JP2013104111A - Composite material including polyacetal as main material and method for producing the same - Google Patents
Composite material including polyacetal as main material and method for producing the same Download PDFInfo
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- JP2013104111A JP2013104111A JP2011249965A JP2011249965A JP2013104111A JP 2013104111 A JP2013104111 A JP 2013104111A JP 2011249965 A JP2011249965 A JP 2011249965A JP 2011249965 A JP2011249965 A JP 2011249965A JP 2013104111 A JP2013104111 A JP 2013104111A
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- polyacetal
- electroless
- plating
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- electroless plating
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- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 61
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000007747 plating Methods 0.000 claims abstract description 81
- 238000007772 electroless plating Methods 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 11
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000007788 roughening Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 229910001080 W alloy Inorganic materials 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 24
- 239000002134 carbon nanofiber Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910018104 Ni-P Inorganic materials 0.000 description 3
- 229910018536 Ni—P Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
Description
本発明は、ポリアセタール樹脂成形物の摺動特性を向上させ得るポリアセタールを主材とする複合材およびその製造方法に関する。 The present invention relates to a composite material mainly composed of polyacetal that can improve the sliding properties of a polyacetal resin molded product, and a method for producing the same.
ポリアセタールは極めて優れた機械特性を有するエンジニアリングプラスチックであり、プリンタギア等の摺動部品等、金属部品の代替材料として広く利用されている。ところで、摺動部品等に利用する場合には、摩擦・摩耗特性のさらなる向上が求められる。
特許文献１には、ポリアセタールの表面処理として、ポリアセタール樹脂成形物の表面に金属めっき皮膜を形成し、摺動特性を向上させることが記載されている。
Polyacetal is an engineering plastic having extremely excellent mechanical properties, and is widely used as an alternative material for metal parts such as sliding parts such as printer gears. By the way, when using for sliding parts etc., the further improvement of a friction and wear characteristic is calculated | required.
Patent Document 1 describes that as a surface treatment of polyacetal, a metal plating film is formed on the surface of a polyacetal resin molded article to improve sliding characteristics.
特許文献１に示すものでは、ポリアセタール樹脂成形物表面を粗面化し、次いで、無電解めっきを行って無電解めっき皮膜を形成し、この無電解めっき皮膜を給電層として電解めっきを行い、電解めっき皮膜を形成するものである。このように、特許文献１のものでは、ポリアセタール樹脂成形物の表面にめっき皮膜を形成して、摩耗・摩擦特性を向上させるものである。
しかしながら、この特許文献１のものでは、無電解めっきと電解めっきの２段階に亘るめっき処理が必要で、工数が多く、コストが増大するという課題がある。
また、摩擦・摩耗特性のさらなる向上が求められる。
In the one shown in Patent Document 1, the surface of the polyacetal resin molded product is roughened, and then electroless plating is performed to form an electroless plating film, and the electroless plating film is used as a power feeding layer to perform electroplating. A film is formed. Thus, in the thing of patent document 1, a plating film is formed in the surface of a polyacetal resin molding, and an abrasion and a friction characteristic are improved.
However, the thing of this patent document 1 has the subject that the plating process over two steps of electroless plating and electrolytic plating is required, man-hours are many, and cost increases.
In addition, further improvement in friction and wear characteristics is required.
本発明は上記課題を解決すべくなされたものであり、その目的とするところは、無電解めっきだけの１段階のめっきですみ、コストの低減化が図れるとともに、摩擦・摩耗特性の向上が図れるポリアセタールを主材とする複合材およびその製造方法を提供することにある。 The present invention has been made to solve the above-mentioned problems, and the object of the present invention is only one-stage plating with only electroless plating, which can reduce costs and improve friction and wear characteristics. An object of the present invention is to provide a composite material mainly composed of polyacetal and a method for producing the same.
本発明に係るポリアセタールを主材とする複合材は、粗面化処理したポリアセタール樹脂成形物上に、カーボンナノチューブ（ＣＮＴ）を含む無電解めっき皮膜が形成されていることを特徴とする。 The composite material mainly composed of polyacetal according to the present invention is characterized in that an electroless plating film containing carbon nanotubes (CNT) is formed on a roughened polyacetal resin molded product.
