JP2024041591A - Metal-containing resin molded product and its molding method - Google Patents
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- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
【課題】合成樹脂中に金属を均一に分散させることが可能であり、成形品の特性を高く保持することが可能な金属含有樹脂成形品の成形方法を提供する。【解決手段】チップ状のＡＢＳ樹脂を、クロム酸と硫酸とを所定の割合で混合して所定の温度に加熱した浴内で所定の時間に亘って浸漬させることによって、ＡＢＳ樹脂の表面にエッチング処理を施した。しかる後、そのエッチング処理を施したＡＢＳ樹脂の表面に、無電解めっき法によって銀をめっきした。そして、その金属（銀）めっき後のチップ状のＡＢＳ樹脂を、溶融押出装置を利用して所定の温度で溶融押出した後に、金属製の型に射出することによって、直方体状の成形品を得た。【選択図】なし[Problem] To provide a molding method for metal-containing resin molded products, which makes it possible to uniformly disperse metal in synthetic resin and maintain the properties of the molded products at a high level. [Solution] ABS resin chips are immersed for a predetermined time in a bath of chromic acid and sulfuric acid mixed in a predetermined ratio and heated to a predetermined temperature, thereby etching the surface of the ABS resin. Thereafter, the surface of the etched ABS resin is plated with silver by electroless plating. The metal (silver)-plated chipped ABS resin is then melt-extruded at a predetermined temperature using a melt extrusion device, and then injected into a metal mold to obtain a rectangular parallelepiped molded product. [Selected Figure] None
Description
本発明は、合成樹脂中に金属を分散させてなる金属含有樹脂成形品、および、その金属含有樹脂成形品を成形するための成形方法に関するものである。 The present invention relates to a metal-containing resin molded article made by dispersing a metal in a synthetic resin, and a molding method for molding the metal-containing resin molded article.
従来から、各種の合成樹脂製の成形品を成形するための方法として、合成樹脂を溶融押出しして金型に流し込んで成形する射出成形方法や、合成樹脂を溶融させてノズルやダイスから押出すことによって繊維やフィルムを成形する方法が知られている。また、そのように合成樹脂を溶融押出しする方法で合成樹脂製の成形品を成形する際には、合成樹脂製の成形品の改質や装飾性の付与等の目的で、合成樹脂原料中に微細な金属粉末を分散させることもある（特許文献１）。 Traditionally, methods for molding various synthetic resin molded products include injection molding, in which synthetic resin is melted and extruded and poured into a mold, and synthetic resin is melted and extruded through a nozzle or die. A method of forming fibers and films by using the above method is known. In addition, when molding synthetic resin products using such a method of melt-extruding synthetic resins, additives are added to the synthetic resin raw materials for the purpose of modifying the synthetic resin moldings or adding decorative properties. Fine metal powder may also be dispersed (Patent Document 1).
そして、そのように成形品の合成樹脂中に金属微粉末を分散させるための方法としては、合成樹脂と金属微粉末とを混合してなる混合組成物を溶融・混練して金属微粉末を分散させた合成樹脂を調製し、その金属微粉末を分散させた合成樹脂を溶融押出しすることにより成形品を成形する方法（以下、混合組成物溶融・混練法という）や、金属微粉末を添加したモノマーを用いて合成樹脂を重合し、その金属微粉末を添加してなる合成樹脂を溶融押出しすることにより成形品を成形する方法（以下、重合時金属添加法という）が知られている。 The method for dispersing fine metal powder in the synthetic resin of molded products is to melt and knead a mixed composition made by mixing synthetic resin and fine metal powder to disperse the fine metal powder. There is a method in which a molded article is prepared by preparing a synthetic resin with a fine metal powder dispersed therein and then melting and extruding the synthetic resin in which fine metal powder is dispersed (hereinafter referred to as a mixed composition melting/kneading method), or a method in which a fine metal powder is added. BACKGROUND ART A method is known in which a molded article is formed by polymerizing a synthetic resin using a monomer and melt-extruding the synthetic resin obtained by adding fine metal powder (hereinafter referred to as a metal addition method during polymerization).
しかしながら、上記した混合組成物溶融・混練法では、合成樹脂中に金属微粉末を均一に分散させることが困難であるため、添加した金属微粉末の偏在によって成形品の特性（たとえば、曲げ強度等の機械的な特性）を低下させてしまう、という不具合があった。一方、重合時金属添加法では、合成樹脂中に金属微粉末をある程度均一に分散させることが可能であるものの、一度に多くの樹脂を重合しなければロスが大きくなってしまうため、成形品のラインナップに合わせて、合成樹脂中に分散させる金属微粉末の種類や量を変更するのが難しい、という不具合がある。 However, in the mixed composition melting and kneading method described above, it is difficult to uniformly disperse the metal fine powder in the synthetic resin, so the uneven distribution of the added metal fine powder may affect the properties of the molded product (for example, bending strength, etc.). The problem was that the mechanical properties of the On the other hand, with the metal addition method during polymerization, it is possible to disperse fine metal powder into the synthetic resin to some extent, but if a large amount of resin is not polymerized at once, there will be large losses, so There is a problem in that it is difficult to change the type and amount of fine metal powder dispersed in the synthetic resin according to the lineup.
