレンサルファイド（ＰＰＳ）或いはこれらを主とする樹脂を好適に用いることができる。また、ＰＢＴ単独のポリマー、ＰＢＴとポリカーボネート（ＰＣ）のポリマーコンパウンド、ＰＢＴとアクリロニトリル・ブタジエン・スチレン樹脂（ＡＢＳ樹脂）のポリマーコンパウンド、ＰＢＴとポリエチレンテレフタレート（ＰＥＴ）のポリマーコンパウンド等も用いることができる。特に好ましいのは、熱可塑性エラストマー、例えばオレフィン系エラストマーを添加した樹脂である。熱可塑性エラストマーを添加することにより、熱可塑性樹脂組成物の過冷却領域を広げ、比較的低温でも樹脂組成物に流動性を持たせることが可能となる。また、金属と熱可塑性樹脂組成物との熱膨張率の差を小さくすると共に、接合強度を向上させるために、フィラーを添加した熱可塑性樹脂組成物を用いることが好ましい。   The thermoplastic resin is not limited to a specific type, but is a resin containing polyalkylene terephthalate, polyalkylene sulfide or polyphenylene sulfide, preferably polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polyphenylene sulfide (PPS) or a resin mainly containing these can be preferably used. In addition, a single polymer of PBT, a polymer compound of PBT and polycarbonate (PC), a polymer compound of PBT and acrylonitrile / butadiene / styrene resin (ABS resin), a polymer compound of PBT and polyethylene terephthalate (PET), and the like can also be used. Particularly preferred is a resin to which a thermoplastic elastomer, for example, an olefin elastomer is added. By adding the thermoplastic elastomer, the supercooling region of the thermoplastic resin composition can be expanded, and the resin composition can be made fluid even at a relatively low temperature. Moreover, it is preferable to use a thermoplastic resin composition to which a filler is added in order to reduce the difference in coefficient of thermal expansion between the metal and the thermoplastic resin composition and to improve the bonding strength.

フィラーの含有は、金属材と熱可塑性樹脂組成物との熱膨張率の差を小さくするという観点から重要である。フイラーとしては、ガラス繊維、炭素繊維、アラミド繊維、その他これらに類する高強度繊維が好ましい。また、炭酸カルシウム、炭酸マグネシウム、シリカ、タルク、粘土、炭素繊維やアラミド繊維の粉砕物、その他これらに類する樹脂充填用無機フィラーを含有した熱可塑性樹脂組成物であることが好ましい。このようなフィラーを含む熱可塑性樹脂組成物を用いることにより、成形された複合体を温度サイクル試験にかけた時の接合強度低下を防止し、また、インサート成形後の金属の冷却縮みと熱可塑性樹脂組成物の成形収縮の差を小さくし、僅かな衝撃で界面破壊が起こって剥がれる原因となる金属と樹脂の界面での内部歪の発生を防止することが可能となる。フィラーの含有率は高い方が好ましく、通常、２０質量％以上、より好ましくは３０質量％以上であり、一般には３０〜５０質量％の含有率が好ましい。   The inclusion of the filler is important from the viewpoint of reducing the difference in coefficient of thermal expansion between the metal material and the thermoplastic resin composition. As the filler, glass fiber, carbon fiber, aramid fiber, and other high strength fibers similar to these are preferable. Further, it is preferably a thermoplastic resin composition containing calcium carbonate, magnesium carbonate, silica, talc, clay, pulverized carbon fiber or aramid fiber, and other similar resin-filled inorganic fillers. By using a thermoplastic resin composition containing such a filler, it is possible to prevent a reduction in bonding strength when the molded composite is subjected to a temperature cycle test, and to cool shrinkage of the metal after insert molding and the thermoplastic resin. It is possible to reduce the difference in molding shrinkage of the composition, and to prevent the occurrence of internal strain at the interface between the metal and the resin that causes the interface to break and peel off with a slight impact. The content of the filler is preferably higher, usually 20% by mass or more, more preferably 30% by mass or more, and generally 30 to 50% by mass is preferable.

本発明においては、所望の形状に成形された金属材を、射出成形に先立って、温水中に浸漬する処理を行って水酸基含有皮膜を形成した後、これを乾燥し、射出成形金型に挿入して金型を閉め、金属材表面の水酸基含有皮膜と金型キャビティ内周面とによって形成される空間に熱可塑性樹脂組成物を射出する。射出条件としては、前記熱可塑性樹脂組成物を使用する場合の通常の射出成形とほぼ同様の条件で充分である。   In the present invention, a metal material molded into a desired shape is immersed in warm water prior to injection molding to form a hydroxyl group-containing film, which is then dried and inserted into an injection mold Then, the mold is closed, and the thermoplastic resin composition is injected into a space formed by the hydroxyl group-containing film on the surface of the metal material and the inner peripheral surface of the mold cavity. As the injection conditions, substantially the same conditions as those for normal injection molding when the thermoplastic resin composition is used are sufficient.