また、カーボンナノチューブの一部が無電解めっき皮膜表面から露出しており、かつ、下記条件下、ボールオンディスク法で測定した、前記カーボンナノチューブの一部が露出している前記無電解めっき皮膜表面の動摩擦係数が、０．１〜０．２であることを特徴とする。
前記ボールオンディスク法の条件：
ボール：直径６ｍｍのＡｌ２Ｏ３製、荷重：２．００Ｎ、摺動半径：２．００ｍｍ、速度：１．００ｃｍ／ｓｅｃ、温度：室温、雰囲気：大気中、潤滑材：無し、摺動距離：１２．６ｍ（１０００回転）以内。
In addition, a part of the carbon nanotube is exposed from the surface of the electroless plating film, and the surface of the electroless plating film is exposed by a ball-on-disk method under the following conditions: The dynamic friction coefficient is 0.1 to 0.2.
Conditions for the ball-on-disk method:
Ball: made of Al 2 O 3 having a diameter of 6 mm, load: 2.00 N, sliding radius: 2.00 mm, speed: 1.00 cm / sec, temperature: room temperature, atmosphere: air, lubricant: none, sliding distance : Within 12.6 m (1000 rpm).
あるいは前記動摩擦係数が０．１１〜０．１３であることを特徴とする。
無電解めっきが、無電解Ｎｉ−Ｐ−Ｗ合金めっきであることを特徴とする。これによれば、めっき皮膜の耐摩耗性も向上できる。
Alternatively, the dynamic friction coefficient is 0.11 to 0.13.
The electroless plating is electroless Ni—P—W alloy plating. According to this, the wear resistance of the plating film can also be improved.
また、本発明に係るポリアセタールを主材とする複合材の製造方法は、ポリアセタール樹脂成形物表面を粗面化する工程と、分散剤によりカーボンナノチューブ（ＣＮＴ）が分散された無電解めっき液を準備する工程と、該無電解めっき液を用い、前記粗面化されたポリアセタール樹脂成形物表面に、カーボンナノチューブの一部がめっき皮膜表面から露出した無電解めっき皮膜を形成する工程とを含むことを特徴とする。 In addition, the method for producing a composite material mainly composed of polyacetal according to the present invention includes a step of roughening the surface of a polyacetal resin molding and an electroless plating solution in which carbon nanotubes (CNTs) are dispersed by a dispersant. And a step of forming an electroless plating film in which a part of the carbon nanotubes is exposed from the surface of the plating film on the surface of the roughened polyacetal resin molding using the electroless plating solution. Features.
無電解めっきが、無電解Ｎｉ−Ｐ−Ｗ合金めっきであることを特徴とする。これによれば、めっき皮膜の耐摩耗性も向上できる。またこの場合、カーボンナノチューブの分散剤に、トリメチルステアリルアンモニウムクロリドを用いると好適である。 The electroless plating is electroless Ni—P—W alloy plating. According to this, the wear resistance of the plating film can also be improved. In this case, it is preferable to use trimethylstearyl ammonium chloride as the carbon nanotube dispersant.
本発明によれば、無電解めっきだけの１段階のめっきですみ、工数を減らせ、コストの低減化が図れるとともに、摩擦・摩耗特性の向上が図れるポリアセタールを主材とする複合材およびその製造方法を提供できる。 According to the present invention, only one step of electroless plating is required, the number of steps can be reduced, the cost can be reduced, and the composite material mainly composed of polyacetal capable of improving the friction and wear characteristics, and the manufacturing method thereof Can provide.
以下本発明の好適な実施の形態を添付図面に基づいて詳細に説明する。
上記のように、本実施の形態におけるポリアセタールを主材とする複合材は、粗面化処理したポリアセタール樹脂成形物上に、カーボンナノチューブ（ＣＮＴ）を含む無電解めっき皮膜が形成されていることを特徴とする。
Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
As described above, in the composite material mainly composed of polyacetal in the present embodiment, an electroless plating film containing carbon nanotubes (CNT) is formed on a roughened polyacetal resin molded product. Features.