本発明の目的は、上記従来の金属含有樹脂成形品の成形方法の問題点を解消し、合成樹脂中に金属を均一に分散させることが可能であり、成形品の特性を高く保持することが可能である上、成形品のラインナップに合わせて、合成樹脂中に分散させる金属の種類や量を容易に変更することが可能な金属含有樹脂成形品の成形方法を提供することにある。また、合成樹脂中に金属が均一に分散しているため、合成樹脂本来の特性にきわめて近い特性を発現させることが可能な金属含有樹脂成形品を提供することにある。 The purpose of the present invention is to solve the above-mentioned problems of the conventional method of molding metal-containing resin molded products, to make it possible to uniformly disperse metal in a synthetic resin, and to maintain high properties of the molded product. It is an object of the present invention to provide a method for molding a metal-containing resin molded product, which is not only possible but also allows the type and amount of metal dispersed in a synthetic resin to be easily changed according to the lineup of molded products. Another object of the present invention is to provide a metal-containing resin molded product that can exhibit properties extremely close to those inherent to the synthetic resin because the metal is uniformly dispersed in the synthetic resin.
本発明の内、請求項１に記載された発明は、合成樹脂中に金属を分散させてなる金属含有樹脂成形品を成形するための成形方法であって、溶融押出しする前のチップ状の合成樹脂の表面に金属を付着させる金属付着工程を有することを特徴とするものである。 The invention described in claim 1 of the present invention is a molding method for molding a metal-containing resin molded article made by dispersing metal in a synthetic resin, the method comprising: It is characterized by having a metal adhesion step of adhering metal to the surface of the resin.
請求項２に記載された発明は、請求項１に記載された発明において、前記金属付着工程が、めっきによってチップ状の合成樹脂の表面に金属を付着させるものであるとともに、金属を付着させる前のチップ状の合成樹脂の表面をエッチングするエッチング工程を有することを特徴とするものである。 The invention set forth in claim 2 is the invention set forth in claim 1, in which the metal attachment step attaches metal to the surface of the chip-shaped synthetic resin by plating, and before attaching the metal. The method is characterized by having an etching step for etching the surface of the chip-shaped synthetic resin.
請求項３に記載された発明は、請求項１、または２に記載された発明において、前記チップ状の合成樹脂の表面に付着させる金属として銀を用いることを特徴とするものである。 The invention set forth in claim 3 is the invention set forth in claim 1 or 2, characterized in that silver is used as the metal adhered to the surface of the chip-shaped synthetic resin.
請求項４に記載された発明は、請求項１～３のいずれかに記載された発明において、前記合成樹脂として、ＡＢＳ樹脂、ポリアミド樹脂、ポリオレフィン、ポリエステルの内の１種、あるいはそれらの内の２種以上の混合物を用いることを特徴とするものである。 The invention described in claim 4 is the invention described in any one of claims 1 to 3, in which the synthetic resin is one of ABS resin, polyamide resin, polyolefin, polyester, or one of them. It is characterized by using a mixture of two or more types.
請求項５に記載された発明は、請求項１～４のいずれかの成形方法によって成形されたことを特徴とする金属含有樹脂成形品である。 The invention set forth in claim 5 is a metal-containing resin molded article, characterized in that it is molded by the molding method according to any one of claims 1 to 4.
請求項６に記載の金属含有樹脂成形品は、合成樹脂中に金属が分散してなる金属含有樹脂成形品であって、任意の断面で裁断した場合に、当該断面における１～２００μｍの長径を有する金属凝集物の存在割合が５～５０個／ｍｍ２であることを特徴とするものである。なお、１～２００μｍの長径を有する金属凝集物の存在割合が５～３０個／ｍｍ２であるとより好ましい。 The metal-containing resin molded article according to claim 6 is a metal-containing resin molded article in which metal is dispersed in a synthetic resin, and when cut in an arbitrary cross section, the major axis of the cross section is 1 to 200 μm. It is characterized in that the proportion of metal aggregates present is 5 to 50 pieces/mm 2 . It is more preferable that the proportion of metal aggregates having a long axis of 1 to 200 μm is 5 to 30 pieces/mm 2 .
請求項１に記載の金属含有樹脂成形品の成形方法によれば、表面に金属が付着されたチップ状の合成樹脂を単独で、あるいは、金属が付着されていないブランクのチップ状の合成樹脂と混合して溶融押出するだけで、合成樹脂中に金属を均一に分散させることが可能となる。したがって、請求項１に記載の成形方法によれば、合成樹脂中に金属が均一に分散しており、原料である合成樹脂の本来の特性が高く保持された金属含有樹脂成形品を得ることが可能となる。また、請求項１に記載の成形方法によれば、成形品のラインナップに合わせて、合成樹脂中に分散させる金属の種類や量を容易に変更することができる。加えて、請求項１に記載の金属含有樹脂成形品の成形方法によれば、成形後の合成樹脂中にＣｕ，Ｎｉ，Ａｇ等の金属を均一に分散させることによって、成形後の合成樹脂の表面にもＣｕ，Ｎｉ，Ａｇ等の金属を多く析出させることが可能となるため、合成樹脂製の成形品に抗菌機能、除菌機能を発現させることも可能である。 According to the method for molding a metal-containing resin molded article according to claim 1, a chip-shaped synthetic resin with metal attached to the surface is used alone or with a blank chip-shaped synthetic resin to which no metal is attached. Just by mixing and melt-extruding, it becomes possible to uniformly disperse the metal in the synthetic resin. Therefore, according to the molding method according to claim 1, it is possible to obtain a metal-containing resin molded product in which the metal is uniformly dispersed in the synthetic resin and the original properties of the synthetic resin as a raw material are highly maintained. It becomes possible. Further, according to the molding method according to the first aspect, the type and amount of metal dispersed in the synthetic resin can be easily changed according to the lineup of molded products. In addition, according to the method for molding a metal-containing resin molded article according to claim 1, by uniformly dispersing metals such as Cu, Ni, Ag, etc. in the synthetic resin after molding, Since it is possible to precipitate a large amount of metals such as Cu, Ni, and Ag on the surface, it is also possible to make the synthetic resin molded product exhibit antibacterial and sterilizing functions.