前記温水処理は、金属を約５０℃以上、１００℃未満、好ましくは６０〜９０℃の温水に、約３０秒以上、好ましくは１〜３０分接触させる処理であり、温水中への浸漬や、温水のスプレー、水蒸気の噴霧などの処理方法が採用できるが、作業性や設備コスト等の点から、好ましくは浸漬処理により行う。
このような温水処理により、金属の表面に少なくとも５ｎｍ以上の厚さ、好ましくは５ｎｍ〜１００ｎｍの厚さの微多孔質の水酸基含有皮膜が形成される。温水の温度が高いほど処理時間を短くし、温水の温度が低いほど処理時間を長くして、所望の膜厚が得られるように調整することができる。 The hot water treatment is a treatment in which a metal is brought into contact with hot water of about 50 ° C. or more and less than 100 ° C., preferably 60 to 90 ° C. for about 30 seconds or more, preferably 1 to 30 minutes. Although treatment methods such as spraying of warm water and spraying of water vapor can be adopted, it is preferably carried out by dipping treatment from the viewpoint of workability and equipment cost.
By such warm water treatment, a microporous hydroxyl group-containing film having a thickness of at least 5 nm, preferably 5 nm to 100 nm, is formed on the metal surface. The treatment time can be shortened as the temperature of the warm water is higher, and the treatment time can be lengthened as the temperature of the warm water is lowered so that a desired film thickness can be obtained.

前記したように金属材と樹脂とが一体成形された複合材は、アルカリや酸の水溶液に浸漬することにより、アルカリや酸の水溶液が金属材と樹脂との界面に浸透して水酸基含有皮膜を溶解するので、比較的簡単に金属材と樹脂を剥離することができる。従って、製品廃棄時には、アルカリや酸の水溶液に浸漬することで容易に金属と樹脂の分離が可能であり、製品のリサイクル性にも優れている。一方、リサイクル性を考慮しない場合には、耐食性を向上させるために、一体成形体の金属材と樹脂との境界部を塗装処理することが好ましい。これにより、例えば、樹脂が接合されていないアルミニウム合金表面に、接合強度を低下させることなく、後処理として陽極酸化皮膜を形成することもできる。   As described above, a composite material in which a metal material and a resin are integrally formed is immersed in an aqueous solution of an alkali or an acid, so that the aqueous solution of an alkali or an acid penetrates into the interface between the metal material and the resin to form a hydroxyl-containing film. Since it melt | dissolves, a metal material and resin can be peeled comparatively easily. Therefore, when the product is discarded, it is possible to easily separate the metal and the resin by immersing in an aqueous solution of alkali or acid, and the product is excellent in recyclability. On the other hand, when recyclability is not taken into consideration, it is preferable to paint the boundary portion between the metal material and the resin of the integrally molded body in order to improve the corrosion resistance. Thereby, for example, an anodized film can be formed as a post-treatment on the surface of an aluminum alloy to which no resin is bonded without reducing the bonding strength.

さらに、予め金属材の特定部位に固着硬化喪失処理を行った後、前記した温水処理及び射出成形を実施することで、部分的に非一体化させることもできる。このような固着硬化喪失処理としては、金属材の特定部位に、（１）例えばエポキシ系のインクや塗料、低温で硬化する２液性ウレタン硬化系のインクや塗料、１液性アクリル系インク等のコーティング剤で印刷又は筆塗りによる被覆方法、（２）マスキングテープを貼り付ける方法、（３）リューター（回転砥石）又はサンドペーパーにより表面を剥がし取る方法、（４）レーザーを照射して固着効果を喪失させる方法などである。   Furthermore, after performing a fixed hardening loss process to the specific site | part of a metal material previously, it can also be made non-integrated partially by implementing the above-mentioned warm water process and injection molding. Such fixed curing loss treatment includes (1), for example, epoxy-based ink or paint, two-component urethane-cured ink or paint that is cured at low temperature, one-component acrylic ink, etc. (2) A method of applying a masking tape, (3) A method of peeling off the surface with a router (rotary grindstone) or sandpaper, (4) A fixing effect by irradiating a laser It is a method of losing.