また、摺動性に優れるカーボンナノチューブの一部が無電解めっき皮膜表面から露出しており、これにより、動摩擦係数を小さくすることができ、摩擦特性を向上させることができる。
動摩擦係数の測定は種々の方法があるが、下記条件下、ボールオンディスク法で測定した、前記カーボンナノチューブの一部が露出している前記無電解めっき皮膜表面の動摩擦係数は、０．１〜０．２の範囲にあり、小さく、かつ安定した動摩擦係数が得られた。
≪前記ボールオンディスク法の条件≫
ボール：直径６ｍｍのＡｌ２Ｏ３製、荷重：２．００Ｎ、摺動半径：２．００ｍｍ、速度：１．００ｃｍ／ｓｅｃ、温度：室温、雰囲気：大気中、潤滑材：無し、摺動距離：１２．６ｍ（１０００回転）以内。
In addition, a part of the carbon nanotubes having excellent slidability is exposed from the surface of the electroless plating film, whereby the dynamic friction coefficient can be reduced and the friction characteristics can be improved.
Although there are various methods for measuring the dynamic friction coefficient, the dynamic friction coefficient of the surface of the electroless plating film in which a part of the carbon nanotube is exposed, measured by a ball-on-disk method under the following conditions, is 0.1 to A small and stable dynamic friction coefficient was obtained in the range of 0.2.
≪Conditions of the ball-on-disk method≫
Ball: made of Al 2 O 3 having a diameter of 6 mm, load: 2.00 N, sliding radius: 2.00 mm, speed: 1.00 cm / sec, temperature: room temperature, atmosphere: air, lubricant: none, sliding distance : Within 12.6 m (1000 rpm).
あるいは動摩擦係数が上記条件下、０．１１〜０．１７、もしくは０．１１〜０．１７の範囲内とする。
因みに、カーボンナノチューブ自体の動摩擦係数は０．０９前後であり、ポリアセタール樹脂成形物の動摩擦係数は０．２９程度であるから、本実施の形態における複合材の動摩擦係数は、カーボンナノチューブ単体に近い数値が得られており、優れた摩擦特性が得られている。
Alternatively, the dynamic friction coefficient is within the range of 0.11 to 0.17 or 0.11 to 0.17 under the above conditions.
Incidentally, the dynamic friction coefficient of the carbon nanotube itself is around 0.09, and the dynamic friction coefficient of the polyacetal resin molding is about 0.29. Therefore, the dynamic friction coefficient of the composite material in the present embodiment is a numerical value close to that of the carbon nanotube alone. Is obtained, and excellent friction characteristics are obtained.
無電解めっきの種類は特に限定されるものではないが、無電解Ｎｉ−Ｐ−Ｗ合金めっき、無電解Ｎｉ−Ｐ合金めっき、無電解Ｎｉめっき、無電解Ｃｕめっきが好適に適用できる。特に、無電解Ｎｉ−Ｐ−Ｗ合金めっきの場合、タングステンが共析することから、めっき皮膜の硬度が高くなり、耐摩耗性も向上する。 The type of electroless plating is not particularly limited, but electroless Ni—P—W alloy plating, electroless Ni—P alloy plating, electroless Ni plating, and electroless Cu plating can be suitably applied. In particular, in the case of electroless Ni—P—W alloy plating, since tungsten is eutectoid, the hardness of the plating film is increased and the wear resistance is also improved.
ポリアセタールを主材とする複合材の製造方法は、前記のように、ポリアセタール樹脂成形物表面を粗面化する工程と、分散剤によりカーボンナノチューブ（ＣＮＴ）が分散された無電解めっき液を準備する工程と、該無電解めっき液を用い、前記粗面化されたポリアセタール樹脂成形物表面に、カーボンナノチューブの一部がめっき皮膜表面から露出した無電解めっき皮膜を形成する工程とを含むことを特徴とする。 As described above, the method for producing a composite material containing polyacetal as a main material prepares an electroless plating solution in which carbon nanotubes (CNTs) are dispersed by a dispersing agent, and a step of roughening the surface of a polyacetal resin molded product. And a step of forming an electroless plating film in which a part of the carbon nanotubes is exposed from the surface of the plating film on the surface of the roughened polyacetal resin molding using the electroless plating solution. And
ポリアセタール樹脂成形物の表面は平滑であって、そのままでは、無電解めっき皮膜がほとんど密着しない。そこで、無電解めっき処理の前に、粗面化処理を行って、ポリアセタール樹脂成形物の表面に凹凸を形成するとよい。これにより、アンカー効果が生じ、ポリアセタール樹脂成形物と無電解めっき皮膜の密着性が向上する。粗面化処理も特に限定されるものではないが、塩酸と硫酸との混酸により粗面化すると好適である。 The surface of the polyacetal resin molding is smooth, and the electroless plating film hardly adheres as it is. Therefore, before the electroless plating treatment, roughening treatment may be performed to form irregularities on the surface of the polyacetal resin molded product. Thereby, an anchor effect arises and the adhesiveness of a polyacetal resin molding and an electroless-plating film improves. The surface roughening treatment is not particularly limited, but it is preferable to roughen the surface with a mixed acid of hydrochloric acid and sulfuric acid.