請求項２に記載の金属含有樹脂成形品の成形方法によれば、エッチング後のチップ状の合成樹脂の表面にめっきすることでより多くの金属を付着させることができるため、合成樹脂成形品中により多くの金属を均一に分散させることが可能となる。 According to the method for molding a metal-containing resin molded product according to claim 2, more metal can be attached by plating the surface of the chip-shaped synthetic resin after etching. It becomes possible to uniformly disperse more metals.
請求項３に記載の金属含有樹脂成形品の成形方法は、合成樹脂中に分散させる金属が銀または銅であるため、金属の添加量が少ないにも拘わらず高い抗菌性および静電気除去特性を有する金属含有樹脂成形品を得ることができる。 The method for molding a metal-containing resin molded article according to claim 3 has high antibacterial properties and static electricity removal properties despite the small amount of metal added, since the metal dispersed in the synthetic resin is silver or copper. A metal-containing resin molded product can be obtained.
請求項４に記載の金属含有樹脂成形品の成形方法によれば、チップ状の合成樹脂の表面に容易に金属を付着させることができるため、多くの金属を均一に添加してなる金属含有樹脂成形品をより安価に製造することができる。 According to the method for molding a metal-containing resin molded article according to claim 4, since metal can be easily attached to the surface of a chip-shaped synthetic resin, a metal-containing resin formed by uniformly adding a large amount of metal can be used. Molded products can be manufactured at lower cost.
請求項５に記載の金属含有樹脂成形品は、合成樹脂中に金属が均一に分散しているため、合成樹脂本来の特性にきわめて近い特性を発現させることができる。 Since the metal-containing resin molded article according to claim 5 has metal uniformly dispersed in the synthetic resin, it is possible to exhibit properties extremely close to those inherent to the synthetic resin.
請求項６に記載の金属含有樹脂成形品は、合成樹脂中に大きな金属凝集物がほとんど存在しないので、合成樹脂本来の特性（良好な耐久強度等）を発現させることができる上、通常の合成樹脂製の成形品と変わらない外観を発現させることができる。 The metal-containing resin molded article according to claim 6 has almost no large metal aggregates in the synthetic resin, so it can exhibit the characteristics inherent to the synthetic resin (such as good durability and strength), and can also be used in conventional synthetic resins. It is possible to create an appearance similar to that of resin molded products.
本発明に係る金属含有樹脂成形品の成形方法は、予め金属を付着させた合成樹脂原料を溶融押出しすることによって成形品を形成するものであり、金属を付着させた合成樹脂原料を溶融させて金型内に射出して成形する射出成形方法の他に、金属を付着させた合成樹脂原料を溶融させてノズルやダイスから押し出して繊維、フィルムやシートを成形する成形方法等も含まれる。 The method for molding a metal-containing resin molded article according to the present invention is to form a molded article by melting and extruding a synthetic resin raw material to which a metal has been attached in advance. In addition to the injection molding method in which the material is injected into a mold, it also includes a molding method in which a synthetic resin raw material to which metal is attached is melted and extruded through a nozzle or die to mold fibers, films, or sheets.
本発明に係る成形方法は、合成樹脂原料を溶融押出しする前に、合成樹脂原料を、一旦、チップ状（ペレット状）に形成し、そのチップ状の合成樹脂の表面に金属を付着させる工程（すなわち、金属付着工程）を有していることを特徴としている。すなわち、本発明に係る成形方法は、従来の金属含有樹脂成形品を成形する場合のように、重合時に金属を添加してなる合成樹脂原料を用いる方法や、重合した後のチップ状の合成樹脂原料を溶融させて押し出す際に金属粉末と混合する方法とは異なり、重合後にチップ状にした合成樹脂の表面に金属を付着させて、その金属を付着させた合成樹脂チップを溶融押出して成形に供することを特徴としている。 The molding method according to the present invention includes a step of once forming a synthetic resin raw material into a chip shape (pellet shape) and attaching a metal to the surface of the chip-shaped synthetic resin before melting and extruding the synthetic resin raw material. That is, it is characterized by having a metal adhesion step). That is, the molding method according to the present invention includes a method using a synthetic resin raw material with a metal added during polymerization, as in the case of molding conventional metal-containing resin molded products, and a method using a synthetic resin material in the form of chips after polymerization. Unlike the method of melting raw materials and mixing them with metal powder when extruding, metal is attached to the surface of synthetic resin chips that are made into chips after polymerization, and the synthetic resin chips with the metal attached are melt-extruded and molded. It is characterized by providing
上記の如く、金属を付着させたチップ状の合成樹脂を溶融押出しして成形に供することによって、金属を合成樹脂中に高い均一性で（凝集を存在させることなく）分散させることが可能となる。そのため、本発明に係る成形方法によれば、原料である合成樹脂本来の良好な特性（機械的特性、熱的特性、電気的特性等）が損なわれていない金属含有樹脂成形品を得ることが可能となる。 As mentioned above, by melt-extruding chip-shaped synthetic resin to which metal is attached and subjecting it to molding, it becomes possible to disperse the metal in the synthetic resin with high uniformity (without agglomeration). . Therefore, according to the molding method of the present invention, it is possible to obtain a metal-containing resin molded product in which the original good properties (mechanical properties, thermal properties, electrical properties, etc.) of the synthetic resin as a raw material are not impaired. It becomes possible.