以下に実施例等を示して本発明について具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。また、本発明はその趣旨を逸脱しない範囲で当業者の知識に基づき、種々なる改良、変更、修正を加えた様態で実施しうるものである。   EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples. The present invention can be carried out in various modifications, changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

なお、以下の実施例において実施した金属材と樹脂の接合強度の測定は、図１に示すように、水酸基含有皮膜を形成した４４ｍｍ×１８ｍｍ×１．６ｍｍの金属板１の表面に４０ｍｍ×１０ｍｍ×３．０ｍｍのサイズの熱可塑性樹脂を射出して作製した試験片を、標点間距離４０ｍｍとなるように両端部をチャックに挟んで引張試験機にかけ、ＪＩＳ Ｋ６８４９に従って引張剪断試験を行った。   In addition, as shown in FIG. 1, the measurement of the bonding strength between the metal material and the resin carried out in the following examples was performed on the surface of a metal plate 1 of 44 mm × 18 mm × 1.6 mm on which a hydroxyl group-containing film was formed. A test piece produced by injecting a thermoplastic resin having a size of × 3.0 mm was subjected to a tensile tester with both ends sandwiched between chucks so that the distance between the marks was 40 mm, and a tensile shear test was conducted according to JIS K6849. .

実施例１
常法に従って脱脂、エッチング（苛性ソーダ）、中和（スマット除去）の前処理を行ったアルミニウム合金Ａ５０５２ＰＨ３４を、７０℃の温水に５分浸漬し、水酸基含有皮膜を形成した。これを金型内にインサートし、ポリブチレンテレフタレート（ＰＢＴ；融点２２３℃）＋熱可塑性オレフィン系エラストマー（融点１０４℃）５５質量％、ガラス繊維４０質量％、ポリエチレンテレフタレート（ＰＥＴ；融点２５０℃）５質量％を含むＰＢＴ樹脂組成物を、射出温度２６０℃、射出時間３．５秒の条件で射出し、図１に示すような試験片を作製した。作製した試験片について、前記したようにＪＩＳ Ｋ６８４９に従って引張剪断試験を行ったところ、２６ＭＰａの接着強度を示した。 Example 1
Aluminum alloy A5052PH34, which had been pretreated by degreasing, etching (caustic soda) and neutralization (smut removal) according to a conventional method, was immersed in warm water at 70 ° C. for 5 minutes to form a hydroxyl group-containing film. This was inserted into a mold, and polybutylene terephthalate (PBT; melting point 223 ° C.) + Thermoplastic olefin elastomer (melting point 104 ° C.) 55% by mass, glass fiber 40% by mass, polyethylene terephthalate (PET; melting point 250 ° C.) 5 A PBT resin composition containing% by mass was injected under the conditions of an injection temperature of 260 ° C. and an injection time of 3.5 seconds to produce a test piece as shown in FIG. The prepared test piece was subjected to a tensile shear test according to JIS K6849 as described above, and showed an adhesive strength of 26 MPa.

また、上記のように水酸基含有皮膜を形成したアルミニウム合金のオージェ電子分光による深さ方向分析を行った結果を図２に示す。尚、測定機としては、日本電子（株）製のオージェ電子分光装置、型式ＪＡＭＰ−１０ＳＸを用いた。また、皮膜厚さの評価は、膜厚既知の試料を用いてイオンスパッタリングによるスパッタリング深さを求める方法によった。すなわち、厚さ既知の膜が付いた試料を標準試料として使用し、その膜をスパッタリングし終るまでの時間を測定して、そのイオンビーム条件でのスパッタリング速度を決定し、その後、被検試料について同じスパッタリング速度でスパッタリングして測定した時間を標準試料と対比して膜厚を決定する。標準膜試料としては、表面に酸化膜の付いたシリコンウェハーを用いた。厳密には試料によってスパッタリング速度は異なるので、元素ごとのスパッタリング速度（正確にはスパッタリング収率）のデータを用いて補正する必要がある（元素ごとのスパッタリング速度については、「ユーザーのための実用オージェ電子分光法」、１９８９年６月１０日共立出版株式会社発行の付録表１０のスパッタリング速度を参照）。
図２に示されるように、約１０ｎｍの皮膜が形成されており、この皮膜は表面にいくほど酸素濃度が高く、水酸基もしくは酸素原子が多量に存在していることがわかる。また、表面を透過型電子顕微鏡で観察したところ、孔が金属面に対して網目状に入り込んだ微多孔質構造を有し、どちらかといえば毛羽立った構造を有していた。 Moreover, the result of having conducted the depth direction analysis by the Auger electron spectroscopy of the aluminum alloy which formed the hydroxyl-containing film | membrane as mentioned above is shown in FIG. As a measuring device, an Auger electron spectrometer manufactured by JEOL Ltd., model JAMP-10SX was used. Moreover, evaluation of film thickness was based on the method of calculating | requiring the sputtering depth by ion sputtering using the sample with a known film thickness. That is, a sample with a film having a known thickness is used as a standard sample, and the time until the film is completely sputtered is measured to determine the sputtering rate under the ion beam conditions. The film thickness is determined by comparing the time measured by sputtering at the same sputtering rate with the standard sample. As a standard film sample, a silicon wafer having an oxide film on the surface was used. Strictly speaking, since the sputtering rate varies depending on the sample, it is necessary to correct by using the data of the sputtering rate for each element (precisely, the sputtering yield). Electron Spectroscopy ", see Sputtering Rate in Appendix Table 10, published June 10, 1989 by Kyoritsu Shuppan Co., Ltd.).
As shown in FIG. 2, a film having a thickness of about 10 nm is formed. It can be seen that the oxygen concentration increases toward the surface of the film, and a large amount of hydroxyl groups or oxygen atoms are present. Further, when the surface was observed with a transmission electron microscope, it had a microporous structure in which pores entered into a network shape with respect to the metal surface, and had a rather fluffy structure.