無電解めっきは通常の工程で行えばよい。すなわち、対象物（ポリアセタール樹脂基板）表面の脱脂を行い、上記粗面化処理を行い、キャタリストを行い、アクセレーターを行って後、無電解めっきを行う。
上記のように、無電解めっきの種類は特に限定されるものではないが、耐摩耗性も向上させるためには、無電解Ｎｉ−Ｐ−Ｗ合金めっきを行うと好適である。
めっき液中へのカーボンナノチューブの分散には分散剤を用いるようにする。無電解Ｎｉ−Ｐ−Ｗ合金めっき液の場合には、カーボンナノチューブの分散剤として、トリメチルステアリルアンモニウムクロリドを好適に用いることができる。
The electroless plating may be performed by a normal process. That is, the surface of the object (polyacetal resin substrate) is degreased, the roughening treatment is performed, the catalyst is performed, the accelerator is performed, and then the electroless plating is performed.
As described above, the type of electroless plating is not particularly limited. However, in order to improve wear resistance, it is preferable to perform electroless Ni—P—W alloy plating.
A dispersant is used to disperse the carbon nanotubes in the plating solution. In the case of an electroless Ni—P—W alloy plating solution, trimethylstearyl ammonium chloride can be suitably used as the carbon nanotube dispersant.
〔粗面化処理（エッチング）〕
通常の脱脂処理を行った後、塩酸：１５０ｇｄｍ‐３、硫酸：６２０ｇｄｍ‐３の混酸を用い、３０℃、５分、１０分、１５分、２０分、３０分の粗面化処理を行った。
粗面化処理を行ったポリアセタール樹脂基板（３．３ｃｍ×３ｃｍ）の表面のＳＥＭ写真を図１〜図６に示す（図１は無処理）。図から明らかなように、粗面化処理を行うことによって、ポリアセタール樹脂基板に凹凸が生じる。後に示すように、１５分程度粗面化処理を行った場合が、めっき皮膜の密着強度が高かった。
[Roughening treatment (etching)]
After performing normal degreasing treatment, a roughening treatment was performed using a mixed acid of hydrochloric acid: 150 gdm -3 and sulfuric acid: 620 gdm -3 at 30 ° C, 5 minutes, 10 minutes, 15 minutes, 20 minutes, and 30 minutes. .
SEM photographs of the surface of the polyacetal resin substrate (3.3 cm × 3 cm) subjected to the roughening treatment are shown in FIGS. 1 to 6 (FIG. 1 is untreated). As is apparent from the drawing, the roughening treatment causes unevenness on the polyacetal resin substrate. As shown later, the adhesion strength of the plating film was high when the surface was roughened for about 15 minutes.
〔前処理〕
上記粗面化処理後、水酸化ナトリウム：１５０ｇｄｍ‐３水溶液で、７５℃、６分のアルカリ処理を行い、次いで、有機酸：１５０ｇｄｍ‐３水溶液で、７５℃、１０分の中和処理を行い、さらに塩化スズ−塩化パラジウム溶液で常法によりキャタリストを行った。
〔Preprocessing〕
After the surface roughening treatment, an alkali treatment with sodium hydroxide: 150 gdm -3 aqueous solution is performed at 75 ° C for 6 minutes, and then an organic acid: 150 gdm -3 aqueous solution is subjected to neutralization treatment at 75 ° C for 10 minutes. Further, the catalyst was conducted by a conventional method using a tin chloride-palladium chloride solution.