本発明に係る成形方法に用いられる合成樹脂は、溶融押出しが可能なものであれば特に限定されず、通常の成形に使用されるポリスチレン、高密度ポリエチレン、低密度ポリエチレン、ポリプロピレン等のポリオレフィン、ポリ塩化ビニル、エチレン・酢酸ビニル共重合体、アクリロニトリル・ブタジエン・スチレン共重合体、ＡＢＳ樹脂等の汎用性の高い合成樹脂、ポリカーボネート、ポリアミド、ポリアセタール、変性ポリフェニレンエーテル、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等のエンジニアプラスチック、スチレン系、オレフィン系、ウレタン系、アミド系等の各種の熱可塑性エラストマーやアイオノマー等を単独で、あるいは２種以上を混合して用いることができ、それらの合成樹脂の一部を変性した変性物を用いることも可能である。また、合成樹脂として、ＡＢＳ樹脂、ポリアミド樹脂、ポリオレフィン、ポリエステルの内の１種、あるいはそれらの内の２種以上の混合物を用いると、チップ状の合成樹脂の表面に容易に金属を付着させることができるため、多くの金属を均一に分散させてなる金属含有樹脂成形品をより安価に製造することができる。 The synthetic resin used in the molding method of the present invention is not particularly limited as long as it can be melt-extruded, and polyolefins such as polystyrene, high-density polyethylene, low-density polyethylene, and polypropylene, which are used in ordinary molding, Engineers of highly versatile synthetic resins such as vinyl chloride, ethylene/vinyl acetate copolymer, acrylonitrile/butadiene/styrene copolymer, ABS resin, polycarbonate, polyamide, polyacetal, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, etc. Various thermoplastic elastomers and ionomers such as plastics, styrene-based, olefin-based, urethane-based, amide-based, etc. can be used alone or in combination of two or more, and some of these synthetic resins are modified. It is also possible to use modified products. Furthermore, if one of ABS resin, polyamide resin, polyolefin, polyester, or a mixture of two or more of these is used as the synthetic resin, metal can be easily attached to the surface of the chip-shaped synthetic resin. Therefore, a metal-containing resin molded product in which many metals are uniformly dispersed can be manufactured at a lower cost.
さらに、チップ状の合成樹脂の表面に金属を付着させる方法も、特に限定されず、金属をめっきする方法、コーティングする方法や蒸着する方法等を用いることができる。また、めっきする方法としては、置換めっき、電気めっき、無電解めっき等の各種の湿式のめっき処理方法を好適に用いることができる。一方、金属を蒸着する方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法（ＩＰ法）や気相成長法（ＰＶＤ法）を好適に用いることができる。それらの金属蒸着方法を用いると、チップ状の合成樹脂の表面に均一な蒸着膜を形成することができ、最終的な金属含有樹脂成形品における金属の分散性をより高いものとすることが可能となるので好ましい。また、金属による化学反応を利用した無電解めっき方法を用いると、合成樹脂の表面に付着させる金属層の厚みを容易に厚くすることができるため、多くの金属を合成樹脂中に含有させることが可能となるので好ましい。 Further, the method for attaching metal to the surface of the synthetic resin chip is not particularly limited, and methods such as plating, coating, and vapor deposition may be used. Furthermore, as a plating method, various wet plating methods such as displacement plating, electroplating, and electroless plating can be suitably used. On the other hand, as a method for vapor depositing metal, a vacuum vapor deposition method, a sputtering method, an ion plating method (IP method), or a vapor phase growth method (PVD method) can be suitably used. By using these metal vapor deposition methods, it is possible to form a uniform vapor deposition film on the surface of chip-shaped synthetic resin, and it is possible to improve the dispersibility of metal in the final metal-containing resin molded product. This is preferable. In addition, by using an electroless plating method that utilizes chemical reactions with metals, the thickness of the metal layer attached to the surface of the synthetic resin can be easily increased, making it possible to incorporate many metals into the synthetic resin. This is preferable because it is possible.
上記した金属めっきや金属蒸着によってチップ状の合成樹脂の表面に形成する金属膜の厚みは、特に限定されないが、０．０１～１０μｍの範囲に調整すると、最終的な金属含有樹脂成形品における金属の分散性を一段と高いものとし、曲げ強度を向上させる、すなわち製品肉厚を低減させることが可能となるので好ましい。 The thickness of the metal film formed on the surface of the chip-shaped synthetic resin by the metal plating or metal vapor deposition described above is not particularly limited, but when adjusted to a range of 0.01 to 10 μm, the thickness of the metal film in the final metal-containing resin molded product is This is preferable because it can further improve the dispersibility of the material and improve the bending strength, that is, reduce the thickness of the product.
また、金属を付着させる合成樹脂のチップの形状も、特に限定されないが、円柱状や楕球状のものであると、金属付着工程の実施時に金属を多く付着させ易いので好ましい。また、金属を付着させる合成樹脂のチップの大きさも、特に限定されないが、体積（平均の体積）が３～３０ｍｍ３であると、溶融押出し後の金属の分散性が良好なものとなるので好ましく、５～２０ｍｍ３であると、特に好ましい。合成樹脂のチップの体積が、３ｍｍ３を下回ると、金属を付着させる際に斑が生じ易くなり、溶融押出し後の金属の分散性が低下するので好ましくなく、反対に、３０ｍｍ３以上になった場合でも同様に、溶融押出し後の金属の分散性が低下するので好ましくない。 Further, the shape of the synthetic resin chip to which the metal is attached is not particularly limited, but it is preferable to use a cylindrical or elliptical shape, since this facilitates the attachment of a large amount of metal during the metal attachment step. Further, the size of the synthetic resin chips to which the metal is attached is not particularly limited, but it is preferable that the volume (average volume) is 3 to 30 mm 3 because the dispersibility of the metal after melt extrusion will be good. , 5 to 20 mm 3 is particularly preferred. If the volume of the synthetic resin chip is less than 3 mm 3 , spots will easily occur when metal is attached, and the dispersibility of the metal after melt extrusion will decrease, which is undesirable . Even in this case, the dispersibility of the metal after melt extrusion decreases, which is not preferable.