実施例２
前記実施例１において、温水処理を６０℃×１０分に変えた以外は、前記実施例１と同様にして試験片を作製した。作製した試験片について、前記したようにＪＩＳ Ｋ６８４９に従って引張剪断試験を行ったところ、２４ＭＰａの接着強度を示した。 Example 2
A test piece was prepared in the same manner as in Example 1 except that the hot water treatment was changed to 60 ° C. × 10 minutes in Example 1. The prepared test piece was subjected to a tensile shear test according to JIS K6849 as described above, and showed an adhesive strength of 24 MPa.

比較例１
前記実施例１において、温水処理を行わなかった以外は、前記実施例１と同様にして試験片を作製したが、樹脂がアルミニウム合金に充分に接合しておらず、簡単に剥がれてしまった。 Comparative Example 1
In Example 1, a test piece was prepared in the same manner as in Example 1 except that the hot water treatment was not performed. However, the resin was not sufficiently bonded to the aluminum alloy and was easily peeled off.

実施例３
前記実施例１において、熱可塑性樹脂組成物としてポリフェニレンサルファイド（ＰＰＳ；融点２８１℃）＋熱可塑性オレフィン系エラストマー（融点１９２℃）７９質量％、ガラス繊維２１質量％を含むＰＰＳ樹脂組成物を用い、射出温度を３１０℃に変えた以外は、前記実施例１と同様にして試験片を作製した。作製した試験片について、前記したようにＪＩＳ Ｋ６８４９に従って引張剪断試験を行ったところ、２１ＭＰａの接着強度を示した。 Example 3
In Example 1, a PPS resin composition containing 79% by mass of polyphenylene sulfide (PPS; melting point 281 ° C.) + Thermoplastic olefin elastomer (melting point 192 ° C.) and 21% by mass of glass fiber is used as the thermoplastic resin composition. A test piece was prepared in the same manner as in Example 1 except that the injection temperature was changed to 310 ° C. The produced test piece was subjected to a tensile shear test according to JIS K6849 as described above, and showed an adhesive strength of 21 MPa.

実施例４
前記実施例３において、温水処理を６０℃×１０分に変えた以外は、前記実施例１と同様にして試験片を作製した。作製した試験片について、前記したようにＪＩＳ Ｋ６８４９に従って引張剪断試験を行ったところ、２５ＭＰａの接着強度を示した。 Example 4
In Example 3, a test piece was prepared in the same manner as in Example 1 except that the hot water treatment was changed to 60 ° C. × 10 minutes. The prepared test piece was subjected to a tensile shear test according to JIS K6849 as described above, and showed an adhesive strength of 25 MPa.

比較例２
前記実施例３において、温水処理を行わなかった以外は、前記実施例３と同様にして試験片を作製したが、樹脂がアルミニウム合金に充分に接合しておらず、簡単に剥がれてしまった。 Comparative Example 2
In Example 3, a test piece was prepared in the same manner as in Example 3 except that the hot water treatment was not performed. However, the resin was not sufficiently bonded to the aluminum alloy and was easily peeled off.

実施例５
常法に従って脱脂、エッチング、中和の前処理を行った真鍮（Ｃｕ６５％，Ｚｎ３５％）を、７０℃の温水に１０分浸漬し、水酸基含有皮膜を形成した。これを金型内にインサートし、ポリブチレンテレフタレート（ＰＢＴ；融点２２３℃）＋熱可塑性オレフィン系エラストマー（融点１０４℃）５５質量％、ガラス繊維４０質量％、ポリエチレンテレフタレート（ＰＥＴ；融点２５０℃）５質量％を含むＰＢＴ樹脂組成物を、射出温度２６０℃、射出時間３．５秒の条件で射出したところ、充分な接着強度を示した。 Example 5
Brass (Cu65%, Zn35%) pretreated by degreasing, etching and neutralization according to a conventional method was immersed in warm water at 70 ° C. for 10 minutes to form a hydroxyl group-containing film. This was inserted into a mold, and polybutylene terephthalate (PBT; melting point 223 ° C.) + Thermoplastic olefin elastomer (melting point 104 ° C.) 55% by mass, glass fiber 40% by mass, polyethylene terephthalate (PET; melting point 250 ° C.) 5 When a PBT resin composition containing mass% was injected under the conditions of an injection temperature of 260 ° C. and an injection time of 3.5 seconds, sufficient adhesive strength was exhibited.