〔無電解めっき〕
次に、ポリアセタール樹脂基板（３．３ｃｍ×３ｃｍ）上に無電解Ｎｉ−Ｐ−Ｗ合金／ＶＧＣＦ複合めっきを行った。
無電解めっき液の組成は次のとおり。
ＮｉＳＯ４・６Ｈ２Ｏ ０．０５Ｍ
Ｎａ３Ｃ６Ｈ５Ｏ７・２Ｈ２Ｏ ０．３Ｍ
ＮａＨ２ＰＯ２・Ｈ２Ｏ ０．１Ｍ
Ｎａ２ＷＯ４・２Ｈ２Ｏ ０．３Ｍ
トリメチルステアリル−
アンモニウムクロリド 適量
ＣＮＴ １ｇ／ｌ
トリメチルステアリルアンモニウムクロリドは、ＣＮＴの分散剤である。
なお、ＣＮＴは昭和電工製ＭＷＣＮＴ（商品名：ＶＧＣＦ）、直径：100〜200ｎｍ、長さ：10〜20ｎｍを用いた。
めっき条件は次のとおり。
ｐＨ：９．０、浴温：７５℃、撹拌：スターラー撹拌（開始から５分は撹拌なし）
[Electroless plating]
Next, electroless Ni—P—W alloy / VGCF composite plating was performed on a polyacetal resin substrate (3.3 cm × 3 cm).
The composition of the electroless plating solution is as follows.
NiSO 4 · 6H 2 O 0.05M
Na 3 C 6 H 5 O 7 · 2H 2 O 0.3M
NaH 2 PO 2 · H 2 O 0.1M
Na 2 WO 4 · 2H 2 O 0.3M
Trimethylstearyl-
Ammonium chloride appropriate amount CNT 1g / l
Trimethylstearyl ammonium chloride is a CNT dispersant.
The CNT used was MWCNT (trade name: VGCF) manufactured by Showa Denko, diameter: 100 to 200 nm, and length: 10 to 20 nm.
The plating conditions are as follows.
pH: 9.0, bath temperature: 75 ° C., stirring: Stirrer stirring (no stirring for 5 minutes from the start)
図７〜図１２に、無電解Ｎｉ−Ｐ−Ｗ合金めっき皮膜の低倍率のＳＥＭ写真を示し、図１３〜図１８に高倍率のＳＥＭ写真を示し、図１９〜図２４にその断面のＳＥＭ写真を示す。なお、粗面化処理はいずれも１５分のものである。めっき時間が長くなるほど、めっき膜の表面の平滑性が増す。図１３〜図１８からわかるように、めっき時間が１２０分のものが、十分な量のカーボンナノチューブ（ＣＮＴ）が無電解めっき皮膜に取り込まれているのがわかる。なお、カーボンナノチューブの一部が無電解めっき皮膜の表面に露出している。また、図１９〜図２４からわかるように、めっき時間が１２０分以上の場合に、粗面化処理で形成された凹凸の凹部内にまでめっき皮膜が十分に形成されている。めっき厚は、無電解めっきであるので、それ程厚くはないが、めっき時間が１２０分のもので１０μｍ程度のめっき厚が得られており、めっき厚としては十分である。 7 to 12 show low-magnification SEM photographs of the electroless Ni—P—W alloy plating film, FIGS. 13 to 18 show high-magnification SEM photographs, and FIGS. 19 to 24 show cross-sectional SEM photographs. Show photos. Note that the roughening treatment is for 15 minutes. The longer the plating time, the more smooth the surface of the plating film. As can be seen from FIG. 13 to FIG. 18, it can be seen that when the plating time is 120 minutes, a sufficient amount of carbon nanotubes (CNT) is taken into the electroless plating film. A part of the carbon nanotube is exposed on the surface of the electroless plating film. Further, as can be seen from FIGS. 19 to 24, when the plating time is 120 minutes or more, the plating film is sufficiently formed even in the concave and convex portions formed by the roughening treatment. Since the plating thickness is electroless plating, it is not so thick, but a plating thickness of about 10 μm is obtained with a plating time of 120 minutes, which is sufficient as the plating thickness.