さらに、上記の如く、金属めっきや金属蒸着によってチップ状の合成樹脂の表面に金属を付着させる前には、チップ状の合成樹脂の表面に、エッチング（粗面化処理）を施すのが好ましい。エッチングの方法は、特に限定されず、液体を用いたウェットエッチングや、反応性のガスを用いたドライエッチングを好適に用いることができる。また、液体を用いたウェットエッチングをチップ状の合成樹脂の表面に施す場合には、合成樹脂の種類に応じて、酢酸、塩酸等の各種の酸の一種あるいは二種以上の混合物や、水酸化ナトリウム、炭酸ナトリウム、水酸化カリウム等のアルカリの一種あるいは二種以上の混合物を選択して用いることができる。 Further, as described above, before metal is attached to the surface of the synthetic resin chip by metal plating or metal vapor deposition, it is preferable to perform etching (roughening treatment) on the surface of the synthetic resin chip. The etching method is not particularly limited, and wet etching using a liquid or dry etching using a reactive gas can be suitably used. In addition, when performing wet etching using a liquid on the surface of a chip-shaped synthetic resin, depending on the type of synthetic resin, one or a mixture of two or more of various acids such as acetic acid and hydrochloric acid, hydroxide, etc. One or a mixture of two or more alkalis such as sodium, sodium carbonate, and potassium hydroxide can be selected and used.
また、チップ状のＡＢＳ樹脂の表面に金属めっきを施す場合には、クロム酸、硫酸を用いてエッチングするのが好ましく、エッチングした後にめっき処理（無電解めっき等）を施す前に、中和（クロム酸の除去等）、キャタリスト（パラジウム等の触媒の付与）、アクセレーター（キャタリスト処理によって吸着されたスズ－パラジウムコロイドの内のスズの除去等）を施すのが好ましい。 In addition, when applying metal plating to the surface of chip-shaped ABS resin, it is preferable to perform etching using chromic acid or sulfuric acid. It is preferable to perform a catalyst treatment (removal of chromic acid, etc.), a catalyst (application of a catalyst such as palladium), and an accelerator (removal of tin from tin-palladium colloid adsorbed by catalyst treatment, etc.).
さらに、上記の如く、金属めっきによってチップ状の合成樹脂の表面に金属を付着させる場合には、金属めっき処理を多数回繰り返すことによって、多層の金属層をチップ状の合成樹脂の表面に積層させることも可能である。また、そのように、多層の金属層をチップ状の合成樹脂の表面に積層させる場合には、２回目以降の金属めっき処理を施す前のチップ状の合成樹脂の表面に、塩酸、硫酸等を用いた活性化処理を施すことも可能である。 Furthermore, as mentioned above, when metal is attached to the surface of a synthetic resin chip by metal plating, multiple metal layers are laminated on the surface of the synthetic resin chip by repeating the metal plating process many times. It is also possible. In addition, when laminating multiple metal layers on the surface of a synthetic resin chip in this way, hydrochloric acid, sulfuric acid, etc. are applied to the surface of the synthetic resin chip before the second or subsequent metal plating treatment. It is also possible to perform an activation treatment using
また、本発明に係る金属含有樹脂成形品の成形方法においては、原料である合成樹脂中に、必要に応じて、各種の充填材、難燃剤、抗菌剤、安定剤、紫外線吸収剤、酸化防止剤等を添加することも可能である。 In addition, in the method for molding metal-containing resin molded products according to the present invention, various fillers, flame retardants, antibacterial agents, stabilizers, ultraviolet absorbers, antioxidants, etc. are added to the synthetic resin as a raw material, as necessary. It is also possible to add agents, etc.
以下、実施例・比較例によって本発明に係る金属含有樹脂成形品およびその成形方法について詳細に説明するが、本発明に係る金属含有樹脂成形品およびその成形方法は、かかる実施例の態様に何ら限定されるものではなく、本発明の趣旨を逸脱しない範囲で、必要に応じて適宜変更することが可能である。また、実施例および比較例における特性の評価方法は以下の通りである。 Hereinafter, the metal-containing resin molded product and the molding method thereof according to the present invention will be explained in detail with reference to Examples and Comparative Examples. The present invention is not limited thereto, and can be modified as necessary without departing from the spirit of the present invention. Further, the evaluation method of characteristics in Examples and Comparative Examples is as follows.
＜成形品の曲げ強度の変動率＞
各実施例・各比較例で得られた金属含有樹脂成形品の曲げ強度（Ｓｍ）を、試験温度２３℃の条件で、精密万能試験機（株式会社島津製作所製、商品名：オートグラフＡＧ－５０００Ｂ）を用いて、ＪＩＳ Ｋ ７１７１（２０１６）に準拠した方法によって測定した。なお、測定条件は以下の通りとした。
・ポンチ半径：５ｍｍ
・支点半径：２ｍｍ
・支点間距離：１６ｈ（ｈ＝試料の厚み）
また、金属を含有していない樹脂成形品（金属含有樹脂成形品と同一のＡＢＳ樹脂、ＰＥＴによって成形されたもの）の曲げ強度（Ｓｂ）を、同様の方法によって測定した。そして、下式１を用いて、曲げ強度の低下率を測定した。
Ｄｂ＝（Ｓｍ－Ｓｂ）／Ｓｂ×１００（％） ・・式１
<Variation rate of bending strength of molded product>
The bending strength (Sm) of the metal-containing resin molded products obtained in each example and each comparative example was measured using a precision universal testing machine (manufactured by Shimadzu Corporation, product name: Autograph AG-) at a test temperature of 23°C. 5000B) by a method based on JIS K 7171 (2016). The measurement conditions were as follows.