また、上記のように水酸基含有皮膜を形成した真鍮の、前記実施例１と同様にして測定したオージェ電子分光による深さ方向分析の結果を図３に示す。
図３に示されるように、約１７ｎｍの皮膜が形成されており、この皮膜は表面にいくほど酸素濃度が高く、水酸基もしくは酸素原子が多量に存在していることがわかる。 Moreover, the result of the depth direction analysis by Auger electron spectroscopy measured in the same manner as in Example 1 of the brass having the hydroxyl group-containing film formed as described above is shown in FIG.
As shown in FIG. 3, a film having a thickness of about 17 nm is formed. It can be seen that the oxygen concentration increases toward the surface of the film, and a large amount of hydroxyl groups or oxygen atoms are present.

本発明の金属と樹脂の複合体の製造方法は、各種金属と熱可塑性樹脂とを一体化する技術に好適に用いることができ、ＩＣ等を内蔵した電子機器の筐体、構造用部品など、産業用の各種制御機器、家庭用電化製品、携帯電話等の通信機器、医療機器、車両搭載用や建築資材用の筐体、構造用部材もしくは部品、外装用部材もしくは部品等の金属−樹脂複合体の製造に有用である。   The method for producing a composite of a metal and a resin of the present invention can be suitably used in a technique for integrating various metals and a thermoplastic resin, such as a housing for an electronic device incorporating an IC, a structural component, Metal-resin composites for various industrial control devices, household appliances, communication devices such as mobile phones, medical devices, housings for vehicles and building materials, structural members or parts, exterior members or parts, etc. Useful for body production.

各実施例で用いた試験片の概略斜視図である。It is a schematic perspective view of the test piece used in each Example. 実施例１で温水処理したアルミニウム合金片のオージェ電子分光による深さ方向分析結果を示すグラフである。It is a graph which shows the depth direction analysis result by the Auger electron spectroscopy of the aluminum alloy piece which carried out the hot water process in Example 1. FIG. 実施例５で温水処理した真鍮片のオージェ電子分光による深さ方向分析結果を示すグラフである。It is a graph which shows the depth direction analysis result by the Auger electron spectroscopy of the brass piece which carried out the hot water process in Example 5. FIG.

符号の説明Explanation of symbols

１ 金属板
２ 熱可塑性樹脂 1 Metal plate 2 Thermoplastic resin

Claims (12)