図２５は、無電解めっき時間と、無電解めっき皮膜の密着強度を示すグラフである。この密着試験における密着強度は、ピンを強力な接着剤によりめっき皮膜表面に接着し、垂直に引き上げ、素地（ポリアセタール樹脂基板）とめっき皮膜との間で剥離した際の力：Ｋｇ／ｃｍ２で示した。めっき時間が１２０分のものが密着強度に優れていることがわかる。 FIG. 25 is a graph showing the electroless plating time and the adhesion strength of the electroless plating film. The adhesion strength in this adhesion test is the force when the pin is adhered to the surface of the plating film with a strong adhesive, pulled up vertically, and peeled between the substrate (polyacetal resin substrate) and the plating film: Kg / cm 2 Indicated. It can be seen that a plating time of 120 minutes is excellent in adhesion strength.
図２６は、動摩擦係数を計測したグラフを示す。
試験サンプルは、未処理のポリアセタール基板と、本実施の形態におけるポリアセタール基板（Ｎｉ−15at.％、Ｐ−2.5at.％、Ｗ合金／ＶＧＣＦの複合めっきをしたポリアセタール樹脂基板：図１７に示すポリアセタール樹脂基板）である。
試験方法は、ボールオンディスク法で、次の条件下で行った。
ボール：直径６ｍｍのＡｌ２Ｏ３製、
荷重：２．００Ｎ、
摺動半径：２．００ｍｍ、
速度：１．００ｃｍ／ｓｅｃ、
温度：室温、
雰囲気：大気中、
摺動距離：１２．６ｍ（１０００回転）
FIG. 26 shows a graph obtained by measuring the dynamic friction coefficient.
The test sample was an untreated polyacetal substrate and a polyacetal substrate in the present embodiment (Ni-15 at.%, P-2.5 at.%, Polyacetal resin substrate with composite plating of W alloy / VGCF: polyacetal shown in FIG. Resin substrate).
The test method was a ball-on-disk method and was performed under the following conditions.
Ball: made of Al 2 O 3 with a diameter of 6 mm,
Load: 2.00N
Sliding radius: 2.00 mm,
Speed: 1.00 cm / sec,
Temperature: room temperature,
Atmosphere: in air
Sliding distance: 12.6m (1000 rotations)
図２６に示されるように、未処理のポリアセタール基板の動摩擦係数は０．２９前後であるのに対し、本実施例におけるポリアセタール基板の場合には、動摩擦係数が０．１〜０．２の範囲（０．１１〜０．１３の範囲内で安定）であり、摺動距離が１２．６ｍ経過後も安定しており、摩擦特性が改善されている。 As shown in FIG. 26, the dynamic friction coefficient of the untreated polyacetal substrate is around 0.29, whereas in the case of the polyacetal substrate in this example, the dynamic friction coefficient is in the range of 0.1 to 0.2. (Stable within a range of 0.11 to 0.13), the sliding distance is stable even after 12.6 m, and the friction characteristics are improved.
以上の実施例では、無電解Ｎｉ−Ｐ−Ｗ合金めっきとＶＧＣＦの複合めっきの例で示したが、無電解Ｎｉ−Ｐ合金めっきとＶＧＣＦの複合めっき、無電解ＮｉめっきとＶＧＣＦの複合めっき、無電解ＣｕめっきとＶＧＣＦの複合めっきの場合にも、ポリアセタール樹脂基板の特に摩擦特性が改善された。 In the above examples, the example of the electroless Ni—P—W alloy plating and VGCF composite plating is shown, but the electroless Ni—P alloy plating and VGCF composite plating, the electroless Ni plating and VGCF composite plating, Also in the case of the electroless Cu plating and VGCF composite plating, the friction characteristics of the polyacetal resin substrate were particularly improved.