・Punch radius: 5mm
・Fulcrum radius: 2mm
・Distance between fulcrums: 16h (h = sample thickness)
In addition, the bending strength (Sb) of a resin molded product that does not contain metal (molded from the same ABS resin and PET as the metal-containing resin molded product) was measured by the same method. Then, the rate of decrease in bending strength was measured using Equation 1 below.
Db=(Sm-Sb)/Sb×100(%)...Formula 1
＜金属の分散状態＞
各実施例・各比較例で得られた金属含有樹脂成形品における金属の分散状態を、拡大率１０倍のルーペを用いて目視によって下記の４段階で官能評価した。
○：成形品中に金属の凝集が見られず、均一に分散している
△：成形品中に小さな金属の凝集がわずかに散点状に認められる
×：成形品中に多数の金属の凝集が認められる
<Dispersion state of metal>
The dispersion state of the metal in the metal-containing resin molded product obtained in each Example and each Comparative Example was visually evaluated using a magnifying glass of 10 times and sensory evaluated on the following four levels.
○: Metal agglomeration is not observed in the molded product and is uniformly dispersed. △: Small metal agglomerations are observed in the molded product in scattered spots. ×: A large number of metal agglomerations are observed in the molded product. is recognized
［実施例１］
＜金属めっきした合成樹脂の調製＞
テクノＵＭＧ社製のチップ状のＡＢＳ樹脂 約５．０ｋｇを、４２０ｇ／ｌのクロム酸と２００ｍｌ／ｌの硫酸とを混合して７０℃に加熱した浴内で１０分間に亘って浸漬させることによって、ＡＢＳ樹脂の表面にエッチング処理を施した。なお、ＡＢＳ樹脂は、略円柱形状のチップ状に形成されており、直径（平均直径）＝約２．０ｍｍであり、高さ（平均高さ）＝約３．０ｍｍであった（平均体積＝９．４２ｍｍ３）。しかる後、（・・・社製の・・・装置を用いて）無電解めっき法によって、強酸性タイプの無電解 置換型 銀めっき浴を用いて、エッチング処理を施したＡＢＳ樹脂の表面に銀をめっきした。なお、無電解めっきの時間を調整することによって、めっき量（表面への付着量）が合成樹脂に対して、５，０００ｐｐｍ（０．５質量％）となるように調整した。
[Example 1]
<Preparation of metal-plated synthetic resin>
By immersing approximately 5.0 kg of ABS resin chips manufactured by Techno UMG in a bath heated to 70°C in which 420 g/l chromic acid and 200 ml/l sulfuric acid were mixed for 10 minutes. , etching treatment was performed on the surface of ABS resin. The ABS resin was formed into a substantially cylindrical chip shape, with a diameter (average diameter) of approximately 2.0 mm and a height (average height) of approximately 3.0 mm (average volume = 9.42mm3 ). After that, silver is applied to the surface of the etched ABS resin using a strongly acidic electroless displacement silver plating bath using an electroless plating method (using equipment manufactured by ... company). plated. In addition, by adjusting the electroless plating time, the amount of plating (the amount of adhesion to the surface) was adjusted to 5,000 ppm (0.5% by mass) based on the synthetic resin.
＜金属めっきした合成樹脂を用いた射出成形＞
上記の如く得られた金属（銀）めっき後のチップ状のＡＢＳ樹脂を、溶融押出装置を利用して１２０℃の温度で溶融押出した後に、金属製の型に射出することによって、長さ×幅×厚さ＝８０ｍｍ×１０ｍｍ×４ｍｍの直方体状の成形品を得た。そして、得られた成形品を用いて、上記した方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
<Injection molding using metal-plated synthetic resin>
The chip-shaped ABS resin after metal (silver) plating obtained as described above is melt-extruded at a temperature of 120°C using a melt extrusion device, and then injected into a metal mold, so that the length x A rectangular parallelepiped molded product with width x thickness = 80 mm x 10 mm x 4 mm was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated by the method described above. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and melt extrusion conditions.
［実施例２］
エッチング処理を施したチップ状のＡＢＳ樹脂の表面にめっきする金属をＣｕに変更した以外は、実施例１と同様にして、金属（Ｃｕ）めっき後のチップ状のＡＢＳ樹脂を得た。なお、Ｃｕめっきの際には、強酸性タイプの無電解 置換型 胴めっき浴を用いた。しかる後、得られた金属（Ｃｕ）めっき後のＡＢＳ樹脂を用いて、実施例１と同様な射出成形方法によって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。また、得られた成形品（金属めっき後に溶融押出し成形されたもの）の断面（長手方向に沿った断面）の電子顕微鏡（ＳＥＭ）による拡大写真を図１、図２に示す（図１は、約１３９倍の拡大写真であり、図２は、約２，２１９倍の拡大写真である）。それらの写真から、得られた成形品においては、８０％以上の個数の金属（Ｃｕ）粒子の長軸が、溶融押出し時の樹脂の流れ方向（写真における左右方向）を向いている（±１０°の範囲で樹脂の流れ方向に沿っている）ことが分かる。
[Example 2]
A chip-shaped ABS resin plated with metal (Cu) was obtained in the same manner as in Example 1, except that the metal plated on the surface of the etched ABS resin chip was changed to Cu. For Cu plating, a strongly acidic electroless displacement type body plating bath was used. Thereafter, a molded article having the same shape as in Example 1 was obtained by the same injection molding method as in Example 1 using the obtained ABS resin after metal (Cu) plating. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and melt extrusion conditions. In addition, enlarged photographs of the cross section (cross section along the longitudinal direction) of the obtained molded product (melt extrusion molded after metal plating) are shown in Figures 1 and 2 using an electron microscope (SEM). (This is an approximately 139x magnification photograph, and Figure 2 is an approximately 2,219x magnification photograph.) These photographs show that in the molded product obtained, the long axis of more than 80% of the metal (Cu) particles is oriented in the flow direction of the resin during melt extrusion (left-right direction in the photograph) (±10 It can be seen that the flow direction is along the flow direction of the resin within a range of .