微多孔質の水酸基含有皮膜が形成された金属の表面に、熱可塑性樹脂を射出し、上記皮膜を介して金属と熱可塑性樹脂とを一体化することを特徴とする金属と樹脂の複合体の製造方法。   A composite of a metal and a resin characterized by injecting a thermoplastic resin onto the surface of a metal on which a microporous hydroxyl group-containing film is formed, and integrating the metal and the thermoplastic resin through the film. Production method. 前記金属は、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅又は銅合金のいずれかの金属である請求項１に記載の方法。   The method according to claim 1, wherein the metal is one of aluminum, an aluminum alloy, magnesium, a magnesium alloy, copper, and a copper alloy. 前記金属は、陽極酸化皮膜が形成されたアルミニウム又はアルミニウム合金である請求項１又は２に記載の方法。   The method according to claim 1, wherein the metal is aluminum or an aluminum alloy on which an anodized film is formed. 前記金属の表面に少なくとも５ｎｍ以上の厚さの微多孔質の水酸基含有皮膜が形成されている請求項１乃至３のいずれか一項に記載の方法。   The method according to any one of claims 1 to 3, wherein a microporous hydroxyl group-containing film having a thickness of at least 5 nm or more is formed on the surface of the metal. 前記金属の表面に５ｎｍ〜１００ｎｍの厚さの微多孔質の水酸基含有皮膜が形成されている請求項１乃至３のいずれか一項に記載の方法。   The method according to any one of claims 1 to 3, wherein a microporous hydroxyl-containing film having a thickness of 5 nm to 100 nm is formed on the surface of the metal. 前記金属の表面に温水処理を施し、表面に微多孔質の水酸基含有皮膜を形成する請求項１乃至５のいずれか一項に記載の方法。   The method according to any one of claims 1 to 5, wherein the surface of the metal is subjected to hot water treatment to form a microporous hydroxyl group-containing film on the surface. 前記温水処理は、金属を５０℃以上の温水に３０秒以上浸漬する処理である請求項６に記載の方法。   The method according to claim 6, wherein the hot water treatment is a treatment of immersing a metal in hot water of 50 ° C. or higher for 30 seconds or longer. 前記温水処理は、金属を６０〜９０℃の温水に１〜３０分浸漬する処理である請求項６に記載の方法。   The method according to claim 6, wherein the warm water treatment is a treatment of immersing the metal in warm water at 60 to 90 ° C. for 1 to 30 minutes. 前記熱可塑性樹脂は、ポリアルキレンテレフタレート、ポリアルキレンサルファイド又はポリフェニレンサルファイドを含む樹脂である請求項１乃至８のいずれか一項に記載の方法。   The method according to any one of claims 1 to 8, wherein the thermoplastic resin is a resin containing polyalkylene terephthalate, polyalkylene sulfide, or polyphenylene sulfide. 前記熱可塑性樹脂は、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンサルファイド或いはこれらを主とするものである請求項１乃至９のいずれか一項に記載の方法。   The method according to any one of claims 1 to 9, wherein the thermoplastic resin is polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide or the main component thereof. 前記熱可塑性樹脂は、熱可塑性エラストマーを添加した樹脂である請求項１乃至１０のいずれか一項に記載の方法。   The method according to any one of claims 1 to 10, wherein the thermoplastic resin is a resin to which a thermoplastic elastomer is added. 金型内に前記微多孔質の水酸基含有皮膜が形成された金属を配し、上記金属表面の水酸基含有皮膜と金型内周面とによって形成される空間に熱可塑性樹脂を射出する請求項１乃至１１のいずれか一項に記載の方法。   The metal on which the microporous hydroxyl group-containing film is formed is disposed in a mold, and a thermoplastic resin is injected into a space formed by the hydroxyl group-containing film on the metal surface and the inner peripheral surface of the mold. The method as described in any one of thru | or 11.
JP2006353914A 2006-12-28 2006-12-28 Method for producing composite of metal and resin Active JP5058593B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006353914A JP5058593B2 (en) 2006-12-28 2006-12-28 Method for producing composite of metal and resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006353914A JP5058593B2 (en) 2006-12-28 2006-12-28 Method for producing composite of metal and resin

Publications (2)

Publication Number Publication Date
JP2008162115A true JP2008162115A (en) 2008-07-17
JP5058593B2 JP5058593B2 (en) 2012-10-24

Family

ID=39692237

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006353914A Active JP5058593B2 (en) 2006-12-28 2006-12-28 Method for producing composite of metal and resin

Country Status (1)

Country Link
JP (1) JP5058593B2 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008146794A1 (en) * 2007-05-29 2008-12-04 Ykk Corporation Metal/resin composite article with sliding contact surface with mate member and process for producing the same
WO2011071102A1 (en) * 2009-12-11 2011-06-16 日本軽金属株式会社 Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for same
WO2011071061A1 (en) * 2009-12-11 2011-06-16 日本軽金属株式会社 Aluminium/resin/copper composite, manufacturing method for same, and lid member for sealed battery
CN102652059A (en) * 2009-12-11 2012-08-29 日本轻金属株式会社 Bonded aluminium composite and manufacturing method for the same
WO2015145253A1 (en) 2014-03-26 2015-10-01 Toyota Jidosha Kabushiki Kaisha Joining method
KR20150134384A (en) 2013-03-26 2015-12-01 니폰게이긴조쿠가부시키가이샤 Metal-resin bonded body, and production method therefor
JP2017218616A (en) * 2016-06-03 2017-12-14 三井化学株式会社 Method for producing surface roughened metal member and method for producing metal/resin composite structure
JP2017218615A (en) * 2016-06-03 2017-12-14 三井化学株式会社 Method for producing surface roughened metal member and method for producing metal/resin composite structure
JP2018144475A (en) * 2017-03-03 2018-09-20 三井化学株式会社 Aluminum-based metal/resin composite structure, aluminum-based metallic member, production method of aluminum-based metallic member and production method of aluminum-based metal/resin composition structure
JP2019018547A (en) * 2017-07-14 2019-02-07 三井化学株式会社 Metal/resin composite structure, and manufacturing method of metal/resin composite structure
WO2019082983A1 (en) 2017-10-27 2019-05-02 三井化学株式会社 Metal/resin composite structure and method for manufacturing metal/resin composite structure
CN111088495A (en) * 2019-12-02 2020-05-01 深圳市裕展精密科技有限公司 Metal part processing method, metal part, shell and metal composite
WO2020158820A1 (en) 2019-01-29 2020-08-06 三井化学株式会社 Aluminum-based metal-resin composite structure, aluminum-based metal member, method for manufacturing aluminum-based metal member, and method for manufacturing aluminum-based metal-resin composite structure
JP2020151981A (en) * 2019-03-20 2020-09-24 三井化学株式会社 Method for producing metal-resin composite and metal-resin composite
WO2020241314A1 (en) 2019-05-28 2020-12-03 三井化学株式会社 Cooling device and method for manufacturing cooling device
US10907267B2 (en) 2013-12-06 2021-02-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Metal-resin composite material, method for producing the same, and aluminum substrate having aluminum oxide coating
WO2021066044A1 (en) 2019-10-04 2021-04-08 三井化学株式会社 Heating element accommodation case and structure
WO2021153778A1 (en) 2020-01-31 2021-08-05 三井化学株式会社 Member for electric conduction, method for manufacturing member for electric conduction, power conversion device, motor, secondary battery module, and secondary battery pack
WO2021256328A1 (en) 2020-06-15 2021-12-23 三井化学株式会社 Metal-resin complex, cooling device, method for manufacturing metal-resin complex, and safety valve structure
WO2022014598A1 (en) 2020-07-14 2022-01-20 三井化学株式会社 Heat exchanger and method for manufacturing heat exchanger
WO2022118936A1 (en) 2020-12-02 2022-06-09 三井化学株式会社 Temperature control unit and method for manufacturing temperature control unit
WO2023013557A1 (en) 2021-08-05 2023-02-09 三井化学株式会社 Antibacterial metal material and antibacterial article