因みに、無電解Ｎｉ−Ｐ合金めっきとＶＧＣＦの複合めっきの場合は次のめっき液の組成で行った。
組成 濃度Ｍ（mol/l）
ＮｉＳＯ４・６Ｈ２Ｏ ０．１
ＮａＨ２ＰＯ２・Ｈ２Ｏ ０．２
Ｃ６Ｈ５Ｎａ３Ｏ７ ０．５
(ＮＨ４)２ＳＯ４ ０．５
ＴＷＳＡＣ ０．６（ｇ/ｌ）
ＭＷＣＮＴ ２（ｇ/ｌ）
上記のように、界面活性剤（分散剤）として、トリメチルセチルアンモニウムクロリド（ＴＭＳＡＣ）を０．６ｇ／ｌ添加した。
Incidentally, in the case of electroless Ni—P alloy plating and VGCF composite plating, the following plating solution composition was used.
Composition Concentration M (mol / l)
NiSO 4 · 6H 2 O 0.1
NaH 2 PO 2 · H 2 O 0.2
C 6 H 5 Na 3 O 7 0.5
(NH 4 ) 2 SO 4 0.5
TWSAC 0.6 (g / l)
MWCNT 2 (g / l)
As described above, 0.6 g / l of trimethylcetylammonium chloride (TMSAC) was added as a surfactant (dispersant).
また、無電解ＣｕめっきとＶＧＣＦの複合めっきの場合は次のめっき液の組成で行った。
ＣｕＳＯ４・５Ｈ２Ｏ ０．０６Ｍ
ＣＨＯＣＯＯＨ・Ｈ２Ｏ ０．０３Ｍ
ＥＤＴＡ・２Ｎａ ０．１Ｍ
分散剤ＴＭＳＡＣ 1.7×10−３、1.7×10−４、1.7×10−５Ｍ
ＣＮＴ ２ｇ/ｌ
ＣＮＴは、ILIJIN社製のＭＷＣＮＴ：直径10〜15ｎｍ、長さ10〜20μｍのものを用いた。
In the case of electroless Cu plating and VGCF composite plating, the following plating solution composition was used.
CuSO 4 · 5H 2 O 0.06M
CHOCOOH · H 2 O 0.03M
EDTA · 2Na 0.1M
Dispersant TMSAC 1.7 × 10 −3 , 1.7 × 10 −4 , 1.7 × 10 −5 M
CNT 2g / l
As the CNT, MWCNT manufactured by ILIJIN: 10 to 15 nm in diameter and 10 to 20 μm in length was used.
Claims (7)
かつ、下記条件下、ボールオンディスク法で測定した、前記カーボンナノチューブの一部が露出している前記無電解めっき皮膜表面の動摩擦係数が、０．１〜０．２であることを特徴とする請求項１記載のポリアセタールを主材とする複合材。
前記ボールオンディスク法の条件：
ボール：直径６ｍｍのＡｌ２Ｏ３製、荷重：２．００Ｎ、摺動半径：２．００ｍｍ、速度：１．００ｃｍ／ｓｅｃ、温度：室温、雰囲気：大気中、潤滑材：無し、摺動距離：１２．６ｍ（１０００回転）以内。 A part of the carbon nanotube is exposed from the electroless plating film surface,
And the dynamic friction coefficient of the surface of the electroless plating film in which a part of the carbon nanotube is exposed, measured by a ball-on-disk method under the following conditions, is 0.1 to 0.2. A composite material comprising the polyacetal according to claim 1 as a main material.
Conditions for the ball-on-disk method:
Ball: made of Al 2 O 3 having a diameter of 6 mm, load: 2.00 N, sliding radius: 2.00 mm, speed: 1.00 cm / sec, temperature: room temperature, atmosphere: air, lubricant: none, sliding distance : Within 12.6 m (1000 rpm).