［実施例３］
エッチング処理を施したチップ状のＡＢＳ樹脂の表面にめっきする金属をＮｉに変更した以外は、実施例１と同様にして、金属（Ｎｉ）めっき後のチップ状のＡＢＳ樹脂を得た。なお、Ｎｉめっきの際には、強酸性タイプの無電解 置換型 ニッケルめっき浴を用いた。しかる後、得られた金属（Ｎｉ）めっき後のＡＢＳ樹脂を用いて、実施例１と同様な射出成形方法によって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Example 3]
A chip-shaped ABS resin plated with metal (Ni) was obtained in the same manner as in Example 1, except that the metal plated on the surface of the etched ABS resin chip was changed to Ni. For Ni plating, a strongly acidic electroless displacement nickel plating bath was used. Thereafter, a molded article having the same shape as in Example 1 was obtained by the same injection molding method as in Example 1 using the obtained ABS resin after metal (Ni) plating. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［実施例４］
クラレ社製のチップ状のＰＥＴ（ポリエチレンテレフタレート） ５．０ｋｇを、実施例１と同一の浴内で１０分間に亘って浸漬させることによって、ＰＥＴの表面にエッチング処理を施した。なお、ＰＥＴ樹脂は、略円柱形状のチップ状に形成されており、直径（平均直径）＝約２．０ｍｍであり、高さ（平均高さ）＝約３．０ｍｍであった。しかる後、（・・・社製の・・・装置を用いて）無電解めっき法によって、強酸性タイプの無電解 置換型 銀めっき浴を用いて、エッチング処理を施したＰＥＴの表面に銀をめっきした。なお、無電解めっきの時間を調整することによって、めっき量（表面への付着量）が合成樹脂に対して、８，０００ｐｐｍ（０．８質量％）となるように調整した。
[Example 4]
Etching treatment was performed on the surface of PET by immersing 5.0 kg of chip-shaped PET (polyethylene terephthalate) manufactured by Kuraray Co., Ltd. in the same bath as in Example 1 for 10 minutes. The PET resin was formed into a substantially cylindrical chip shape, with a diameter (average diameter) of approximately 2.0 mm and a height (average height) of approximately 3.0 mm. After that, silver is applied to the etched surface of the PET using a strongly acidic electroless displacement silver plating bath (using equipment manufactured by...). Plated. In addition, by adjusting the electroless plating time, the amount of plating (the amount of adhesion to the surface) was adjusted to 8,000 ppm (0.8% by mass) based on the synthetic resin.
そして、得られた金属（Ａｇ）めっき後のＰＥＴ樹脂を、実施例１と同じ溶融押出装置を利用して２６５℃の温度で溶融押出した後に、実施例１と同じ金属製の型に射出することによって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。 Then, the obtained PET resin after metal (Ag) plating is melt extruded at a temperature of 265° C. using the same melt extrusion device as in Example 1, and then injected into the same metal mold as in Example 1. As a result, a molded article having the same shape as in Example 1 was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［実施例５］
エッチング処理を施したチップ状のＰＥＴの表面にめっきする金属をＣｕに変更した以外は、実施例４と同様にして、金属（Ｃｕ）めっき後のチップ状のＰＥＴを得た。なお、Ｃｕめっきの際には、強酸性タイプの無電解 置換型 胴めっき浴を用いた。しかる後、得られた金属（Ｃｕ）めっき後のＰＥＴを用いて、実施例１と同様な射出成形方法によって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Example 5]
A PET chip after metal (Cu) plating was obtained in the same manner as in Example 4, except that the metal plated on the surface of the etched PET chip was changed to Cu. For Cu plating, a strongly acidic electroless displacement type body plating bath was used. Thereafter, a molded article having the same shape as in Example 1 was obtained by the same injection molding method as in Example 1 using the obtained PET after metal (Cu) plating. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［実施例６］
エッチング処理を施したチップ状のＰＥＴの表面にめっきする金属をＮｉに変更した以外は、実施例１と同様にして、金属（Ｎｉ）めっき後のチップ状のＰＥＴを得た。なお、Ｎｉめっきの際には、強酸性タイプの無電解 置換型 ニッケルめっき浴を用いた。しかる後、得られた金属（Ｎｉ）めっき後のＰＥＴを用いて、実施例１と同様な射出成形方法によって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Example 6]
A PET chip after being plated with metal (Ni) was obtained in the same manner as in Example 1, except that the metal plated on the surface of the etched PET chip was changed to Ni. For Ni plating, a strongly acidic electroless displacement nickel plating bath was used. Thereafter, a molded article having the same shape as in Example 1 was obtained by the same injection molding method as in Example 1 using the obtained PET after metal (Ni) plating. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［比較例１］
実施例１と同じチップ状のＡＢＳ樹脂 約５．０ｋｇと、銀粉末２５ｇとを容器内で十分に撹拌混合した。しかる後、その混合組成物を、実施例１と同じ溶融押出装置を利用して１２０℃の温度で溶融押出した後に、実施例１と同じ金属製の型に射出することによって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Comparative example 1]
About 5.0 kg of the same chip-shaped ABS resin as in Example 1 and 25 g of silver powder were sufficiently stirred and mixed in a container. Thereafter, the mixed composition was melt-extruded at a temperature of 120° C. using the same melt-extrusion apparatus as in Example 1, and then injected into the same metal mold as in Example 1. A molded article of the same shape was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［比較例２］
実施例１と同じチップ状のＡＢＳ樹脂 約５．０ｋｇと、Ｎｉ粉末２５ｇとを容器内で十分に撹拌混合した。しかる後、その混合組成物を、実施例１と同じ溶融押出装置を利用して１２０℃の温度で溶融押出した後に、実施例１と同じ金属製の型に射出することによって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Comparative example 2]