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08142110A (en) * 1994-11-25 1996-06-04 Fujitsu Ltd In-mold forming method and frame
JP2005342895A (en) * 2004-05-31 2005-12-15 Taisei Plas Co Ltd Metal/resin compound object and its manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08142110A (en) * 1994-11-25 1996-06-04 Fujitsu Ltd In-mold forming method and frame
JP2005342895A (en) * 2004-05-31 2005-12-15 Taisei Plas Co Ltd Metal/resin compound object and its manufacturing method

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008146794A1 (en) * 2007-05-29 2008-12-04 Ykk Corporation Metal/resin composite article with sliding contact surface with mate member and process for producing the same
WO2011071102A1 (en) * 2009-12-11 2011-06-16 日本軽金属株式会社 Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for same
WO2011071061A1 (en) * 2009-12-11 2011-06-16 日本軽金属株式会社 Aluminium/resin/copper composite, manufacturing method for same, and lid member for sealed battery
JP2011121306A (en) * 2009-12-11 2011-06-23 Nippon Light Metal Co Ltd Aluminum and resin composite article excellent in weatherability, and method for manufacturing same
CN102652058A (en) * 2009-12-11 2012-08-29 日本轻金属株式会社 Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for the same
CN102652059A (en) * 2009-12-11 2012-08-29 日本轻金属株式会社 Bonded aluminium composite and manufacturing method for the same
KR20150134384A (en) 2013-03-26 2015-12-01 니폰게이긴조쿠가부시키가이샤 Metal-resin bonded body, and production method therefor
US10907267B2 (en) 2013-12-06 2021-02-02 Kabushiki Kaisha Toyota Chuo Kenkyusho Metal-resin composite material, method for producing the same, and aluminum substrate having aluminum oxide coating
US10173370B2 (en) 2014-03-26 2019-01-08 Toyota Jidosha Kabushiki Kaisha Joining method
WO2015145253A1 (en) 2014-03-26 2015-10-01 Toyota Jidosha Kabushiki Kaisha Joining method
JP2017218616A (en) * 2016-06-03 2017-12-14 三井化学株式会社 Method for producing surface roughened metal member and method for producing metal/resin composite structure
JP2017218615A (en) * 2016-06-03 2017-12-14 三井化学株式会社 Method for producing surface roughened metal member and method for producing metal/resin composite structure
JP2018144475A (en) * 2017-03-03 2018-09-20 三井化学株式会社 Aluminum-based metal/resin composite structure, aluminum-based metallic member, production method of aluminum-based metallic member and production method of aluminum-based metal/resin composition structure
JP2019018547A (en) * 2017-07-14 2019-02-07 三井化学株式会社 Metal/resin composite structure, and manufacturing method of metal/resin composite structure
JP7049792B2 (en) 2017-07-14 2022-04-07 三井化学株式会社 Metal / Resin Composite Structure and Method for Manufacturing Metal / Resin Composite Structure
WO2019082983A1 (en) 2017-10-27 2019-05-02 三井化学株式会社 Metal/resin composite structure and method for manufacturing metal/resin composite structure
KR20210109010A (en) 2019-01-29 2021-09-03 미쯔이가가꾸가부시끼가이샤 An aluminum-based metal-resin composite structure, an aluminum-based metal member, a manufacturing method of an aluminum-based metal member, and a manufacturing method of an aluminum-based metal-resin composite structure
WO2020158820A1 (en) 2019-01-29 2020-08-06 三井化学株式会社 Aluminum-based metal-resin composite structure, aluminum-based metal member, method for manufacturing aluminum-based metal member, and method for manufacturing aluminum-based metal-resin composite structure
KR20230054479A (en) 2019-01-29 2023-04-24 미쯔이가가꾸가부시끼가이샤 Aluminum-based metal-resin composite structure, aluminum-based metal member, method for manufacturing aluminum-based metal member, and method for manufacturing aluminum-based metal-resin composite structure
EP4209617A1 (en) 2019-01-29 2023-07-12 Mitsui Chemicals, Inc. Aluminum-based metal-resin composite structure, aluminum-based metal member, method for manufacturing aluminum-based metal member, and method for manufacturing aluminum-based metal-resin composite structure
JP2020151981A (en) * 2019-03-20 2020-09-24 三井化学株式会社 Method for producing metal-resin composite and metal-resin composite
WO2020241314A1 (en) 2019-05-28 2020-12-03 三井化学株式会社 Cooling device and method for manufacturing cooling device
WO2021066044A1 (en) 2019-10-04 2021-04-08 三井化学株式会社 Heating element accommodation case and structure
CN111088495A (en) * 2019-12-02 2020-05-01 深圳市裕展精密科技有限公司 Metal part processing method, metal part, shell and metal composite
WO2021153778A1 (en) 2020-01-31 2021-08-05 三井化学株式会社 Member for electric conduction, method for manufacturing member for electric conduction, power conversion device, motor, secondary battery module, and secondary battery pack
WO2021256328A1 (en) 2020-06-15 2021-12-23 三井化学株式会社 Metal-resin complex, cooling device, method for manufacturing metal-resin complex, and safety valve structure
WO2022014598A1 (en) 2020-07-14 2022-01-20 三井化学株式会社 Heat exchanger and method for manufacturing heat exchanger
WO2022118936A1 (en) 2020-12-02 2022-06-09 三井化学株式会社 Temperature control unit and method for manufacturing temperature control unit
WO2023013557A1 (en) 2021-08-05 2023-02-09 三井化学株式会社 Antibacterial metal material and antibacterial article