ポリアセタール樹脂成形物表面を粗面化する工程と、
分散剤によりカーボンナノチューブ（ＣＮＴ）が分散された無電解めっき液を準備する工程と、
該無電解めっき液を用い、前記粗面化されたポリアセタール樹脂成形物表面に、カーボンナノチューブの一部がめっき皮膜表面から露出した無電解めっき皮膜を形成する工程とを含むことを特徴とするポリアセタールを主材とする複合材の製造方法。 In the method for producing a composite material mainly composed of polyacetal,
A step of roughening the surface of the polyacetal resin molding,
Preparing an electroless plating solution in which carbon nanotubes (CNT) are dispersed by a dispersant;
A step of forming an electroless plating film in which a part of the carbon nanotubes is exposed from the surface of the plating film on the surface of the roughened polyacetal resin molding using the electroless plating solution. The manufacturing method of the composite material which uses as a main material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185185A (en) * | 2012-03-07 | 2013-09-19 | Shinshu Univ | Ni-W ALLOY/CNT COMPOSITE PLATING METHOD AND Ni-W ALLOY/CNT COMPOSITE PLATING LIQUID |
| JP2017052978A (en) * | 2015-09-07 | 2017-03-16 | 新光電気工業株式会社 | Heat radiation part and production method thereof |
| US10316424B2 (en) | 2016-02-23 | 2019-06-11 | Samsung Electronics Co., Ltd. | Flexible electrically conductive structure, flexible wiring board, production method thereof, and electronic device includng the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039151B2 (en) * | 1981-07-03 | 1985-09-04 | 国産金属工業株式会社 | Resin surface treatment method |
| JPH09302476A (en) * | 1996-05-10 | 1997-11-25 | Daiwa Kasei Kenkyusho:Kk | Electroless tin-silver alloy plating bath |
| JPH1150295A (en) * | 1997-07-28 | 1999-02-23 | Daiwa Kasei Kenkyusho:Kk | Plating bath |
| JP2006523774A (en) * | 2003-04-16 | 2006-10-19 | アーハーツェー オーバーフレッヒェンテヒニーク ゲゼルシャフト ミット ベシュレンクテル ハフト ウント コンパニー オッフェネ ハンデルスゲゼルシャフト | Use of articles as molding tools |
| JP2007023316A (en) * | 2005-07-13 | 2007-02-01 | Kobe Steel Ltd | Wear-resistant member and motive-power transmitting component |
| JP2010215977A (en) * | 2009-03-17 | 2010-09-30 | Shinshu Univ | ELECTROLESS Ni-P PLATING LIQUID AND ELECTROLESS Ni-P PLATING METHOD |
-
2011
- 2011-11-15 JP JP2011249965A patent/JP2013104111A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039151B2 (en) * | 1981-07-03 | 1985-09-04 | 国産金属工業株式会社 | Resin surface treatment method |
| JPH09302476A (en) * | 1996-05-10 | 1997-11-25 | Daiwa Kasei Kenkyusho:Kk | Electroless tin-silver alloy plating bath |
| JPH1150295A (en) * | 1997-07-28 | 1999-02-23 | Daiwa Kasei Kenkyusho:Kk | Plating bath |
| JP2006523774A (en) * | 2003-04-16 | 2006-10-19 | アーハーツェー オーバーフレッヒェンテヒニーク ゲゼルシャフト ミット ベシュレンクテル ハフト ウント コンパニー オッフェネ ハンデルスゲゼルシャフト | Use of articles as molding tools |
| JP2007023316A (en) * | 2005-07-13 | 2007-02-01 | Kobe Steel Ltd | Wear-resistant member and motive-power transmitting component |
| JP2010215977A (en) * | 2009-03-17 | 2010-09-30 | Shinshu Univ | ELECTROLESS Ni-P PLATING LIQUID AND ELECTROLESS Ni-P PLATING METHOD |
Non-Patent Citations (1)
| Title |
|---|
| JPN6015024816; 鈴木 好治: '「特集／エンジニアリングプラスチックへのめっき ポリアセタール（ＰＯＭ）へのめっき」' 実務表面技術 Ｖｏｌ．３３ Ｎｏ．１２, 198612, Ｐａｇｅ．４９８-５０５ * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185185A (en) * | 2012-03-07 | 2013-09-19 | Shinshu Univ | Ni-W ALLOY/CNT COMPOSITE PLATING METHOD AND Ni-W ALLOY/CNT COMPOSITE PLATING LIQUID |
| JP2017052978A (en) * | 2015-09-07 | 2017-03-16 | 新光電気工業株式会社 | Heat radiation part and production method thereof |
| US10316424B2 (en) | 2016-02-23 | 2019-06-11 | Samsung Electronics Co., Ltd. | Flexible electrically conductive structure, flexible wiring board, production method thereof, and electronic device includng the same |
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