About 5.0 kg of the same chip-shaped ABS resin as in Example 1 and 25 g of Ni powder were sufficiently stirred and mixed in a container. Thereafter, the mixed composition was melt-extruded at a temperature of 120° C. using the same melt-extrusion apparatus as in Example 1, and then injected into the same metal mold as in Example 1. A molded article of the same shape was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［比較例３］
実施例４と同じチップ状のＰＥＴ 約５．０ｋｇと、銀粉末５０ｇとを容器内で十分に撹拌混合した。しかる後、その混合組成物を、実施例１と同じ溶融押出装置を利用して２６５℃の温度で溶融押出した後に、実施例１と同じ金属製の型に射出することによって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Comparative example 3]
About 5.0 kg of the same chip-shaped PET as in Example 4 and 50 g of silver powder were sufficiently stirred and mixed in a container. Thereafter, the mixed composition was melt-extruded at a temperature of 265° C. using the same melt-extrusion apparatus as in Example 1, and then injected into the same metal mold as in Example 1. A molded article of the same shape was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
［比較例４］
実施例４と同じチップ状のＰＥＴ 約５．０ｋｇと、Ｎｉ粉末２５ｇとを容器内で十分に撹拌混合した。しかる後、その混合組成物を、実施例１と同じ溶融押出装置を利用して２６５℃の温度で溶融押出した後に、実施例１と同じ金属製の型に射出することによって、実施例１と同じ形状の成形品を得た。そして、得られた成形品を用いて、実施例１と同様な方法によって、曲げ強度の低下率および金属の分散状態を評価した。評価結果を成形原料の特性・溶融押出しの条件とともに表１に示す。
[Comparative example 4]
Approximately 5.0 kg of the same chip-shaped PET as in Example 4 and 25 g of Ni powder were sufficiently stirred and mixed in a container. Thereafter, the mixed composition was melt-extruded at a temperature of 265° C. using the same melt-extrusion apparatus as in Example 1, and then injected into the same metal mold as in Example 1. A molded article of the same shape was obtained. Then, using the obtained molded product, the rate of decrease in bending strength and the state of metal dispersion were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 along with the properties of the molding raw materials and the melt extrusion conditions.
表１から、溶融押出しする前のチップ状の合成樹脂の表面に金属を付着させる工程（金属付着工程）を備えた成形方法によって成形された実施例１～６の合成樹脂成形品は、いずれも、金属の分散性が良好であり（すなわち、金属が高い均一性で合成樹脂中に分散しており）、その結果として、曲げ強度の低下率が低くなっていることが分かる。それに対して、金属付着工程を備えていない成形方法によって成形された比較例１～４の合成樹脂成形品は、いずれも、金属の分散性が不良であり（すなわち、合成樹脂中に金属の凝集が散点しており）、その結果として、曲げ強度が高くなっていることが分かる。 From Table 1, all of the synthetic resin molded products of Examples 1 to 6 that were molded by a molding method that included a step of attaching metal to the surface of a chip-shaped synthetic resin before melt extrusion (metal attachment step) It can be seen that the dispersibility of the metal is good (that is, the metal is highly uniformly dispersed in the synthetic resin), and as a result, the rate of decrease in bending strength is low. On the other hand, the synthetic resin molded products of Comparative Examples 1 to 4, which were molded by a molding method that does not include a metal adhesion step, all had poor metal dispersibility (i.e., metal agglomeration in the synthetic resin). are scattered), and as a result, it can be seen that the bending strength is high.
本発明に係る金属含有樹脂成形品の成形方法は、上記の如く優れた効果を奏するものであるので、各種の合成樹脂成形品（金属を含有したもの）を成形するための方法として好適に用いることができる。 Since the method for molding metal-containing resin molded products according to the present invention has excellent effects as described above, it can be suitably used as a method for molding various synthetic resin molded products (those containing metal). be able to.
Claims (6)
溶融押出しする前のチップ状の合成樹脂の表面に金属を付着させる金属付着工程を有することを特徴とする金属含有樹脂成形品の成形方法。 A molding method for molding a metal-containing resin molded product made by dispersing metal in a synthetic resin, the method comprising:
A method for molding a metal-containing resin molded article, comprising a metal adhesion step of adhering metal to the surface of a chip-shaped synthetic resin before melt extrusion.
金属を付着させる前のチップ状の合成樹脂の表面をエッチングするエッチング工程を有することを特徴とする請求項１に記載の金属含有樹脂成形品の成形方法。 The metal attachment step attaches metal to the surface of the chip-shaped synthetic resin by plating, and
2. The method for molding a metal-containing resin molded article according to claim 1, further comprising an etching step of etching the surface of the chip-shaped synthetic resin before the metal is attached.
任意の断面で裁断した場合に、当該断面における１～２００μｍの長径を有する金属凝集物の存在割合が５～５０個／ｍｍ２であることを特徴とする金属含有樹脂成形品。 A metal-containing resin molded product made by dispersing metal in a synthetic resin,
A metal-containing resin molded article characterized in that, when cut in an arbitrary cross section, the proportion of metal aggregates having a long axis of 1 to 200 μm in the cross section is 5 to 50 pieces/mm 2 .
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