Also Published As

Publication number Publication date
JP5058593B2 (en) 2012-10-24

Similar Documents

Publication Publication Date Title
JP5058593B2 (en) Method for producing composite of metal and resin
JP4685139B2 (en) Aluminum alloy / resin composite and method for producing the same
JP5581680B2 (en) Aluminum / resin composite with excellent weather resistance and method for producing the same
JP6368667B2 (en) Metal / resin composite structure, metal member, and method of using metal member
JP5648212B2 (en) Iron alloy article, iron alloy member and manufacturing method thereof
JP4292514B2 (en) Composite of aluminum alloy and resin composition and method for producing the same
JP4927871B2 (en) Metal-resin composite and method for producing the composite
JP5531326B2 (en) Method for producing aluminum-resin composite
JP4202015B2 (en) Metal-resin composite and method for producing the same
WO2014024877A1 (en) Aluminum resin bonded body and method for producing same
JP2013177004A (en) Method of manufacturing integrally injection-molded aluminum/resin article
JP2009298144A (en) Bonded composite article of a plurality of metallic shaped bodies, and method for production thereof
WO2003064150A1 (en) Composite material of aluminum alloy and resin and production method therefor
KR20090085663A (en) Process for production of highly corrosion-resistant composite
JP6469403B2 (en) Method for producing metal / resin composite structure
JP3967104B2 (en) Metal-resin composite and method for producing the same
JP2007203585A (en) Composite of aluminum alloy and resin, and its manufacturing method
JP5673814B2 (en) Aluminum shape body for manufacturing aluminum / resin injection integrated molded article, aluminum / resin injection integrated molded article using the same, and manufacturing method thereof
WO2011071061A1 (en) Aluminium/resin/copper composite, manufacturing method for same, and lid member for sealed battery
JP2017500228A (en) Portable electronic device parts
JP2007313750A (en) Composite of metal with resin and process for producing the same
JP6482417B2 (en) Metal / resin composite structure and method for producing metal / resin composite structure
JP4365578B2 (en) Aluminum alloy-resin composite and its manufacturing method
JP2016117228A (en) Metal/resin composite structure, sliding component and method for producing metal/resin composite structure
CN111386361A (en) An etching agent for roughening the surface of a base material at least the whole or part of the surface of which is made of aluminum or an aluminum alloy, a method for producing a roughened base material, a method for producing a base material-cured resin product combination, and a base material-cured resin product combination

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20081212

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20110408

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110419

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110603

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120221

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120417

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20120731

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20120801

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20150810

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Ref document number: 5058593

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150